JP6354417B2 - Paper strength enhancer, paper obtained thereby, and method for producing paper - Google Patents
Paper strength enhancer, paper obtained thereby, and method for producing paper Download PDFInfo
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- JP6354417B2 JP6354417B2 JP2014149733A JP2014149733A JP6354417B2 JP 6354417 B2 JP6354417 B2 JP 6354417B2 JP 2014149733 A JP2014149733 A JP 2014149733A JP 2014149733 A JP2014149733 A JP 2014149733A JP 6354417 B2 JP6354417 B2 JP 6354417B2
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- Prior art keywords
- meth
- acrylamide
- mol
- paper
- water
- Prior art date
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- 239000003623 enhancer Substances 0.000 title claims description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000000178 monomer Substances 0.000 claims description 147
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 85
- 229920003169 water-soluble polymer Polymers 0.000 claims description 73
- 239000000203 mixture Substances 0.000 claims description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 229920002554 vinyl polymer Polymers 0.000 claims description 45
- 238000006116 polymerization reaction Methods 0.000 claims description 32
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 19
- 239000013055 pulp slurry Substances 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 14
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 12
- 229940073608 benzyl chloride Drugs 0.000 claims description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 11
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 11
- 235000011152 sodium sulphate Nutrition 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- CEJFYGPXPSZIID-UHFFFAOYSA-N chloromethylbenzene;2-(dimethylamino)ethyl prop-2-enoate Chemical compound ClCC1=CC=CC=C1.CN(C)CCOC(=O)C=C CEJFYGPXPSZIID-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims 2
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims 1
- 239000000123 paper Substances 0.000 description 116
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 38
- 230000000694 effects Effects 0.000 description 20
- 238000000034 method Methods 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 17
- -1 dimethylaminoethyl Chemical group 0.000 description 13
- 229920000831 ionic polymer Polymers 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 11
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 11
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 11
- 125000002091 cationic group Chemical group 0.000 description 10
- 230000001965 increasing effect Effects 0.000 description 10
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 10
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 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 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000002708 enhancing effect Effects 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000007870 radical polymerization initiator Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000010893 paper waste Substances 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000470 constituent Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 125000001302 tertiary amino group Chemical group 0.000 description 4
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001768 cations Chemical group 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000013054 paper strength agent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-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
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical class OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical group 0.000 description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 230000014759 maintenance of location Effects 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
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 1
- JDCBWJCUHSVVMN-SCSAIBSYSA-N (2r)-but-3-en-2-amine Chemical class C[C@@H](N)C=C JDCBWJCUHSVVMN-SCSAIBSYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- RWXMAAYKJDQVTF-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl prop-2-enoate Chemical compound OCCOCCOC(=O)C=C RWXMAAYKJDQVTF-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- QENRKQYUEGJNNZ-UHFFFAOYSA-N 2-methyl-1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(C)C(S(O)(=O)=O)NC(=O)C=C QENRKQYUEGJNNZ-UHFFFAOYSA-N 0.000 description 1
- FXBJYRVIFGLPBC-UHFFFAOYSA-N 2-methyl-n,n-bis(2-methylprop-2-enyl)prop-2-en-1-amine Chemical compound CC(=C)CN(CC(C)=C)CC(C)=C FXBJYRVIFGLPBC-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
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- PCUPXNDEQDWEMM-UHFFFAOYSA-N 3-(diethylamino)propyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCCOC(=O)C(C)=C PCUPXNDEQDWEMM-UHFFFAOYSA-N 0.000 description 1
- WWJCRUKUIQRCGP-UHFFFAOYSA-N 3-(dimethylamino)propyl 2-methylprop-2-enoate Chemical compound CN(C)CCCOC(=O)C(C)=C WWJCRUKUIQRCGP-UHFFFAOYSA-N 0.000 description 1
- TVZRAEYQIKYCPH-UHFFFAOYSA-N 3-(trimethylsilyl)propane-1-sulfonic acid Chemical compound C[Si](C)(C)CCCS(O)(=O)=O TVZRAEYQIKYCPH-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
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 1
- VNFYMAPAENTMMO-UHFFFAOYSA-N 5-chloro-2-methylquinoline Chemical compound ClC1=CC=CC2=NC(C)=CC=C21 VNFYMAPAENTMMO-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 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
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- VJMAITQRABEEKP-UHFFFAOYSA-N [6-(phenylmethoxymethyl)-1,4-dioxan-2-yl]methyl acetate Chemical compound O1C(COC(=O)C)COCC1COCC1=CC=CC=C1 VJMAITQRABEEKP-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
- 239000008351 acetate buffer Substances 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229940008075 allyl sulfide Drugs 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 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
- 239000010897 cardboard waste Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- ZTUMLBMROBHIIH-UHFFFAOYSA-N chloromethylbenzene;2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound ClCC1=CC=CC=C1.CN(C)CCOC(=O)C(C)=C ZTUMLBMROBHIIH-UHFFFAOYSA-N 0.000 description 1
- ADWWPMVBHMYTOQ-UHFFFAOYSA-N chloromethylbenzene;prop-2-enoic acid Chemical compound OC(=O)C=C.ClCC1=CC=CC=C1 ADWWPMVBHMYTOQ-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007334 copolymerization reaction 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZDGGJQMSELMHLK-UHFFFAOYSA-N m-Trifluoromethylhippuric acid Chemical compound OC(=O)CNC(=O)C1=CC=CC(C(F)(F)F)=C1 ZDGGJQMSELMHLK-UHFFFAOYSA-N 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
- 238000000691 measurement method Methods 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012898 sample dilution Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- HWEXKRHYVOGVDA-UHFFFAOYSA-M sodium;3-trimethylsilylpropane-1-sulfonate Chemical compound [Na+].C[Si](C)(C)CCCS([O-])(=O)=O HWEXKRHYVOGVDA-UHFFFAOYSA-M 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Paper (AREA)
Description
本発明は、両性(メタ)アクリルアミド系ポリマーを含有する紙力増強剤、紙力増強剤を用いて得られる紙、および紙の製造方法に関する The present invention relates to a paper strength enhancer containing an amphoteric (meth) acrylamide polymer, a paper obtained using the paper strength enhancer, and a method for producing the paper.
紙は、リサイクル可能な資源として、様々な用途で活用されている。製紙業界では環境対策の一環として古紙のリサイクルや用水使用量の削減(クローズド化)に取り組み、そのリサイクル率及びクローズド化率は年々向上傾向にある。古紙をリサイクルし続けると、パルプ表面のフィブリルは減少し、紙にした際の繊維間結合が減少する。さらに、パルプ繊維自体の強度も低下するため、得られる紙の強度は低下する。その結果、紙抄造時には強度の低下を補うために紙力増強剤は不可欠なものとなっている。 Paper is used for various purposes as a recyclable resource. In the paper industry, efforts are being made to recycle waste paper and reduce the amount of water used (closed) as part of environmental measures, and the recycling rate and closed rate are increasing year by year. If you continue to recycle waste paper, the fibrils on the pulp surface will decrease and the fiber-to-fiber bonds will decrease when you make paper. Furthermore, since the strength of the pulp fiber itself is also reduced, the strength of the obtained paper is reduced. As a result, a paper strength enhancer is indispensable to make up for the decrease in strength during papermaking.
また、古紙のリサイクルやクローズド化が進むことで、抄紙系内には微細繊維や溶存電解質物質が蓄積され、抄紙系の電気伝導度は上昇傾向にあり、一般的には電気伝導度が3mS/cmを超えると電気伝導度は高いとされるが、電気伝導度が4mS/cmを超えるパルプスラリーを用いて抄紙する場合も増えている。このような状況下で、両性紙力増強剤はイオン部が溶存電解質によって遮蔽されるため、本来の紙力増強効果を発揮し難くなっている。このような製紙用添加剤の一つにポリアクリルアミド系紙力増強剤がある。 In addition, as recycled paper is recycled and closed, fine fibers and dissolved electrolyte substances are accumulated in the papermaking system, and the electrical conductivity of the papermaking system is on the rise. Generally, the electrical conductivity is 3 mS / If it exceeds cm, the electric conductivity is considered to be high, but the case of making paper using a pulp slurry having an electric conductivity exceeding 4 mS / cm is also increasing. Under such circumstances, the amphoteric paper strength enhancer is difficult to exert its original paper strength enhancing effect because the ionic portion is shielded by the dissolved electrolyte. One such papermaking additive is a polyacrylamide paper strength enhancer.
ポリアクリルアミド系紙力増強剤はイオン性によりアニオンタイプ、カチオンタイプ、及び両性タイプに分類できる。現在は両性タイプが主流である。両性タイプのポリアクリルアミド系紙力増強剤は、アクリルアミドにカチオン性モノマーやアニオン性モノマー等の各種重合成分を共重合して得られる両性アクリルアミド系水溶性ポリマーを含有している。両性アクリルアミド系水溶性ポリマーは等電点を持ち、等電点付近のpHでポリイオンコンプレックスを形成する。等電点とはpHを変化させた時にポリマー全体としての電荷が0になるpHのことであり、ポリイオンコンプレックスとはアニオン基やカチオン基を持つポリマー同士がイオン結合により結合して形成される水不溶性物質のことである。ポリイオンコンプレックスを形成すると、白濁する現象が見られ、更には、不均一な状態になる場合や不溶化物を生成する場合もある。ポリイオンコンプレックスを形成することで、両性(メタ)アクリルアミド系水溶性ポリマーは、高い濾水性、歩留性及び紙力増強効果を発揮することが知られている。しかしながら、電気伝導度の高いパルプスラリーを用いて抄紙する場合は、既存の両性(メタ)アクリルアミド系水溶性ポリマーではポリイオンコンプレックスの形成を制御できておらず、紙力増強効果等の効果を十分に発揮する両性(メタ)アクリルアミド系水溶性ポリマーは、未だ開発されていない。 Polyacrylamide type paper strength enhancers can be classified into anionic type, cationic type and amphoteric type according to ionicity. At present, the gender type is the mainstream. The amphoteric type polyacrylamide-based paper strength enhancer contains an amphoteric acrylamide-based water-soluble polymer obtained by copolymerizing acrylamide with various polymerization components such as a cationic monomer and an anionic monomer. The amphoteric acrylamide-based water-soluble polymer has an isoelectric point, and forms a polyion complex at a pH near the isoelectric point. The isoelectric point is a pH at which the electric charge of the entire polymer becomes 0 when the pH is changed, and the polyion complex is a water formed by ionic bonds of polymers having an anion group or a cation group. It is an insoluble substance. When a polyion complex is formed, a phenomenon of white turbidity is observed, and further, a non-uniform state or an insolubilized product may be generated. It is known that by forming a polyion complex, an amphoteric (meth) acrylamide-based water-soluble polymer exhibits high drainage, retention, and paper strength enhancing effects. However, when making paper using pulp slurry with high electrical conductivity, existing amphoteric (meth) acrylamide-based water-soluble polymers cannot control the formation of polyion complexes, and the effects such as paper strength enhancement effects are sufficient. The amphoteric (meth) acrylamide-based water-soluble polymer to be exhibited has not been developed yet.
これに対しては、エステル構造を有するベンジル系4級アンモニウム塩基含有カチオン性モノマーを構成成分とした製紙用添加剤(特許文献1)やアミド構造を有するベンジル系4級アンモニウム塩基含有カチオン性モノマーを構成成分とした製紙用添加剤(特許文献2、3)が知られている。しかし、上記方法においても電気伝導度の高い抄紙系においては、濾水性・歩留性や紙力効果の向上については満足できる結果には至っていない。 For this, a papermaking additive (Patent Document 1) containing a benzylic quaternary ammonium base-containing cationic monomer having an ester structure as a constituent component or a benzylic quaternary ammonium base-containing cationic monomer having an amide structure is used. Papermaking additives (Patent Documents 2 and 3) are known as constituents. However, even in the above method, a papermaking system having high electrical conductivity has not yet achieved satisfactory results in terms of improvement in drainage, yield and paper strength effect.
本発明の目的は、3mS/cm未満の電気伝導度のパルプスラリーを用いて抄紙する場合及び3mS/cm以上の電気伝導度の高いパルプスラリーを用いて抄紙する場合においても、高い濾水性・歩留性を発揮しつつ、かつ、過度な凝集は起こさず、良好な地合いを実現し、紙力効果を向上させる両性(メタ)アクリルアミド系水溶性ポリマーを含有する紙力増強剤およびその製造方法を提供することにある。 The object of the present invention is to provide high drainage and a high step even when making paper using a pulp slurry having an electrical conductivity of less than 3 mS / cm and when making paper using a pulp slurry having a high electrical conductivity of 3 mS / cm or more. A paper strength enhancer containing an amphoteric (meth) acrylamide-based water-soluble polymer that achieves good texture and improves paper strength effects while exhibiting retention, and a method for producing the same It is to provide.
