JP5467516B2 - Paper sizing agent and paper - Google Patents
Paper sizing agent and paper Download PDFInfo
- Publication number
- JP5467516B2 JP5467516B2 JP2010061397A JP2010061397A JP5467516B2 JP 5467516 B2 JP5467516 B2 JP 5467516B2 JP 2010061397 A JP2010061397 A JP 2010061397A JP 2010061397 A JP2010061397 A JP 2010061397A JP 5467516 B2 JP5467516 B2 JP 5467516B2
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- JP
- Japan
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- sizing agent
- surface sizing
- paper
- Prior art date
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- 238000004513 sizing Methods 0.000 title claims description 46
- -1 maleic acid diesters Chemical class 0.000 claims description 55
- 239000000178 monomer Substances 0.000 claims description 54
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 50
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 48
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 45
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 45
- 239000011976 maleic acid Substances 0.000 claims description 45
- 229920001577 copolymer Polymers 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 239000003795 chemical substances by application Substances 0.000 claims description 39
- 239000000839 emulsion Substances 0.000 claims description 33
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 13
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 13
- 239000003995 emulsifying agent Substances 0.000 claims description 11
- 150000003440 styrenes Chemical class 0.000 claims description 11
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 10
- 230000002209 hydrophobic effect Effects 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 8
- 239000012986 chain transfer agent Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 150000002430 hydrocarbons Chemical group 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical group OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 4
- 150000003926 acrylamides Chemical class 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 125000005156 substituted alkylene group Chemical group 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical group 0.000 claims description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 claims 1
- 150000002830 nitrogen compounds Chemical class 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 129
- 238000006243 chemical reaction Methods 0.000 description 52
- 239000000123 paper Substances 0.000 description 44
- 238000003786 synthesis reaction Methods 0.000 description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 35
- 239000007864 aqueous solution Substances 0.000 description 34
- 230000015572 biosynthetic process Effects 0.000 description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 30
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- 230000005476 size effect Effects 0.000 description 22
- 239000011259 mixed solution Substances 0.000 description 20
- 229940035429 isobutyl alcohol Drugs 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- 238000006386 neutralization reaction Methods 0.000 description 17
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000007865 diluting Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 description 13
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 235000019441 ethanol Nutrition 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
- 239000004711 α-olefin Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 239000001254 oxidized starch Substances 0.000 description 3
- 235000013808 oxidized starch Nutrition 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- XHSDDKAGJYJAQM-ULDVOPSXSA-N dioctadecyl (e)-but-2-enedioate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCCCCCCCCCCCC XHSDDKAGJYJAQM-ULDVOPSXSA-N 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
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- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000008234 soft water Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZDLBWMYNYNATIW-UHFFFAOYSA-N tetracos-1-ene Chemical compound CCCCCCCCCCCCCCCCCCCCCCC=C ZDLBWMYNYNATIW-UHFFFAOYSA-N 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- ATQUFXWBVZUTKO-UHFFFAOYSA-N 1-methylcyclopentene Chemical compound CC1=CCCC1 ATQUFXWBVZUTKO-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- LAAVYEUJEMRIGF-UHFFFAOYSA-N 2,4,4-trimethylpent-2-ene Chemical compound CC(C)=CC(C)(C)C LAAVYEUJEMRIGF-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paper (AREA)
Description
本発明は製紙用表面サイズ剤、および該製紙用表面サイズ剤を紙に塗工してなる紙に関する。 The present invention relates to a paper sizing surface sizing agent and paper obtained by coating the paper sizing surface sizing agent on paper.
製紙用表面サイズ剤は、原紙表面にほぼ１００％歩留まるのでサイズ効果を効率よく発揮する。また、紙に直接塗工するので、抄紙系の温度が多少変化してもサイズ効果に大きな影響はない。こうした製紙用表面サイズ剤は、一般に水溶液型とエマルジョン型とに大別できるが、後者は固形分を高く設定しても比較的低粘度であり、ハンドリング性に長ける等の利点を有する。 Since the surface sizing agent for papermaking yields almost 100% on the surface of the base paper, the size effect is exhibited efficiently. In addition, since the coating is performed directly on the paper, the size effect is not greatly affected even if the temperature of the papermaking system changes slightly. Such paper surface sizing agents can generally be roughly classified into an aqueous solution type and an emulsion type, but the latter has advantages such as a relatively low viscosity even when the solid content is set high, and an excellent handling property.
かかるエマルジョン型の表面サイズ剤としては、例えばアニオン性やノニオン性の乳化剤の存在下に各種不飽和単量体類を乳化重合してなるエマルジョンを用いたものが一般的であるが、サイズ効果が十分ではなく、また、ロッドメタリングサイズプレスやゲートロール等のように強い剪断力を伴う塗工方式において糟を多量に生ずるなど、機械的安定性が極端に悪い。 As such an emulsion type surface sizing agent, for example, an emulsion obtained by emulsion polymerization of various unsaturated monomers in the presence of an anionic or nonionic emulsifier is generally used. It is not sufficient, and mechanical stability is extremely poor, such as a large amount of wrinkles generated in a coating method with a strong shearing force such as a rod metering size press or a gate roll.
機械的安定性を改善する方法としては、例えば、前記乳化剤と共に、高分子量化合物を保護コロイドとして用いる手段が考えられ、例えば、特定分子量のスチレン−マレイン酸系共重合体塩の存在下で、スチレン類等の疎水性不飽和単量体類を乳化重合してなるエマルジョンを含む表面サイズ剤が提案されている（特許文献１を参照）。しかし、該表面サイズ剤はサイズ効果や機械的安定性が依然不十分であり、しかも、紙へ塗工する際の泡立ちが大きいという問題があった。 As a method for improving the mechanical stability, for example, a means of using a high molecular weight compound as a protective colloid together with the emulsifier may be considered. For example, in the presence of a styrene-maleic acid copolymer salt having a specific molecular weight, styrene There has been proposed a surface sizing agent containing an emulsion obtained by emulsion polymerization of hydrophobic unsaturated monomers such as a kind (see Patent Document 1). However, the surface sizing agent is still insufficient in size effect and mechanical stability and has a problem that foaming is large when applied to paper.
本発明は、機械的安定性およびサイズ効果に優れ、かつ、紙へ塗工する際に泡立ちが少ない（以下、低発泡性という）、エマルジョン型の製紙用表面サイズ剤を提供することを目的とする。 An object of the present invention is to provide an emulsion-type surface sizing agent for papermaking that is excellent in mechanical stability and size effect and has less foaming when applied to paper (hereinafter referred to as low foaming property). To do.
本発明者は鋭意検討した結果、以下の表面サイズ剤であれば前記課題を解決できることを見出した。即ち本発明は、不飽和ジカルボン酸類およびスチレン類を含み、かつ不飽和モノカルボン酸類を含まない単量体群（ａ）が重合反応してなり、かつ、そのカルボキシル基が下記一般式（１）で表される含窒素化合物と塩を形成しており、かつ、重量平均分子量が５０００〜２００００である共重合体（Ａ）、ならびに水溶性連鎖移動剤（Ｂ）の存在下で、親水性不飽和単量体類および疎水性不飽和単量体類を含む単量体群（Ｃ）を乳化重合してなるエマルジョン、を含有する製紙用表面サイズ剤、ならびに該サイズ剤を紙に塗工してなる紙、に関する。 As a result of intensive studies, the present inventors have found that the above-described problems can be solved by the following surface sizing agents. That is, the present invention comprises a monomer group (a) containing unsaturated dicarboxylic acids and styrenes and not containing unsaturated monocarboxylic acids, and the carboxyl group is represented by the following general formula (1). In the presence of a copolymer (A) having a weight average molecular weight of 5,000 to 20,000 and a water-soluble chain transfer agent (B). A surface sizing agent for papermaking containing an emulsion obtained by emulsion polymerization of a monomer group (C) containing saturated monomers and hydrophobic unsaturated monomers, and coating the sizing agent on paper Related to paper.
本発明の製紙用表面サイズ剤は、これをなすエマルジョンの機械的安定性が優れるので、強い剪断力を伴う塗工方式においても糟を生じにくく、特に硬水で希釈した場合にも同様に糟が発生しにくい。また、各種サイズ効果（特にステキヒトサイズ度やペン書きサイズ度）に優れるだけでなく、塗工時の発泡も少ない。当該サイズ剤を塗工した紙は、各種印刷用紙として好適である。 The surface sizing agent for papermaking of the present invention is excellent in mechanical stability of the emulsion forming it, so that it is difficult to cause wrinkles even in a coating method with a strong shearing force. Hard to occur. Moreover, not only is it excellent in various size effects (particularly, steecht sizing and pen writing sizing), but there is also little foaming during coating. The paper coated with the sizing agent is suitable as various printing papers.
本発明の製紙用表面サイズ剤をなす共重合体（Ａ）（以下、（Ａ）成分という）は、不飽和ジカルボン酸類およびスチレン類を含み、かつ不飽和モノカルボン酸類を含まない単量体群（ａ）（以下、（ａ）成分という）を重合反応させてなるものである。 The copolymer (A) (hereinafter referred to as “component (A)”) that forms the paper sizing agent of the present invention contains unsaturated dicarboxylic acids and styrenes, and does not contain unsaturated monocarboxylic acids. A polymerization reaction of (a) (hereinafter referred to as component (a)).
