JP2024062577A - Water-in-oil emulsion paper strength agent - Google Patents
Water-in-oil emulsion paper strength agent Download PDFInfo
- Publication number
- JP2024062577A JP2024062577A JP2022170496A JP2022170496A JP2024062577A JP 2024062577 A JP2024062577 A JP 2024062577A JP 2022170496 A JP2022170496 A JP 2022170496A JP 2022170496 A JP2022170496 A JP 2022170496A JP 2024062577 A JP2024062577 A JP 2024062577A
- Authority
- JP
- Japan
- Prior art keywords
- water
- paper strength
- oil emulsion
- paper
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000007762 w/o emulsion Substances 0.000 title claims description 50
- 239000013054 paper strength agent Substances 0.000 title claims description 33
- 239000000178 monomer Substances 0.000 claims abstract description 87
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 239000004094 surface-active agent Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 15
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 13
- 238000012726 Water-in-Oil Emulsion Polymerization Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 238000006116 polymerization reaction Methods 0.000 claims description 33
- 125000002091 cationic group Chemical group 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 14
- 125000000129 anionic group Chemical group 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 230000001965 increasing effect Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000001302 tertiary amino group Chemical group 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 25
- 239000003623 enhancer Substances 0.000 abstract description 18
- 239000000243 solution Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000002708 enhancing effect Effects 0.000 abstract description 4
- 239000012141 concentrate Substances 0.000 abstract 1
- 239000000123 paper Substances 0.000 description 60
- 238000012360 testing method Methods 0.000 description 44
- 239000000047 product Substances 0.000 description 25
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 23
- 229920000642 polymer Polymers 0.000 description 21
- 238000005259 measurement Methods 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 239000003921 oil Substances 0.000 description 17
- 239000002270 dispersing agent Substances 0.000 description 16
- 239000000839 emulsion Substances 0.000 description 16
- 229920000831 ionic polymer Polymers 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- 238000004090 dissolution Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 11
- 229910001873 dinitrogen Inorganic materials 0.000 description 10
- -1 dimethylaminoethyl Chemical group 0.000 description 9
- 239000013055 pulp slurry Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 230000006835 compression Effects 0.000 description 8
- 238000007906 compression Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- 238000010790 dilution Methods 0.000 description 7
- 239000012895 dilution Substances 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 6
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229920002401 polyacrylamide Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 5
- 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 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 4
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 229920001214 Polysorbate 60 Polymers 0.000 description 4
- 239000004147 Sorbitan trioleate Substances 0.000 description 4
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000005215 alkyl ethers Chemical class 0.000 description 4
- 229960004543 anhydrous citric acid Drugs 0.000 description 4
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 4
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 4
- 239000001593 sorbitan monooleate Substances 0.000 description 4
- 235000011069 sorbitan monooleate Nutrition 0.000 description 4
- 229940035049 sorbitan monooleate Drugs 0.000 description 4
- 235000019337 sorbitan trioleate Nutrition 0.000 description 4
- 229960000391 sorbitan trioleate Drugs 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007874 V-70 Substances 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- IMNDHOCGZLYMRO-UHFFFAOYSA-N n,n-dimethylbenzamide Chemical compound CN(C)C(=O)C1=CC=CC=C1 IMNDHOCGZLYMRO-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- 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 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 2
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- 239000012298 atmosphere Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- ZGCZDEVLEULNLJ-UHFFFAOYSA-M benzyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 ZGCZDEVLEULNLJ-UHFFFAOYSA-M 0.000 description 2
- LBSPZZSGTIBOFG-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene;dihydrochloride Chemical compound Cl.Cl.N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LBSPZZSGTIBOFG-UHFFFAOYSA-N 0.000 description 2
- 239000011111 cardboard Substances 0.000 description 2
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 2
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- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 2
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
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- DWSMBORYMHSAEA-UHFFFAOYSA-N 3-[(4-amino-4-iminobutan-2-yl)diazenyl]butanimidamide;dihydrochloride Chemical compound Cl.Cl.NC(=N)CC(C)N=NC(C)CC(N)=N DWSMBORYMHSAEA-UHFFFAOYSA-N 0.000 description 1
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- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
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- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 240000001931 Ludwigia octovalvis Species 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- PZXSLFQJOZPCJG-UHFFFAOYSA-N bis[2-(5-methyl-4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene;dihydrochloride Chemical compound Cl.Cl.N1C(C)CN=C1C(C)(C)N=NC(C)(C)C1=NCC(C)N1 PZXSLFQJOZPCJG-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Chemical compound CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 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
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-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
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/32—Polymerisation in water-in-oil emulsions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Paper (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
【課題】抄紙工程における成紙に紙力を付与する紙力増強剤に関するものであり、紙力増強方法を提供することを課題とする。従来の水溶液形態の紙力増強剤は、製造時、使用時のハンドリング性確保の観点から高濃度化が困難であった。高い紙力効果を維持しつつ、取り扱い容易で物流コスト削減が可能な紙力増強剤を提供することを課題とする。【解決手段】特定の単量体組成を含有する単量体混合物水溶液を、界面活性剤存在下、油中水滴型エマルジョン重合して得られる水溶性高分子を紙力増強剤として添加することで課題を達成できる。従来品と比較しハンドリング性改善、高濃度化、高分散性で優れた溶解性により簡易溶解も可能である。【選択図】 なし[Problem] This relates to a paper strength enhancer that imparts strength to finished paper during the papermaking process, and the objective is to provide a method for enhancing paper strength. Conventional paper strength enhancers in the form of an aqueous solution are difficult to concentrate in order to ensure ease of handling during production and use. The objective is to provide a paper strength enhancer that is easy to handle and allows for reduced logistics costs while maintaining a high paper strength effect. [Solution] This objective can be achieved by adding, as a paper strength enhancer, a water-soluble polymer obtained by subjecting an aqueous monomer mixture solution containing a specific monomer composition to water-in-oil emulsion polymerization in the presence of a surfactant. Compared to conventional products, this product has improved handleability, is highly concentrated, has high dispersibility, and has excellent solubility, making it easy to dissolve. [Selected Figures] None
Description
本発明は、抄紙工程において使用する紙力増強剤及びそれを用いた紙力増強方法に関するものであり、詳しくは特定の単量体を必須成分として含有する単量体（混合物）を、特定の重合法により製造された水溶性高分子からなる紙力増強剤及びその使用方法に関するものである。 The present invention relates to a paper strength agent used in the papermaking process and a method for increasing paper strength using the same. More specifically, the present invention relates to a paper strength agent consisting of a water-soluble polymer produced by a specific polymerization method from a monomer (mixture) containing a specific monomer as an essential component, and a method for using the same.
紙に強度を付与する紙力増強剤に関する研究は旧来より盛んに行われてきた。アクリルアミドを主成分とし、カチオン単量体、アニオン単量体、架橋性単量体等を共重合した両性ＰＡＭ（ポリアクリルアミド）の技術は、公知技術として広範に活用されている。
両性ＰＡＭの紙力発現には、重合体中アミド基等の官能基とセルロース中水酸基間の水素結合の形成と、数１００万台の高分子量化が必要と認識されている。高分子量化は紙力増強効果を高めるが、同時に製品粘度も向上することが、障壁となる。
現在市場における主流な紙力増強剤の製品形態は水溶液状である。ポリマー濃度（製品濃度）は１５～２０質量％なものが多く、Ｂ型粘度計測定による製品粘度は数千～数万ｍＰａ・ｓの高粘度を示す。この様な高粘度では製品移送時に高圧ポンプが必要になる他、紙料への製品添加時に希釈水への分散性が低下する等、取り扱い困難である。高分子量化による更なる紙力向上や、物流コスト削減目的の高濃度化も、水溶液形態では達成し難い。
一方、界面活性剤存在下、油中水滴型エマルジョン重合を用いると、分散性に優れた高濃度、低製品粘度の高分子分散液を得られることは知られている（特許文献１）。又、紙力増強剤の製造に関して、一般的な重合法の例として乳化重合の記載があるものはあるが、実際に油中水滴型エマルジョンの紙力増強剤として具体的に報告された例は見当たらない（特許文献２～５）。
界面活性剤存在下、油中水滴型エマルジョン重合を行う場合、界面活性剤や乳化手段の選定、適切な装置の準備等、目的とする製品を得るには特殊な装置が必要となる。特に工業的な製造を行う場合、特殊な装置を所有しない場合は実質上製造できない。そこで、実用的な油中水滴型エマルジョンの紙力増強剤の開発が要望されている。
Research into paper strength agents that give strength to paper has been actively conducted for a long time. Amphoteric PAM (polyacrylamide) technology, which uses acrylamide as the main component and copolymerizes cationic monomers, anionic monomers, crosslinkable monomers, etc., is widely used as a publicly known technology.
It is recognized that the development of amphoteric PAM requires the formation of hydrogen bonds between functional groups such as amide groups in the polymer and hydroxyl groups in cellulose, and the molecular weight to several million. Increasing the molecular weight increases the paper strength effect, but at the same time, the viscosity of the product also increases, which is an obstacle.
The mainstream paper strength agents currently on the market are in the form of an aqueous solution. Many of them have a polymer concentration (product concentration) of 15 to 20% by mass, and the product viscosity measured with a B-type viscometer is high, ranging from several thousand to several tens of thousands of mPa·s. Such high viscosities require a high-pressure pump when transferring the product, and are difficult to handle due to reduced dispersibility in dilution water when added to paper stock. It is difficult to achieve further improvements in paper strength through higher molecular weights and higher concentrations for the purpose of reducing logistics costs in the form of an aqueous solution.
On the other hand, it is known that a polymer dispersion with excellent dispersibility and high concentration and low product viscosity can be obtained by using water-in-oil emulsion polymerization in the presence of a surfactant (Patent Document 1). In addition, although there are some descriptions of emulsion polymerization as an example of a general polymerization method for producing paper strength agents, there are no specific examples of water-in-oil emulsion paper strength agents (Patent Documents 2 to 5).
When performing water-in-oil emulsion polymerization in the presence of a surfactant, special equipment is required to obtain the desired product, including the selection of the surfactant and emulsification means, and the preparation of appropriate equipment. In particular, when performing industrial production, production is virtually impossible without special equipment. Therefore, there is a demand for the development of a practical water-in-oil emulsion paper strength agent.
本発明は、抄紙工程において紙に強度を付与する紙力増強剤に関するものであり、従来の紙力増強剤に比べて数１００万の分子量に到達しても高濃度製品形態にすることが可能、かつ紙力増強効果が高く取り扱いも容易で、高い分散性と溶解性を有する紙力増強剤及びそれを用いた紙力増強方法も提供することを課題とする。 The present invention relates to a paper strength agent that imparts strength to paper during the papermaking process, and aims to provide a paper strength agent that, compared to conventional paper strength agents, can be made into a highly concentrated product form even when it reaches a molecular weight of several million, has a high paper strength enhancing effect, is easy to handle, and has high dispersibility and solubility, as well as a paper strength enhancing method using the same.
本発明者は上記課題を解決するため鋭意検討を行った結果、下記のような発明に達した。特定の単量体混合物水溶液を、界面活性剤存在下、油中水滴型エマルジョン重合して製造した水溶性高分子の油中水滴型エマルジョンを紙力増強剤として適用することで前記課題を解決できることを見出したものである。 The inventors conducted extensive research to solve the above problems, and arrived at the following invention. They discovered that the above problems can be solved by using a water-in-oil emulsion of a water-soluble polymer produced by water-in-oil emulsion polymerization of a specific monomer mixture aqueous solution in the presence of a surfactant as a paper strength agent.