本発明者らは、上記課題を解決するために鋭意検討した結果、電気伝導度が高い水を用いて抄紙する場合、両性(メタ)アクリルアミド系水溶性ポリマーが、水溶液中のイオン電荷の遮蔽によりポリイオンコンプレックスを形成し難くなり、本来の効果が発揮できていないことを見出し、両性(メタ)アクリルアミド系水溶性ポリマーを含む紙力増強剤であって、両性(メタ)アクリルアミド系水溶性ポリマーの重量平均分子量を特定の範囲内とし、脱イオン水を硫酸ナトリウムで調整した電気伝導度4mS/cm・25℃の水で希釈した該両性(メタ)アクリルミド系水溶性ポリマーの1%水溶液のpH3〜9における濁度の分布が一つの極大値を有する分布となり、濁度の極大値を特定の範囲内に制御することにより、前記課題を解決しうることを見出し、本発明を完成させるに至った。 As a result of intensive investigations to solve the above problems, the present inventors have found that when paper is made using water having high electrical conductivity, the amphoteric (meth) acrylamide-based water-soluble polymer is blocked by ionic charge in the aqueous solution. It is difficult to form a polyion complex, and it has been found that the original effect has not been achieved. A paper strength enhancer containing an amphoteric (meth) acrylamide water-soluble polymer, the weight of the amphoteric (meth) acrylamide water-soluble polymer The average molecular weight is within a specific range, and the pH of a 1% aqueous solution of the amphoteric (meth) acrylimide water-soluble polymer diluted with water having an electric conductivity of 4 mS / cm · 25 ° C. adjusted with sodium sulfate in deionized water is 3 to 3. The distribution of turbidity at 9 has a single maximum value, and the above problem is solved by controlling the maximum value of turbidity within a specific range. Heading the Rukoto, it has led to the completion of the present invention.
すなわち、本願発明は、両性(メタ)アクリルアミド系水溶性ポリマーを固形分7〜30重量%含有する紙力増強剤であって、両性(メタ)アクリルアミド系水溶性ポリマーの重量平均分子量が、1,600,000〜10,000,000、脱イオン水を硫酸ナトリウムで調製した電気伝導度4mS/cm・25℃の水で希釈した該両性(メタ)アクリルミド系水溶性ポリマーの1%水溶液のpH3〜9における濁度の分布が一つの極大値を有し、その極大値が15〜2,000NTUであることを特徴とする紙力増強剤である(本発明1)。 That is, the present invention is a paper strength enhancer containing an amphoteric (meth) acrylamide water-soluble polymer in a solid content of 7 to 30% by weight, wherein the amphoteric (meth) acrylamide water-soluble polymer has a weight average molecular weight of 1, PH 3 of a 1% aqueous solution of the amphoteric (meth) acrylimide water-soluble polymer diluted with water having an electric conductivity of 4 mS / cm · 25 ° C. prepared with sodium sulfate from 600,000 to 10,000,000 The paper strength enhancer is characterized in that the turbidity distribution at -9 has one maximum value, and the maximum value is 15-2,000 NTU (Invention 1).
また、本発明2は、上記両性(メタ)アクリルアミド系水溶性ポリマーの重量平均分子量(が2,500,000〜7,000,000、上記濁度の極大値が20〜1,000NTUであることを特徴とする請求項1記載の紙力増強剤である。 In the present invention 2, the amphoteric (meth) acrylamide-based water-soluble polymer has a weight average molecular weight (2,500,000 to 7,000,000 and a maximum value of the turbidity of 20 to 1,000 NTU. The paper strength enhancer according to claim 1.
また、本発明3は、本発明1の紙力増強剤において、上記両性(メタ)アクリルアミド系水溶性ポリマーが、(メタ)アクリルアミド(a)59.0〜96.98mol%、カチオン性ビニルモノマー(b)2.0〜15.0mol%、アニオン性ビニルモノマー(c)1.0〜12.0mol%、架橋性モノマー(d)0.01〜2.0mol%、及び連鎖移動性モノマー(e)0.01〜2mol%を含む重合性成分を共重合して得られるものである。 In addition, the present invention 3 relates to the paper strength enhancer of the present invention 1, wherein the amphoteric (meth) acrylamide-based water-soluble polymer comprises (meth) acrylamide (a) 59.0 to 96.98 mol%, a cationic vinyl monomer ( b) 2.0-15.0 mol%, anionic vinyl monomer (c) 1.0-12.0 mol%, crosslinkable monomer (d) 0.01-2.0 mol%, and chain transfer monomer (e) It is obtained by copolymerizing a polymerizable component containing 0.01 to 2 mol%.
また、本発明4は、本発明1〜3のいずれかの紙力増強剤において、上記カチオン性ビニルモノマー(b)が、ジメチルアミノエチルメタクリレート、ジメチルアミノエチルアクリレートのベンジルクロライド4級化物及びジメチルアミノエチルメタクリレートのベンジルクロライド4級化物をそれぞれ0.05〜14.9mol%含有するものである。 Also, the present invention 4 provides the paper strength enhancer according to any one of the present invention 1 to 3, wherein the cationic vinyl monomer (b) is dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate benzyl chloride quaternized product and dimethylamino. Each contains 0.05 to 14.9 mol% of benzyl chloride quaternized product of ethyl methacrylate.
また、本発明5は、本発明1〜4のいずれかの紙力増強剤において、両性(メタ)アクリルアミド系水溶性ポリマーの1H−NMRスペクトルにおける0.9〜1.35ppmに検出される高磁場側シグナルAと低磁場側シグナルBのシグナル面積比[As/(As+Bs)](AsはシグナルA、BsはシグナルBの面積を表わす)が、20%以上である。 In addition, the present invention 5 is the paper strength enhancer of any one of the present inventions 1 to 4, wherein a high level of 0.9 to 1.35 ppm detected in the 1 H-NMR spectrum of the amphoteric (meth) acrylamide water-soluble polymer. The signal area ratio [As / (As + Bs)] of the magnetic field side signal A and the low magnetic field side signal B (As represents the area of the signal A and Bs represents the area of the signal B) is 20% or more.
また、本発明6は、上記両性(メタ)アクリルアミド系水溶性ポリマーが(メタ)アクリルアミド(a)を必須成分とした2種類以上のモノマー混合液を重合して得られるものであり、該モノマー混合液が下記(1)式及び(2)式(式中の各含有量の単位はmol%である。)を満たす紙力増強剤である。
カチオン性ビニルモノマー(b)含有量が最も多いモノマー混合液中のカチオン性ビニルモノマー含有量(i)/カチオン性ビニルモノマー(b)含有量が最も少ないモノマー混合液中のカチオン性ビニルモノマー含有量(ii)≧1.5 (1)
アニオン性ビニルモノマー(c)含有量が最も多いモノマー混合液中のアニオン性ビニルモノマー含有量(iii)/アニオン性ビニルモノマー(c)含有量が最も少ないモノマー混合液中のアニオン性ビニルモノマー含有量(iv)≧1.5 (2)
In addition, the present invention 6 is obtained by polymerizing the amphoteric (meth) acrylamide-based water-soluble polymer with a mixture of two or more monomers containing (meth) acrylamide (a) as an essential component. The liquid is a paper strength enhancer that satisfies the following formulas (1) and (2) (the unit of each content in the formula is mol%).
Cationic vinyl monomer content (i) in the monomer mixture with the largest cationic vinyl monomer (b) content / cationic vinyl monomer content in the monomer mixture with the smallest cationic vinyl monomer (b) content (Ii) ≧ 1.5 (1)
Anionic vinyl monomer content (iii) in the monomer mixture with the highest anionic vinyl monomer (c) content / Anionic vinyl monomer content in the monomer mixture with the lowest anionic vinyl monomer (c) content (Iv) ≧ 1.5 (2)
また、本発明7は、本発明6におけるモノマー混合液の重合が滴下重合を含む紙力増強剤である。 In addition, the present invention 7 is a paper strength enhancer in which the polymerization of the monomer mixture in the present invention 6 includes dropping polymerization.
また、本発明8は、本発明1〜7のいずれかに記載の紙力増強剤を用いて得られる紙である。 Moreover, this invention 8 is paper obtained using the paper strength enhancer in any one of this invention 1-7.
また、本発明9は、本発明1〜6のいずれかに記載の紙力増強剤を電気伝導度が3mS/cm以上のパルプスラリーに添加する紙の製造方法である。 The present invention 9 is a paper manufacturing method in which the paper strength enhancer according to any one of the present inventions 1 to 6 is added to a pulp slurry having an electric conductivity of 3 mS / cm or more.
本発明の紙力増強剤は電気伝導度が3mS/cm未満のパルプスラリーを用いて抄紙する場合及び3mS/cm以上のパルプスラリーを用いて抄紙する場合においても、パルプへの定着性に優れ、また、パルプに対する高い凝集力を示しながら、得られる紙の地合いが良好であり、高い紙力増強効果を発揮することができる。 The paper strength enhancer of the present invention has excellent fixability to pulp even when making paper using a pulp slurry having an electrical conductivity of less than 3 mS / cm and when making paper using a pulp slurry of 3 mS / cm or more, Moreover, while showing the high cohesion force with respect to a pulp, the texture of the paper obtained is favorable and can show the high paper strength enhancement effect.
本発明の紙力増強剤は、少なくとも(メタ)アクリルアミド(a)(以下、(a)成分という)、カチオン性ビニルモノマー(b)(以下、(b)成分という)およびアニオン性ビニルモノマー(c)(以下、(c)成分という)を共重合し得られる両性(メタ)アクリルアミド系水溶性ポリマーを溶媒中に固形分7〜30重量%含有する。好ましくは固形分10〜25重量%含有する。固形分7重量%未満の場合は紙力増強剤の輸送効率が悪く、固形分30重量%を越える場合には紙力増強剤の安定性が悪くなる。 The paper strength enhancer of the present invention comprises at least (meth) acrylamide (a) (hereinafter referred to as component (a)), cationic vinyl monomer (b) (hereinafter referred to as component (b)) and anionic vinyl monomer (c). ) (Hereinafter referred to as the component (c)) an amphoteric (meth) acrylamide-based water-soluble polymer obtained by copolymerization is contained in a solvent in a solid content of 7 to 30% by weight. The solid content is preferably 10 to 25% by weight. When the solid content is less than 7% by weight, the transport efficiency of the paper strength enhancer is poor, and when the solid content exceeds 30% by weight, the stability of the paper strength enhancer is deteriorated.
本発明の紙力増強剤の溶媒としては、両性(メタ)アクリルアミド系水溶性ポリマーを溶解または分散させることができれば、特に限定されないが、水を使うことが好ましい。また、紙力増強剤中には必要に応じて、炭酸カルシウムやタルクなどの公知の填料や硫酸ナトリウムや硫酸アンモニウム、塩化ナトリウムなどの塩類、防腐剤およびその他の添加剤(消泡剤、pH調整剤など)を含有することができる。 The solvent of the paper strength enhancer of the present invention is not particularly limited as long as it can dissolve or disperse the amphoteric (meth) acrylamide water-soluble polymer, but it is preferable to use water. In addition, in the paper strength enhancer, if necessary, known fillers such as calcium carbonate and talc, salts such as sodium sulfate, ammonium sulfate, and sodium chloride, preservatives and other additives (antifoaming agent, pH adjusting agent) Etc.) can be contained.
上記(a)成分の構成比率としては、特に限定されないが、十分な紙力効果を確保する観点から両性(メタ)アクリルアミド系水溶性ポリマーの全構成成分に対し、59〜96.98mol%が好ましく、より好ましくは70〜96.98mol%である。この場合、紙力向上効果に有効な水素結合能を有する(メタ)アクリルアミドの含有量が少なくならず、両性(メタ)アクリルアミド系水溶性ポリマーが十分な紙力向上効果を発揮することができる。 Although it does not specifically limit as a structural ratio of the said (a) component, 59-96.98 mol% is preferable with respect to all the structural components of an amphoteric (meth) acrylamide type water-soluble polymer from a viewpoint of ensuring sufficient paper strength effect. More preferably, it is 70-96.98 mol%. In this case, the content of (meth) acrylamide having hydrogen bonding ability effective for the paper strength improving effect is not decreased, and the amphoteric (meth) acrylamide water-soluble polymer can exhibit a sufficient paper strength improving effect.