該不飽和ジカルボン酸類としては、各種公知のものを用い得る。具体的には、例えば、不飽和ジカルボン酸類〔マレイン酸、フマル酸、イタコン酸、シトラコン酸等〕およびその中和塩、不飽和ジカルボン酸無水物類〔無水マレイン酸、無水シトラコン酸等〕、不飽和ジカルボン酸アルキルエステル類、およびそれらの中和塩、ならびに不飽和ジカルボン酸ジアルキルエステル類等が挙げられる。該不飽和ジカルボン酸類としては、サイズ効果等の点より、マレイン酸、無水マレイン酸およびマレイン酸モノエステルからなる群より選ばれる少なくとも１種が好ましい。 As the unsaturated dicarboxylic acids, various known ones can be used. Specifically, for example, unsaturated dicarboxylic acids (maleic acid, fumaric acid, itaconic acid, citraconic acid, etc.) and neutralized salts thereof, unsaturated dicarboxylic anhydrides (maleic anhydride, citraconic anhydride, etc.), unsaturated Examples thereof include saturated dicarboxylic acid alkyl esters and neutralized salts thereof, and unsaturated dicarboxylic acid dialkyl esters. The unsaturated dicarboxylic acids are preferably at least one selected from the group consisting of maleic acid, maleic anhydride and maleic acid monoester from the viewpoint of size effect and the like.
なお、不飽和ジカルボン酸アルキルエステル類とは、前記不飽和ジカルボン酸のカルボキシル基の一つと、炭素数１〜１８程度のアルキル基（直鎖状、分岐鎖状、環状のいずれであってもよい。以下、同様。）を有するアルコールとがエステル化反応してなるモノエステル化合物をいう。また、「不飽和ジカルボン酸ジアルキルエステル」とは、前記不飽和ジカルボン酸のカルボキシル基の全てと当該アルコールとがエステル化反応してなるジエステル化合物をいう。また、該炭素数１〜１８程度のアルキル基としては、例えばメチル、エチル基、ノルマルブチル基、イソブチル基、ターシャリーブチル基、ノルマルオクチル基、２−エチルヘキシル基、デシル基、ドデシル基、ヘキサデシル基、オクタデシル基、オクタデセニル基、ドコシル基、シクロペンチル基、シクロヘキシル基等が挙げられる（以下、同様。）。また、中和塩を形成するための中和剤としては、後述の含窒素化合物等が利用できる。 Note that the unsaturated dicarboxylic acid alkyl ester may be one of the carboxyl groups of the unsaturated dicarboxylic acid and an alkyl group having about 1 to 18 carbon atoms (straight, branched or cyclic). The same shall apply hereinafter)) refers to a monoester compound formed by an esterification reaction. The “unsaturated dicarboxylic acid dialkyl ester” refers to a diester compound obtained by esterifying all of the carboxyl groups of the unsaturated dicarboxylic acid and the alcohol. Examples of the alkyl group having about 1 to 18 carbon atoms include methyl, ethyl group, normal butyl group, isobutyl group, tertiary butyl group, normal octyl group, 2-ethylhexyl group, decyl group, dodecyl group, hexadecyl group. , Octadecyl group, octadecenyl group, docosyl group, cyclopentyl group, cyclohexyl group and the like (hereinafter the same). Moreover, the below-mentioned nitrogen-containing compound etc. can be utilized as a neutralizing agent for forming neutralized salt.
（Ａ）成分には、不飽和ジカルボン酸、不飽和ジカルボン酸無水物、不飽和ジカルボン酸モノアルキルエステルによってカルボキシル基が導入される。また、不飽和ジカルボン酸ジアルキルエステルは、（Ａ）成分のカルボキシル基の一部が後述の含窒素化合物と塩を形成している限りにおいて併用可能であり、サイズ効果等の点よりマレイン酸ジエステルが好ましい。 A carboxyl group is introduced into the component (A) by an unsaturated dicarboxylic acid, an unsaturated dicarboxylic acid anhydride, or an unsaturated dicarboxylic acid monoalkyl ester. The unsaturated dicarboxylic acid dialkyl ester can be used in combination as long as a part of the carboxyl group of the component (A) forms a salt with the nitrogen-containing compound described later. preferable.
スチレン類としては、例えば、スチレン、α−メチルスチレン、ｔ−ブチルスチレン、ジメチルスチレン、アセトキシスチレン、ヒドロキシスチレン、ビニルトルエン、クロルビニルトルエン等の単核体等が挙げられる。スチレン類としては、サイズ効果等の点よりスチレンおよび／またはα−メチルスチレンが好ましい。 Examples of styrenes include mononuclear substances such as styrene, α-methylstyrene, t-butylstyrene, dimethylstyrene, acetoxystyrene, hydroxystyrene, vinyltoluene, chlorovinyltoluene, and the like. As styrenes, styrene and / or α-methylstyrene is preferable from the viewpoint of size effect and the like.
また、（ａ）成分には、アクリル酸、メタクリル酸、クロトン酸、およびこれらの中和塩等の不飽和モノカルボン酸類が含まれない。これらが含まれると、エマルジョン粒子が過大となり、サイズ効果が劣る傾向にあるためである。 Further, the component (a) does not include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and neutralized salts thereof. If these are included, the emulsion particles become excessive and the size effect tends to be inferior.
なお、（ａ）成分には、本発明の所期の効果を損なわない限りにおいて、後述の（Ｃ）成分として例示する（メタ）アクリルアミド類、不飽和モノアルコール類、ポリアルキレングリコール系不飽和単量体類、不飽和ジカルボン酸ジアルキルエステル類、不飽和モノカルボン酸アルキルエステル類、αオレフィン類、Ｎ，Ｎ−アミノアルキル系不飽和単量体類、ビニルエステル系単量体類、およびニトリル系単量体類を他のモノマー類として適宜含ませることができる。 The component (a) includes (meth) acrylamides, unsaturated monoalcohols, polyalkylene glycol-based unsaturated monomers exemplified as the component (C) described below, as long as the intended effect of the present invention is not impaired. Isomers, unsaturated dicarboxylic acid dialkyl esters, unsaturated monocarboxylic acid alkyl esters, alpha olefins, N, N-aminoalkyl unsaturated monomers, vinyl ester monomers, and nitriles Monomers can be appropriately included as other monomers.
（ａ）成分における前記不飽和ジカルボン酸類およびスチレン類ならびに他のモノマー類の含有量は、（ａ）成分を１００重量部とした場合において、通常、順に、２０〜８０重量部程度、８０〜２０重量部程度、および０〜１０重量部程度であり、好ましくは２５〜７５重量部程度、７５〜２５重量部、および０〜５重量部である。 The content of the unsaturated dicarboxylic acids, styrenes, and other monomers in the component (a) is usually about 20 to 80 parts by weight, in the order of 80 to 20 parts when the component (a) is 100 parts by weight. About 0 to 10 parts by weight, preferably about 25 to 75 parts by weight, 75 to 25 parts by weight, and 0 to 5 parts by weight.
また、（Ａ）成分は、サイズ効果の点よりそのカルボキシル基の一部または全部が下記一般式（１）で表される含窒素化合物と塩を形成している必要がある。 In addition, the component (A) needs to form a salt with a nitrogen-containing compound represented by the following general formula (1), part or all of the carboxyl group from the point of size effect.
（式（１）中、Ｘ１、Ｘ２およびＸ３は水素または炭素数１〜３のアルキル基を表す。） (In formula (1), X 1 , X 2 and X 3 represent hydrogen or an alkyl group having 1 to 3 carbon atoms.)
当該含窒素化合物としては、例えば、アンモニア、アルキル基の炭素数１〜３程度の脂肪族アミン類〔モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、モノプロピルアミン、ジプロピルアミン、トリプロピルアミン等〕などが挙げられる。これらの中でも、サイズ効果等の点より、アンモニアおよび／またはモノメチルアミンが好ましい。 Examples of the nitrogen-containing compounds include ammonia and aliphatic amines having about 1 to 3 carbon atoms of an alkyl group [monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, monopropylamine, dipropylamine, tripropylamine. Etc.]. Among these, ammonia and / or monomethylamine are preferable from the viewpoint of size effect and the like.
本発明では、サイズ効果の点より、共重合体（Ａ）の全カルボキシル基のうち５０〜１００モル％が、好ましくは８０〜１００モル％が前記一般式（１）で表される含窒素化合物と塩を形成しているのがよい。 In the present invention, from the viewpoint of the size effect, the nitrogen-containing compound in which 50 to 100 mol%, preferably 80 to 100 mol% of the total carboxyl groups of the copolymer (A) is represented by the general formula (1). It is good to form a salt.
なお、（Ａ）成分をなす全カルボキシル基のうち２０モル％未満ないし５０モル％未満は、他の塩基性化合物、例えば脂環族アミン類〔シクロヘキシルアミン等〕、芳香族アミン類〔アニリン等〕、アルカリ金属化合物〔水酸化ナトリウム、水酸化カリウム等〕、およびアルカリ土類金属化合物〔水酸化カルシウム、水酸化マグネシウム等〕などと塩を形成していてもよい。 In addition, less than 20 mol% to less than 50 mol% of the total carboxyl groups constituting the component (A) are other basic compounds such as alicyclic amines [cyclohexylamine etc.], aromatic amines [aniline etc.]. Further, a salt may be formed with an alkali metal compound [sodium hydroxide, potassium hydroxide, etc.] and an alkaline earth metal compound [calcium hydroxide, magnesium hydroxide, etc.].
また、（Ａ）成分は、サイズ効果とハンドリング性等の点より、重量平均分子量が５０００〜２００００程度、好ましくは６０００〜１５０００である。５０００未満であるとサイズ効果が劣り、２００００を超えるとエマルジョンの製品粘度が高くなりすぎハンドリング性が劣る。ここに「重量平均分子量」とは、ゲルパーミエーションクロマトグラフィーにおけるポリスチレン換算値をいう。該重量平均分子量は後述のラジカル重合開始剤の量により調節できる。 The component (A) has a weight average molecular weight of about 5000 to 20000, preferably 6000 to 15000, from the viewpoint of size effect and handling property. If it is less than 5000, the size effect is inferior, and if it exceeds 20000, the product viscosity of the emulsion becomes too high and the handling property is inferior. Here, the “weight average molecular weight” means a polystyrene equivalent value in gel permeation chromatography. The weight average molecular weight can be adjusted by the amount of the radical polymerization initiator described later.