本発明における油中水滴型エマルジョン形態の製品は、高濃度でありながら製品粘度が低く、且つ分散性に優れる。紙力効果向上に必要な高分子量化が可能なだけでなく、物流コスト削減が達成できる。優れた分散性と溶解性を有するため、通常高濃度エマルジョン製品の溶解には溶解設備が一～複数個必要となるが、本発明品は簡易な溶解設備でも使用可能である。 The product in the form of a water-in-oil emulsion of the present invention is highly concentrated, yet has low product viscosity and excellent dispersibility. Not only is it possible to achieve the high molecular weight required to improve paper strength, but it is also possible to reduce logistics costs. Because it has excellent dispersibility and solubility, one or more dissolving equipment is usually required to dissolve a high-concentration emulsion product, but the product of the present invention can be used with simple dissolving equipment.
本発明における水溶性高分子としては、下記一般式（１）で表される三級アミノ基含有カチオン性単量体１～２０モル％、四級アミノ基含有カチオン性単量体０～８モル％、下記一般式（２）で表されるアニオン性単量体０．１～１０モル％及び非イオン性単量体６２～９８．９モル％を構成単位とする。
一般式（１）
Ｒ１は水素又はメチル基、Ｒ２、Ｒ３は炭素数１～３のアルキルあるいはアルコキシ基、Ｒ４は水素、炭素数１～３のアルキルあるいはアルコキシ基、７～２０のアルキル基あるいはアリール基、Ａは酸素またはＮＨ、Ｂは炭素数２～４のアルキレン基を表わす、Ｘ１
－は陰イオンをそれぞれ表わす。
Ｒ５は水素、メチル基またはカルボキシメチル基、ＱはＳＯ３
－、ＣＨ２ＳＯ３
―、Ｃ６Ｈ４ＳＯ３
－、ＣＯＮＨＣ（ＣＨ３）２ＣＨ２ＳＯ３
－、Ｃ６Ｈ４ＣＯＯ－あるいはＣＯＯ－、Ｒ６は水素またはＣＯＯ－Ｙ２
＋、Ｙ１あるいはＹ２は水素または陽イオンをそれぞれ表わす。
The water-soluble polymer in the present invention comprises, as constituent units, 1 to 20 mol % of a tertiary amino group-containing cationic monomer represented by the following general formula (1), 0 to 8 mol % of a quaternary amino group-containing cationic monomer, 0.1 to 10 mol % of an anionic monomer represented by the following general formula (2), and 62 to 98.9 mol % of a nonionic monomer:
General formula (1)
R1 represents hydrogen or a methyl group, R2 and R3 represent an alkyl or alkoxy group having 1 to 3 carbon atoms, R4 represents hydrogen, an alkyl or alkoxy group having 1 to 3 carbon atoms, an alkyl or aryl group having 7 to 20 carbon atoms, A represents oxygen or NH, B represents an alkylene group having 2 to 4 carbon atoms, and X1- represents an anion.
R5 represents hydrogen, a methyl group or a carboxymethyl group, Q represents SO3- , CH2SO3- , C6H4SO3- , CONHC( CH3 ) 2CH2SO3- , C6H4COO- or COO- , R6 represents hydrogen or COO - Y2 + , and Y1 and Y2 represent hydrogen or a cation.
一般式（１）で表わされるカチオン性単量体の三級アミノ基含有として、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリレート、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）アクリルアミド等が挙げられる。
一般式（１）で表されるカチオン性単量体の四級アミノ基含有カチオン性単量体として、（メタ）アクリロイルオキシエチルトリメチルアンモニウム塩化物、（メタ）アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物、（メタ）アクリロイルアミノプロピルトリメチルアンモニウム塩化物、（メタ）アクリロイルアミノプロピルジメチルベンジルアンモニウム塩化物等が挙げられる。これらを二種以上、組み合わせても差し支えない。一般式（１）で表わされる三級アミノ基含有カチオン性単量体３～１８モル％、四級アミノ基含有カチオン性単量体０～５モル％含有することが好ましい。
一般式（２）で表されるアニオン性単量体としては、（メタ）アクリル酸、アクリルアミド－２－メチルプロパンスルホン酸、メタクリル酸、イタコン酸あるいはこれらの塩等が挙げられる。これらを二種以上、組み合わせても差し支えない。一般式（２）で表されるアニオン性単量体０．５～８モル％含有することが好ましい。
又、一般式（１）で表わされるカチオン性単量体のモル％をＣ、一般式（２）で表わされるアニオン性単量体のモル％をＡとした時のＣ／Ａ比が１．５～２．５の範囲が好ましく、１．７～２．３が特に好ましい。
Examples of the cationic monomer represented by the general formula (1) containing a tertiary amino group include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylaminopropyl (meth)acrylamide, and diethylaminopropyl (meth)acrylamide.
Examples of the quaternary amino group-containing cationic monomer represented by the general formula (1) include (meth)acryloyloxyethyl trimethyl ammonium chloride, (meth)acryloyloxyethyl dimethyl benzyl ammonium chloride, (meth)acryloylaminopropyl trimethyl ammonium chloride, (meth)acryloylaminopropyl dimethyl benzyl ammonium chloride, etc. Two or more of these may be combined. It is preferable to contain 3 to 18 mol % of the tertiary amino group-containing cationic monomer represented by the general formula (1) and 0 to 5 mol % of the quaternary amino group-containing cationic monomer.
Examples of the anionic monomer represented by the general formula (2) include (meth)acrylic acid, acrylamido-2-methylpropanesulfonic acid, methacrylic acid, itaconic acid, and salts thereof. Two or more of these may be combined. It is preferable to contain 0.5 to 8 mol % of the anionic monomer represented by the general formula (2).
In addition, when the mol % of the cationic monomer represented by the general formula (1) is C and the mol % of the anionic monomer represented by the general formula (2) is A, the C/A ratio is preferably in the range of 1.5 to 2.5, particularly preferably 1.7 to 2.3.
本発明で使用する非イオン性単量体としては、（メタ）アクリルアミド、Ｎ，Ｎ’－ジメチルアクリルアミド、アクリロニトリル、（メタ）アクリル酸－２－ヒドロキシエチル、ジアセトンアクリルアミド、Ｎ－ビニルピロリドン、Ｎ－ビニルホルムアミド、Ｎ－ビニルアセトアミド、アクリロイルモルホリン等が挙げられる。これらの中で（メタ）アクリルアミドが好ましい。これらを二種以上、組み合わせても差し支えない。 The nonionic monomers used in the present invention include (meth)acrylamide, N,N'-dimethylacrylamide, acrylonitrile, 2-hydroxyethyl (meth)acrylate, diacetone acrylamide, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, acryloylmorpholine, and the like. Of these, (meth)acrylamide is preferred. Two or more of these may be combined.
本発明における水溶性高分子は油中水滴型エマルジョン重合により製造することができる。即ち、カチオン性単量体、アニオン性単量体、及び非イオン性単量体から選択される単量体を含有する単量体混合物を水、少なくとも水と非混和性の炭化水素からなる油状物質、油中水滴型エマルジョンを形成するに有効な量とＨＬＢを有する少なくとも一種類の界面活性剤を混合し、強攪拌し油中水滴型エマルジョンを形成させた後、重合する。又、単量体混合物を分割して連続的あるいは間歇的に添加し重合し製造しても良い。 The water-soluble polymer of the present invention can be produced by water-in-oil emulsion polymerization. That is, a monomer mixture containing a monomer selected from a cationic monomer, an anionic monomer, and a nonionic monomer is mixed with water, an oily substance consisting of at least a water-immiscible hydrocarbon, and at least one surfactant having an effective amount and HLB for forming a water-in-oil emulsion, and the mixture is stirred vigorously to form a water-in-oil emulsion, which is then polymerized. Alternatively, the monomer mixture may be divided and added continuously or intermittently to produce the polymer.
分散媒として使用する炭化水素からなる油状物質の例としては、パラフィン類、ナフテン類、あるいは灯油、軽油、中油等の鉱油、あるいはこれらと実質的に同じ範囲の沸点や粘度等の特性を有する炭化水素系合成油、あるいはこれらの混合物が挙げられる。含有量としては、油中水滴型エマルジョン全量に対して２０～５０質量％の範囲であり、好ましくは２０～３５質量％の範囲である。 Examples of oily substances made of hydrocarbons used as dispersion media include paraffins, naphthenes, mineral oils such as kerosene, light oil, and medium-weight oil, synthetic hydrocarbon oils having substantially the same range of boiling point, viscosity, and other properties as these, and mixtures of these. The content is in the range of 20 to 50% by mass, and preferably 20 to 35% by mass, based on the total amount of the water-in-oil emulsion.
油中水滴型エマルジョンを形成するに有効な量とＨＬＢを有する少なくとも一種類の界面活性剤としては、ＨＬＢが８～１５の高ＨＬＢ界面活性剤を使用して乳化する。高ＨＬＢ以外の界面活性剤を組み合わせても差し支えない。界面活性剤の例としてはノニオン性界面活性剤であり、その具体例としては、ソルビタンモノオレート、ソルビタンモノステアレート、ソルビタンモノパルミテート、ポリオキシエチレンソルビタントリオレート、ポリオキシエチレンノニルフェニルエーテル等が挙げられる。これらを二種以上、組み合わせても差し支えない。これら界面活性剤の添加率としては、油中水滴型エマルジョン全量に対して０．５～１０質量％であり、好ましくは１～５質量％の範囲である。 As at least one type of surfactant having an effective amount and HLB for forming a water-in-oil emulsion, a high HLB surfactant with an HLB of 8 to 15 is used for emulsification. Surfactants other than those with high HLB may also be combined. Examples of surfactants include nonionic surfactants, and specific examples thereof include sorbitan monooleate, sorbitan monostearate, sorbitan monopalmitate, polyoxyethylene sorbitan trioleate, polyoxyethylene nonylphenyl ether, etc. Two or more of these may also be combined. The addition rate of these surfactants is 0.5 to 10% by mass, preferably 1 to 5% by mass, based on the total amount of the water-in-oil emulsion.
単量体混合物のｐＨは３～８に調整する。ｐＨ３．５～７．５が好ましい。ｐＨの調整は酸又はアルカリで行なう。酸としては、塩酸、硫酸等の無機酸、ギ酸、酢酸、プロピオン酸、シュウ酸、アジピン酸、コハク酸、クエン酸等の有機酸、アルカリとしては、水酸化ナトリウム、水酸化カルシウム等が挙げられる。 The pH of the monomer mixture is adjusted to 3 to 8. A pH of 3.5 to 7.5 is preferred. The pH is adjusted with an acid or alkali. Examples of acids include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, adipic acid, succinic acid, and citric acid, and examples of alkalis include sodium hydroxide and calcium hydroxide.