上記(b)成分としては、カチオン性を有するビニルモノマーであれば特に限定されない。(b)成分の具体例としては、ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート、ジメチルアミノプロピル(メタ)アクリルアミド、ジエチルアミノプロピル(メタ)アクリルアミドなどの第三級アミノ基を有するビニルモノマーまたはそれらの無機酸もしくは有機酸の塩類、またはこれらの第3級アミノ基含有ビニルモノマーとメチルクロライド、ベンジルクロライド、ジメチル硫酸、エピクロロヒドリンなどの四級化剤との反応によって得られる第四級アンモニウム塩を有するビニルモノマーなどが挙げられる。これらは1種を単独で用いても良いし、2種以上を併用しても良い。 The component (b) is not particularly limited as long as it is a vinyl monomer having a cationic property. Specific examples of the component (b) include vinyl monomers having a tertiary amino group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide and the like. Or a salt of an inorganic acid or an organic acid thereof, or a tertiary amino group-containing vinyl monomer and a quaternary agent obtained by a reaction of a quaternizing agent such as methyl chloride, benzyl chloride, dimethyl sulfate, or epichlorohydrin. And vinyl monomers having a quaternary ammonium salt. These may be used alone or in combination of two or more.
上記(b)成分の構成比率としては、十分な紙力増強効果を確保し、かつ凝集性が強くなり過ぎることにより生ずる紙の地合いの乱れを防止する観点から、両性(メタ)アクリルアミド系水溶性ポリマーの全構成成分に対し2.0〜15.0mol%が好ましく、より好ましくは2.0〜10.0mol%である。 The component ratio of the component (b) is amphoteric (meth) acrylamide water-soluble from the viewpoint of securing a sufficient paper strength enhancing effect and preventing the paper texture from being disturbed due to excessive cohesion. 2.0-15.0 mol% is preferable with respect to all the structural components of a polymer, More preferably, it is 2.0-10.0 mol%.
さらに、(b)成分としては共重合性の異なる成分を2種類以上併用することができ、特にジメチルアミノエチルメタクリレート、ジメチルアミノエチルアクリレートのベンジルクロライド4級化物とジメチルアミノエチルメタクリレートのベンジルクロライド4級化物を併用することでポリマー中のカチオン部位の配置や分子量の制御が容易となるうえ、さらに高電気伝導度においてもカチオン性を維持しやすく良好な性能を発揮できる。ジメチルアミノエチルメタクリレート、ジメチルアミノエチルアクリレートのベンジルクロライド4級化物とジメチルアミノエチルメタクリレートのベンジルクロライド4級化物の構成比率としては両性(メタ)アクリルアミド系水溶性ポリマーの全構成成分に対し、0.05〜14.9mol%使用することが好ましい。より好ましくは0.05〜10.0mol%である。この場合、両性(メタ)アクリルアミド系水溶性ポリマーの凝集性は低くなり過ぎず、過凝集になるほど強くならないため、地合を乱さずに高い紙力増強効果が得られる。また、さらに他の(b)成分を併用することもできる。 Further, as the component (b), two or more components having different copolymerizability can be used in combination. In particular, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate benzyl chloride quaternized compound and dimethylaminoethyl methacrylate benzyl chloride quaternized compound. By using a compound together, the arrangement of the cation moiety in the polymer and the control of the molecular weight can be easily performed, and the cationic property can be easily maintained even at high electrical conductivity, and good performance can be exhibited. The composition ratio of benzyl chloride quaternized product of dimethylaminoethyl methacrylate and dimethylaminoethyl acrylate and benzyl chloride quaternized product of dimethylaminoethyl methacrylate is 0.05 to the total components of the amphoteric (meth) acrylamide water-soluble polymer. It is preferable to use ˜14.9 mol%. More preferably, it is 0.05-10.0 mol%. In this case, the cohesiveness of the amphoteric (meth) acrylamide-based water-soluble polymer does not become too low and does not become so strong as to be over-aggregated, so that a high paper strength enhancing effect can be obtained without disturbing formation. Furthermore, other component (b) can be used in combination.
上記(c)成分としては、アニオン性基を有するビニルモノマーであれば特に限定されない。(c)成分の具体例としては、アクリル酸、クロトン酸等の不飽和モノカルボン酸、マレイン酸、フマル酸、イタコン酸、ムコン酸等の不飽和ジカルボン酸、ビニルスルホン酸、スチレンスルホン酸、2−アクリルアミド−2−メチルプロパンスルホン酸などの有機スルホン酸、前記各種有機酸これらのナトリウム塩、カリウム塩等のアルカリ金属塩並びにこれらのアンモニウム塩等があげられる。これらは1種を単独で用いても良いし、2種以上を併用しても良い。
なお、本発明においては、後述するメタリルスルホン酸等の連鎖移動性モノマーは、(c)成分に含まない。
The component (c) is not particularly limited as long as it is a vinyl monomer having an anionic group. Specific examples of the component (c) include unsaturated monocarboxylic acids such as acrylic acid and crotonic acid, unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid and muconic acid, vinyl sulfonic acid, styrene sulfonic acid, 2 -Organic sulfonic acids such as acrylamido-2-methylpropane sulfonic acid, alkali metal salts such as sodium salts and potassium salts of the above various organic acids, and ammonium salts thereof. These may be used alone or in combination of two or more.
In the present invention, a chain transfer monomer such as methallylsulfonic acid described later is not included in the component (c).
上記(c)成分の構成比率としては、特に限定されないが、十分な紙力増強効果を確保し、かつ凝集性が強くなり過ぎることにより生ずる紙の地合いの乱れを防止する観点から両性(メタ)アクリルアミド系水溶性ポリマーの全構成成分に対し1.0〜12.0mol%が好ましく、より好ましくは1〜6mol%である。 The component ratio of the component (c) is not particularly limited, but it is amphoteric (meta) from the viewpoint of securing a sufficient paper strength enhancing effect and preventing the paper texture from being disturbed due to excessive cohesion. 1.0-12.0 mol% is preferable with respect to all the structural components of an acrylamide type water-soluble polymer, More preferably, it is 1-6 mol%.
本発明の両性(メタ)アクリルアミド水溶性ポリマーの重合には架橋性モノマー(d)(以下、(d)成分という)を併用することが好ましい。(d)成分としては、メチレンビスアクリルアミド等の多官能(メタ)アクリルアミド類、N,N−ジメチルアクリルアミド等のN置換(メタ)アクリルアミド類、エチレングリコールジアクリレート、ジアリルアミン、N−メチロールアクリルアミド等の2官能モノマー、トリアリルイソシアネートなどの3官能モノマー、テトラアリルオキシエタン等の4官能性モノマーや、アリルアクリレート、ジエチレングリコールモノアクリレート等のビニルモノマー等が挙げられる。これらの中では特に分岐および架橋反応の確実性から、メチレンビスアクリルアミド、N,N−ジメチルアクリルアミドを使用することが好ましい。これらは1種を単独で用いても良いし、2種以上を併用しても良い。 In the polymerization of the amphoteric (meth) acrylamide water-soluble polymer of the present invention, it is preferable to use a crosslinkable monomer (d) (hereinafter referred to as component (d)) in combination. As the component (d), 2 functional groups such as polyfunctional (meth) acrylamides such as methylenebisacrylamide, N-substituted (meth) acrylamides such as N, N-dimethylacrylamide, ethylene glycol diacrylate, diallylamine, N-methylolacrylamide, etc. Examples thereof include functional monomers, trifunctional monomers such as triallyl isocyanate, tetrafunctional monomers such as tetraallyloxyethane, vinyl monomers such as allyl acrylate and diethylene glycol monoacrylate, and the like. Of these, methylenebisacrylamide and N, N-dimethylacrylamide are preferably used because of the certainty of the branching and crosslinking reaction. These may be used alone or in combination of two or more.
上記(d)成分の構成比率としては、特に限定されないが、通常、両性(メタ)アクリルアミド水溶性ポリマーの全構成成分に対し0.01〜2.0mol%程度、好ましくは0.05〜1.0mol%である。この場合、両性(メタ)アクリルアミド水溶性ポリマーの分子量を高め、十分な紙力向上効果を発現でき、さらにゲル状物を発生させずに分子量を高めることもできるため、両性(メタ)アクリルアミド水溶性ポリマーに高い凝集性と紙力向上効果を付与できる。 Although it does not specifically limit as a structural ratio of the said (d) component, Usually, about 0.01-2.0 mol% with respect to all the structural components of an amphoteric (meth) acrylamide water-soluble polymer, Preferably it is 0.05-1. 0 mol%. In this case, the molecular weight of the amphoteric (meth) acrylamide water-soluble polymer can be increased, a sufficient paper strength improvement effect can be expressed, and the molecular weight can be increased without generating a gel-like substance. High cohesion and paper strength improvement effect can be imparted to the polymer.
本発明の両性(メタ)アクリルアミド水溶性ポリマーの重合には連鎖移動性モノマー(e)(以下、(e)成分という)を併用することが好ましい。(e)成分としては、(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、アリルスルファイド類、アリルメルカプタン類等の分子内に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が挙げられる。これらの中では特にメタリルスルホン酸ナトリウムを使用することが好ましい。これらは1種を単独で用いても良いし、2種以上を併用しても良い。 In the polymerization of the amphoteric (meth) acrylamide water-soluble polymer of the present invention, it is preferable to use a chain transfer monomer (e) (hereinafter referred to as component (e)) in combination. (E) Component includes (meth) allyl alcohol and its ester derivatives, (meth) allylamine, diallylamine, dimethallylamine and its amide derivatives, triallylamine, trimethallylamine, (meth) allylsulfonic acid and its salt, allyl sulfide And compounds having one or more carbon-carbon unsaturated bonds in the molecule, such as allyl mercaptans. Of these, sodium methallyl sulfonate is particularly preferably used. These may be used alone or in combination of two or more.
上記(e)成分の構成比率としては、特に限定されないが、通常、両性(メタ)アクリルアミド水溶性ポリマーの全構成成分に対し0.01〜2.0mol%、好ましくは0.30〜1.0mol%である。この場合、両性(メタ)アクリルアミド水溶性ポリマーの分子量を高め、十分な紙力向上効果を発現でき、さらにゲル状物を発生させずに分子量を高めることもできるため、両性(メタ)アクリルアミド水溶性ポリマーに高い凝集性と紙力向上効果を付与できる。 Although it does not specifically limit as a structural ratio of the said (e) component, Usually, 0.01-2.0 mol% with respect to all the structural components of an amphoteric (meth) acrylamide water-soluble polymer, Preferably it is 0.30-1.0 mol. %. In this case, the molecular weight of the amphoteric (meth) acrylamide water-soluble polymer can be increased, a sufficient paper strength improvement effect can be expressed, and the molecular weight can be increased without generating a gel-like substance. High cohesion and paper strength improvement effect can be imparted to the polymer.
本発明の両性(メタ)アクリルアミド水溶性ポリマーの重合には必要により(a)〜(e)以外のモノマーを併用してもよい。(a)〜(e)成分以外のモノマーとしては、ノニオン性ビニルモノマーなどがあげられる。ノニオン性ビニルモノマーとしては、(c)成分のアルキルエステル(特に、アルキル基の炭素数1〜8が好ましい)、アクリロニトリル、スチレン類、酢酸ビニル、メチルビニルエーテルなどが挙げられる。 For polymerization of the amphoteric (meth) acrylamide water-soluble polymer of the present invention, monomers other than (a) to (e) may be used in combination, if necessary. Examples of the monomer other than the components (a) to (e) include nonionic vinyl monomers. Examples of the nonionic vinyl monomer include (c) component alkyl esters (particularly, alkyl groups having 1 to 8 carbon atoms are preferred), acrylonitrile, styrenes, vinyl acetate, methyl vinyl ether, and the like.
上記(a)〜(e)成分以外のモノマーの構成比率としては、両性(メタ)アクリルアミド水溶性ポリマーの全構成成分に対して10mol%以下が好ましく、より好ましくは、5mol%以下である。この場合、両性(メタ)アクリルアミド水溶性ポリマーの紙力増強効果を損なわない。 The constituent ratio of the monomers other than the components (a) to (e) is preferably 10 mol% or less, more preferably 5 mol% or less, with respect to all constituent components of the amphoteric (meth) acrylamide water-soluble polymer. In this case, the paper strength enhancing effect of the amphoteric (meth) acrylamide water-soluble polymer is not impaired.