（Ａ）成分は各種公知の方法で製造できる。具体的には、（ａ）成分を反応溶媒中、ラジカル重合開始剤の存在下、通常８０〜１８０℃程度において、通常１〜１０時間程度重合反応させる。その後、得られた共重合体を、水の存在下、前記含窒素化合物および必要に応じて用いる他の中和化合物により中和すればよい。この際、該含窒素化合物を、（Ａ）成分の全カルボキシル基に対し通常５０〜１５０モル％程度の範囲となるように使用すれば、（Ａ）成分の全カルボキシル基のうち５０〜１００モル％を該含窒素化合物と塩形成させることができる。また、（ａ）成分をなす前記不飽和ジカルボン酸類およびスチレン類の添加順序は問わない。 The component (A) can be produced by various known methods. Specifically, the component (a) is subjected to a polymerization reaction in a reaction solvent in the presence of a radical polymerization initiator, usually at about 80 to 180 ° C., usually for about 1 to 10 hours. Then, what is necessary is just to neutralize the obtained copolymer with the said nitrogen-containing compound and the other neutralization compound used as needed in presence of water. Under the present circumstances, if this nitrogen-containing compound is used so that it may become normally the range of about 50-150 mol% with respect to all the carboxyl groups of (A) component, 50-100 mol among all the carboxyl groups of (A) component. % Can be salted with the nitrogen-containing compound. The order of addition of the unsaturated dicarboxylic acids and styrenes constituting the component (a) is not limited.
該反応溶媒としては、アルコール類〔エチルアルコール、プロピルアルコール等〕、低級ケトン類〔アセトン、メチルエチルケトン〕、芳香族炭化水素類〔トルエン、ベンゼン等〕、酢酸エチル、クロロホルム、ジメチルホルムアミド等が挙げられ、これらは１種を単独で、或いは２種以上を組み合わせて用い得る。 Examples of the reaction solvent include alcohols (ethyl alcohol, propyl alcohol, etc.), lower ketones (acetone, methyl ethyl ketone), aromatic hydrocarbons (toluene, benzene, etc.), ethyl acetate, chloroform, dimethylformamide, and the like. These may be used alone or in combination of two or more.
該ラジカル重合開始剤としては、例えば、無機過酸化物類〔過酸化水素、過硫酸アンモニウム、過硫酸カリウム等〕、有機過酸化物類〔ｔ-ブチルパーオキシベンゾエート、ジクミルパーオキサイド、ラウリルパーオキサイド等〕、アゾ系化合物〔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等〕などが挙げられ、１種を単独で、あるいは２種以上を用いることができる。また、その使用量は、（Ａ）成分の重量平均分子量を前記範囲とできる量であれば特に限定されないが、通常は、（ａ）成分の総量を１００重量部とした場合において、０．０１〜１０重量部程度、好ましくは０．５〜３重量部である。 Examples of the radical polymerization initiator include inorganic peroxides [hydrogen peroxide, ammonium persulfate, potassium persulfate, etc.], organic peroxides [t-butylperoxybenzoate, dicumyl peroxide, lauryl peroxide, etc. Etc.], azo compounds [2,2′-azobisisobutyronitrile, dimethyl-2,2′-azobisisobutyrate, etc.], etc., and the like. be able to. The amount used thereof is not particularly limited as long as the weight average molecular weight of the component (A) can be within the above range, but is usually 0.01 when the total amount of the component (a) is 100 parts by weight. About 10 to 10 parts by weight, preferably 0.5 to 3 parts by weight.
なお、（Ａ）成分の重量平均分子量を調節する目的で、各種の油溶性連鎖移動剤を併用することもできる。ここに「油溶性」とは、水（２５℃）に不溶若しくは難溶であるこという。具体的には、水（２５℃）への溶解度が０．１ｇ／１００ｇ未満であることをいう。該油溶性連鎖移動剤としては、例えば、ｔ−ドデシルメルカプタン、ｎ−ドデシルメルカプタン、ｎ−オクチルメルカプタンクメン、ブロムトリクロルメタン、２−メルカプトベンゾチアゾール等が挙げられる。また、その使用量は、（Ａ）成分をなす不飽和単量体類の総量を１００重量部とした場合において、通常０．０１〜５重量部程度である。 In addition, in order to adjust the weight average molecular weight of (A) component, various oil-soluble chain transfer agents can also be used together. Here, “oil-soluble” means insoluble or hardly soluble in water (25 ° C.). Specifically, it means that the solubility in water (25 ° C.) is less than 0.1 g / 100 g. Examples of the oil-soluble chain transfer agent include t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan men, bromotrichloromethane, 2-mercaptobenzothiazole and the like. Moreover, the usage-amount is about 0.01-5 weight part normally when the total amount of the unsaturated monomers which make (A) component is 100 weight part.
こうして（Ａ）成分を含む水溶液が得られるが、その不揮発分は通常１０〜３０重量％程度、ｐＨは通常７〜１０程度、粘度（２０重量％の水溶液の場合における、Ｂ型粘度計による２５℃での測定値をいう）は通常２０〜１０００ｍＰａ・ｓ程度である。 In this way, an aqueous solution containing the component (A) is obtained. The nonvolatile content is usually about 10 to 30% by weight, the pH is usually about 7 to 10 and the viscosity (in the case of a 20% by weight aqueous solution, 25 by a B-type viscometer (Measured value in ° C.) is usually about 20 to 1000 mPa · s.
本発明に係るエマルジョンは、（Ａ）成分および水溶性連鎖移動剤（Ｂ）（以下、（Ｂ）成分という）の存在下で、親水性不飽和単量体類および疎水性不飽和単量体類を含む単量体群（Ｃ）（以下、（Ｃ）成分という）を乳化重合してなるものである。 The emulsion according to the present invention comprises hydrophilic unsaturated monomers and hydrophobic unsaturated monomers in the presence of component (A) and water-soluble chain transfer agent (B) (hereinafter referred to as component (B)). A monomer group (C) containing a polymer (hereinafter referred to as “component (C)”) is emulsion-polymerized.
ここに「水溶性」とは、（Ｂ）成分が水（２５℃）に混和すること又は易溶であることをいう。具体的には、（Ｂ）成分の水への溶解度（２５℃）が少なくとも０．１ｇ／１００ｇ以上、いっそう具体的には１ｇ／１００ｇ以上であることを意味する。 Here, “water-soluble” means that component (B) is miscible with water (25 ° C.) or easily soluble. Specifically, it means that the solubility (25 ° C.) of the component (B) in water is at least 0.1 g / 100 g or more, more specifically 1 g / 100 g or more.
（Ｂ）成分の具体例としては、例えば、非重合型チオール類〔エタンチオール、プロパンチオール等〕およびその中和塩、チオール酸類〔チオグリコール酸、チオリンゴ酸、ジメチルジチオカルバミン酸等〕およびその中和塩、第２級アルコール類〔イソプロパノール等〕、ならびに次亜リン酸塩類〔次亜リン酸ナトリウム塩〕、下記一般式（２）で表される化合物等が挙げられる。 Specific examples of the component (B) include, for example, non-polymerized thiols [ethane thiol, propane thiol, etc.] and neutralized salts thereof, thiolic acids [thioglycolic acid, thiomalic acid, dimethyldithiocarbamic acid, etc.] and neutralization thereof. Examples thereof include salts, secondary alcohols [isopropanol and the like], hypophosphites [hypophosphite sodium salt], compounds represented by the following general formula (2), and the like.
（式（２）中、Ｙ１は水素またはメチル基を、ｌは１〜４の整数を、Ｙ２は水素又はアルカリ金属原子を示す。） (In formula (2), Y 1 represents hydrogen or a methyl group, l represents an integer of 1 to 4, and Y 2 represents hydrogen or an alkali metal atom.)
一般式（２）で表される化合物としては、例えば、アリルスルホン酸、アリルスルホン酸の中和塩、メタリルスルホン酸、およびメタリルスルホン酸の中和塩などが挙げられる。また、中和塩としてはリチウム塩、ナトリウム、カリウム等が挙げられる。これらの中でも、入手が容易であることを考慮すると、アリルスルホン酸ナトリウム塩および／またはメタリルスルホン酸ナトリウム塩が好ましい。 Examples of the compound represented by the general formula (2) include allyl sulfonic acid, allyl sulfonic acid neutralized salt, methallyl sulfonic acid, and methallyl sulfonic acid neutralized salt. Moreover, lithium salt, sodium, potassium etc. are mentioned as neutralization salt. Among these, in view of availability, allyl sulfonic acid sodium salt and / or methallyl sulfonic acid sodium salt are preferable.
（Ｃ）成分は、親水性不飽和単量体類及び疎水性不飽和単量体類の双方を含む点に特徴があり、例えば親水性不飽和単量体類を欠くとサイズ効果が低下し、また機械的安定性も悪化する。 Component (C) is characterized in that it contains both hydrophilic unsaturated monomers and hydrophobic unsaturated monomers. For example, the lack of hydrophilic unsaturated monomers reduces the size effect. Also, the mechanical stability is deteriorated.
ここに「親水性不飽和単量体」とは、分子内にカルボキシル基、アミド基、水酸基、エーテル基、スルホ基、リン酸基等から選ばれる１種の親水性官能基を少なくとも１つ有する不飽和単量体をいう。また、「疎水性不飽和単量体」とは、分子内に芳香環部位、長鎖アルキルエステル部位および長鎖オレフィン部位等から選ばれる疎水部位を有し、かつ、前記親水性官能基を有さない不飽和単量体をいう。 Here, the “hydrophilic unsaturated monomer” has at least one hydrophilic functional group selected from a carboxyl group, an amide group, a hydroxyl group, an ether group, a sulfo group, a phosphoric acid group and the like in the molecule. An unsaturated monomer. The “hydrophobic unsaturated monomer” means that the molecule has a hydrophobic moiety selected from an aromatic ring moiety, a long-chain alkyl ester moiety, a long-chain olefin moiety, etc., and has the hydrophilic functional group. Unsaturated monomer.