単量体の重合時濃度は２５～５０質量％の範囲であり、単量体の組成、開始剤の選択によって適宜重合の濃度と温度を設定する。製品の高濃度化の観点から重合時濃度３０～５０質量％が好ましく、３５～５０質量％が更に好ましい。重合温度としては２０～８０℃、好ましくは２０～６０℃の範囲で行なう。重合開始はラジカル重合開始剤を使用する。これら開始剤は油溶性或いは水溶性のどちらでも良く、アゾ系、レドックス系、過酸化物系の何れでも重合することが可能である。油溶性アゾ系開始剤の例としては、２、２’－アゾビスイソブチロニトリル、ジメチル－２、２’－アゾビスイソブチレート、１、１’－アゾビス（シクロヘキサン－１－カルボニトリル）、２、２’－アゾビス（２－メチルブチロニトリル）、ジメチル－２、２’－アゾビス（２－メチルプロピオネート）、２、２’－アゾビス（４－メトキシ－２、４－ジメチルバレロニトリル）等が挙げられる。 The monomer concentration during polymerization is in the range of 25 to 50% by mass, and the polymerization concentration and temperature are set appropriately depending on the monomer composition and the selection of initiator. From the viewpoint of increasing the concentration of the product, a polymerization concentration of 30 to 50% by mass is preferred, with 35 to 50% by mass being even more preferred. The polymerization temperature is in the range of 20 to 80°C, preferably 20 to 60°C. A radical polymerization initiator is used to start the polymerization. These initiators may be either oil-soluble or water-soluble, and polymerization can be carried out with any of the azo, redox, and peroxide types. Examples of oil-soluble azo initiators include 2,2'-azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2-methylbutyronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), etc.
水溶性アゾ系開始剤の例としては、２、２’－アゾビス（アミジノプロパン）二塩化水素化物、２、２’－アゾビス［２－（５－メチル－イミダゾリン－２－イル）プロパン］二塩化水素化物、４、４’－アゾビス（４－シアノ吉草酸）等が挙げられる。又、レドックス系の例としては、ペルオキソ二硫酸アンモニウムと亜硫酸ナトリウム、亜硫酸水素ナトリウム、トリメチルアミン、テトラメチルエチレンジアミン等との組み合わせが挙げられる。更に過酸化物系の例としては、ペルオキソ二硫酸アンモニウム或いはカリウム、過酸化水素、ベンゾイルペルオキサイド、ラウロイルペルオキサイド、オクタノイルペルオキサイド、サクシニックペルオキサイド、ｔ－ブチルペルオキシ－２－エチルヘキサノエート、ｔ－ブチルヒドロペルオキシド等を挙げることができる。 Examples of water-soluble azo initiators include 2,2'-azobis(amidinopropane) dihydrochloride, 2,2'-azobis[2-(5-methyl-imidazolin-2-yl)propane] dihydrochloride, and 4,4'-azobis(4-cyanovaleric acid). Examples of redox initiators include combinations of ammonium peroxodisulfate with sodium sulfite, sodium hydrogensulfite, trimethylamine, and tetramethylethylenediamine. Examples of peroxide initiators include ammonium or potassium peroxodisulfate, hydrogen peroxide, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, succinic peroxide, t-butylperoxy-2-ethylhexanoate, and t-butyl hydroperoxide.
本発明における油中水滴型エマルジョンを製造する際の重合時、イオン性高分子分散剤を添加して製造した油中水滴型エマルジョンは、製紙原料に添加した際の分散効果が高まり、紙の地合いを損なうことなく紙力効果が向上するため好ましい。イオン性高分子分散剤は、単量体混合物水溶液中に含有させて重合しても良いし、重合中に添加しても良い。イオン性高分子分散剤の製造は水溶液重合、乳化重合、分散重合、懸濁重合等の公知の方法で得ることができる。イオン性高分子分散剤の内、カチオン性高分子分散剤としては、カチオン性単量体として、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、（メタ）アクリロイルオキシエチルトリメチルアンモニウム塩化物、ジメチルジアリルアンモニウム塩化物あるいはこれらの塩等を重合したもの、あるいはこれらカチオン性単量体と非イオン性単量体との共重合体も使用可能である。非イオン性単量体の例としては、アクリルアミド、Ｎ－ビニルホルムアミド、Ｎ－ビニルアセトアミド、Ｎ－ビニルピロリドン、Ｎ、Ｎ’－ジメチルアクリルアミド、アクリロニトリル、ジアセトンアクリルアミド、２－ヒドロキシエチル（メタ）アクリレート等が挙げられる。イオン性高分子分散剤の内、両性高分子分散剤として、前記カチオン性単量体、あるいは前記カチオン性単量体と前記非イオン性単量体とアニオン性単量体を共重合したものである。アニオン性単量体としては、（メタ）アクリル酸、アクリルアミド－２－メチルプロパンスルホン酸、メタクリルスルホン酸、イタコン酸あるいはこれらの塩等が挙げられる。イオン性高分子分散剤の重量平均分子量としては、５０００～５０万、好ましくは１万～１０万である。添加率は油中水滴型エマルジョン液量に対して０．１～１０質量％が好ましく、０．５～１０質量％が更に好ましい。 The water-in-oil emulsion produced by adding an ionic polymer dispersant during polymerization to produce the water-in-oil emulsion of the present invention is preferable because it enhances the dispersion effect when added to papermaking raw materials and improves the paper strength effect without impairing the texture of the paper. The ionic polymer dispersant may be polymerized by being contained in an aqueous monomer mixture solution, or may be added during polymerization. Ionic polymer dispersants can be produced by known methods such as aqueous solution polymerization, emulsion polymerization, dispersion polymerization, and suspension polymerization. Among ionic polymer dispersants, cationic polymer dispersants include polymerized cationic monomers such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, (meth)acryloyloxyethyl trimethylammonium chloride, dimethyldiallylammonium chloride, or salts thereof, or copolymers of these cationic monomers and nonionic monomers. Examples of nonionic monomers include acrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, N,N'-dimethylacrylamide, acrylonitrile, diacetoneacrylamide, and 2-hydroxyethyl (meth)acrylate. Among the ionic polymer dispersants, the amphoteric polymer dispersant is a copolymer of the cationic monomer, or the cationic monomer, the nonionic monomer, and the anionic monomer. Examples of the anionic monomer include (meth)acrylic acid, acrylamido-2-methylpropanesulfonic acid, methacrylic sulfonic acid, itaconic acid, or salts thereof. The weight average molecular weight of the ionic polymer dispersant is 5,000 to 500,000, preferably 10,000 to 100,000. The addition rate is preferably 0.1 to 10% by mass, more preferably 0.5 to 10% by mass, based on the amount of the water-in-oil emulsion.
本発明における水溶性高分子を製造する際の重合時あるいは重合後、構造変性剤として架橋性単量体を使用すると、紙力増強効果が向上する傾向にあるため好ましい。使用する場合は、架橋性単量体を単量体総量に対し、０．０００５～０．５質量％の範囲内で存在させる。０．００１～０．１質量％が好ましい。架橋性単量体の例としては、Ｎ，Ｎ’－メチレンビス（メタ）アクリルアミド、トリアリルアミン、ジメタクリル酸エチレングリコール、ジメタクリル酸ジエチレングリコール、ジメタクリル酸トリエチレングリコール、ジメタクリル酸テトラエチレングリコール、ジメタクリル酸－１，３－ブチレングリコール、ジ（メタ）アクリル酸ポリエチレングリコール、Ｎ－ビニル（メタ）アクリルアミド、Ｎ－メチルアリルアクリルアミド、アクリル酸グリシジル、ポリエチレングリコールジグリシジルエーテル、アクロレイン、グリオキザール、ビニルトリメトキシシラン等が挙げられ、Ｎ，Ｎ’－メチレンビス（メタ）アクリルアミドが好ましい。 When a crosslinkable monomer is used as a structural modifier during or after polymerization in producing the water-soluble polymer of the present invention, the paper strength enhancing effect tends to be improved, and this is preferable. When used, the crosslinkable monomer is present in the range of 0.0005 to 0.5 mass% relative to the total amount of monomers. 0.001 to 0.1 mass% is preferable. Examples of crosslinkable monomers include N,N'-methylenebis(meth)acrylamide, triallylamine, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, polyethylene glycol di(meth)acrylate, N-vinyl(meth)acrylamide, N-methylallylacrylamide, glycidyl acrylate, polyethylene glycol diglycidyl ether, acrolein, glyoxal, vinyltrimethoxysilane, etc., and N,N'-methylenebis(meth)acrylamide is preferable.
又、重合度を調節する連鎖移動剤としてイソプロピルアルコールを対単量体０．１～５質量％併用、あるいはギ酸塩を対単量体０．０１～０．５質量％や次亜リン酸塩を対単量体０．１～５質量％併用すると効果的である。重合時又は重合後に塩を添加して製品粘度を調整することができる。塩としては塩化ナトリウム、塩化カリウム、塩化カルシウム、塩化リチウム、硫酸ナトリウム、硫酸アンモニウム、硫酸マグネシウム、炭酸ナトリウム、炭酸カルシウム等が挙げられる。これらを二種以上添加しても良い。 It is also effective to use isopropyl alcohol at 0.1 to 5% by mass relative to the monomer as a chain transfer agent to adjust the degree of polymerization, or to use formate at 0.01 to 0.5% by mass relative to the monomer or hypophosphite at 0.1 to 5% by mass relative to the monomer. The viscosity of the product can be adjusted by adding a salt during or after polymerization. Examples of salts include sodium chloride, potassium chloride, calcium chloride, lithium chloride, sodium sulfate, ammonium sulfate, magnesium sulfate, sodium carbonate, calcium carbonate, etc. Two or more of these may be added.
重合後は、必要に応じて転相剤と呼ばれる親水性界面活性剤を添加して油の膜で被われたエマルジョン粒子が水に馴染み易くし、中の水溶性高分子が溶解し易くする処理を行い、水で希釈しそれぞれの用途に用いる。親水性界面活性剤の例としては、カチオン性界面活性剤やＨＬＢ９～１５のノニオン性界面活性剤であり、ポリオキシエチレンポリオキシプロピレンアルキルエーテル系、ポリオキシエチレンアルコールエーテル系等が挙げられる。 After polymerization, if necessary, a hydrophilic surfactant called a phase inversion agent is added to make the emulsion particles covered with an oil film more compatible with water and to make the water-soluble polymer inside more soluble, and the emulsion is then diluted with water for use in its intended purpose. Examples of hydrophilic surfactants include cationic surfactants and nonionic surfactants with an HLB of 9 to 15, such as polyoxyethylene polyoxypropylene alkyl ethers and polyoxyethylene alcohol ethers.
本発明における水溶性高分子は、紙力増強剤として性能を発揮するには一定の分子量が必要である。分子量の指標として固有粘度がある。本発明における水溶性高分子の２５℃で測定した１規定食塩水溶液中の固有粘度２～２０ｄＬ／ｇが好ましく、３～１５ｄＬ／ｇがより好ましく、５～１５ｄＬ／ｇがより一層好ましい。２ｄＬ／ｇより低いと従来の水溶液重合体タイプの紙力増強剤よりも高い紙力増強効果が得られず、２０ｄＬ／ｇより高いと凝集力が高くなりすぎ紙の地合いが損なわれるためである。固有粘度は、柴山科学機械製作所製自動粘度測定装置ＳＳ－１２０－Ｌ１型等の一般的な装置を使用して測定する。重量平均分子量としては２００万～１０００万が好ましい範囲である。 The water-soluble polymer in the present invention needs a certain molecular weight to perform as a paper strength enhancer. Intrinsic viscosity is an index of molecular weight. The intrinsic viscosity of the water-soluble polymer in the present invention in a 1N saline solution measured at 25°C is preferably 2 to 20 dL/g, more preferably 3 to 15 dL/g, and even more preferably 5 to 15 dL/g. If it is lower than 2 dL/g, the paper strength enhancer will not be as high as that of conventional aqueous polymer-type paper strength enhancers, and if it is higher than 20 dL/g, the cohesive force will be too high and the texture of the paper will be damaged. The intrinsic viscosity is measured using a general device such as the automatic viscosity measuring device SS-120-L1 model manufactured by Shibayama Scientific Machinery Manufacturing Co., Ltd. The weight average molecular weight is preferably in the range of 2 million to 10 million.