本発明の両性(メタ)アクリルアミド系水溶性ポリマーは、上記構成成分を共重合して得られるが、さらに重量平均分子量(ゲルパーメーションクロマトグラフィー法によるポリエチレンオキサイド換算値)が、通常1,600,000〜10,000,000である。好ましくは、2,500,000〜7,000,000で、通常、水溶液として取得することが好ましい。重量平均分子量が1,600,000を下回ると高電気伝導度の抄紙系においてはポリイオンコンプレックスを十分に形成することができず定着性が不十分となる場合があり、10,000,000を超えると凝集性が高くなりすぎる場合がある。 The amphoteric (meth) acrylamide-based water-soluble polymer of the present invention can be obtained by copolymerizing the above components, and the weight average molecular weight (polyethylene oxide equivalent by gel permeation chromatography) is usually 1,600, 000 to 10,000,000. Preferably, it is preferably 2,500,000 to 7,000,000, usually obtained as an aqueous solution. When the weight average molecular weight is less than 1,600,000, in a papermaking system having high electrical conductivity, a polyion complex cannot be formed sufficiently, and the fixability may be insufficient, which exceeds 10,000,000. And the cohesion may become too high.
本発明の両性(メタ)アクリルアミド系水溶性ポリマーは、脱イオン水を硫酸ナトリウムで調製した電気伝導度4mS/cm・25℃の水で希釈した該両性(メタ)アクリルミド系水溶性ポリマーの1重量%水溶液のpH3〜9における濁度分布が一つの極大値を有し、濁度の極大値が15〜2,000NTUである。好ましくは20〜1,000NTUである。 The amphoteric (meth) acrylamide water-soluble polymer of the present invention is one of the amphoteric (meth) acrylimide water-soluble polymers diluted with water having an electric conductivity of 4 mS / cm · 25 ° C. prepared with sodium sulfate. The turbidity distribution of the weight% aqueous solution at pH 3 to 9 has one maximum value, and the maximum value of turbidity is 15 to 2,000 NTU. Preferably it is 20-1,000 NTU.
上記濁度とは、濁りの度合いであって、ANALITE NEPHELOMETER 152(Mc Van Instruments社製)を用いて900nmの赤外光を利用した180度の散乱光を測定することにより得られた値であり、測定値は標準物質(ホルマジン標準液 400NTU、和光純薬工業(株)製)に対する相対的な評価値をいう。 The turbidity is the degree of turbidity, and is a value obtained by measuring 180-degree scattered light using 900 nm infrared light using ANALITE NEPHELOMETER 152 (manufactured by Mc Van Instruments). The measured value refers to a relative evaluation value with respect to a standard substance (formazine standard solution 400 NTU, manufactured by Wako Pure Chemical Industries, Ltd.).
上記濁度測定の際に用いた水は、脱イオン水を硫酸ナトリウムで調整したものである。この脱イオン水はイオン交換樹脂を通し電気伝導度を0.2mS/cm以下とした水である。ここで濁度測定の際にこの脱イオン水を硫酸ナトリウムで調整した水を用いたのは、抄紙する際の白水中には硫酸イオンやナトリウムイオンが多く存在するため、硫酸ナトリウムを使用することで抄紙する際の環境と近い環境を作ることができ、容易に電気伝導度を高めることができるためである。 The water used for the turbidity measurement is deionized water adjusted with sodium sulfate. This deionized water is water that has passed through an ion exchange resin and has an electric conductivity of 0.2 mS / cm or less. The reason why this deionized water prepared with sodium sulfate was used for turbidity measurement was that sodium sulfate was used because white water during paper making contained a lot of sulfate ions and sodium ions. This is because an environment close to that used in papermaking can be created, and the electrical conductivity can be easily increased.
両性(メタ)アクリルアミド系水溶性ポリマーは、ポリマー中にアニオン性およびカチオン性の官能基を持つため、希釈液のpHが等電点付近に近づくことでポリイオンコンプレックスを形成する。濁度を測定することで両性(メタ)アクリルアミド系水溶性ポリマーの希釈液のポリイオンコンプレックスの形成度合いが測定できる。両性(メタ)アクリルアミド系水溶性ポリマーがポリイオンコンプレックスを形成し始めると、希釈液に濁りが発生する。過大なポリイオンコンプレックスを形成すると、沈殿を生成することもあり、ある程度まで沈殿を生成すると濁度測定値は低下に転じることがある。これは溶解していたポリイオンコンプレックスが析出し、希釈水中の濁りがなくなるためである。この場合、図1に示すようにpHを3〜9に変化させた時の濁度分布は二つの極大値を有する(以降、二山と称す)。二山の濁度分布において、その山と山の間の谷の部分では、ポリイオンコンプレックスは過剰に大きくなり、凝集性は高いが地合を著しく乱し、紙力効果に悪影響を及ぼす。高い電気伝導度下においても、凝集性と地合いを高く維持し、優れた紙力効果を発揮するためには、高い電気伝導度下で測定した濁度分布は一つの極大値を有する(以下、一山とも称する)ことが必要である。 Since the amphoteric (meth) acrylamide-based water-soluble polymer has anionic and cationic functional groups in the polymer, a polyion complex is formed when the pH of the diluent approaches the isoelectric point. By measuring the turbidity, the degree of formation of the polyion complex in the dilute solution of the amphoteric (meth) acrylamide water-soluble polymer can be measured. When the amphoteric (meth) acrylamide-based water-soluble polymer starts to form a polyion complex, turbidity occurs in the diluted solution. When an excessive polyion complex is formed, a precipitate may be generated, and when the precipitate is generated to some extent, the turbidity measurement value may start to decrease. This is because the dissolved polyion complex is precipitated and the turbidity in the diluted water is eliminated. In this case, as shown in FIG. 1, the turbidity distribution when the pH is changed to 3 to 9 has two maximum values (hereinafter referred to as “two peaks”). In the turbidity distribution of two mountains, the polyion complex becomes excessively large in the valley portion between the mountains, and the cohesiveness is high, but the formation is remarkably disturbed, and the paper strength effect is adversely affected. The turbidity distribution measured under high electrical conductivity has one maximum value in order to maintain high cohesiveness and texture even under high electrical conductivity and to exert an excellent paper strength effect (hereinafter referred to as “maximum turbidity distribution”). Also called a mountain).
本発明の両性(メタ)アクリルアミド系水溶性ポリマーは、上記条件で測定した濁度の最大値が15NTU未満であると、凝集性が低く紙力増強効果も十分でなく、2000NTUを超えると過凝集が起こり、地合が悪くなる。 The amphoteric (meth) acrylamide water-soluble polymer of the present invention has a low cohesiveness when the maximum value of turbidity measured under the above conditions is less than 15 NTU, and the effect of enhancing paper strength is insufficient. Happens and the formation becomes worse.
本発明の両性(メタ)アクリルアミド系水溶性ポリマーは、両性(メタ)アクリルアミド系水溶性ポリマーの1H−NMRスペクトルにおける0.9〜1.35ppmに検出される高磁場側シグナルAと低磁場側シグナルBのシグナル面積比[As/(As+Bs)](AsはシグナルA、BsはシグナルBの面積を表わす)が、20%以上である場合に、高い電気伝導度下においても、パルプへの定着性を高めることでより優れた紙力効果を発揮する。 The amphoteric (meth) acrylamide-based water-soluble polymer of the present invention has a high magnetic field side signal A and a low magnetic field side detected at 0.9 to 1.35 ppm in the 1 H-NMR spectrum of the amphoteric (meth) acrylamide water-soluble polymer. When the signal area ratio of signal B [As / (As + Bs)] (As is signal A, Bs is the area of signal B) is 20% or more, it is fixed to pulp even under high electrical conductivity. By improving the properties, better paper strength effect is demonstrated.
上記シグナルAおよびシグナルBは、共に(b)成分に含まれるαメチル基由来のシグナルである。高磁場側のシグナルAについては、両性(メタ)アクリルアミド系水溶性ポリマー内においてαメチル基がモノマー単位で連続した場合に観測されるシグナルである。シグナルAの面積Asの割合が高まるということは、両性(メタ)アクリルアミド系水溶性ポリマー中に(b)成分が連続して存在する割合が高いことを示す。すなわち、前記2つのシグナルのうち、高磁場側シグナルAと低磁場側シグナルBのシグナル面積比[As/(As+Bs)]が高まるということは両性(メタ)アクリルアミド系水溶性ポリマー中のカチオンが局在化していることを示すものと考えられる。なお、本発明におけるシグナルAおよびBの検出範囲0.9〜1.35ppmは、内部標準物質として3−(トリメチルシリル)−1−プロパンスルホン酸ナトリウム(DSS)を使用した場合の値である。 Both the signal A and the signal B are signals derived from the α methyl group contained in the component (b). Signal A on the high magnetic field side is a signal observed when α-methyl groups are continuous in monomer units in the amphoteric (meth) acrylamide water-soluble polymer. An increase in the ratio of the area As of the signal A indicates that the ratio of the component (b) continuously present in the amphoteric (meth) acrylamide-based water-soluble polymer is high. That is, of the two signals, the signal area ratio [As / (As + Bs)] of the high magnetic field side signal A and the low magnetic field side signal B is increased. This indicates that the cation in the amphoteric (meth) acrylamide-based water-soluble polymer is localized. It is considered to indicate that it is present. In the present invention, the signal A and B detection ranges of 0.9 to 1.35 ppm are values when sodium 3- (trimethylsilyl) -1-propanesulfonate (DSS) is used as the internal standard substance.
上記「αメチル基」とは、ビニル基及びカチオン性官能基を有するモノマーにおいて、該ビニル基のα炭素に結合したメチル基を意味する。(b)成分としては、αメチル基を含有するカチオン性ビニルモノマーが好ましく、各種公知のものを特に制限なく使用できる。 The “α methyl group” means a methyl group bonded to the α carbon of the vinyl group in a monomer having a vinyl group and a cationic functional group. As the component (b), a cationic vinyl monomer containing an α-methyl group is preferable, and various known ones can be used without particular limitation.
上記(b)成分がαメチル基を有する場合の具体例としては、例えば、第3級アミノ基含有メタクリレート化合物と四級化剤との反応によって得られる第4級塩構造含有メタクリレート化合物が挙げられる。該第3級アミノ基含有メタクリレート化合物としては、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が挙げられる。また、該四級化剤としては、例えば、メチルクロライド、ベンジルクロライド、ジメチル硫酸及びエピクロロヒドリン等が挙げられる。 Specific examples of the case where the component (b) has an α methyl group include, for example, a quaternary salt structure-containing methacrylate compound obtained by a reaction between a tertiary amino group-containing methacrylate compound and a quaternizing agent. . Examples of the tertiary amino group-containing methacrylate compound include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylate and diethylaminopropyl methacrylate. Examples of the quaternizing agent include methyl chloride, benzyl chloride, dimethyl sulfate and epichlorohydrin.
本発明の両性(メタ)アクリルアミド系水溶性ポリマーの製造方法としては、特に制限されず、従来公知の重合方法を採用することができる。例えば、モノマー混合液に公知のラジカル重合開始剤を加えることにより行われる。好ましくは、滴下重合法を含む重合方法、滴下重合とモノマー混合液を一括して仕込む同時重合法を組み合わせることによる多段階の工程を含む重合方法が好ましい。2種類以上のモノマー混合液を用いる多段階の工程を含む重合方法としては、例えば、各モノマー混合液を別々に重合する方法、一種類以上のモノマー混合液の重合が終わってから、残りのモノマー混合液を滴下する重合方法、一種類以上のモノマー混合液を重合している途中から残りのモノマー混合液を滴下する重合方法、一種類以上のモノマー混合液の重合が終わってから、残りのモノマー混合液を混合して重合する方法、一種類以上のモノマー混合液を重合している途中から残りのモノマー混合液を混合して重合する方法、一種類以上のモノマー混合液を滴下重合して、残りのモノマー混合液を混合して重合する方法、各モノマー混合液をそれぞれ別々に重合して後で各重合物を混合する方法等が挙げられる。また両性(メタ)アクリルミド系水溶性ポリマーの合成に用いる全構成成分を複数のモノマー混合液に配分し、1部の混合液中の(b)成分や(c)成分の量を多くしてこれらの混合液を順次反応させたり、(b)成分や(c)成分を重合反応中のある時点で追加したりするなど、重合反応中のいずれかの段階において、反応に関与するカチオン性モノマーやアニオン性モノマーの濃度が高まるような操作を行えば、より好ましい。 The production method of the amphoteric (meth) acrylamide water-soluble polymer of the present invention is not particularly limited, and a conventionally known polymerization method can be adopted. For example, it is performed by adding a known radical polymerization initiator to the monomer mixture. Preferably, a polymerization method including a dropping polymerization method, and a polymerization method including a multi-stage process by combining the dropping polymerization and a simultaneous polymerization method in which a monomer mixed solution is charged together are preferable. Examples of the polymerization method including a multi-step process using two or more kinds of monomer mixed liquids include, for example, a method in which each monomer mixed liquid is polymerized separately, and the remaining monomer after the polymerization of one or more monomer mixed liquids is completed. A polymerization method in which a mixed liquid is dropped, a polymerization method in which the remaining monomer mixed liquid is dropped in the middle of polymerization of one or more types of monomer mixed liquid, and a remaining monomer after the polymerization of one or more types of monomer mixed liquid is completed. A method of mixing and polymerizing a mixture, a method of mixing and polymerizing the remaining monomer mixture from the middle of polymerization of one or more types of monomer mixture, a drop polymerization of one or more types of monomer mixture, Examples thereof include a method in which the remaining monomer mixture is mixed and polymerized, and a method in which each monomer mixture is separately polymerized and then each polymer is mixed. In addition, all components used for the synthesis of the amphoteric (meth) acrylimide-based water-soluble polymer are distributed to a plurality of monomer mixed solutions, and the amount of the (b) component and (c) component in one part of the mixed solution is increased. Cationic monomers that are involved in the reaction at any stage during the polymerization reaction, such as reacting these mixed solutions in sequence or adding the component (b) or component (c) at a certain point during the polymerization reaction. It is more preferable to perform an operation that increases the concentration of the anionic monomer.