親水性不飽和単量体類の具体例としては、前記不飽和ジカルボン酸類（不飽和ジカルボン酸ジアルキルエステル類を除く）、前記不飽和モノカルボン酸類、（メタ）アクリルアミド類、不飽和モノアルコール類、ポリアルキレングリコール系不飽和単量体類等からなる群より選ばれる少なくとも１種が挙げられる。 Specific examples of the hydrophilic unsaturated monomers include the unsaturated dicarboxylic acids (excluding unsaturated dicarboxylic acid dialkyl esters), the unsaturated monocarboxylic acids, (meth) acrylamides, unsaturated monoalcohols, There may be mentioned at least one selected from the group consisting of polyalkylene glycol unsaturated monomers and the like.
該不飽和ジカルボン酸類としては、マレイン酸、無水マレイン酸およびマレイン酸モノエステルからなる群より選ばれる少なくとも１種が好ましい。 The unsaturated dicarboxylic acids are preferably at least one selected from the group consisting of maleic acid, maleic anhydride and maleic acid monoester.
該不飽和モノカルボン酸類としては、エマルジョンの機械的安定性等の点より、アクリル酸、メタクリル酸、およびこれらの中和塩からなる群より選ばれる少なくとも１種が好ましい。 The unsaturated monocarboxylic acids are preferably at least one selected from the group consisting of acrylic acid, methacrylic acid and neutralized salts thereof from the viewpoint of mechanical stability of the emulsion.
該（メタ）アクリルアミド類としては、各種公知のものを用い得る。具体的には、例えば、アクリルアミド、メタクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ−エチル（メタ）アクリルアミド、Ｎ−（２‐ヒドロキシエチル）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミドなどが挙げられる。これらの中でも、エマルジョンの機械的安定性、特に硬水系における機械的安定性を考慮すると、特にアクリルアミドおよび／またはメタクリルアミドが好ましい。 As the (meth) acrylamides, various known ones can be used. Specific examples include acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N- (2-hydroxyethyl) acrylamide, N, N-dimethyl (meth) acrylamide and the like. It is done. Among these, acrylamide and / or methacrylamide are particularly preferable in consideration of the mechanical stability of the emulsion, particularly the mechanical stability in a hard water system.
該不飽和モノアルコール類としては、例えば、（メタ）アクリル酸ヒドロキシアルキルエステル類〔２−ヒドロキシメチル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート等〕、アリルアルコール、メタリルアルコール等が挙げられる。これらの中でも、エマルジョンの機械的安定性が良好になることから、当該（メタ）アクリル酸ヒドロキシアルキル類が、特に２−ヒドロキシメチル（メタ）アクリレートが好ましい。 Examples of the unsaturated monoalcohols include (meth) acrylic acid hydroxyalkyl esters [2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypropyl (meth) ) Acrylate etc.], allyl alcohol, methallyl alcohol and the like. Among these, since the mechanical stability of the emulsion is improved, the hydroxyalkyl (meth) acrylate is particularly preferably 2-hydroxymethyl (meth) acrylate.
該ポリアルキレングリコール系不飽和単量体類としては、例えば、ジエチレングリコールモノ（メタ）アクリレート、トリエチレングリコールモノ（メタ）アクリレート、テトラエチレングリコールモノ（メタ）アクリレート、ジプロピレングリコールモノ（メタ）アクリレート、トリプロピレングリコールモノ（メタ）アクリレート、テトラプロピレングリコールモノ（メタ）アクリレート、ジプロピレングリコールモノ（メタ）アクリレート、ジプロピレングリコールモノ（メタ）アクリレート等が挙げられる。 Examples of the polyalkylene glycol unsaturated monomers include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, Examples include tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, and dipropylene glycol mono (meth) acrylate.
一方、疎水性不飽和単量体類としては、前記スチレン類、前記不飽和ジカルボン酸ジアルキルエステル類、不飽和モノカルボン酸アルキルエステル類、αオレフィン類、Ｎ，Ｎ−アミノアルキル系不飽和単量体類ビニルエステル系単量体類、およびニトリル類等からなる群より選ばれる少なくとも１種が挙げられる。これらの中でもサイズ効果の観点より、スチレン類および／または不飽和モノカルボン酸アルキルエステル類が好ましく、特に、両者の併用が好ましい。 On the other hand, as the hydrophobic unsaturated monomers, the styrenes, the unsaturated dicarboxylic acid dialkyl esters, the unsaturated monocarboxylic acid alkyl esters, the α-olefins, and the N, N-aminoalkyl unsaturated monomers. And at least one selected from the group consisting of vinyl ester monomers and nitriles. Among these, from the viewpoint of the size effect, styrenes and / or unsaturated monocarboxylic acid alkyl esters are preferable, and the combination of both is particularly preferable.
該スチレン類としては、サイズ効果等の点よりスチレンおよび／またはα−メチルスチレンが好ましい。 The styrenes are preferably styrene and / or α-methylstyrene from the viewpoint of size effect and the like.
該不飽和ジカルボン酸ジアルキルエステル類としては、ジエチルマレエート、ジブチルマレエート、ジイソブチルマレエート、ジオクチルマレエート、ジデシルマレエート、ジドデシルマレエート、ジヘキサデシルマレエート、ジオクタデシルマレエート、ジオクタデセニルマレエート、ジイコシルマレエート等が挙げられる。 Examples of the unsaturated dicarboxylic acid dialkyl esters include diethyl maleate, dibutyl maleate, diisobutyl maleate, dioctyl maleate, didecyl maleate, didodecyl maleate, dihexadecyl maleate, dioctadecyl maleate, dioctadecyl maleate Examples include decenyl maleate and diicosyl maleate.
該不飽和モノカルボン酸アルキルエステル類とは、前記不飽和モノカルボン酸と、前記炭素数１〜１８程度のアルキル基を有するアルコールとがエステル化反応してなるエステル化合物をいう。具体例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ノルマルブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ターシャリーブチル（メタ）アクリレート、ノルマルオクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、オクタデシル（メタ）アクリレート、オクタデセニル（メタ）アクリレート、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート等が挙げられる。 The unsaturated monocarboxylic acid alkyl ester refers to an ester compound obtained by an esterification reaction between the unsaturated monocarboxylic acid and the alcohol having an alkyl group having about 1 to 18 carbon atoms. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, normal butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, normal octyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, octadecenyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like.
該αオレフィン類としては、ジイソブチレン（２，４，４−トリメチルペンテン−１および／または２，４，４−トリメチルペンテン−２をいう）、３−メチル−１−ブテン、３−メチル−１−ペンテン、４−メチル−１−ペンテン、１−ヘキセン、１−オクテン、１−デセン、１−ドデセン、１−テトラデセン、１−ヘキサデセン、１−オクタデセン、１−エイコセン、１−テトラコセン、１−トリアコンテン、シクロヘキセン、メチルシクロヘキセン、ビニルシクロヘキサン、４−ビニルシクロヘキセン、シクロペンテン、メチルシクロペンテン等が挙げられる。 Examples of the α-olefins include diisobutylene (referred to as 2,4,4-trimethylpentene-1 and / or 2,4,4-trimethylpentene-2), 3-methyl-1-butene, and 3-methyl-1 -Pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-tetracosene, 1-tria Examples include content, cyclohexene, methylcyclohexene, vinylcyclohexane, 4-vinylcyclohexene, cyclopentene, and methylcyclopentene.
該Ｎ，Ｎ−アミノアルキル系不飽和単量体類としては、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノプロピル（メタ）アクリレートＮ，Ｎ−ジエチルアミノブチル（メタ）アクリレート等が挙げられる。 Examples of the N, N-aminoalkyl unsaturated monomers include N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate N, N-diethylaminobutyl (meth) acrylate, and the like. Can be mentioned.
該ビニルエステル系単量体類としてはプロピオン酸ビニル、酢酸ビニル等が、（メタ）アクリル酸ベンジルエステル類としては（メタ）アクリル酸ベンジル等が挙げられる。 Examples of the vinyl ester monomers include vinyl propionate and vinyl acetate, and examples of the (meth) acrylic acid benzyl esters include benzyl (meth) acrylate.
該ニトリル系単量体類としては、アクリロニトリル、メタクリロニトリル等が挙げられる。 Examples of the nitrile monomers include acrylonitrile and methacrylonitrile.
（Ｃ）成分には、サイズ効果を高める目的で、必要に応じて各種公知の架橋性単量体類を含めることができる。具体的には、例えば、ポリビニルモノマー〔ジビニルベンゼン、トリビニルベンゼン、ジビニルスルホン〕、ポリアクリレートモノマー〔ポリエチレングリコールジアクリレート、プロピレングリコールジアクリレート、トリメチロールプロパントリアクリレート、テトラメチロールメタンテトラアクリレート、エチレングリコールジメタクリレート、ジプロピレングリコールジメタクリレート等〕、ビスアクリルアミド類〔Ｎ，Ｎ'−プロピレンビスアクリルアミド、ジアクリルアミドジメチルエーテル、Ｎ，Ｎ'−メチレンビスアクリルアミド等〕などが挙げられ、１種を単独で、あるいは２種以上を用いることができる。これらの中でも、サイズ効果の点より該ビスアクリルアミド類が、特にＮ，Ｎ'−メチレンビスアクリルアミドが好ましい。 In the component (C), various known crosslinkable monomers can be included as necessary for the purpose of enhancing the size effect. Specifically, for example, polyvinyl monomers [divinylbenzene, trivinylbenzene, divinylsulfone], polyacrylate monomers [polyethylene glycol diacrylate, propylene glycol diacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol diacrylate. Methacrylate, dipropylene glycol dimethacrylate, etc.], bisacrylamides [N, N′-propylene bisacrylamide, diacrylamide dimethyl ether, N, N′-methylene bisacrylamide, etc.] and the like. More than seeds can be used. Among these, the bisacrylamides are preferable from the viewpoint of size effect, and N, N′-methylenebisacrylamide is particularly preferable.