本発明における油中水滴型エマルジョンの２５℃で測定した製品粘度は１５００ｍＰａ・ｓ以下が好ましく、１０００ｍＰａ・ｓが更に好ましい。１５００ｍＰａ・ｓ以下であると製品を移送時に費やされるエネルギーがより削減でき、使用時に水と希釈する際の分散性が優れ溶解トラブルが生じ難くなる。
従来の水溶液重合体では、製品粘度が数千～数万ｍＰａ・ｓであり、本発明における油中水滴型エマルジョンは、紙力効果は維持でき、且つ製品粘度が従来品より低く溶解性が優れる様に単量体組成、界面活性剤種と量、連鎖移動剤量等の各種重合条件を調整したものである。
The product viscosity of the water-in-oil emulsion of the present invention measured at 25° C. is preferably 1500 mPa·s or less, more preferably 1000 mPa·s. If the viscosity is 1500 mPa·s or less, the energy consumed during the transportation of the product can be further reduced, and the dispersibility when diluted with water during use is excellent, making it difficult for dissolution problems to occur.
Conventional aqueous solution polymers have a product viscosity of several thousand to several tens of thousands of mPa·s, whereas the water-in-oil emulsion of the present invention maintains its paper strength effect while adjusting various polymerization conditions such as monomer composition, type and amount of surfactant, amount of chain transfer agent, etc., so that the product viscosity is lower than that of conventional products and the solubility is excellent.
本発明における油中水滴型エマルジョンの動的光散乱測定による粒径は、１００～１０００ｎｍであることが好ましい。動的光散乱測定は、大塚電子社製ＥＬＳ－Ｚ（ゼータ電位・粒径測定システム）を使用し以下の様に行なう。０．０１質量％のエマルジョン希釈液を調整し、光路長１０ｍｍプラスチックデポジットセル（材質：メタクリレート）に入れ、測定条件は、温度２５℃、溶媒：４質量％ソルビタン脂肪酸エステル（ＨＬＢ＝４．０～５．０）含有ミネラルスピリット、屈折率１．４３８により測定し、Ｃｕｍｕｌａｎｔ法にて解析し求める。尚、同じ測定原理のものであれば同様な粒子径測定装置が適宜に使用できる。 The particle size of the water-in-oil emulsion of the present invention, as measured by dynamic light scattering, is preferably 100 to 1000 nm. Dynamic light scattering measurements are performed using an ELS-Z (zeta potential/particle size measurement system) manufactured by Otsuka Electronics Co., Ltd., as follows. A 0.01% by mass diluted emulsion is prepared and placed in a plastic deposit cell (material: methacrylate) with an optical path length of 10 mm. Measurement conditions are: temperature 25°C, solvent: mineral spirits containing 4% by mass of sorbitan fatty acid ester (HLB = 4.0 to 5.0), refractive index 1.438, and the particle size is determined by analysis using the Cumulant method. Note that similar particle size measurement devices using the same measurement principle can be used as appropriate.
本発明の油中水滴型エマルジョンは、製造時に高ＨＬＢ界面活性剤を使用して乳化する。その理由は以下の様である。油中水滴型エマルジョンは、製品の状態では粘性は低いが、水を加えて希釈すると高粘性のものとなる。しかし、本発明の油中水滴型エマルジョンは、製造乳化時に高ＨＬＢ界面活性剤を使用しているため溶解性が優れており、速やかに希釈、溶解でき連続溶解に適している。 The water-in-oil emulsion of the present invention is emulsified using a high HLB surfactant during production. The reason is as follows. A water-in-oil emulsion has low viscosity in its finished state, but becomes highly viscous when diluted with water. However, the water-in-oil emulsion of the present invention has excellent solubility because a high HLB surfactant is used during production and emulsification, and it can be quickly diluted and dissolved, making it suitable for continuous dissolution.
本発明の油中水滴型エマルジョンを、通常高濃度エマルジョン製品の溶解の際に必要な攪拌機を有する溶解設備を用いなくても溶解できる。油中水滴型エマルジョンと水とを混合する手段を配管途中に連結し連続溶解した油中水滴型エマルジョンの希釈液を抄紙前の製紙原料中に添加することができる。油中水滴型エマルジョンと水とを混合する手段の例としてラインミキサーが挙げられる。ラインミキサーとしては、例えば、特開平７－３２８３１９号公報に開示されているもの等一般的なものが使用できる。連続溶解する場合は、製品原液の供給と希釈水の供給をタイミングよく行なわないと未溶解粒子が希釈液中に多量に発生し、薬剤が効率的に使用されなくなるばかりか、連続溶解そのものが運転停止に至ることになる。従来、一般的に薬剤として使用されている油中水滴型エマルジョン製品は、低ＨＬＢ界面活性剤を水非混和性有機液体と単量体水溶液混合物に添加し、油中水滴型エマルジョンを調製し、重合した後、高ＨＬＢ界面活性剤を加え、希釈水と混合した場合、水に馴染みやすく溶解しやすいように処理されている。 The water-in-oil emulsion of the present invention can be dissolved without using a dissolving equipment having an agitator, which is usually required for dissolving high-concentration emulsion products. A means for mixing the water-in-oil emulsion and water can be connected to the middle of the piping, and the diluted solution of the continuously dissolved water-in-oil emulsion can be added to the papermaking raw material before papermaking. An example of a means for mixing the water-in-oil emulsion and water is a line mixer. As a line mixer, for example, a general one such as that disclosed in JP-A-7-328319 can be used. In the case of continuous dissolution, if the supply of the product stock solution and the supply of the dilution water are not timed, a large amount of undissolved particles will be generated in the dilution solution, which will not only result in efficient use of the chemicals, but will also lead to the stop of operation of the continuous dissolution itself. Conventionally, water-in-oil emulsion products that are commonly used as pharmaceuticals are prepared by adding a low HLB surfactant to a mixture of a water-immiscible organic liquid and an aqueous monomer solution to prepare a water-in-oil emulsion, polymerizing it, and then adding a high HLB surfactant, which is then treated so that it is compatible with water and easily soluble when mixed with dilution water.
本発明の油中水滴型エマルジョンを水により希釈する場合、高ＨＬＢの適正な界面活性剤と量を選択することによって乳化時に水とのなじみが向上し、更に急激に粘性を帯びずに希釈液を調製することができる。これは、高ＨＬＢ界面活性剤は親水性であり、油とは混じらず水に拡散していき、エマルジョン粒子表面から剥離していく油の膜を水中に分散させていくのを助ける。その結果、スムーズに希釈、溶解していくと考えられる。これに対し、低ＨＬＢ界面活性剤（すなわち疎水性界面活性剤）により乳化し、重合した場合は、重合後高ＨＬＢ界面活性剤を添加し、油中水滴型エマルジョンの溶解を助けている。高ＨＬＢ界面活性剤は水中に拡散していくが、表面が疎水性乳化剤と油の膜で覆われたエマルジョン粒子が取り残される。水中には高ＨＬＢ界面活性剤が存在するので油は、水中に乳化していくが、この高ＨＬＢ界面活性剤の水中への拡散と、油中水滴型エマルジョン表面の油の水中への乳化のずれが、不溶解物の発生要因になっていると推測される。本発明における油中水滴型エマルジョンでは、高ＨＬＢ界面活性剤の使用と適正な量により乳化、更に転相後の高分子がより溶解しやすい単量体組成によって、水中への溶解がよりスムーズに行われると考えられる。 When diluting the water-in-oil emulsion of the present invention with water, by selecting the appropriate surfactant with a high HLB and the amount, compatibility with water during emulsification is improved, and furthermore, a dilution can be prepared without suddenly becoming viscous. This is because the high HLB surfactant is hydrophilic, does not mix with oil, and diffuses into water, helping to disperse the oil film peeling off from the emulsion particle surface in water. As a result, it is thought that the emulsion is diluted and dissolved smoothly. In contrast, when emulsified with a low HLB surfactant (i.e., a hydrophobic surfactant) and polymerized, a high HLB surfactant is added after polymerization to help dissolve the water-in-oil emulsion. The high HLB surfactant diffuses into the water, but the emulsion particles whose surfaces are covered with a hydrophobic emulsifier and an oil film are left behind. Since a high HLB surfactant is present in the water, the oil is emulsified in the water, but it is speculated that the difference between the diffusion of the high HLB surfactant into the water and the emulsification of the oil on the surface of the water-in-oil emulsion into the water is the cause of the generation of insoluble matter. In the water-in-oil emulsion of the present invention, emulsification is achieved by using a high HLB surfactant in an appropriate amount, and the monomer composition makes the polymer more soluble after phase inversion, which is believed to facilitate dissolution in water.
本発明における紙力増強剤の添加場所としては、リファイナー、原料配合チェスト、ミキシングチェスト、マシンチェスト、種箱等、製紙工程上流のパルプ乾燥固形分濃度が２．０質量％以上の抄紙前の製紙原料に添加する。
又、製紙工程において上流からパルプ乾燥固形分濃度が２．０質量％以上で移送されてきた高濃度の製紙原料が抄紙機の直前では白水や清水等によりパルプ乾燥固形分濃度が２．０質量％より低い製紙原料に希釈されている。一般的には０．５～１．５質量％に希釈されており、これらはインレット原料やヘッドボックス原料と呼ばれており、これら原料（以下、インレット原料とする。）に対して添加することができる。この場合の工程の添加場所としては、せん断工程であるファンポンプ前後やスクリーン前後が適用される。
The paper strength agent in the present invention is added to the raw paper material before papermaking where the pulp dry solids concentration is 2.0 mass% or more upstream of the papermaking process, such as a refiner, a raw material blending chest, a mixing chest, a machine chest, or a seed box.
In the papermaking process, high-concentration papermaking raw material with a pulp dry solids concentration of 2.0% by mass or more is diluted with white water or clean water just before the papermaking machine to a papermaking raw material with a pulp dry solids concentration of less than 2.0% by mass. Generally, it is diluted to 0.5 to 1.5% by mass, and these are called inlet raw material or headbox raw material, and it can be added to these raw materials (hereinafter referred to as inlet raw material). In this case, the addition location of the process is before or after the fan pump or before or after the screen, which is the shearing process.
本発明における紙力増強剤を添加する紙の種類としては、紙力の付与がより要望されるライナーや中芯原紙の板紙が挙げられるが、新聞用紙、上質印刷用紙、中質印刷用紙、グラビア印刷用紙、ＰＰＣ用紙、塗工原紙、微塗工紙、包装用紙等でも適用できる。 The types of paper to which the paper strength enhancer of the present invention is added include liner and core base paper board, which are in high demand for paper strength, but it can also be applied to newsprint, fine printing paper, medium printing paper, gravure printing paper, PPC paper, coated base paper, lightly coated paper, packaging paper, etc.