本発明の両性(メタ)アクリルアミド系水溶性ポリマーは、(メタ)アクリルアミド(a)を必須成分とした2種類以上のモノマー混合液を重合して得られるものであり、モノマー混合液が下記(1)式及び(2)式(式中の各含有量の単位はmol%である。)を満たすことが好ましい。
カチオン性ビニルモノマー(b)含有量が最も多いモノマー混合液中のカチオン性ビニルモノマー含有量(i)/カチオン性ビニルモノマー(b)含有量が最も少ないモノマー混合液中のカチオン性ビニルモノマー含有量(ii)≧1.5 (1)
アニオン性ビニルモノマー(c)含有量が最も多いモノマー混合液中のアニオン性ビニルモノマー含有量(iii)/アニオン性ビニルモノマー(c)含有量が最も少ないモノマー混合液中のアニオン性ビニルモノマー含有量(iv)≧1.5 (2)
ここで、カチオン性ビニルモノマー含有量は両性(メタ)アクリルアミド水溶性ポリマーの合成に用いる全構成成分に対するカチオン性ビニルモノマーのmol%を示す。アニオン性ビニルモノマー含有量は両性(メタ)アクリルアミド水溶性ポリマーの合成に用いる全構成成分に対するアニオン性ビニルモノマーのmol%を示す。
The amphoteric (meth) acrylamide-based water-soluble polymer of the present invention is obtained by polymerizing two or more types of monomer mixtures containing (meth) acrylamide (a) as an essential component. It is preferable to satisfy the formulas (2) and (2) (the unit of each content in the formula is mol%).
Cationic vinyl monomer content (i) in the monomer mixture with the largest cationic vinyl monomer (b) content / cationic vinyl monomer content in the monomer mixture with the smallest cationic vinyl monomer (b) content (Ii) ≧ 1.5 (1)
Anionic vinyl monomer content (iii) in the monomer mixture with the highest anionic vinyl monomer (c) content / Anionic vinyl monomer content in the monomer mixture with the lowest anionic vinyl monomer (c) content (Iv) ≧ 1.5 (2)
Here, the content of the cationic vinyl monomer indicates mol% of the cationic vinyl monomer with respect to all components used for the synthesis of the amphoteric (meth) acrylamide water-soluble polymer. An anionic vinyl monomer content shows mol% of anionic vinyl monomer with respect to all the structural components used for the synthesis | combination of an amphoteric (meth) acrylamide water-soluble polymer.
本発明のモノマー混合液に用いる溶媒としては、各構成成分を溶解または分散させ、重合反応に悪影響を与えないものであれば特に限定されないが、通常、水を用いることが好ましい。 The solvent used in the monomer mixture of the present invention is not particularly limited as long as it dissolves or disperses each component and does not adversely affect the polymerization reaction, but it is usually preferable to use water.
重合反応は、モノマー混合液にラジカル重合開始剤を加え、撹拌しながら、反応温度50〜100℃程度で行えばよい。反応時間は1〜10時間程度である。ラジカル重合開始剤としては、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩、またはこれらと亜硫酸水素ナトリウムのごとき還元剤とを組み合わせた形のレドックス系重合開始剤等の通常のラジカル重合開始剤を使用できる。また、前記ラジカル重合開始剤には、アゾ系開始剤を使用してもよい。ラジカル重合開始剤の使用量は、各モノマー混合液中の構成成分の総重量和に対し0.05〜2.0重量%、好ましくは0.1〜0.5重量%である。この場合、重合反応を十分に進行することができ、両性(メタ)アクリルアミド系水溶性ポリマーを高分子量化できる。なお、各モノマー混合液を反応溶液に投入後、過酸化物系の重合開始剤のみを投入して後重合反応と架橋反応を実施してもよい。 The polymerization reaction may be performed at a reaction temperature of about 50 to 100 ° C. while adding a radical polymerization initiator to the monomer mixture and stirring. The reaction time is about 1 to 10 hours. As the radical polymerization initiator, a normal radical polymerization initiator such as a persulfate such as potassium persulfate or ammonium persulfate, or a redox polymerization initiator in the form of a combination of these with a reducing agent such as sodium bisulfite is used. it can. An azo initiator may be used as the radical polymerization initiator. The usage-amount of a radical polymerization initiator is 0.05 to 2.0 weight% with respect to the total weight sum of the structural component in each monomer liquid mixture, Preferably it is 0.1 to 0.5 weight%. In this case, the polymerization reaction can proceed sufficiently, and the amphoteric (meth) acrylamide-based water-soluble polymer can have a high molecular weight. In addition, after adding each monomer mixed solution to the reaction solution, only the peroxide polymerization initiator may be added to perform the post-polymerization reaction and the crosslinking reaction.
本発明の紙力増強剤は、かかる両性(メタ)アクリルアミド系水溶性ポリマーの水溶液をそのまま用いてもよいが、通常は、固形分濃度を0.01〜2.0重量%程度まで水等で希釈して調製し使用することが好ましい。また、製紙用サイズ剤その他の製紙用添加剤を配合して調製してもよい。 As the paper strength enhancer of the present invention, an aqueous solution of such an amphoteric (meth) acrylamide-based water-soluble polymer may be used as it is. Usually, the solid content concentration is about 0.01 to 2.0% by weight with water or the like. It is preferable to prepare and use after dilution. Further, it may be prepared by blending a paper sizing agent and other papermaking additives.
本発明の紙力増強剤は、目的とする紙の種類や使用するパルプ繊維スラリーの種類に限定されず、紙の製造に使用することができる。紙の種類としては、ライナー原紙、中芯原紙、紙管原紙、白板紙、クラフト紙、上質紙、新聞紙などが挙げられ、パルプスラリーとしては、クラフトパルプ、サルファイトパルプ等の晒あるいは未晒化学パルプ、砕木パルプ、機械パルプ、サーモメカニカルパルプ等の晒あるいは未晒高収率のパルプ、新聞古紙、雑誌古紙、ダンボール古紙、脱墨古紙等の古紙パルプなどが挙げられる。 The paper strength enhancer of the present invention is not limited to the type of the target paper or the type of pulp fiber slurry to be used, and can be used for paper production. Examples of paper types include liner base paper, core base paper, paper tube base paper, white paperboard, kraft paper, high-quality paper, and newsprint. Pulp slurries include bleached or unbleached chemicals such as kraft pulp and sulfite pulp. Examples thereof include bleached or unbleached high yield pulp such as pulp, groundwood pulp, mechanical pulp, and thermomechanical pulp, and waste paper pulp such as waste newspaper, magazine waste paper, cardboard waste paper, and deinked waste paper.
本発明の紙力増強剤の添加量は、抄紙する際に用いる水の電荷がプラスにならない範囲で、上記紙やパルプスラリーの種類、抄紙条件によって適宜決定すればよいが、通常は、紙力増強剤をアクリルアミド系反応物の固形分重量換算で、パルプスラリーの固形分重量に対し、0.1重量%以上である。また、パルプスラリーには硫酸アルミニウムやサイズ剤、その他の製紙用添加剤を添加してもよい。 The addition amount of the paper strength enhancer of the present invention may be determined as appropriate depending on the type of paper and pulp slurry and papermaking conditions as long as the charge of water used for papermaking does not become positive. The enhancer is 0.1% by weight or more based on the solid content weight of the pulp slurry in terms of the solid content weight of the acrylamide-based reactant. Further, aluminum sulfate, a sizing agent, and other papermaking additives may be added to the pulp slurry.
上記紙力増強剤を用いて得られた紙もまた本発明の一つである。紙の種類は特に限定されず、上述した紙が挙げられる。本発明の紙力増強剤を用いた場合、既存紙力剤に比べ電気伝導度の高い水を用いて抄紙する際に特に効果が高いため、特に古紙の使用比率が高く、高い電気伝導度の水を使用している場合の多いライナー原紙、中芯原紙、紙管原紙などに用いることが好適である。 Paper obtained using the paper strength enhancer is also one aspect of the present invention. The type of paper is not particularly limited, and examples include the paper described above. When the paper strength enhancer of the present invention is used, it is particularly effective when making paper using water having a higher electrical conductivity than existing paper strength agents. It is preferably used for liner base paper, core base paper, paper tube base paper and the like that often use water.
本発明の紙の製造方法は、電気伝導度が3mS/cm以上のパルプスラリーに上記両性(メタ)アクリルアミド系水溶性ポリマーを含有する紙力増強剤を添加した後に抄紙する工程を含む。3mS/cm以上のパルプスラリーに上記両性(メタ)アクリルアミド系水溶性ポリマーを含有する紙力増強剤を添加する以外は、一般的な、紙の製造方法と同様の条件を採用できる。この製造方法により、高い電気伝導度のパルプスラリーを用いて抄紙する場合においても、高い濾水性・歩留まり性を発揮しつつ、過度な凝集を起こさず、良好な地合いを有し、紙力効果を向上させることができる。
尚、本発明の紙の製造方法は電気伝導度3mS/cm以上で明確な効果が現れるが、3mS/cm未満の電気伝導度でも高い効果を発揮する。
The paper manufacturing method of the present invention includes a step of making paper after adding a paper strength enhancer containing the amphoteric (meth) acrylamide water-soluble polymer to a pulp slurry having an electrical conductivity of 3 mS / cm or more. Except for adding the paper strength enhancer containing the amphoteric (meth) acrylamide-based water-soluble polymer to a pulp slurry of 3 mS / cm or more, the same conditions as in a general paper manufacturing method can be adopted. With this manufacturing method, even when making paper using pulp slurry with high electrical conductivity, it exhibits high drainage and yield, does not cause excessive aggregation, has a good texture, and has a paper strength effect. Can be improved.
The paper production method of the present invention exhibits a clear effect when the electrical conductivity is 3 mS / cm or more, but also exhibits a high effect even when the electrical conductivity is less than 3 mS / cm.
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、本発明はこれら各例に限定されるものではない。尚、各例中、部及び%は特記しない限りすべて重量基準である。各例の物性値は、以下の方法により測定した値である。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to these examples. In each example, all parts and% are based on weight unless otherwise specified. The physical property value of each example is a value measured by the following method.
(1)粘度
B型粘度計を用いて、25℃にて測定した。
(2)重量平均分子量
以下の測定条件にて測定した。
GPC本体:東ソー(株)製
カラム:東ソー(株)製ガードカラムPWXL1本およびGMPWXL2本(カラムの温度40℃に設定した。)
溶離液:N/2酢酸緩衝液(N/2酢酸(和光純薬工業(株)製)+N/2酢酸ナトリウム(キシダ化学(株)製)水溶液、pH4.2)
流速:0.8ml/分
検出器:
RALLS法:ビスコテック社製TDA MODEL301(濃度検出器および90°光散乱検出器および粘度検出器(各検出器の温度を40℃に設定した。)。
測定サンプル:両性(メタ)アクリルアミド系水溶性ポリマーを脱イオン水で固形分0.5%に希釈し、苛性ソーダにてpH10〜12に調整する。その後、80℃以上の湯浴に1時間浸した後、硫酸でpH4〜5に調整し上記溶離液で0.025%に希釈して測定した。
(3)濁度の測定方法
濁度計:ANALITE NEPHELOMETER 152(Mc Van Instruments社製)
赤外波長:900nm
標準物質:ホルマジン標準液 400NTU、和光純薬工業(株)製)
サンプル濃度:1%(紙力増強剤濃度)
サンプル希釈用の水:脱イオン水を硫酸ナトリウムにて4mS/cm・25℃に調整した水
サンプル温度:25℃
測定方法:1%希釈液をスターラーにて500rpmで攪拌しつつ、pHを高める場合は1%苛性ソーダ液、pHを低くする場合は1%硫酸液をpHを0.1ずつ変化させるように滴下し、pHに対する濁度の値を測定する。濁度値が安定しない時は安定するまで待ち、安定したところの数値を濁度値とする。測定サンプルはpHを高める時はpHを高める時の濁度測定にのみ使用し、pHを低くする時はpHを低くする時の濁度測定にのみ使用する。
(1) Viscosity The viscosity was measured at 25 ° C. using a B-type viscometer.