（Ｃ）成分における親水性不飽和単量体および疎水性不飽和単量体ならびに架橋性単量体類の含有量は特に制限されないが、通常は、（Ｃ）成分を１００重量部とした場合において、順に、２〜５０重量部および５０〜９８重量部程度ならびに０〜３重量部、好ましくは、３．５〜１５重量部および８５〜９６．５重量部ならびに０．０１〜１重量部である。 The content of the hydrophilic unsaturated monomer, the hydrophobic unsaturated monomer and the crosslinkable monomer in the component (C) is not particularly limited, but usually when the component (C) is 100 parts by weight. In order of 2 to 50 parts by weight and 50 to 98 parts by weight and 0 to 3 parts by weight, preferably 3.5 to 15 parts by weight and 85 to 96.5 parts by weight and 0.01 to 1 part by weight. is there.
本発明に係るエマルジョンは、各種公知の方法で製造できる。例えば、適当な反応容器に前記（Ａ）成分、（Ｂ）成分、および（Ｃ）成分、ならびに水、必要に応じて反応溶媒を仕込み、撹拌下に通常４０〜１５０℃程度、２〜１２時間程度、乳化重合反応を行うことにより製造できる。また、必要により前記含窒素化合物や塩基性化合物を用いてもよい。 The emulsion according to the present invention can be produced by various known methods. For example, the components (A), (B), and (C), water, and a reaction solvent as necessary are charged in a suitable reaction vessel, and are usually about 40 to 150 ° C. for 2 to 12 hours with stirring. It can be produced by carrying out an emulsion polymerization reaction to a certain extent. Moreover, you may use the said nitrogen-containing compound and a basic compound as needed.
（Ａ）成分の使用量は特に制限されないが、通常は（Ｃ）成分１００重量部に対して不揮発分換算で通常５〜２００重量部程度、好ましくは１０〜１００重量部の範囲とするのがよい。５重量部以上とすることによりエマルジョンの機械的安定性が良好になる等の、また２００重量部以下とすることによりサイズ効果に優れる等の利点がある。 The amount of component (A) used is not particularly limited, but is usually in the range of about 5 to 200 parts by weight, preferably 10 to 100 parts by weight in terms of non-volatile content with respect to 100 parts by weight of component (C). Good. When the amount is 5 parts by weight or more, the mechanical stability of the emulsion is improved, and when the amount is 200 parts by weight or less, there are advantages such as excellent size effect.
また、（Ｂ）成分の使用量も特に制限されないが、通常は（Ｃ）成分１００重量部に対して通常０．０１〜５重量部程度、好ましくは０．１〜１重量部の範囲とするのがよい。０．０１重量部以上とすることによりエマルジョンの貯蔵安定性に優れる等の、また５重量部以下とすることによりサイズ効果に優れる等の利点がある。 The amount of component (B) used is not particularly limited, but is usually about 0.01 to 5 parts by weight, preferably 0.1 to 1 part by weight per 100 parts by weight of component (C). It is good. When the amount is 0.01 parts by weight or more, there are advantages such as excellent storage stability of the emulsion, and when the amount is 5 parts by weight or less, the size effect is excellent.
乳化重合反応は各種公知の乳化剤の存在下で実施できる。具体的には、非反応性タイプのものとして、アニオン性界面活性剤〔アルキル硫酸塩、アルキルベンゼンスルフォン酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸塩、ジアルキルスルホコハク酸エステル塩、アルキルスルフォン酸塩、ポリオキシエチレンアルキルエーテルスルホコハク酸塩、ポリオキシエチレンスチリルフェニルエーテルスルホコハク酸エステル塩、ポリオキシエチレンアルキルエーテルリン酸塩エステル、α―オレフィンスルホン酸塩、ナフタリンスルホン酸ホルマリン縮合物、ポリオキシエチレンアルキルフェニルエーテルスルホエステル塩等〕、ノニオン性界面活性剤〔ポリエチレングリコール、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンスチリルフェニルエーテル、ポリオキシエチレンソルビタン脂肪酸エステル等〕などが挙げられる。 The emulsion polymerization reaction can be carried out in the presence of various known emulsifiers. Specifically, anionic surfactants [alkyl sulfates, alkyl benzene sulfonates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, dialkyl sulfosuccinates as non-reactive types , Alkyl sulfonate, polyoxyethylene alkyl ether sulfosuccinate, polyoxyethylene styryl phenyl ether sulfosuccinate ester salt, polyoxyethylene alkyl ether phosphate ester, α-olefin sulfonate, naphthalene sulfonate formalin condensate, Polyoxyethylene alkylphenyl ether sulfoester salts, etc.), nonionic surfactants (polyethylene glycol, polyoxyethylene alkyl ether, polyoxyethylene amines, etc.) Kill phenyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitan fatty acid ester, etc.] and the like.
また、エマルジョンの機械的安定性を向上させる目的で、反応性乳化剤として、例えば下記一般式（３）または一般式（４）で表されるものを使用できる。 For the purpose of improving the mechanical stability of the emulsion, for example, those represented by the following general formula (3) or general formula (4) can be used as reactive emulsifiers.
（式（３）中、Ｒ１は炭素数１〜２０の炭化水素基、または、炭素数１〜２０の炭化水素基を有する芳香環を示す。ｍは０または１の整数を示す。（ＡＯ）のうちＡは炭素数２〜４のアルキレン基もしくは置換アルキレン基を示す。ｎは１〜１００の整数を示す。Ｚ１は炭素−炭素二重結合を有する共重合性の官能基を示す。Ｚ２は水素、スルホン酸基、リン酸基、スルホコハク酸基およびこれらの塩ならびにスルホコハク酸基エステルから選ばれる１種を示す。） (In Formula (3), R 1 represents an aromatic ring having a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms. M represents an integer of 0 or 1 (AO). A represents an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, n represents an integer of 1 to 100, and Z 1 represents a copolymerizable functional group having a carbon-carbon double bond. Z 2 represents one selected from hydrogen, sulfonic acid group, phosphoric acid group, sulfosuccinic acid group and salts thereof, and sulfosuccinic acid group ester.)
（式（４）中、Ｒ２およびＲ３はそれぞれ水素原子または炭素数１〜２０の炭化水素基を示す。（ＡＯ）のうちＡは炭素数２〜４のアルキレン基もしくは置換アルキレン基を示す。ｎは１〜１００の整数を示す。Ｚ１は炭素−炭素二重結合を有する共重合性の官能基を示す。Ｚ２は水素、スルホン酸基、リン酸基、スルホコハク酸基およびこれらの塩ならびにスルホコハク酸基エステルから選ばれる１種を示す。） (In Formula (4), R 2 and R 3 each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. In (AO), A represents an alkylene group or substituted alkylene group having 2 to 4 carbon atoms. N represents an integer of 1 to 100. Z 1 represents a copolymerizable functional group having a carbon-carbon double bond, Z 2 represents hydrogen, a sulfonic acid group, a phosphoric acid group, a sulfosuccinic acid group, and these 1 type selected from a salt and a sulfosuccinic acid group ester.)
式（３）および式（４）におけるＺ１としては、（メタ）アクリル基、１−プロペニル基、２−メチルー１−プロペニル基、イソプロペニル基、ビニル基、（メタ）アクリロイル基から選ばれる１種が挙げられる。 Z 1 in Formula (3) and Formula (4) is 1 selected from a (meth) acryl group, 1-propenyl group, 2-methyl-1-propenyl group, isopropenyl group, vinyl group, and (meth) acryloyl group. Species are mentioned.
反応性乳化剤としては式（３）で表されるものが好ましく、具体例としては、ポリオキシエチレン−１−（アリルオキシメチル）アルキルエーテル硫酸塩、ポリオキシエチレンノニルプロペニルフェニルエーテル硫酸塩、ポリオキシエチレン−１−（アリルオキシメチル）アルキルエーテル、ポリオキシエチレンノニルプロペニルフェニルエーテルなどが挙げられる。 As the reactive emulsifier, those represented by the formula (3) are preferable, and specific examples include polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate, polyoxyethylene nonylpropenyl phenyl ether sulfate, polyoxy Examples include ethylene-1- (allyloxymethyl) alkyl ether, polyoxyethylene nonylpropenyl phenyl ether, and the like.
これら乳化剤の使用量は通常、（Ｃ）成分１００重量部（不揮発分）に対して、通常０〜１０重量部、好ましくは０．５〜５重量部である。 The amount of these emulsifiers is usually 0 to 10 parts by weight, preferably 0.5 to 5 parts by weight, with respect to 100 parts by weight (nonvolatile content) of component (C).
こうして得られるエマルジョンは通常、ｐＨが通常６．０〜１０．０程度、粘度が５〜２００ｍＰａ・ｓ（不揮発分２０％）程度、および粒径が通常５０〜１５０ｎｍ程度、好ましくは７０〜１１０ｎｍである。なお、「粒子径」とは、具体的にはエマルジョン粒子の平均一次粒子径をいい、例えば、動的光散乱法や自然沈降法等の各種公知の方法により測定できる。また、粒子径が大きくなりすぎると、サイズ効果が低下する傾向にある。 The emulsion thus obtained usually has a pH of usually about 6.0 to 10.0, a viscosity of about 5 to 200 mPa · s (nonvolatile content 20%), and a particle size of usually about 50 to 150 nm, preferably 70 to 110 nm. is there. The “particle diameter” specifically refers to the average primary particle diameter of the emulsion particles, and can be measured by various known methods such as a dynamic light scattering method and a natural sedimentation method. Moreover, when the particle diameter becomes too large, the size effect tends to decrease.