本発明における紙力増強剤は、水で０．０１～１０質量％に希釈溶解して使用することができる。溶解する水は、蒸留水、イオン交換水、水道水、工業用水等が使用できる。これらが混合されていても差し支えない。希釈溶解液を更に二次希釈、三次希釈しても差し支えない。又、希釈することなく原液のまま添加することもできる。
紙力増強剤の添加率は、紙料固形分濃度に対して０．００１～３質量％（ポリマー純分）の範囲である。
The paper strength agent of the present invention can be used by diluting and dissolving it in water to 0.01 to 10% by mass. The water to be used for dissolution can be distilled water, ion-exchanged water, tap water, industrial water, etc. A mixture of these waters can also be used. The diluted solution can also be further diluted a second or third time. It can also be added as is without dilution.
The addition rate of the paper strength agent is in the range of 0.001 to 3 mass % (pure polymer content) based on the solid content concentration of the paper stock.
本発明における紙力増強剤は、サイズ剤、凝結剤、硫酸バンド、歩留向上剤、濾水性向上剤等の製紙用薬品と併用することができる。 The paper strength agent of the present invention can be used in combination with papermaking chemicals such as sizing agents, coagulants, aluminum sulfate, retention aids, and drainage aids.
以下に本発明における紙力増強剤について具体的に説明するが、本発明は以下の実施例に限定されるものではない。 The paper strength agent of the present invention will be specifically described below, but the present invention is not limited to the following examples.
本発明における水溶性高分子の油中水滴型エマルジョンを製造する際に用いることができるイオン性高分子分散剤を下記の様に製造した。
（イオン性高分子分散剤の製造）
窒素導入管、攪拌機、温度計、酸素濃度計を装備した２０００ｍＬ容量のステンレス製重合反応槽に、水溶性単量体としてジメチルアミノエチルメタクリレート（以下ＤＡＭと略記）２００．０ｇ、無水クエン酸８１．６ｇ、次亜リン酸ナトリウム４．０ｇ、及び純水７１４．４ｇを順次投入し、単量体反応液を調製した。
次いで、単量体反応液に窒素ガスを吹き込み、重合反応槽の気液相部を窒素ガスで置換しながら、単量体反応液の溶液温度を４８℃に調節した。窒素ガス吹き込み開始２０分後、ラジカル開始剤として２質量％２，２’－アゾビス－［２－（２－イミダゾリン－２－イル）プロパン］二塩酸塩水溶液３．０ｇを単量体反応液に投入した。ついで、窒素ガスの吹き込みを停止し、窒素ガス雰囲気下で自己発熱による断熱重合により重合反応を行い、ポリジメチルアミノエチルメタクリレートを得た。これをイオン性高分子分散剤試料Ａとする。この水溶液状重合体粘度は、６００ｍＰａ・ｓであり、重量平均分子量５万であった。同様な製造方法によりポリアクリロイルオキシエチルトリメチルアンモニウム塩化物（イオン性高分子分散剤試料Ｂ、重合体粘度１１２９ｍＰａ・ｓ、重量平均分子量８万）、ポリアクリロイルオキシエチルジメチルベンジルアンモニウム塩化物（イオン性高分子分散剤試料Ｃ、重合体粘度１００ｍＰａ・ｓ、重量平均分子量は３万）を製造した。
An ionic polymer dispersant that can be used in producing a water-in-oil emulsion of a water-soluble polymer in the present invention was prepared as follows.
(Production of ionic polymer dispersant)
Into a 2000 mL capacity stainless steel polymerization reaction tank equipped with a nitrogen inlet tube, a stirrer, a thermometer, and an oxygen concentration meter, 200.0 g of dimethylaminoethyl methacrylate (hereinafter abbreviated as DAM) as a water-soluble monomer, 81.6 g of anhydrous citric acid, 4.0 g of sodium hypophosphite, and 714.4 g of pure water were sequentially charged to prepare a monomer reaction liquid.
Next, nitrogen gas was blown into the monomer reaction liquid, and the solution temperature of the monomer reaction liquid was adjusted to 48°C while replacing the gas-liquid phase of the polymerization reaction tank with nitrogen gas. 20 minutes after the start of nitrogen gas blowing, 3.0 g of a 2 mass% 2,2'-azobis-[2-(2-imidazolin-2-yl)propane] dihydrochloride aqueous solution was added to the monomer reaction liquid as a radical initiator. Next, the blowing of nitrogen gas was stopped, and a polymerization reaction was carried out by adiabatic polymerization due to self-heating under a nitrogen gas atmosphere, to obtain polydimethylaminoethyl methacrylate. This is ionic polymer dispersant sample A. The viscosity of this aqueous solution polymer was 600 mPa·s, and the weight average molecular weight was 50,000. Using a similar manufacturing method, polyacryloyloxyethyl trimethylammonium chloride (ionic polymer dispersant sample B, polymer viscosity 1,129 mPa·s, weight average molecular weight 80,000) and polyacryloyloxyethyl dimethylbenzylammonium chloride (ionic polymer dispersant sample C, polymer viscosity 100 mPa·s, weight average molecular weight 30,000) were manufactured.
（実施例１～５、８）
攪拌機および温度制御装置を備えた反応槽に沸点１９０℃ないし２３０℃のイソパラフィン２５８ｇにポリオキシエチレンソルビタントリオレート（ＨＬＢ４．３）１５ｇとソルビタンモノオレート（ＨＬＢ１１．０）７．５ｇを仕込み溶解させた。別にジメチルアミノエチルメタクリレート（以下ＤＡＭと略記）５９．４ｇ、アクリルアミド（ＡＡＭと略記）５０質量％水溶液５８７．８ｇ、アクリル酸（ＡＡＣと略記）８０質量％水溶液１７．０ｇ、無水クエン酸２４．２ｇ、次亜リン酸ナトリウム０．６６ｇ（対単量体０．２質量％）、メチレンビスアクリルアミド０．００７ｇ（対単量体０．００２質量％）、ポリジメチルアミノエチルメタクリレート２０．０ｇ（対液２質量％）、イオン交換水を採取し、混合し完全に溶解させた。その後油と水溶液を混合し、ホモジナイザーにて５０００ｒｐｍで１５分間攪拌乳化した。この時の単量体組成は、ＤＡＭ／ＡＡＣ／ＡＡＭ＝８／４／８８（モル％）である。得られたエマルジョンを単量体溶液の温度を２５～３０℃に保ち、窒素置換を３０分行なった後、２，２’ーアゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）（富士フィルム和光純薬製Ｖ－７０）０．０５５ｇ（対単量体０．０１５質量％）を加え、重合反応を開始させた。反応温度を２７±２℃で２４時間重合させ反応を完結させた。重合後、生成した油中水滴型エマルジョンに転相剤としてＨＬＢ１１．７のポリオキシエチレンポリオキシプロピレンアルキルエ－テル３０．０ｇ（対液３質量％）を添加混合し全量１ｋｇの油中水滴型エマルジョンが得られた。油中水滴型エマルジョン粘度は、３８０ｍＰａ・ｓであり、固有粘度は７．８ｄＬ／ｇであった。これを実施例１とし、組成、物性を表１に示す。実施例１と単量体組成比、イオン性高分子分散剤の有無、種類、量を変更した他は実施例１と同様にして油中水滴型エマルジョンを製造した。これらを実施例２～５、８とし、これらの組成、物性を表１に示す。
(Examples 1 to 5 and 8)
In a reaction vessel equipped with a stirrer and a temperature control device, 15 g of polyoxyethylene sorbitan trioleate (HLB 4.3) and 7.5 g of sorbitan monooleate (HLB 11.0) were charged and dissolved in 258 g of isoparaffin having a boiling point of 190 ° C. to 230 ° C. Separately, 59.4 g of dimethylaminoethyl methacrylate (hereinafter abbreviated as DAM), 587.8 g of 50% by weight aqueous solution of acrylamide (abbreviated as AAM), 17.0 g of 80% by weight aqueous solution of acrylic acid (abbreviated as AAC), 24.2 g of anhydrous citric acid, 0.66 g of sodium hypophosphite (0.2% by weight of monomer), 0.007 g of methylenebisacrylamide (0.002% by weight of monomer), 20.0 g of polydimethylaminoethyl methacrylate (2% by weight of liquid), and ion-exchanged water were collected, mixed, and completely dissolved. The oil and the aqueous solution were then mixed and emulsified by stirring for 15 minutes at 5000 rpm with a homogenizer. The monomer composition at this time was DAM/AAC/AAM=8/4/88 (mol%). The temperature of the monomer solution of the obtained emulsion was kept at 25-30°C, and nitrogen substitution was performed for 30 minutes, after which 0.055 g (0.015 mass% relative to monomer) of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to initiate the polymerization reaction. The reaction was carried out at a reaction temperature of 27±2°C for 24 hours to complete the reaction. After polymerization, 30.0 g (3 mass% relative to liquid) of polyoxyethylene polyoxypropylene alkyl ether with HLB of 11.7 was added as a phase inversion agent to the water-in-oil emulsion produced and mixed to obtain a total of 1 kg of water-in-oil emulsion. The viscosity of the water-in-oil emulsion was 380 mPa·s and the intrinsic viscosity was 7.8 dL/g. This is Example 1, and its composition and physical properties are shown in Table 1. Water-in-oil emulsions were produced in the same manner as in Example 1, except that the monomer composition ratio and the presence or absence, type and amount of an ionic polymer dispersant were changed from those in Example 1. These are Examples 2 to 5 and 8, and their compositions and physical properties are shown in Table 1.