(2) Weight average molecular weight
The measurement was performed under the following measurement conditions.
GPC body: Tosoh Co., Ltd. column: Tosoh Co., Ltd. guard column 1 PWXL and 2 GMPWXL (column temperature set to 40 ° C.)
Eluent: N / 2 acetate buffer (N / 2 acetic acid (Wako Pure Chemical Industries, Ltd.) + N / 2 sodium acetate (Kishida Chemical Co., Ltd.) aqueous solution, pH 4.2)
Flow rate: 0.8 ml / min Detector:
RALLS method: TDA MODEL301 (concentration detector, 90 ° light scattering detector, and viscosity detector (the temperature of each detector was set at 40 ° C.) manufactured by Viscotech).
Measurement sample: Amphoteric (meth) acrylamide-based water-soluble polymer is diluted with deionized water to a solid content of 0.5%, and adjusted to pH 10-12 with caustic soda. Then, after immersing in a hot water bath at 80 ° C. or higher for 1 hour, the pH was adjusted to 4 to 5 with sulfuric acid and diluted to 0.025% with the above eluent.
(3) Turbidity measurement method Turbidimeter: ANALITE NEPHELOMETER 152 (Mc Van Instruments)
Infrared wavelength: 900 nm
Standard substance: Formazine standard solution 400 NTU, manufactured by Wako Pure Chemical Industries, Ltd.)
Sample concentration: 1% (Paper strength enhancer concentration)
Sample dilution water: Deionized water adjusted to 4 mS / cm · 25 ° C. with sodium sulfate Sample temperature: 25 ° C.
Measuring method: While stirring 1% diluted solution at 500 rpm with a stirrer, 1% caustic soda solution is added dropwise to increase the pH, and 1% sulfuric acid solution is added dropwise to change the pH by 0.1 to lower the pH. Measure turbidity value against pH. If the turbidity value is not stable, wait until it stabilizes, and use the value at the stable point as the turbidity value. When the pH is increased, the measurement sample is used only for turbidity measurement when the pH is raised, and when the pH is lowered, it is used only for the turbidity measurement when the pH is lowered.
実施例1
撹拌機、温度計、還流冷却管、窒素ガス導入管および3つの滴下ロートを備えた反応装置に、イオン交換水276.1部を入れ、窒素ガスを通じて反応系内の酸素を除去した後、90℃まで加熱した。滴下ロート(1)にアクリルアミド70.5部(21.3mol%)、ジメチルアミノエチルメタクリレート58.7部(8.0mol%)、イタコン酸2.4部(0.4mol%)、メタリルスルホン酸ナトリウム1.11部(0.15mol%)、62.5%硫酸28.7部、メチレンビスアクリルアミド0.36部(0.05mol%)、N,N−ジメチルアクリルアミド0.23部(0.05mol%)、およびイオン交換水218.9部を仕込み、硫酸によりpHを3.0付近に調整した(混合液(I))。また滴下ロート(2)にアクリルアミド203.9部(61.4mol%)、ジメチルアミノエチルメタクリレート58.7部(8.0mol%)、イタコン酸2.4部(0.4mol%)、メタリルスルホン酸ナトリウム1.11部(0.15mol%)、62.5%硫酸28.7部、メチレンビスアクリルアミド0.36部(0.05mol%)、N,N−ジメチルアクリルアミド0.23部(0.05mol%)、およびイオン交換水466.6部を仕込み、硫酸によりpHを3.0付近に調整した(混合液(II))。滴下ロート(3)に過硫酸アンモニウム0.6部とイオン交換水180部を仕込んだ。次に、滴下ロート(3)より系内触媒を約3時間かけて滴下した。並行して滴下ロート(1)、(2)のモノマー混合液(I)、(II)をこの順番に一定流量で約3時間かけて滴下した。滴下終了後、過硫酸アンモニウム0.4部とイオン交換水10部を入れ1時間保温し、イオン交換水580部を投入し、固形分20.0%、粘度(25℃)が8,500mPa・sの共重合体水溶液を得た。本実施例で得られた共重合体の全モノマー組成を表1に、その合成に用いたモノマー混合液(I)および(II)の組成を表2、および得られた水溶性ポリマーの性状値を表3に示す。
Example 1
In a reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and three dropping funnels, 276.1 parts of ion-exchanged water was added, and oxygen in the reaction system was removed through nitrogen gas. Heated to ° C. In the dropping funnel (1), acrylamide 70.5 parts (21.3 mol%), dimethylaminoethyl methacrylate 58.7 parts (8.0 mol%), itaconic acid 2.4 parts (0.4 mol%), methallylsulfonic acid Sodium 1.11 parts (0.15 mol%), 62.5% sulfuric acid 28.7 parts, methylenebisacrylamide 0.36 parts (0.05 mol%), N, N-dimethylacrylamide 0.23 parts (0.05 mol) %) And 218.9 parts of ion-exchanged water, and the pH was adjusted to around 3.0 with sulfuric acid (mixed solution (I)). Further, 203.9 parts (61.4 mol%) of acrylamide, 58.7 parts (8.0 mol%) of dimethylaminoethyl methacrylate, 2.4 parts (0.4 mol%) of itaconic acid, methallyl sulfone were added to the dropping funnel (2). Sodium acid 1.11 parts (0.15 mol%), 62.5% sulfuric acid 28.7 parts, methylenebisacrylamide 0.36 parts (0.05 mol%), N, N-dimethylacrylamide 0.23 parts (0. 05 mol%) and 466.6 parts of ion-exchanged water, and the pH was adjusted to around 3.0 with sulfuric acid (mixed solution (II)). To the dropping funnel (3), 0.6 part of ammonium persulfate and 180 parts of ion-exchanged water were charged. Next, the catalyst in the system was dropped from the dropping funnel (3) over about 3 hours. In parallel, the monomer mixture (I) and (II) of the dropping funnels (1) and (2) were dropped in this order at a constant flow rate over about 3 hours. After completion of the dropping, 0.4 part of ammonium persulfate and 10 parts of ion-exchanged water were added, and the temperature was kept for 1 hour, 580 parts of ion-exchanged water was added, the solid content was 20.0%, and the viscosity (25 ° C.) was 8,500 mPa · s. An aqueous copolymer solution was obtained. Table 1 shows the total monomer composition of the copolymer obtained in this example, Table 2 shows the composition of the monomer mixture liquids (I) and (II) used for the synthesis, and property values of the water-soluble polymer obtained. Is shown in Table 3.
実施例2、3
表1に示すようにモノマー組成を変更し、各モノマー混合液のモノマー配合を表2に示すように変更した以外は実施例1と同様の操作を行い両性(メタ)アクリルアミド系水溶性ポリマーを得た。得られた水溶性ポリマーの性状値を表3に示す。
Examples 2 and 3
The monomer composition was changed as shown in Table 1, and the same operation as in Example 1 was performed except that the monomer composition of each monomer mixture was changed as shown in Table 2. Thus, an amphoteric (meth) acrylamide water-soluble polymer was obtained. It was. Table 3 shows property values of the obtained water-soluble polymer.
実施例4
上記と同様の反応容器にイオン交換水984.3部、アクリルアミド206.7部(66.7mol%)、60%のジメチルアミノエチルメタクリレートのベンジルクロライド4級化物水溶液117.6部(5.7mol%)、ジメチルアミノエチルメタクリレート39.1部(5.7mol%)、イタコン酸2.3部(0.4mol%)、メタリルスルホン酸ナトリウム1.38部(0.2mol%)および62.5%硫酸19.1部を仕込み、硫酸によりpHを3.0付近に調整した(モノマー混合液(I))。反応容器内のモノマーを攪拌溶解し、窒素ガスを吹き込みながら60℃まで昇温し、反応系内の酸素を除去した。攪拌しながら過硫酸アンモニウム0.6gを加え、重合を開始した。さらに次段階として滴下ロート(1)にアクリルアミド51.6部(16.6mol%)、60%のジメチルアミノエチルメタクリレートのベンジルクロライド4級化物水溶液6.2部(0.3mol%)、ジメチルアミノエチルメタクリレート2.1部(0.3mol%)、イタコン酸20.4部(3.6mol%)、62.5%硫酸1.0部、N,N−ジメチルアクリルアミド2.16部(0.5mol%)およびイオン交換水145.1部を仕込み、硫酸を用いてpH3.0付近に調整した(モノマー混合液(II))。フラスコ内が65℃になった時点から30分かけてモノマー混合液(II)を滴下した。滴下終了後過硫酸アンモニウム0.4部とイオン交換水10部を入れ1時間保温し、イオン交換水470部を投入し、固形分20.0%、粘度(25℃)が8,600mPa・sの共重合体水溶液を得た。本実施例で得られた共重合体の全モノマー組成を表1に、その合成に用いたモノマー混合液(I)および(II)の組成を表2、および得られた水溶性ポリマーの性状値を表3に示す。
Example 4
In a reaction vessel similar to the above, 984.3 parts of ion-exchanged water, 206.7 parts of acrylamide (66.7 mol%), and 117.6 parts (5.7 mol%) of a benzyl chloride quaternized aqueous solution of 60% dimethylaminoethyl methacrylate. ), Dimethylaminoethyl methacrylate 39.1 parts (5.7 mol%), itaconic acid 2.3 parts (0.4 mol%), sodium methallylsulfonate 1.38 parts (0.2 mol%) and 62.5%. 19.1 parts of sulfuric acid was charged, and the pH was adjusted to around 3.0 with sulfuric acid (monomer mixture (I)). The monomer in the reaction vessel was stirred and dissolved, and the temperature was raised to 60 ° C. while blowing nitrogen gas to remove oxygen in the reaction system. While stirring, 0.6 g of ammonium persulfate was added to initiate polymerization. Further, in the dropping funnel (1), 51.6 parts (16.6 mol%) of acrylamide, 6.2 parts (0.3 mol%) of an aqueous solution of dimethyl chloride of dimethylaminoethyl methacrylate and 6.2 parts (0.3 mol%) of dimethylaminoethyl were added to the dropping funnel (1). Methacrylate 2.1 parts (0.3 mol%), Itaconic acid 20.4 parts (3.6 mol%), 62.5% sulfuric acid 1.0 part, N, N-dimethylacrylamide 2.16 parts (0.5 mol%) ) And 145.1 parts of ion-exchanged water, and adjusted to around pH 3.0 using sulfuric acid (monomer mixture (II)). The monomer mixture (II) was added dropwise over 30 minutes from the time when the temperature in the flask reached 65 ° C. After completion of dropping, 0.4 part of ammonium persulfate and 10 parts of ion-exchanged water are added, and the temperature is kept for 1 hour, 470 parts of ion-exchanged water is added, the solid content is 20.0%, and the viscosity (25 ° C.) is 8,600 mPa · s. A copolymer aqueous solution was obtained. Table 1 shows the total monomer composition of the copolymer obtained in this example, Table 2 shows the composition of the monomer mixture liquids (I) and (II) used for the synthesis, and property values of the water-soluble polymer obtained. Is shown in Table 3.
実施例5〜8
表1に示すようにモノマー組成を変更し、各モノマー混合液のモノマー配合を表2に示すように変更した以外は実施例1と同様の操作を行い両性(メタ)アクリルアミド系水溶性ポリマーを得た。得られた水溶性ポリマーの性状値を表3に示す。
Examples 5-8
The monomer composition was changed as shown in Table 1, and the same operation as in Example 1 was performed except that the monomer composition of each monomer mixture was changed as shown in Table 2. Thus, an amphoteric (meth) acrylamide water-soluble polymer was obtained. It was. Table 3 shows property values of the obtained water-soluble polymer.