また、該エマルジョンには、各種添加剤、例えば、カルボキシメチルセルロース等のセルロース類、ポリビニルアルコール類、ポリアクリルアミド類、アルギン酸ソーダ等の水溶性高分子等の紙力増強剤や、防滑剤、防腐剤、防錆剤、ｐＨ調整剤、消泡剤（シリコン系消泡剤等）、増粘剤、充填剤、酸化防止剤、耐水化剤、造膜助剤、顔料、染料等を添加することもできる。 In addition, the emulsion includes various additives, for example, paper strength enhancers such as celluloses such as carboxymethyl cellulose, polyvinyl alcohols, polyacrylamides, water-soluble polymers such as sodium alginate, anti-slip agents, preservatives, Rust inhibitors, pH adjusters, antifoaming agents (silicone defoaming agents, etc.), thickeners, fillers, antioxidants, water resistance agents, film-forming aids, pigments, dyes, etc. can also be added. .
本発明の製紙用表面サイズ剤は前記エマルジョンをそのまま用いたものであり、これを各種公知の手段により原紙に塗工することにより、本発明の紙が得られる。なお、当該サイズ剤は、塗工に際し、前記エマルジョンの不揮発分が通常０．０１〜２重量部程度となるよう希釈されたサイズ液として実用に供される。 The surface sizing agent for papermaking of the present invention uses the emulsion as it is, and the paper of the present invention can be obtained by applying it to the base paper by various known means. The sizing agent is practically used as a sizing liquid diluted so that the nonvolatile content of the emulsion is usually about 0.01 to 2 parts by weight during coating.
塗工手段は特に限定されず、例えば、サイズプレス法、ゲートロール法、バーコーター法、カレンダー法、スプレー法等の各種手段が挙げられる。本発明の製紙用表面サイズ剤は前記したように機械的安定性に優れるので、２ロールサイズプレス塗工方式、ロッドメタリングサイズプレス塗工方式やゲートロール塗工方式などの各種塗工マシンで使用可能である。なお、塗布量（固形分）は通常、０．００１〜２ｇ／ｍ２、好ましくは０．００５〜０．５ｇ／ｍ２である。 The coating means is not particularly limited, and examples thereof include various means such as a size press method, a gate roll method, a bar coater method, a calendar method, and a spray method. Since the surface sizing agent for papermaking of the present invention is excellent in mechanical stability as described above, it can be used in various coating machines such as a two-roll size press coating method, a rod metering size press coating method, and a gate roll coating method. It can be used. Incidentally, the coating amount (solid content) is usually, 0.001~2g / m 2, preferably from 0.005 to 0.5 / m 2.
原紙は特に限定されず、例えば、木材セルロース繊維を原料とする未塗工の紙を用いることができる。また、原紙の原料たる抄紙用パルプとしては、ＬＢＫＰ、ＮＢＫＰ等の化学パルプや、ＧＰ、ＴＭＰ等の機械パルプ、その他古紙パルプ等が挙げられる。また、当該原紙中には、内添サイズ剤や填料、紙力剤等の薬品が含まれていてもよい。 The base paper is not particularly limited, and for example, uncoated paper made from wood cellulose fibers can be used. Examples of the papermaking pulp as a raw material for the base paper include chemical pulps such as LBKP and NBKP, mechanical pulps such as GP and TMP, and other waste paper pulps. Further, the base paper may contain chemicals such as an internal sizing agent, a filler, and a paper strength agent.
得られた紙は、記録用紙〔フォーム用紙、ＰＰＣ用紙、感熱記録原紙、感圧記録原紙等〕、コート紙〔アート紙、キャストコート紙、上質コート紙等〕、包装用紙〔クラフト紙、純白ロール紙等〕、洋紙〔ノート用紙、書籍用紙、印刷用紙、新聞用紙等〕、板紙〔マニラボール、白ボール、チップボール、ライナー等〕などの用途に供される。 The obtained paper includes recording paper (form paper, PPC paper, thermal recording base paper, pressure sensitive recording base paper, etc.), coated paper (art paper, cast coated paper, high quality coated paper, etc.), packaging paper (craft paper, pure white roll) Paper, etc.], western paper [note paper, book paper, printing paper, newsprint paper, etc.], paperboard [manila ball, white ball, chip ball, liner, etc.].
以下、参考例および比較例をあげて本発明を具体的に説明するが、本発明はこれら実施例に限定されるものではない。なお各例中、部および％は特記しない限りすべて重量基準である。 Hereinafter, the present invention will be specifically described with reference examples and comparative examples, but the present invention is not limited to these examples. In each example, all parts and% are based on weight unless otherwise specified.
また、各例中、重量平均分子量はゲルパーメーションクロマトグラフィー（ＨＬＣ８１２０ＧＰＣ、使用カラムＴＳＫｇｅｌ ＳｕｐｅｒＨＭ−Ｎを２本使用、展開溶媒ＴＨＦ）にておいて測定いた測定値（ポリスチレン換算値）を、粘度はＢ型粘度計（東機産業（株）製）による測定値を、粒子径はレーザー粒径解析装置（製品名「ＬＰＡ−３０００／３１００」、大塚電子（株）製）による測定値を意味する。 In each example, the weight average molecular weight is measured by gel permeation chromatography (HLC8120GPC, using two columns TSKgel SuperHM-N, developing solvent THF), and the viscosity is measured in terms of polystyrene. The measured value with a B-type viscometer (manufactured by Toki Sangyo Co., Ltd.), and the particle size means the measured value with a laser particle size analyzer (product name “LPA-3000 / 3100”, manufactured by Otsuka Electronics Co., Ltd.). .
事前合成例１
撹拌機、冷却管、２つの滴下ロート、窒素導入管および温度計を備えた反応容器に、マレイン酸２８５部を仕込み、撹拌しながら１００℃まで昇温した。次いで、滴下ロートより、イソブチルアルコール２１５部を、約２時間を要して、反応容器内へと滴下し、約３時間保温・脱水することによりマレイン酸のイソブチルアルコールモノエステルを得た。これを以下の合成例に供した。
Pre-synthesis example 1
A reaction vessel equipped with a stirrer, a cooling tube, two dropping funnels, a nitrogen introducing tube and a thermometer was charged with 285 parts of maleic acid and heated to 100 ° C. while stirring. Next, 215 parts of isobutyl alcohol was dropped from the dropping funnel into the reaction vessel in about 2 hours, and the mixture was kept warm and dehydrated for about 3 hours to obtain isobutyl alcohol monoester of maleic acid. This was subjected to the following synthesis example.
事前合成例２
事前合成例１と同様の反応容器に、マレイン酸２８．５部を仕込み、撹拌しながら１００℃まで昇温した。次いで、滴下ロートより、イソブチルアルコール７１．５部を、約２時間を要して、反応容器内へと滴下し、約３時間保温・脱水することによりマレイン酸のイソブチルアルコールジエステルを得た。これを以下の合成例に供した。
Pre-synthesis example 2
28.5 parts of maleic acid was charged into the same reaction vessel as in the pre-synthesis example 1, and the temperature was raised to 100 ° C. with stirring. Next, 71.5 parts of isobutyl alcohol was dropped into the reaction vessel from the dropping funnel in about 2 hours, and the mixture was kept warm and dehydrated for about 3 hours to obtain isobutyl alcohol diester of maleic acid. This was subjected to the following synthesis example.
事前合成例３
事前合成例１と同様の反応容器に、マレイン酸４３．０部を仕込み、撹拌しながら１００℃まで昇温した。次いで、滴下ロートより、２-エチルヘキシルアルコール５７．０部を、約２時間を要して、反応容器内へと滴下し、約３時間保温・脱水することによりマレイン酸の２−エチルヘキシルアルコールモノエステルを得た。これを以下の合成例に供した。
Pre-synthesis example 3
43.0 parts of maleic acid was charged into the same reaction vessel as in the pre-synthesis example 1, and the temperature was raised to 100 ° C. while stirring. Next, 57.0 parts of 2-ethylhexyl alcohol was dropped into the reaction vessel in about 2 hours from the dropping funnel, and the mixture was kept warm and dehydrated for about 3 hours to give 2-ethylhexyl alcohol monoester of maleic acid. Got. This was subjected to the following synthesis example.
合成例１
撹拌機、冷却管、２つの滴下ロート、窒素導入管および温度計を備えた反応容器に、スチレン４３．５部、マレイン酸２０．５部、マレイン酸のイソブチルアルコールモノエステル３６部およびトルエン１００部を仕込み、窒素気流下に撹拌しながら１１０℃まで昇温した。次いで、一の滴下ロートより、ｔ-ブチルパーオキシベンゾエート２．５部およびトルエン３４部からなる混合液を、約１．５時間を要して、反応容器内へと滴下し、還流下に約３．５時間保温した。その後トルエンを減圧留去した。次いで、反応系に、２８％アンモニア水３４．３部（共重合体中のカルボキシル基総モルの９０％中和）、４８％水酸化ナトリウム水溶液５．２部（共重合体中のカルボキシル基総モルの１０％中和）、および所定量の水からなる混合液を加えることにより、共重合体を中和した。次いで、水で希釈することにより、重量平均分子量が９０００の（Ａ−１）成分を含む水溶液を得た。また当該水溶液は、不揮発分が２０％、２５℃の粘度が３０ｍＰａ・ｓ、およびｐＨが８．８であった。
Synthesis example 1
In a reaction vessel equipped with a stirrer, a condenser, two dropping funnels, a nitrogen inlet tube and a thermometer, 43.5 parts of styrene, 20.5 parts of maleic acid, 36 parts of isobutyl alcohol monoester of maleic acid and 100 parts of toluene Was heated to 110 ° C. while stirring under a nitrogen stream. Next, from one dropping funnel, a mixed solution consisting of 2.5 parts of t-butyl peroxybenzoate and 34 parts of toluene was dropped into the reaction vessel over about 1.5 hours, Incubated for 3.5 hours. Thereafter, toluene was distilled off under reduced pressure. Then, 34.3 parts of 28% aqueous ammonia (90% neutralization of the total moles of carboxyl groups in the copolymer) and 5.2 parts of 48% aqueous sodium hydroxide solution (total number of carboxyl groups in the copolymer) were added to the reaction system. The copolymer was neutralized by adding a liquid mixture consisting of a predetermined amount of water. Subsequently, the aqueous solution containing the (A-1) component whose weight average molecular weight is 9000 was obtained by diluting with water. The aqueous solution had a nonvolatile content of 20%, a viscosity at 25 ° C. of 30 mPa · s, and a pH of 8.8.