（実施例６、７）
攪拌機および温度制御装置を備えた反応槽に沸点１９０℃ないし２３０℃のイソパラフィン２５８ｇにポリオキシエチレンソルビタントリオレート（ＨＬＢ４．３）１５ｇとソルビタンモノオレート（ＨＬＢ１１．０）７．５ｇを仕込み溶解させた。別にジメチルアミノエチルメタクリレート（以下ＤＡＭと略記）２９．４ｇ、アクリルアミド（ＡＡＭと略記）５０質量％水溶液６３５．３ｇ、メタクリルスルホン酸ナトリウム（ＳＭＳと略記）３．０ｇ、無水クエン酸１２．０ｇ、ポリジメチルアミノエチルメタクリレート２０．０ｇ（対液２質量％）、イオン交換水を採取し、混合し完全に溶解させた。その後油と水溶液を混合し、ホモジナイザーにて５０００ｒｐｍで１５分間攪拌乳化した。この時の単量体組成は、ＤＡＭ／ＳＭＳ／ＡＡＭ＝４／０．４／９５．６（モル％）である。得られたエマルジョンを単量体溶液の温度を２５～３０℃に保ち、窒素置換を３０分行なった後、２，２’ーアゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）（富士フィルム和光純薬製Ｖ－７０）０．０５３ｇ（対単量体０．０１５質量％）を加え、重合反応を開始させた。反応温度を２７±２℃で２４時間重合させ反応を完結させた。重合後、生成した油中水滴型エマルジョンに転相剤としてＨＬＢ１１．７のポリオキシエチレンポリオキシプロピレンアルキルエーテル３０．０ｇ（対液３質量％）を添加混合し全量１ｋｇの油中水滴型エマルジョンを得た。油中水滴型エマルジョン粘度は、８７８ｍＰａ・ｓであり、固有粘度は１４．３ｄＬ／ｇであった。これを実施例６とし、組成、物性を表１に示す。実施例６と単量体組成比、イオン性高分子分散剤を添加しない他は実施例６と同様にして油中水滴型エマルジョンを製造した。これを実施例７とし、その組成、物性を表１に示す。
(Examples 6 and 7)
In a reaction vessel equipped with a stirrer and a temperature control device, 15g of polyoxyethylene sorbitan trioleate (HLB 4.3) and 7.5g of sorbitan monooleate (HLB 11.0) were charged and dissolved in 258g of isoparaffin having a boiling point of 190°C to 230°C. Separately, 29.4g of dimethylaminoethyl methacrylate (hereinafter abbreviated as DAM), 635.3g of 50% by weight aqueous solution of acrylamide (hereinafter abbreviated as AAM), 3.0g of sodium methacryloylsulfonate (abbreviated as SMS), 12.0g of anhydrous citric acid, 20.0g of polydimethylaminoethyl methacrylate (2% by weight relative to the liquid), and ion-exchanged water were collected, mixed, and completely dissolved. Then, the oil and the aqueous solution were mixed, and emulsified by stirring with a homogenizer at 5000 rpm for 15 minutes. The monomer composition at this time was DAM/SMS/AAM=4/0.4/95.6 (mol%). The temperature of the monomer solution of the obtained emulsion was kept at 25-30°C, and nitrogen substitution was performed for 30 minutes. Then, 0.053 g (0.015 mass% relative to the monomer) of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to initiate the polymerization reaction. The polymerization was carried out for 24 hours at a reaction temperature of 27±2°C to complete the reaction. After the polymerization, 30.0 g (3 mass% relative to the liquid) of polyoxyethylene polyoxypropylene alkyl ether with HLB of 11.7 was added and mixed as a phase inversion agent to the water-in-oil type emulsion produced, to obtain a water-in-oil type emulsion with a total amount of 1 kg. The viscosity of the water-in-oil type emulsion was 878 mPa·s, and the intrinsic viscosity was 14.3 dL/g. This is Example 6, and the composition and physical properties are shown in Table 1. A water-in-oil type emulsion was produced in the same manner as in Example 6, except that the monomer composition ratio was the same as in Example 6 and no ionic polymer dispersant was added. This was designated Example 7, and its composition and physical properties are shown in Table 1.
（比較例１）
窒素導入管、攪拌機、温度計、酸素濃度計を装備した２０００ｍＬ容量のステンレス製重合反応槽に、水溶性単量体としてジメチルアミノエチルメタクリレート（以下ＤＡＭと略記）３２．１２ｇ、アクリルアミド（ＡＡＭと略記）５０質量％水溶液３１７．７１ｇ、アクリル酸（ＡＡＣと略記）８０質量％水溶液９．２１ｇ、無水クエン酸１３．１０ｇ、次亜リン酸ナトリウム２．００ｇ（対単量体１質量％）、メチレンビスアクリルアミド０．００４ｇ（対単量体 ０．００２質量％）、イオン交換水６２４．２０ｇを順次投入し、単量体反応液を調製した。この時の単量体組成は、ＤＡＭ／ＡＡＣ／ＡＡＭ＝８／４／８８（モル％）である。
次いで、単量体反応液に窒素ガスを吹き込み、重合反応槽の気液相部を窒素ガスで置換しながら、単量体反応液の溶液温度を４８℃に調節した。窒素ガス吹き込み開始２０分後、ラジカル開始剤として２質量％２，２’－アゾビス－［２－（２－イミダゾリン－２－イル）プロパン］二塩酸塩水溶液０．２ｇを単量体反応液に投入した。次いで、窒素ガスの吹き込みを停止し、窒素ガス雰囲気下で自己発熱による断熱重合により重合反応を行い、水溶液状重合体を得た。水溶液状重合体粘度は、４３５０ｍＰａ・ｓであり、固有粘度は０．３ｄＬ／ｇであった。これを比較例１とし、この組成、物性を表１に示す。
(Comparative Example 1)
A 2000mL stainless steel polymerization reaction tank equipped with a nitrogen inlet tube, a stirrer, a thermometer, and an oxygen concentration meter was charged with 32.12g of dimethylaminoethyl methacrylate (hereinafter abbreviated as DAM) as a water-soluble monomer, 317.71g of a 50% by weight aqueous solution of acrylamide (hereinafter abbreviated as AAM), 9.21g of an 80% by weight aqueous solution of acrylic acid (hereinafter abbreviated as AAC), 13.10g of anhydrous citric acid, 2.00g of sodium hypophosphite (1% by weight of monomer), 0.004g of methylenebisacrylamide (0.002% by weight of monomer), and 624.20g of ion-exchanged water in sequence to prepare a monomer reaction solution. The monomer composition at this time is DAM/AAC/AAM=8/4/88 (mol%).
Next, nitrogen gas was blown into the monomer reaction liquid, and the solution temperature of the monomer reaction liquid was adjusted to 48° C. while replacing the gas-liquid phase of the polymerization reactor with nitrogen gas. 20 minutes after the start of nitrogen gas blowing, 0.2 g of a 2 mass % 2,2'-azobis-[2-(2-imidazolin-2-yl)propane] dihydrochloride aqueous solution was added as a radical initiator to the monomer reaction liquid. Next, the blowing of nitrogen gas was stopped, and a polymerization reaction was carried out by adiabatic polymerization due to self-heating under a nitrogen gas atmosphere, to obtain an aqueous solution polymer. The aqueous solution polymer viscosity was 4350 mPa·s, and the intrinsic viscosity was 0.3 dL/g. This is Comparative Example 1, and its composition and physical properties are shown in Table 1.
（比較例２）
攪拌機および温度制御装置を備えた反応槽に沸点１９０°Ｃないし２３０°Ｃのイソパラフィン２５８ｇにポリオキシエチレンソルビタントリオレート（ＨＬＢ４．３） ７.５ｇ、ポリヒドロキシステアリン酸／ポリエチレンオキシド／ポリヒドロキシステアリン酸ブロックコポリマー（ＨＬＢ４．６）７．５ｇ、ソルビタンモノオレート（ＨＬＢ１１．０）７．５ｇを仕込み溶解させた。別にジメチルアミノエチルメタクリレート（ＤＡＭと略記）１３．７ｇ、アクリルアミド（ＡＡＭと略記）５０質量％水溶液５３８．５ｇ、イタコン酸（ＩＡと略記）１１．３ｇ、アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物８０質量％水溶液（ＤＭＢＺと略記）１３２．２ｇ、塩酸３５質量％水溶液９．０８ｇ、３－メルカプトプロピオン酸１．２ｇ、メチレンビスアクリルアミド０．００８ｇ（対単量体２０質量％）、イオン交換水を各々採取し、混合し完全に溶解させた。その後油と水溶液を混合し、ホモジナイザーにて５０００ｒｐｍで１５分間攪拌乳化した。この時の単量体組成は、ＤＡＭ／ＤＭＢＺ／ＩＡ／ＡＡＭ＝２／９／２／８７（モル％）である。得られたエマルジョンを単量体溶液の温度を２５～３０℃に保ち、窒素置換を３０分行なった後、２，２’－アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）（富士フィルム和光純薬製Ｖ－７０）０．０５３ｇ（対単量体０．０１５質量％）を加え、重合反応を開始させた。反応温度を２７±２℃で２４時間重合させ反応を完結させた。重合後、生成した油中水型エマルジョンに転相剤としてＨＬＢ１１．７のポリオキシエチレンポリオキシプロピレンアルキルエーテル３０．０ｇ（対液３質量％）を添加混合し全量１ｋｇの油中水滴型エマルジョンを得た。油中水滴型エマルジョン粘度は、３８１ｍＰａ・ｓであり、固有粘度は２．０ｄＬ／ｇであった。これを比較例２とし、表１に示す。
(Comparative Example 2)
In a reaction vessel equipped with a stirrer and a temperature control device, 258 g of isoparaffin having a boiling point of 190° C. to 230° C. was charged and dissolved therein, along with 7.5 g of polyoxyethylene sorbitan trioleate (HLB 4.3), 7.5 g of polyhydroxystearic acid/polyethylene oxide/polyhydroxystearic acid block copolymer (HLB 4.6), and 7.5 g of sorbitan monooleate (HLB 11.0). Separately, 13.7 g of dimethylaminoethyl methacrylate (abbreviated as DAM), 538.5 g of 50% by weight aqueous solution of acrylamide (abbreviated as AAM), 11.3 g of itaconic acid (abbreviated as IA), 132.2 g of 80% by weight aqueous solution of acryloyloxyethyl dimethylbenzylammonium chloride (abbreviated as DMBZ), 9.08 g of 35% by weight aqueous solution of hydrochloric acid, 1.2 g of 3-mercaptopropionic acid, 0.008 g of methylenebisacrylamide (20% by weight of monomer), and ion-exchanged water were collected, mixed, and completely dissolved. Then, the oil and the aqueous solution were mixed, and emulsified by stirring for 15 minutes at 5000 rpm with a homogenizer. The monomer composition at this time was DAM/DMBZ/IA/AAM=2/9/2/87 (mol%). The temperature of the monomer solution of the obtained emulsion was kept at 25-30°C, and nitrogen substitution was performed for 30 minutes. Then, 0.053 g (0.015 mass% of monomer) of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to initiate the polymerization reaction. The reaction was completed by polymerization for 24 hours at a reaction temperature of 27±2°C. After polymerization, 30.0 g (3 mass% of liquid) of polyoxyethylene polyoxypropylene alkyl ether having an HLB of 11.7 was added and mixed as a phase inversion agent to the water-in-oil emulsion produced, to obtain a water-in-oil emulsion of a total amount of 1 kg. The viscosity of the water-in-oil emulsion was 381 mPa·s, and the intrinsic viscosity was 2.0 dL/g. This is Comparative Example 2 and is shown in Table 1.
（比較例３、４）
紙力増強剤として汎用されている市販品二種（両性ポリアクリルアミド、形態；水溶液重合体、製品濃度２０質量％）を比較例３、４として準備した。これらの組成、物性を表１に示す。
(Comparative Examples 3 and 4)
Two commercially available products (amphoteric polyacrylamide, form: aqueous solution polymer, product concentration: 20% by mass) that are widely used as paper strength agents were prepared as Comparative Examples 3 and 4. The compositions and physical properties of these are shown in Table 1.
（表１）
ＤＭＢＺ：アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物、ＡＡＣ：アクリル酸、ＳＭＳ：メタクリルスルホン酸ナトリウム、
ＩＡ：イタコン酸、ＡＡＭ：アクリルアミド
架橋性単量体；メチレンビスアクリルアミド、添加率（ｐｐｍ）：対単量体
連鎖移動剤；ジ亜リン酸ナトリウム、添加率（質量％）：対単量体
イオン性高分子分散剤；添加率（質量％）：対油中水滴型エマルジョン液量
Ａ：ポリジメチルアミノエチルメタクリレート、
Ｂ：ポリアクリロイルオキシエチルトリメチルアンモニウム塩化物、
Ｃ：ポリアクリロイルオキシエチルジメチルベンジルアンモニウム塩化物
製品粘度：製品を２５℃において測定した粘度。
固有粘度；水溶性高分子の２５℃において測定した１規定食塩水溶液中の固有粘度。
(Table 1)
DMBZ: acryloyloxyethyl dimethylbenzyl ammonium chloride, AAC: acrylic acid, SMS: sodium methacryloylsulfonate,
IA: itaconic acid, AAM: acrylamide crosslinking monomer; methylenebisacrylamide, addition rate (ppm): relative to monomer chain transfer agent; sodium hypophosphite, addition rate (mass%): relative to monomer ionic polymer dispersant; addition rate (mass%): relative to water-in-oil emulsion liquid volume A: polydimethylaminoethyl methacrylate,
B: polyacryloyloxyethyltrimethylammonium chloride,
C: Polyacryloyloxyethyl dimethylbenzyl ammonium chloride Product viscosity: The viscosity of the product measured at 25°C.