実施例9
上記と同様の反応容器にイオン交換水500.5部、アクリルアミド83.1部(23.6mol%)、60%のジメチルアミノエチルメタクリレートのベンジルクロライド4級化物水溶液18.8部(0.8mol%)、75%のジメチルアミノエチルアクリレートのベンジルクロライド4級化物水溶液14.3部(0.8mol%)、ジメチルアミノエチルメタクリレート24.9部(3.2mol%)、イタコン酸1.6部(0.25mol%)、メタリルスルホン酸ナトリウム1.31部(0.17mol%)、62.5%硫酸12.2部、メチレンビスアクリルアミド0.25部(0.033mol%)およびN,N−ジメチルアクリルアミド0.16部(0.033mol%)を仕込み、硫酸によりpHを3.0付近に調整した(モノマー混合液(I))。反応容器内のモノマーを攪拌溶解し、窒素ガスを吹き込みながら60℃まで昇温し、反応系内の酸素を除去した。攪拌しながら過硫酸アンモニウム0.6gを加え、重合を開始した。さらに次段階として滴下ロート(1)にアクリルアミド124.1部(35.2mol%)、60%のジメチルアミノエチルメタクリレートのベンジルクロライド4級化物水溶液2.3部(0.1mol%)、75%のジメチルアミノエチルアクリレートのベンジルクロライド4級化物水溶液1.8部(0.1mol%)、ジメチルアミノエチルメタクリレート3.1部(0.4mol%)、イタコン酸1.6部(0.25mol%)、メタリルスルホン酸ナトリウム1.31部(0.17mol%)、62.5%硫酸1.5部、メチレンビスアクリルアミド0.25部(0.033mol%)、N,N−ジメチルアクリルアミド0.16部(0.033mol%)およびイオン交換水244.7部を仕込み、硫酸を用いてpH3.0付近に調整した(モノマー混合液(II))。また滴下ロート(2)にアクリルアミド112.85部(32.0mol%)、60%のジメチルアミノエチルメタクリレートのベンジルクロライド4級化物水溶液2.3部(0.1mol%)、75%のジメチルアミノエチルアクリレートのベンジルクロライド4級化物水溶液1.8部(0.1mol%)、ジメチルアミノエチルメタクリレート3.1部(0.4mol%)、イタコン酸12.9部(2mol%)、メタリルスルホン酸ナトリウム1.31部(0.17mol%)、メチレンビスアクリルアミド0.25部(0.033mol%)、N,N−ジメチルアクリルアミド0.16部(0.033mol%)およびイオン交換水244.7部を仕込み、硫酸を用いてpH3.0付近に調整した(モノマー混合液(III))。滴下ロート(3)に過硫酸アンモニウム0.6部とイオン交換水180部を仕込んだ。次に、フラスコ内が65℃になった時点から滴下ロート(3)より系内触媒を約3時間かけて滴下した。並行して滴下ロート(1)、(2)のモノマー混合液(I)、(II)をこの順番に一定流量で約3時間かけて滴下した。滴下終了後過硫酸アンモニウム0.4部とイオン交換水10部を入れ1時間保温し、イオン交換水450部を投入し、固形分20.0%、粘度(25℃)が8,500mPa・sの共重合体水溶液を得た。本実施例で得られた共重合体の全モノマー組成を表1に、その合成に用いたモノマー混合液(I)、(II)および(III)の組成を表2、および得られた共重合体水溶液の性状値を表3に示す。
Example 9
In the same reaction vessel as above, 500.5 parts of ion-exchanged water, 83.1 parts of acrylamide (23.6 mol%), 18.8 parts of benzyl chloride quaternized aqueous solution of 60% dimethylaminoethyl methacrylate (0.8 mol%) ), 75% dimethylaminoethyl acrylate benzyl chloride quaternized aqueous solution 14.3 parts (0.8 mol%), dimethylaminoethyl methacrylate 24.9 parts (3.2 mol%), itaconic acid 1.6 parts (0 .25 mol%), sodium methallyl sulfonate 1.31 parts (0.17 mol%), 62.5% sulfuric acid 12.2 parts, methylenebisacrylamide 0.25 parts (0.033 mol%) and N, N-dimethyl. Acrylamide 0.16 part (0.033 mol%) was charged, and the pH was adjusted to around 3.0 with sulfuric acid. The monomer mixture (I)). The monomer in the reaction vessel was stirred and dissolved, and the temperature was raised to 60 ° C. while blowing nitrogen gas to remove oxygen in the reaction system. While stirring, 0.6 g of ammonium persulfate was added to initiate polymerization. Furthermore, as the next step, 124.1 parts (35.2 mol%) of acrylamide, 2.3 parts (0.1 mol%) of a benzyl chloride quaternized solution of dimethylaminoethyl methacrylate, 75%, Dimethylaminoethyl acrylate benzyl chloride quaternized aqueous solution 1.8 parts (0.1 mol%), dimethylaminoethyl methacrylate 3.1 parts (0.4 mol%), itaconic acid 1.6 parts (0.25 mol%), Sodium methallylsulfonate 1.31 parts (0.17 mol%), 1.5 parts of 62.5% sulfuric acid, 0.25 parts (0.033 mol%) of methylenebisacrylamide, 0.16 parts of N, N-dimethylacrylamide (0.033 mol%) and 244.7 parts of ion-exchanged water were added, and the pH was adjusted to around 3.0 using sulfuric acid. Sei was (monomer mixture solution (II)). In addition, 112.85 parts (32.0 mol%) of acrylamide, 2.3 parts (0.1 mol%) of a benzyl chloride quaternized aqueous solution of 60% dimethylaminoethyl methacrylate, 75% dimethylaminoethyl were added to the dropping funnel (2). Acrylate benzyl chloride quaternized aqueous solution 1.8 parts (0.1 mol%), dimethylaminoethyl methacrylate 3.1 parts (0.4 mol%), itaconic acid 12.9 parts (2 mol%), sodium methallylsulfonate 1.31 parts (0.17 mol%), 0.25 parts (0.033 mol%) of methylenebisacrylamide, 0.16 parts (0.033 mol%) of N, N-dimethylacrylamide and 244.7 parts of ion-exchanged water. The solution was charged and adjusted to around pH 3.0 using sulfuric acid (monomer mixture (III)). To the dropping funnel (3), 0.6 part of ammonium persulfate and 180 parts of ion-exchanged water were charged. Next, the catalyst in the system was dropped from the dropping funnel (3) over about 3 hours from the time when the temperature in the flask reached 65 ° C. In parallel, the monomer mixture (I) and (II) of the dropping funnels (1) and (2) were dropped in this order at a constant flow rate over about 3 hours. After completion of dropping, 0.4 part of ammonium persulfate and 10 parts of ion-exchanged water were added and kept for 1 hour, 450 parts of ion-exchanged water were added, the solid content was 20.0%, and the viscosity (25 ° C.) was 8,500 mPa · s. A copolymer aqueous solution was obtained. Table 1 shows the total monomer composition of the copolymer obtained in this example, Table 2 shows the composition of the monomer mixture (I), (II) and (III) used in the synthesis, and the obtained copolymer weight. Table 3 shows the property values of the combined aqueous solution.
実施例10〜19
表1に示すようにモノマー組成を変更し、各モノマー混合液のモノマー配合を表2に示すように変更した以外は実施例1と同様の操作を行い両性(メタ)アクリルアミド系水溶性ポリマーを得た。得られた水溶性ポリマーの性状値を表3に示す。
Examples 10-19
The monomer composition was changed as shown in Table 1, and the same operation as in Example 1 was performed except that the monomer composition of each monomer mixture was changed as shown in Table 2. Thus, an amphoteric (meth) acrylamide water-soluble polymer was obtained. It was. Table 3 shows property values of the obtained water-soluble polymer.
比較例1
上記と同様の反応容器にイオン交換水1165.4部、アクリルアミド329.9部(90.8mol%)、ジメチルアミノエチルメタクリレート48.2部(6mol%)、イタコン酸16.6部(2.5mol%)、メタリルスルホン酸ナトリウム4.04部(0.5mol%)、62.5%硫酸23.6部、メチレンビスアクリルアミド0.79部(0.1mol%)およびN,N−ジメチルアクリルアミド0.51部(0.1mol%)を仕込んだ(モノマー混合液(I))。反応容器内のモノマーを攪拌溶解し、窒素ガスを吹き込みながら60℃まで昇温し、反応系内の酸素を除去した。攪拌しながら過硫酸アンモニウム0.6gを加え、重合を開始した。その後、90℃で3時間保持することで重合を完結させた。イオン交換水480部を投入し、固形分20.0%、粘度(25℃)が8,500mPa・sの共重合体水溶液を得た。本実施例で得られた共重合体の全モノマー組成を表1に、その合成に用いたモノマー混合液の組成を表2、および得られた共重合体水溶液の性状値を表3に示す。
Comparative Example 1
In a reaction vessel similar to the above, 1165.4 parts of ion exchange water, 329.9 parts of acrylamide (90.8 mol%), 48.2 parts (6 mol%) of dimethylaminoethyl methacrylate, 16.6 parts of itaconic acid (2.5 mol) %), Sodium methallylsulfonate 4.04 parts (0.5 mol%), 63.6% sulfuric acid 23.6 parts, methylenebisacrylamide 0.79 parts (0.1 mol%) and N, N-dimethylacrylamide 0 .51 parts (0.1 mol%) was charged (monomer mixture (I)). The monomer in the reaction vessel was stirred and dissolved, and the temperature was raised to 60 ° C. while blowing nitrogen gas to remove oxygen in the reaction system. While stirring, 0.6 g of ammonium persulfate was added to initiate polymerization. Thereafter, the polymerization was completed by maintaining at 90 ° C. for 3 hours. 480 parts of ion-exchanged water was added to obtain a copolymer aqueous solution having a solid content of 20.0% and a viscosity (25 ° C.) of 8,500 mPa · s. Table 1 shows the total monomer composition of the copolymer obtained in this example, Table 2 shows the composition of the monomer mixture used for the synthesis, and Table 3 shows the property values of the resulting aqueous copolymer solution.
比較例2
上記と同様の反応容器にイオン交換水276.1部を入れ、窒素ガスを通じて反応系内の酸素を除去した後、90℃まで加熱した。滴下ロート(1)にアクリルアミド329.9部(90.8mol%)、ジメチルアミノエチルメタクリレート48.2部(6mol%)、イタコン酸16.6部(2.5mol%)、メタリルスルホン酸ナトリウム4.04部(0.5mol%)、62.5%硫酸23.6部、メチレンビスアクリルアミド0.79部(0.1mol%)、N,N−ジメチルアクリルアミド0.51部(0.1mol%)およびイオン交換水719.3部を仕込み、硫酸によりpHを3.0付近に調整した(モノマー混合液(I))。滴下ロート(2)に過硫酸アンモニウム0.6部とイオン交換水180部を仕込んだ。次に、滴下ロート(2)より系内触媒を約3時間かけて滴下した。並行して滴下ロート(1)のモノマー混合液を一定流量で約3時間かけて滴下した。滴下終了後過硫酸アンモニウム0.4部とイオン交換水10部を入れ1時間保温し、イオン交換水480部を投入し、固形分20.0%、粘度(25℃)が8,600mPa・sの共重合体水溶液を得た。本比較例で得られた共重合体の全モノマー組成を表1に、その合成に用いたモノマー混合液(I)の組成を表2、および得られた共重合体水溶液の性状値を表3に示す。
Comparative Example 2
In a reaction vessel similar to the above, 276.1 parts of ion-exchanged water was added, oxygen in the reaction system was removed through nitrogen gas, and then heated to 90 ° C. In the dropping funnel (1), acrylamide 329.9 parts (90.8 mol%), dimethylaminoethyl methacrylate 48.2 parts (6 mol%), itaconic acid 16.6 parts (2.5 mol%), sodium methallylsulfonate 4 .04 parts (0.5 mol%), 23.6 parts of 62.5% sulfuric acid, 0.79 parts (0.1 mol%) of methylenebisacrylamide, 0.51 parts (0.1 mol%) of N, N-dimethylacrylamide In addition, 719.3 parts of ion-exchanged water was charged, and the pH was adjusted to around 3.0 with sulfuric acid (monomer mixture (I)). To the dropping funnel (2), 0.6 part of ammonium persulfate and 180 parts of ion-exchanged water were charged. Next, the catalyst in the system was dropped from the dropping funnel (2) over about 3 hours. In parallel, the monomer mixture of the dropping funnel (1) was added dropwise at a constant flow rate over about 3 hours. After completion of dropping, 0.4 part of ammonium persulfate and 10 parts of ion-exchanged water are added and kept warm for 1 hour, 480 parts of ion-exchanged water are added, and the solid content is 20.0% and the viscosity (25 ° C.) is 8,600 mPa · s. A copolymer aqueous solution was obtained. Table 1 shows the total monomer composition of the copolymer obtained in this Comparative Example, Table 2 shows the composition of the monomer mixture (I) used for the synthesis, and Table 3 shows the property values of the aqueous copolymer solution obtained. Shown in
比較例3〜10
表1に示すようにモノマー組成を変更し、各モノマー混合液のモノマー配合を表2に示すように変更した以外は実施例1と同様の操作を行い両性(メタ)アクリルアミド系水溶性ポリマーを得た。得られた水溶性ポリマーの性状値を表3に示す。
Comparative Examples 3-10
The monomer composition was changed as shown in Table 1, and the same operation as in Example 1 was performed except that the monomer composition of each monomer mixture was changed as shown in Table 2. Thus, an amphoteric (meth) acrylamide water-soluble polymer was obtained. It was. Table 3 shows property values of the obtained water-soluble polymer.