合成例２
合成例１と同様の反応容器に、スチレン４３．５部、マレイン酸２０．５部、マレイン酸のイソブチルアルコールモノエステル３６部およびトルエン１００部を仕込み、窒素気流下に撹拌しながら１１０℃まで昇温した。次いで、一の滴下ロートより、ｔ-ブチルパーオキシベンゾエート２．５部およびトルエン３４部からなる混合液を、約１．５時間を要して、反応容器内へと滴下し、還流下に約３．５時間保温した。その後トルエンを減圧留去した。次いで、反応系に、２８％アンモニア水３８．１部（共重合体中のカルボキシル基総モルの１００％中和）、および所定量の水からなる混合液を加えることにより、共重合体を中和した。次いで、水で希釈することにより、重量平均分子量が１１０００の（Ａ−２）成分を含む水溶液を得た。また当該水溶液は、不揮発分が２０％、２５℃の粘度が４０ｍＰａ・ｓ、およびｐＨが８．７であった。
Synthesis example 2
In the same reaction vessel as in Synthesis Example 1, 43.5 parts of styrene, 20.5 parts of maleic acid, 36 parts of isobutyl alcohol monoester of maleic acid and 100 parts of toluene were charged, and the temperature was raised to 110 ° C. with stirring under a nitrogen stream. Warm up. Next, from one dropping funnel, a mixed solution consisting of 2.5 parts of t-butyl peroxybenzoate and 34 parts of toluene was dropped into the reaction vessel over about 1.5 hours, Incubated for 3.5 hours. Thereafter, toluene was distilled off under reduced pressure. Next, a mixed solution consisting of 38.1 parts of 28% ammonia water (100% neutralization of the total moles of carboxyl groups in the copolymer) and a predetermined amount of water was added to the reaction system, thereby adding the copolymer to the inside. It was summed up. Subsequently, the aqueous solution containing the (A-2) component whose weight average molecular weight is 11000 was obtained by diluting with water. The aqueous solution had a nonvolatile content of 20%, a viscosity at 25 ° C. of 40 mPa · s, and a pH of 8.7.
合成例３
合成例１と同様の反応容器に、スチレン３８．７部、マレイン酸３．６部、マレイン酸のイソブチルアルコールモノエステル５７．６部およびトルエン１００部を仕込み、窒素気流下に撹拌しながら１１０℃まで昇温した。次いで、一の滴下ロートより、ｔ-ブチルパーオキシベンゾエート２．５部およびトルエン３４部からなる混合液を、約１．５時間を要して、反応容器内へと滴下し、還流下に約３．５時間保温した。その後トルエンを減圧留去した。次いで、反応系に、２８％アンモニア水２４．８部（共重合体中のカルボキシル基総モルの１００％中和）、および所定量の水からなる混合液を加えることにより、共重合体を中和した。次いで、水で希釈することにより、重量平均分子量が９５００の（Ａ−３）成分を含む水溶液を得た。また当該水溶液は、不揮発分が２０％、２５℃の粘度が５５ｍＰａ・ｓ、およびｐＨが８．８であった。
Synthesis example 3
A reaction vessel similar to Synthesis Example 1 was charged with 38.7 parts of styrene, 3.6 parts of maleic acid, 57.6 parts of maleic acid isobutyl alcohol monoester and 100 parts of toluene, and stirred at 110 ° C. under a nitrogen stream. The temperature was raised to. Next, from one dropping funnel, a mixed solution consisting of 2.5 parts of t-butyl peroxybenzoate and 34 parts of toluene was dropped into the reaction vessel over about 1.5 hours, Incubated for 3.5 hours. Thereafter, toluene was distilled off under reduced pressure. Next, 24.8 parts of 28% aqueous ammonia (100% neutralization of the total moles of carboxyl groups in the copolymer) and a predetermined amount of water were added to the reaction system, thereby adding the copolymer to the inside. It was summed up. Subsequently, the aqueous solution containing the (A-3) component whose weight average molecular weight is 9500 was obtained by diluting with water. The aqueous solution had a nonvolatile content of 20%, a viscosity at 25 ° C. of 55 mPa · s, and a pH of 8.8.
合成例４
合成例１と同様の反応容器に、スチレン３９部、マレイン酸１８．４部、マレイン酸２エチルヘキシルアルコールモノエステル４２．７部およびトルエン１００部を仕込み、窒素気流下に撹拌しながら１１０℃まで昇温した。次いで、一の滴下ロートより、ｔ-ブチルパーオキシベンゾエート２．５部およびトルエン３４部からなる混合液を、約１．５時間を要して、反応容器内へと滴下し、還流下に約３．５時間保温した。その後トルエンを減圧留去した。次いで、反応系に、２８％アンモニア水３４．２部（共重合体中のカルボキシル基総モルの１００％中和）、および所定量の水からなる混合液を加えることにより、共重合体を中和した。次いで、水で希釈することにより、重量平均分子量が９８００の（Ａ−４）成分を含む水溶液を得た。また当該水溶液は、不揮発分が２０％、２５℃の粘度が１１０ｍＰａ・ｓ、およびｐＨが８．９であった。
Synthesis example 4
In a reaction vessel similar to Synthesis Example 1, 39 parts of styrene, 18.4 parts of maleic acid, 42.7 parts of 2-ethylhexyl alcohol monoester maleate and 100 parts of toluene were charged, and the temperature was raised to 110 ° C. with stirring under a nitrogen stream. Warm up. Next, from one dropping funnel, a mixed solution consisting of 2.5 parts of t-butyl peroxybenzoate and 34 parts of toluene was dropped into the reaction vessel over about 1.5 hours, Incubated for 3.5 hours. Thereafter, toluene was distilled off under reduced pressure. Next, a mixture of 28% ammonia water (34.2 parts) (100% neutralization of the total moles of carboxyl groups in the copolymer) and a predetermined amount of water was added to the reaction system. It was summed up. Subsequently, the aqueous solution containing the (A-4) component whose weight average molecular weight is 9800 was obtained by diluting with water. The aqueous solution had a nonvolatile content of 20%, a viscosity at 25 ° C. of 110 mPa · s, and a pH of 8.9.
合成例５
合成例１と同様の反応容器に、スチレン５１．５部、マレイン酸４８．５部およびトルエン１００部を仕込み、窒素気流下に撹拌しながら１１０℃まで昇温した。次いで、一の滴下ロートより、ｔ-ブチルパーオキシベンゾエート２．５部およびトルエン３４部からなる混合液を、約１．５時間を要して、反応容器内へと滴下し、還流下に約３．５時間保温した。その後トルエンを減圧留去した。次いで、反応系に、２８％アンモニア水６０．１部（共重合体中のカルボキシル基総モルの１００％中和）、および所定量の水からなる混合液を加えることにより、共重合体を中和した。次いで、水で希釈することにより、重量平均分子量が１２０００の（Ａ−５）成分を含む水溶液を得た。また当該水溶液は、不揮発分が２０％、２５℃の粘度が２５ｍＰａ・ｓ、およびｐＨが８．８であった。
Synthesis example 5
In a reaction vessel similar to Synthesis Example 1, 51.5 parts of styrene, 48.5 parts of maleic acid and 100 parts of toluene were charged, and the temperature was raised to 110 ° C. while stirring under a nitrogen stream. Next, from one dropping funnel, a mixed solution consisting of 2.5 parts of t-butyl peroxybenzoate and 34 parts of toluene was dropped into the reaction vessel over about 1.5 hours, Incubated for 3.5 hours. Thereafter, toluene was distilled off under reduced pressure. Subsequently, 60.1 parts of 28% aqueous ammonia (100% neutralization of the total moles of carboxyl groups in the copolymer) and a mixture of a predetermined amount of water were added to the reaction system, thereby adding the copolymer to the reaction system. It was summed up. Subsequently, the aqueous solution containing (A-5) component whose weight average molecular weight is 12000 was obtained by diluting with water. The aqueous solution had a nonvolatile content of 20%, a viscosity at 25 ° C. of 25 mPa · s, and a pH of 8.8.