Intrinsic viscosity: the intrinsic viscosity of a water-soluble polymer in a 1 N saline solution measured at 25°C.
（実施試験例１－１、紙質測定試験）
紙力増強剤の紙質測定試験を実施した。先ず、段ボール古紙をナイアガラ式ビーターで叩解し、叩解度３５０ｍＬに調整した。これをパルプ濃度１質量％のパルプスラリー（ｐＨ６．４、電気伝導度１７．１ｍＳ／ｍ）として使用した。パルプスラリー所定量採取、パルプ固形分に対し硫酸バンド１．５質量％を添加し５００ｒｐｍで３０秒間撹拌後、表１の紙力増強剤試料実施例１をパルプ固形分に対し０．１５質量％添加（ポリマー純分）し、５００ｒｐｍで１分間撹拌した。ＴＡＰＰＩスタンダードシートマシンにて抄紙（８０メッシュワイヤー使用）し、続いて圧力４１０ｋＰａで５分間プレスし、さらに回転型ドラムワイヤーを使用し１０５℃で３分間乾燥した。温度２３℃、湿度５０％の条件下で２４時間調湿して、坪量１００ｇ／ｃｍ２の紙を得た。得られた紙の破裂強度、圧縮強度を測定し、それぞれ比破裂強度、比圧縮強度で表した。破裂強度は、ＫＲＫ破裂度試験機（高圧型、熊谷理機工業社製）を用いてＪＩＳ Ｐ ８１３１、圧縮強度は、ショートスパン圧縮試験機（Ｌ＆Ｗ社製、Ｃｏｍｐｒｅｓｓｉｖｅ Ｓｔｒｅｎｇｔｈ Ｔｅｓｔｅｒ ＳＴＦＩ）を用いてＪＩＳ Ｐ ８１５６に従い実施した。又、紙力増強剤試料実施例２～８についても同様な試験を実施した。これらの結果を表２に示す。
(Test Example 1-1, Paper Quality Measurement Test)
A paper quality measurement test of the paper strength enhancer was carried out. First, the waste corrugated cardboard was beaten with a Niagara beater to adjust the degree of beating to 350 mL. This was used as a pulp slurry with a pulp concentration of 1% by mass (pH 6.4, electrical conductivity 17.1 mS/m). A predetermined amount of pulp slurry was collected, 1.5% by mass of aluminum sulfate was added to the pulp solids and stirred at 500 rpm for 30 seconds, and then 0.15% by mass (pure polymer content) of the paper strength enhancer sample Example 1 in Table 1 was added to the pulp solids and stirred at 500 rpm for 1 minute. Paper was made using a TAPPI standard sheet machine (using an 80 mesh wire), followed by pressing at a pressure of 410 kPa for 5 minutes, and then drying at 105 ° C. for 3 minutes using a rotary drum wire. The paper was conditioned for 24 hours under conditions of a temperature of 23 ° C. and a humidity of 50%, to obtain a paper with a basis weight of 100 g/cm 2 . The burst strength and compression strength of the obtained paper were measured and expressed as specific burst strength and specific compression strength, respectively. The burst strength was measured using a KRK burst strength tester (high pressure type, manufactured by Kumagai Riki Kogyo Co., Ltd.) according to JIS P 8131, and the compression strength was measured using a short span compression tester (manufactured by L&W, Compressive Strength Tester STFI) according to JIS P 8156. The same tests were also carried out for the paper strength agent samples Examples 2 to 8. The results are shown in Table 2.
（比較試験例１－１、紙質測定試験）
実施試験例１－１と同じ原料を用い、表１の紙力増強剤試料比較例を用いて実施試験例１-１と同様な試験を実施した。これらの結果を表２に示す。
(Comparative Test Example 1-1, Paper Quality Measurement Test)
Using the same raw materials as in Example 1-1, tests similar to those in Example 1-1 were carried out using the paper strength agent sample comparison examples in Table 1. The results are shown in Table 2.
（実施試験例１－２、濾水量測定試験）
カナディアンスタンダードフリーネステスターを用いて濾水量測定試験を実施した。実施試験例１－１のパルプスラリーを０．３質量％になる様に水で希釈したパルプスラリー１０００ｍＬを採取し、パルプ固形分に対し１．５質量％硫酸バンドを添加し上下転倒攪拌往復５回、次いで表１の紙力増強剤試料実施例１をパルプ固形分に対し０．３質量％添加（ポリマー純分）し、上下転倒攪拌往復１０回実施した。その後カナディアンスタンダードフリーネステスターに投入し濾水量を測定した。又、紙力増強剤試料実施例２～８についても同様な試験を実施した。これらの結果を表２に示す。
(Test Example 1-2, Filtration Volume Measurement Test)
A test for measuring the amount of filtered water was carried out using a Canadian Standard freeness tester. 1000 mL of pulp slurry was collected by diluting the pulp slurry of the implementation test example 1-1 with water to 0.3% by mass, and 1.5% by mass of aluminum sulfate was added to the pulp solids, and the mixture was stirred by inverting up and down five times. Next, 0.3% by mass (pure polymer content) of the paper strength enhancer sample 1 in Table 1 was added to the pulp solids, and the mixture was stirred by inverting up and down ten times. The mixture was then put into a Canadian Standard freeness tester to measure the amount of filtered water. The same test was also carried out for the paper strength enhancer samples 2 to 8. The results are shown in Table 2.
（比較試験例１－２、濾水量測定試験）
実施試験例１－２と同じ原料を用い、表１の紙力増強剤試料比較例を用いて実施試験例１－２と同様な試験を実施した。これらの結果を表２に示す。
(Comparative Test Example 1-2, Filtration Volume Measurement Test)
Using the same raw materials as in Example 1-2, tests similar to those in Example 1-2 were carried out using the comparative paper strength agent samples in Table 1. The results are shown in Table 2.
（表２）
本発明における油中水滴型エマルジョンを添加した実施例では、本発明の範囲外の紙力増強剤試料を添加した比較例に比べて紙力効果が向上した。又、濾水量も実用可能な範囲を示し、濾水性能も問題ないことを確認できた。 In the examples in which the water-in-oil emulsion of the present invention was added, the paper strength effect was improved compared to the comparative examples in which a paper strength agent sample outside the scope of the present invention was added. In addition, the amount of filtered water was within a practical range, and it was confirmed that there were no problems with the drainage performance.
（実施試験例２－１、紙質測定試験）
板紙ライナー抄造用パルプスラリー（パルプ固形分濃度６２００ｐｐｍ、ｐＨ７．３、電気伝導度７３．０ｍＳ／ｍ）を試験に用いた。パルプスラリーを所定量採取、表１の紙力増強剤試料実施例１をパルプ固形分に対し０．７２質量％添加（ポリマー純分）、８００ｒｐｍで３０秒間撹拌し、０．３質量％硫酸バンドを添加し８００ｒｐｍで１０秒間撹拌後、パルプ固形分に対しアニオン性歩留向上剤（市販品、アニオン性ポリアクリルアミド、形態；油中水滴型エマルジョン）を９０ｐｐｍ添加（ポリマー純分）し８００ｒｐｍで３０秒間撹拌した。ＴＡＰＰＩスタンダードシートマシンにて抄紙（８０メッシュワイヤー使用）し、続いて圧力４１０ｋＰａで５分間プレスし、さらに回転型ドラムワイヤーを使用し１０５℃で３分間乾燥した。温度２３℃、湿度５０％の条件下で２４時間調湿して、坪量１００ｇ／ｃｍ２の紙を得た。得られた紙の破裂強度、圧縮強度を測定し、それぞれ比破裂強度、比圧縮強度で表した。破裂強度は、ＫＲＫ破裂度試験機（高圧型、熊谷理機工業社製）を用いてＪＩＳ Ｐ ８１３１、圧縮強度は、ショートスパン圧縮試験機（Ｌ＆Ｗ社製、Ｃｏｍｐｒｅｓｓｉｖｅ Ｓｔｒｅｎｇｔｈ Ｔｅｓｔｅｒ ＳＴＦＩ）を用いてＪＩＳ Ｐ ８１５６に従い実施した。又、紙力増強剤実施例試料４についても同様な試験を実施した。これらの結果を表３に示す。
(Test Example 2-1, Paper Quality Measurement Test)
Pulp slurry for paperboard liner making (pulp solids concentration 6200 ppm, pH 7.3, electrical conductivity 73.0 mS/m) was used for the test. A predetermined amount of pulp slurry was collected, and 0.72 mass% of the paper strength enhancer sample Example 1 in Table 1 was added to the pulp solids (polymer pure content), and the mixture was stirred at 800 rpm for 30 seconds. 0.3 mass% aluminum sulfate was added and stirred at 800 rpm for 10 seconds, and then 90 ppm of anionic retention aid (commercial product, anionic polyacrylamide, form: water-in-oil emulsion) was added to the pulp solids (polymer pure content), and the mixture was stirred at 800 rpm for 30 seconds. Paper was made using a TAPPI standard sheet machine (using an 80 mesh wire), followed by pressing for 5 minutes at a pressure of 410 kPa, and then drying for 3 minutes at 105°C using a rotary drum wire. The paper was conditioned for 24 hours under conditions of a temperature of 23°C and a humidity of 50%, to obtain a paper having a basis weight of 100 g/ cm2 . The burst strength and compression strength of the obtained paper were measured and expressed as specific burst strength and specific compression strength, respectively. The burst strength was measured using a KRK burst strength tester (high pressure type, manufactured by Kumagai Riki Kogyo Co., Ltd.) according to JIS P 8131, and the compression strength was measured using a short span compression tester (manufactured by L&W, Compressive Strength Tester STFI) according to JIS P 8156. The same test was also carried out on the paper strength agent example sample 4. These results are shown in Table 3.
（比較試験例２－１、紙質測定試験）
実施試験例２－１と同じ原料を用い、表１の紙力増強剤試料比較例を用いて実施試験例２－１と同様な試験を実施した。これらの結果を表３に示す。
(Comparative Test Example 2-1, Paper Quality Measurement Test)
Using the same raw materials as in Example 2-1, tests similar to those in Example 2-1 were carried out using the comparative paper strength agent samples in Table 1. The results are shown in Table 3.