また、実施例中の略語の名称を以下に示す。
AM:アクリルアミド
DM:ジメチルアミノエチルメタクリレート
DML:ジメチルアミノエチルメタクリレートのベンジルクロライド4級化物
APDM:ジメチルアミノプロピルアクリルアミド
BQ:ジメチルアミノエチルアクリレートのベンジルクロライド4級化物
IA:イタコン酸
AA:アクリル酸
DMAA:N,N−ジメチルアクリルアミド
MBAA:メチレンビスアクリルアミド
SMAS:メタリルスルホン酸ナトリウム
Moreover, the name of the abbreviation in an Example is shown below.
AM: Acrylamide DM: Dimethylaminoethyl methacrylate DML: Benzyl chloride quaternized product of dimethylaminoethyl methacrylate APDM: Dimethylaminopropyl acrylamide BQ: Benzyl chloride quaternized product of dimethylaminoethyl acrylate IA: Itaconic acid AA: Acrylic acid DMAA: N , N-dimethylacrylamide MBAA: methylenebisacrylamide SMAS: sodium methallylsulfonate
本実施例におけるカチオン性モノマー(b)、アニオン性モノマー(c)、架橋性モノマー(d)を各モノマー混合液に振り分ける場合、表2に記載したmol%となるように各モノマーを同じ比率で振り分けた。
In the case where the cationic monomer (b), the anionic monomer (c), and the crosslinkable monomer (d) in this example are distributed to each monomer mixture, each monomer is mixed at the same ratio so that the mol% described in Table 2 is obtained. Sorted.
[紙力増強剤の性能評価]
段ボ−ル古紙をナイアガラ式ビーターにて叩解し、カナディアン・スタンダ−ド・フリ−ネス(C.S.F)350mlに調整した紙料に硫酸ナトリウムを添加して電気伝導度を1.0mS/cm、3.0mS/cm及び4.0mS/cmの3種類に調整した。各電気伝導度の紙料を用いて、硫酸バンドをパルプスラリー固形分重量に対して固形分1.0%添加した後、各実施例および比較例で得られた両性(メタ)アクリルアミド系水溶性ポリマー水溶液を紙力増強剤として対パルプスラリー固形分重量に対し、それぞれ固形分1.0%添加した。各パルプスラリーのpHは6.5にそれぞれ調整して評価した。当該スラリーの濾水量及び歩留性を測定した後、当該スラリーをタッピ・シートマシンにて脱水し、5kg/cm2 で2分間プレスして、坪量150g/m2 となるよう抄紙した。次いで回転型乾燥機で105℃において4分間乾燥し、23℃、50%R.H.の条件下に24時間調湿したのち、圧縮強度、内部強度、定着率を測定した。それらの結果を表4に示す。なお、電気伝導度、濾水量、歩留性、破裂強度、圧縮強度、紙力剤定着率、地合変動係数は、以下の方法で測定した。
[Performance evaluation of paper strength enhancer]
Corrugated cardboard paper is beaten with a Niagara-type beater, and sodium sulfate is added to the paper stock adjusted to 350 ml of Canadian Standard Freeness (C.S.F.) to increase the electrical conductivity to 1.0 mS. / Cm, 3.0 mS / cm, and 4.0 mS / cm. Using a paper stock of each electrical conductivity, a sulfuric acid band was added at a solid content of 1.0% with respect to the solid weight of the pulp slurry, and then the amphoteric (meth) acrylamide water-soluble obtained in each of the examples and comparative examples. An aqueous polymer solution was added as a paper strength enhancer, and 1.0% solid content was added to the solid weight of pulp slurry. The pH of each pulp slurry was adjusted to 6.5 and evaluated. After measuring the drainage and yield of the slurry, the slurry was dehydrated with a tapi sheet machine and pressed at 5 kg / cm 2 for 2 minutes to make a paper to a basis weight of 150 g / m 2 . Subsequently, it dried for 4 minutes at 105 degreeC with a rotary dryer, and 23 degreeC and 50% R. H. After adjusting the humidity for 24 hours, the compression strength, internal strength, and fixing rate were measured. The results are shown in Table 4. In addition, electrical conductivity, drainage, yield, burst strength, compressive strength, paper strength agent fixing rate, and formation variation coefficient were measured by the following methods.
(1)電気伝導度
pH/COND METER D−54((株)堀場製作所製)を用いて測定した。
(2)濾水量
カナディアン・スタンダ−ド・フリ−ネス(C.S.F)を用いてJIS P 8121に準拠して測定した。
(3)歩留性(OPR)
DDJ(Dynamic Drainage Jar)を用いて、測定した。DDJ前サンプルの濃度及びDDJ操作により抜き出した初期白水の濃度を求め、それらを用いて以下の式をよりOPRを算出した。
OPR(%)=(DDJ前濃度―初期白水濃度)÷(DDJ前濃度)×100
(4)破裂強度
JIS P 8131に準拠して測定した。
(5)圧縮強度
JIS P 8126に準拠して測定し、比圧縮強度(N・m2/g)で示した。
(6)紙力剤定着率
窒素分析装置(三菱化学(株)製)を用いて、抄紙した紙の窒素分を測定した後、下記の計算式から算出した。
定着率(%)=(紙力増強剤添加紙の窒素分−紙力増強剤無添加紙の窒素分)÷(紙力増強剤の理論窒素分×紙力増強剤添加率)×100
なお、理論窒素分とは、紙力増強剤のモノマー比、及びモノマーの組成式から算出した紙力増強剤中の窒素の重量比
(7)地合変動係数
成紙を通過してくる光(輝度)をパーソナル画像処理システムHyper−700(OBS製)に取り込み、輝度分布を統計解析した。なお、地合変動係数は、測定値が小さい程、地合が良好である。
(1) Electrical conductivity Measured using pH / COND METER D-54 (manufactured by Horiba, Ltd.).
(2) Amount of filtrate Measured according to JIS P 8121 using Canadian Standard Freeness (C.S.F).
(3) Yield (OPR)
Measurement was performed using a DDJ (Dynamic Drainage Jar). The concentration of the sample before DDJ and the concentration of the initial white water extracted by the DDJ operation were determined, and the OPR was calculated from the following equation using them.
OPR (%) = (Concentration before DDJ−Initial white water concentration) ÷ (Concentration before DDJ) × 100
(4) Burst strength Measured according to JIS P 8131.
(5) Compressive strength Measured according to JIS P 8126, and indicated as specific compressive strength (N · m 2 / g).
(6) Paper strength agent fixing rate After measuring the nitrogen content of the paper made using a nitrogen analyzer (manufactured by Mitsubishi Chemical Corporation), it was calculated from the following formula.
Fixing rate (%) = (nitrogen content of paper strength enhancer added paper−nitrogen content of paper without paper strength enhancer) ÷ (theoretical nitrogen content of paper strength enhancer × addition rate of paper strength enhancer) × 100
The theoretical nitrogen content means the monomer ratio of the paper strength enhancer and the weight ratio of nitrogen in the paper strength enhancer calculated from the monomer composition formula (7) Light that passes through the formation coefficient of variation (7) Luminance) was taken into a personal image processing system Hyper-700 (manufactured by OBS), and the luminance distribution was statistically analyzed. In addition, as for a formation variation coefficient, formation is so favorable that a measured value is small.
表4より本発明の紙力増強剤は本願発明の範囲外となる紙力増強剤に対して、紙に高い強度を与えることが明らかと言える。
From Table 4, it can be said that the paper strength enhancer of the present invention gives high strength to the paper as compared with the paper strength enhancer that falls outside the scope of the present invention.
Claims (7)
該両性(メタ)アクリルアミド系水溶性ポリマーの重量平均分子量が1,600,000〜10,000,000、脱イオン水を硫酸ナトリウムで調製した電気伝導度4mS/cm・25℃の水で希釈した該両性(メタ)アクリルミド系水溶性ポリマーの1重量%水溶液のpH3〜9における濁度の分布が一つの極大値を有し、その極大値が15〜2,000NTUであることを特徴とし、上記両性(メタ)アクリルアミド系水溶性ポリマーが、(メタ)アクリルアミド(a)59.0〜96.98mol%、カチオン性ビニルモノマー(b)2.0〜15.0mol%、アニオン性ビニルモノマー(c)1.0〜12.0mol%、架橋性モノマー(d)0.01〜2.0mol%、及び連鎖移動性モノマー(e)0.01〜2mol%を含む重合性成分(重合性成分にはグリオキシル酸類を含まない)の共重合体であり、カチオン性ビニルモノマー(b)が、ジメチルアミノエチルメタクリレート、ジメチルアミノエチルアクリレートのベンジルクロライド4級化物及びジメチルアミノエチルメタクリレートのベンジルクロライド4級化物をそれぞれ0.05〜14.9mol%含有する紙力増強剤。 A paper strength enhancer containing an amphoteric (meth) acrylamide-based water-soluble polymer in a solid content of 7 to 30% by weight,
The amphoteric (meth) acrylamide water-soluble polymer has a weight average molecular weight of 1,600,000 to 10,000,000, and deionized water is diluted with water having an electric conductivity of 4 mS / cm · 25 ° C. prepared with sodium sulfate. The distribution of turbidity at pH 3 to 9 in a 1% by weight aqueous solution of the amphoteric (meth) acrylimide-based water-soluble polymer has one maximum value, and the maximum value is 15 to 2,000 NTU, The amphoteric (meth) acrylamide-based water-soluble polymer is (meth) acrylamide (a) 59.0 to 96.98 mol%, cationic vinyl monomer (b) 2.0 to 15.0 mol%, anionic vinyl monomer (c ) 1.0-12.0 mol%, crosslinkable monomer (d) 0.01-2.0 mol%, and chain transfer monomer (e) 0.01-2 mol% No (the polymerizable component do not contain glyoxylic acid) polymerizable component is a copolymer, cationic vinyl monomer (b) is dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate benzyl chloride quaternary compound and dimethylaminopyridine A paper strength enhancer containing 0.05 to 14.9 mol% of benzyl chloride quaternized ethyl methacrylate.
カチオン性ビニルモノマー(b)含有量が最も多いモノマー混合液中のカチオン性ビニルモノマー含有量(i)/カチオン性ビニルモノマー(b)含有量が最も少ないモノマー混合液中のカチオン性ビニルモノマー含有量(ii)≧1.5 (1)
アニオン性ビニルモノマー(c)含有量が最も多いモノマー混合液中のアニオン性ビニルモノマー含有量(iii)/アニオン性ビニルモノマー(c)含有量が最も少ないモノマー混合液中のアニオン性ビニルモノマー含有量(iv)≧1.5 (2) The amphoteric (meth) acrylamide-based water-soluble polymer is obtained by polymerizing two or more types of monomer mixture containing (meth) acrylamide (a) as an essential component, and the monomer mixture is represented by the following formula (1) And (2) Formula (unit of each content in a formula is mol%) The paper strength enhancer in any one of Claims 1-3 characterized by the above-mentioned.
Cationic vinyl monomer content (i) in the monomer mixture with the largest cationic vinyl monomer (b) content / cationic vinyl monomer content in the monomer mixture with the smallest cationic vinyl monomer (b) content (Ii) ≧ 1.5 (1)
Anionic vinyl monomer content (iii) in the monomer mixture with the highest anionic vinyl monomer (c) content / Anionic vinyl monomer content in the monomer mixture with the lowest anionic vinyl monomer (c) content (Iv) ≧ 1.5 (2)
A method for producing paper, comprising adding the paper strength enhancer according to any one of claims 1 to 5 to a pulp slurry having an electric conductivity of 3 mS / cm or more.
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