（実施試験例２－２、濾水量測定試験）
カナディアンスタンダードフリーネステスターを用いて濾水量測定試験を実施した。実施試験例２－１のパルプスラリーを０．３質量％になる様に水で希釈したパルプスラリー１０００ｍＬを採取し、表１の紙力増強剤試料実施例１をパルプ固形分に対し０．３６質量％添加（ポリマー純分）し上下転倒攪拌往復１０回、次いで０．３質量％硫酸バンドを添加し上下転倒攪拌往復５回、パルプ固形分に対しアニオン性歩留向上剤（市販品、アニオン性ポリアクリルアミド、形態；油中水滴型エマルジョン）を９０ｐｐｍ添加（ポリマー純分）し上下転倒攪拌往復１０回攪拌した。その後カナディアンスタンダードフリーネステスターに投入し濾水量を測定した。又、紙力増強剤実施例試料４についても同様な試験を実施した。これらの結果を表３に示す。
(Test Example 2-2, Filtration Volume Measurement Test)
A test for measuring the amount of filtered water was carried out using a Canadian Standard freeness tester. 1000 mL of pulp slurry was collected by diluting the pulp slurry of the implementation test example 2-1 with water to 0.3% by mass, and 0.36% by mass of the paper strength enhancer sample Example 1 of Table 1 was added to the pulp solids (polymer pure content) and stirred by inverting up and down 10 times, then 0.3% by mass of aluminum sulfate was added and stirred by inverting up and down 5 times, and 90 ppm of an anionic retention aid (commercial product, anionic polyacrylamide, form: water-in-oil emulsion) was added to the pulp solids (polymer pure content) and stirred by inverting up and down 10 times. Then, the sample was put into a Canadian Standard freeness tester and the amount of filtered water was measured. A similar test was also carried out on the paper strength enhancer example sample 4. These results are shown in Table 3.
（比較試験例２－２、濾水量測定試験）
実施試験例２－２と同じ原料を用い、表１の紙力増強剤試料比較例を用いて実施試験例２－２と同様な試験を実施した。これらの結果を表３に示す。
(Comparative Test Example 2-2, Filtration Volume Measurement Test)
Using the same raw materials as in Example 2-2, tests similar to those in Example 2-2 were carried out using the comparative paper strength agent samples in Table 1. The results are shown in Table 3.
（表３）
本発明における油中水滴型エマルジョンを添加した実施例では、市販品の水溶液重合体タイプの紙力増強剤と比べても同程度あるいは同等以上の紙力効果並びに濾水性能を示し実紙料においても有効性が確認できた。 In the examples where the water-in-oil emulsion of the present invention was added, the paper strength effect and drainage performance were equal to or greater than those of commercially available aqueous polymer-type paper strength agents, and the effectiveness was confirmed in actual paper stock.
（実施試験例３、電気伝導度の測定試験）
電気伝導度は、液中に溶けている塩類（あるいはイオン）量の指標であり、油中水型エマルジョン溶解度の指標となる。溶解初期の電気伝導度は低いが溶解が進行するにつれ電気伝導度は高くなり略一定の電気伝導度に到達する。
５００ｍＬビーカーに脱塩水４７３．０ｇ採取し、水中に電気伝導度計を設置した。マグネットスターラーで５００ｒｐｍにて撹拌開始、表１の紙力増強剤試料実施例１を２７．０ｇ添加（２質量％濃度）、１０秒攪拌後回転数を８００ｒｐｍに上げ、電気伝導度値（ｍＳ／ｍ）を２０分間計測した。２０分間撹拌後の電気伝導度の値を１００とし、各分の測定値を％に変換した。紙力増強剤試料実施例４についても２質量％濃度にて同様な試験を実施した。これらの結果を表４に示す。
(Test Example 3, Electrical Conductivity Measurement Test)
Electrical conductivity is an index of the amount of salts (or ions) dissolved in the liquid, and is an index of the solubility of a water-in-oil emulsion. Electrical conductivity is low at the beginning of dissolution, but increases as dissolution progresses, and reaches a substantially constant level.
473.0 g of desalted water was collected in a 500 mL beaker, and an electrical conductivity meter was placed in the water. Stirring was started at 500 rpm with a magnetic stirrer, 27.0 g of paper strength enhancer sample Example 1 in Table 1 was added (2 mass% concentration), and after 10 seconds of stirring, the rotation speed was increased to 800 rpm, and the electrical conductivity value (mS/m) was measured for 20 minutes. The electrical conductivity value after 20 minutes of stirring was set to 100, and the measured value for each minute was converted to %. A similar test was also carried out on paper strength enhancer sample Example 4 at a concentration of 2 mass%. These results are shown in Table 4.
（比較試験例３、電気伝導度の測定試験）
実施試験例３と同様な試験を紙力増強剤試料比較例１あるいは比較例２について２質量％濃度にて同様な試験を実施した。これらの結果を表４に示す。
(Comparative Test Example 3, Electrical Conductivity Measurement Test)
A test similar to that in Example Test 3 was carried out on the paper strength agent samples Comparative Example 1 and Comparative Example 2 at a concentration of 2% by mass. The results are shown in Table 4.
（表４）
実施例１、４試料添加時では０．５分後には２０分間攪拌後の電気伝導度値に対して５０％を超えるのに比べて、比較例１の水溶液重合体試料添加時では５０％を超えるには３分以上要し、水溶液重合体に比べて本発明における油中水滴型エマルジョンの溶解性に優れることが分かった。又、比較例２の油中水滴型エマルジョンは１分までの初期溶解性が実施例に比べて劣った。配管途中に連結したラインミキサーにより水と連続溶解して希釈する等の簡易溶解では、溶解液の配管内での滞留時間は１分以内と想定されることから、試験例３の場合では電気伝導度値が１分で平衡溶解に対して少なくとも７０～８０％程度の溶解が必要と推測される。このことから比較例２よりも本発明における油中水滴型エマルジョンでは簡易溶解に適していると考えられる。 When the samples of Examples 1 and 4 were added, the electrical conductivity exceeded 50% after 0.5 minutes after stirring for 20 minutes, whereas when the aqueous solution polymer sample of Comparative Example 1 was added, it took more than 3 minutes to exceed 50%, demonstrating that the solubility of the water-in-oil emulsion of the present invention is superior to that of the aqueous solution polymer. Furthermore, the initial solubility of the water-in-oil emulsion of Comparative Example 2 was inferior to that of the Examples up to 1 minute. In simple dissolution, such as continuous dissolution and dilution with water using a line mixer connected midway through the piping, the residence time of the dissolving liquid in the piping is assumed to be within 1 minute, so in the case of Test Example 3, it is estimated that at least 70 to 80% of the electrical conductivity value must be dissolved in 1 minute relative to the equilibrium dissolution. From this, it is considered that the water-in-oil emulsion of the present invention is more suitable for simple dissolution than Comparative Example 2.
（実施試験例４、紙質測定試験）
実施試験例３の様に１分間攪拌及び２０分間攪拌溶解した紙力増強剤試料実施例１あるいは２を用いて、段ボール古紙パルプスラリー（濃度１質量％、ｐＨ６．９、電気伝導度４１．８ｍＳ／ｍ、叩解度３５０ｍＬ）を対象として実施試験例１－１と同様にして紙質測定試験を実施した。これらの結果を表５に示す。
(Test Example 4, Paper Quality Measurement Test)
Using the paper strength enhancer sample Example 1 or 2 that had been stirred and dissolved for 1 minute and 20 minutes as in Example 3, paper quality measurement tests were carried out in the same manner as in Example 1-1 for waste cardboard pulp slurry (concentration 1% by mass, pH 6.9, electrical conductivity 41.8 mS/m, beating degree 350 mL). The results are shown in Table 5.
（比較試験例４、紙質測定試験）
実施試験例３の様に１分間攪拌及び２０分間攪拌溶解した紙力増強剤試料比較例３を用いて、実施試験例４と同様な試験を実施した。これらの結果を表５に示す。
(Comparative Test Example 4, Paper Quality Measurement Test)
Tests similar to those in Example 4 were carried out using Comparative Example 3 paper strength agent sample which had been dissolved by stirring for 1 minute and for 20 minutes as in Example 3. The results are shown in Table 5.
（表５）
紙力増強剤試料実施例を１分攪拌溶解し添加した場合は、比較例に比べて紙力向上効果が大きいことが分かり、短時間溶解でも紙力効果の発現が高いことが確認できた。
It was found that when the paper strength agent sample examples were dissolved by stirring for 1 minute and then added, the paper strength improving effect was greater than that of the comparative examples, and it was confirmed that the paper strength effect was high even when dissolved for a short period of time.
Claims (5)
一般式（１）
Ｒ１は水素又はメチル基、Ｒ２、Ｒ３は炭素数１～３のアルキルあるいはアルコキシ基、Ｒ４は水素、炭素数１～３のアルキルあるいはアルコキシ基、７～２０のアルキル基あるいはアリール基、Ａは酸素またはＮＨ、Ｂは炭素数２～４のアルキレン基を表わす、Ｘ１ －は陰イオンをそれぞれ表わす。
Ｒ５は水素、メチル基またはカルボキシメチル基、ＱはＳＯ３ ―、ＣＨ２ＳＯ３ ―、Ｃ６Ｈ４ＳＯ３ ―、ＣＯＮＨＣ（ＣＨ３）２ＣＨ２ＳＯ３ ―、Ｃ６Ｈ４ＣＯＯ―あるいはＣＯＯ―、Ｒ６は水素またはＣＯＯ―Ｙ２ ＋、Ｙ１あるいはＹ２は水素または陽イオンをそれぞれ表わす。 A paper strength agent characterized by comprising a water-in-oil emulsion of a water-soluble polymer produced by subjecting an aqueous monomer mixture solution containing 1 to 20 mol % of a tertiary amino group-containing cationic monomer represented by the following general formula (1), 0 to 8 mol % of a quaternary amino group-containing cationic monomer, 0.1 to 10 mol % of an anionic monomer represented by the following general formula (2), and 62 to 98.9 mol % of a nonionic monomer to water-in-oil emulsion polymerization in the presence of a surfactant.
General formula (1)
R1 represents hydrogen or a methyl group, R2 and R3 represent an alkyl or alkoxy group having 1 to 3 carbon atoms, R4 represents hydrogen, an alkyl or alkoxy group having 1 to 3 carbon atoms, an alkyl or aryl group having 7 to 20 carbon atoms, A represents oxygen or NH, B represents an alkylene group having 2 to 4 carbon atoms, and X1- represents an anion.
R5 represents hydrogen, a methyl group or a carboxymethyl group, Q represents SO3- , CH2SO3- , C6H4SO3- , CONHC( CH3 ) 2CH2SO3- , C6H4COO- or COO- , R6 represents hydrogen or COO - Y2 + , and Y1 and Y2 represent hydrogen or a cation.
3. A method for increasing the strength of paper, comprising the steps of: connecting a means for mixing the water-in-oil emulsion according to claim 1 or 2 with water in a piping; and continuously adding a diluted solution of the dissolved water-in-oil emulsion to the papermaking raw material before papermaking.
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| JPWO2013031245A1 (en) * | 2011-08-29 | 2015-03-23 | ハイモ株式会社 | Powdered hydrophilic polymer, process for producing the same, and aggregating agent using the same |
| CN106930142B (en) * | 2015-12-31 | 2020-03-24 | 艺康美国股份有限公司 | Dry strength agent composition and method for improving dry strength of paper |
| CN108484830A (en) * | 2018-05-07 | 2018-09-04 | 东升新材料（山东）有限公司 | A method of both sexes drying strengthening agent is prepared using inverse emulsion polymerization |
| CN111909296A (en) * | 2018-05-18 | 2020-11-10 | 金学芳 | Method for preparing instant cationic high molecular weight polyacrylamide by two-step method |
| JP7101947B2 (en) * | 2018-08-31 | 2022-07-19 | ハイモ株式会社 | Water-in-oil dispersion with excellent solubility and stability |
-
2022
- 2022-10-25 JP JP2022170496A patent/JP2024062577A/en active Pending
-
2023
- 2023-08-24 WO PCT/JP2023/030428 patent/WO2024089994A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2024089994A1 (en) | 2024-05-02 |
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