合成例６
合成例１と同様の反応容器に、スチレン３８．９部、α−メチルスチレン４．９部、マレイン酸２０．４部、マレイン酸のイソブチルアルコールモノエステル３５．８部およびトルエン１００部を仕込み、窒素気流下に撹拌しながら１１０℃まで昇温した。次いで、一の滴下ロートより、ｔ-ブチルパーオキシベンゾエート２．５部およびトルエン３４部からなる混合液を、約１．５時間を要して、反応容器内へと滴下し、還流下に約３．５時間保温した。その後トルエンを減圧留去した。次いで、反応系に、２８％アンモニア水３７．９部（共重合体中のカルボキシル基総モルの１００％中和）、および所定量の水からなる混合液を加えることにより、共重合体を中和した。次いで、水で希釈することにより、重量平均分子量が８１００の（Ａ−６）成分を含む水溶液を得た。また当該水溶液は、不揮発分が２０％、２５℃の粘度が３０ｍＰａ・ｓ、およびｐＨが８．８であった。
Synthesis Example 6
A reaction vessel similar to Synthesis Example 1 was charged with 38.9 parts of styrene, 4.9 parts of α-methylstyrene, 20.4 parts of maleic acid, 35.8 parts of isobutyl alcohol monoester of maleic acid, and 100 parts of toluene, The temperature was raised to 110 ° C. with stirring under a nitrogen stream. Next, from one dropping funnel, a mixed solution consisting of 2.5 parts of t-butyl peroxybenzoate and 34 parts of toluene was dropped into the reaction vessel over about 1.5 hours, Incubated for 3.5 hours. Thereafter, toluene was distilled off under reduced pressure. Subsequently, 37.9 parts of 28% aqueous ammonia (100% neutralization of the total moles of carboxyl groups in the copolymer) and a predetermined amount of water were added to the reaction system to add the copolymer to the inside. It was summed up. Subsequently, the aqueous solution containing the (A-6) component whose weight average molecular weight is 8100 was obtained by diluting with water. The aqueous solution had a nonvolatile content of 20%, a viscosity at 25 ° C. of 30 mPa · s, and a pH of 8.8.
合成例７
合成例１と同様の反応容器に、スチレン４３．５部、マレイン酸２０．５部、マレイン酸のイソブチルアルコールモノエステル３６部およびトルエン１００部を仕込み、窒素気流下に撹拌しながら１１０℃まで昇温した。次いで、一の滴下ロートより、ｔ-ブチルパーオキシベンゾエート０．８部およびトルエン３４部からなる混合液を、約１．５時間を要して、反応容器内へと滴下し、還流下に約３．５時間保温した。その後トルエンを減圧留去した。次いで、反応系に、２８％アンモニア水３８．１部（共重合体中のカルボキシル基総モルの１００％中和）、および所定量の水からなる混合液を加えることにより、共重合体を中和した。次いで、水で希釈することにより、重量平均分子量が１８０００の（Ａ−７）成分を含む水溶液を得た。また当該水溶液は、不揮発分が２０％、２５℃の粘度が５０ｍＰａ・ｓ、およびｐＨが８．８であった。
Synthesis example 7
In the same reaction vessel as in Synthesis Example 1, 43.5 parts of styrene, 20.5 parts of maleic acid, 36 parts of isobutyl alcohol monoester of maleic acid and 100 parts of toluene were charged, and the temperature was raised to 110 ° C. with stirring under a nitrogen stream. Warm up. Next, from one dropping funnel, a mixed solution consisting of 0.8 part of t-butyl peroxybenzoate and 34 parts of toluene was dropped into the reaction vessel over about 1.5 hours, and the mixture was refluxed. Incubated for 3.5 hours. Thereafter, toluene was distilled off under reduced pressure. Next, a mixed solution consisting of 38.1 parts of 28% ammonia water (100% neutralization of the total moles of carboxyl groups in the copolymer) and a predetermined amount of water was added to the reaction system, thereby adding the copolymer to the inside. It was summed up. Subsequently, the aqueous solution containing (A-7) component whose weight average molecular weight is 18000 was obtained by diluting with water. The aqueous solution had a nonvolatile content of 20%, a viscosity at 25 ° C. of 50 mPa · s, and a pH of 8.8.
合成例８
合成例１と同様の反応容器に、スチレン４３．５部、マレイン酸２０．５部、マレイン酸のイソブチルアルコールモノエステル３６部およびトルエン１００部を仕込み、窒素気流下に撹拌しながら１１０℃まで昇温した。次いで、一の滴下ロートより、ｔ-ブチルパーオキシベンゾエート３．２部およびトルエン３４部からなる混合液を、約１．５時間を要して、反応容器内へと滴下し、還流下に約３．５時間保温した。その後トルエンを減圧留去した。次いで、反応系に、２８％アンモニア水３８．１部（共重合体中のカルボキシル基総モルの１００％中和）、および所定量の水からなる混合液を加えることにより、共重合体を中和した。次いで、水で希釈することにより、重量平均分子量が６５００の（Ａ−８）成分を含む水溶液を得た。また当該水溶液は、不揮発分が２０％、２５℃の粘度が３０ｍＰａ・ｓ、およびｐＨが８．８であった。
Synthesis example 8
In the same reaction vessel as in Synthesis Example 1, 43.5 parts of styrene, 20.5 parts of maleic acid, 36 parts of isobutyl alcohol monoester of maleic acid and 100 parts of toluene were charged, and the temperature was raised to 110 ° C. with stirring under a nitrogen stream. Warm up. Next, from one dropping funnel, a mixed solution consisting of 3.2 parts of t-butyl peroxybenzoate and 34 parts of toluene was dropped into the reaction vessel over about 1.5 hours, and the mixture was refluxed. Incubated for 3.5 hours. Thereafter, toluene was distilled off under reduced pressure. Next, a mixed solution consisting of 38.1 parts of 28% ammonia water (100% neutralization of the total moles of carboxyl groups in the copolymer) and a predetermined amount of water was added to the reaction system, thereby adding the copolymer to the inside. It was summed up. Then, the aqueous solution containing the (A-8) component whose weight average molecular weight is 6500 was obtained by diluting with water. The aqueous solution had a nonvolatile content of 20%, a viscosity at 25 ° C. of 30 mPa · s, and a pH of 8.8.
合成例９
合成例１と同様の反応容器に、スチレン４３．５部、マレイン酸２０．５部、マレイン酸のイソブチルアルコールモノエステル３６部およびトルエン１００部を仕込み、窒素気流下に撹拌しながら１１０℃まで昇温した。次いで、一の滴下ロートより、ｔ-ブチルパーオキシベンゾエート２．５部およびトルエン３４部からなる混合液を、約１．５時間を要して、反応容器内へと滴下し、還流下に約３．５時間保温した。その後トルエンを減圧留去した。次いで、反応系に、４０％のモノメチルアミン４８．７部（共重合体中のカルボキシル基総モルの１００％中和）、および所定量の水からなる混合液を加えることにより、共重合体を中和した。次いで、水で希釈することにより、重量平均分子量が９１００の（Ａ−９）成分を含む水溶液を得た。また当該水溶液は、不揮発分が２０％、２５℃の粘度が５５ｍＰａ・ｓ、およびｐＨが８．８であった。
Synthesis Example 9
In the same reaction vessel as in Synthesis Example 1, 43.5 parts of styrene, 20.5 parts of maleic acid, 36 parts of isobutyl alcohol monoester of maleic acid and 100 parts of toluene were charged, and the temperature was raised to 110 ° C. with stirring under a nitrogen stream. Warm up. Next, from one dropping funnel, a mixed solution consisting of 2.5 parts of t-butyl peroxybenzoate and 34 parts of toluene was dropped into the reaction vessel over about 1.5 hours, Incubated for 3.5 hours. Thereafter, toluene was distilled off under reduced pressure. Next, a copolymer solution comprising 48.7 parts of 40% monomethylamine (100% neutralization of the total moles of carboxyl groups in the copolymer) and a predetermined amount of water was added to the reaction system. Neutralized. Subsequently, the aqueous solution containing the (A-9) component whose weight average molecular weight is 9100 was obtained by diluting with water. The aqueous solution had a nonvolatile content of 20%, a viscosity at 25 ° C. of 55 mPa · s, and a pH of 8.8.
合成例１０
合成例１と同様の反応容器に、スチレン４２．２部、マレイン酸１９．９部、マレイン酸のイソブチルアルコールモノエステル２７．９部、マレイン酸のイソブチルアルコールジエステル１０．０部およびトルエン１００部を仕込み、窒素気流下に撹拌しながら１１０℃まで昇温した。次いで、一の滴下ロートより、ｔ-ブチルパーオキシベンゾエート２．５部およびトルエン３４部からなる混合液を、約１．５時間を要して、反応容器内へと滴下し、還流下に約３．５時間保温した。その後トルエンを減圧留去した。次いで、反応系に、２８％アンモニア水３４．５部（共重合体中のカルボキシル基総モルの１００％中和）、および所定量の水からなる混合液を加えることにより、共重合体を中和した。次いで、水で希釈することにより、重量平均分子量が１１０００の（Ａ−１０）成分を含む水溶液を得た。また当該水溶液は、不揮発分が２０％、２５℃の粘度が５０ｍＰａ・ｓ、およびｐＨが８．７であった。
Synthesis Example 10
In the same reaction vessel as in Synthesis Example 1, 42.2 parts of styrene, 19.9 parts of maleic acid, 27.9 parts of maleic acid isobutyl alcohol monoester, 10.0 parts of maleic acid isobutyl alcohol diester and 100 parts of toluene. The temperature was raised to 110 ° C. while stirring under a nitrogen stream. Next, from one dropping funnel, a mixed solution consisting of 2.5 parts of t-butyl peroxybenzoate and 34 parts of toluene was dropped into the reaction vessel over about 1.5 hours, Incubated for 3.5 hours. Thereafter, toluene was distilled off under reduced pressure. Next, a mixed solution consisting of 34.5 parts of 28% aqueous ammonia (100% neutralization of the total moles of carboxyl groups in the copolymer) and a predetermined amount of water was added to the reaction system, whereby the copolymer was dissolved in the medium. It was summed up. Subsequently, the aqueous solution containing the (A-10) component whose weight average molecular weight is 11000 was obtained by diluting with water. The aqueous solution had a nonvolatile content of 20%, a viscosity at 25 ° C. of 50 mPa · s, and a pH of 8.7.
合成例１１
合成例１と同様の反応容器に、スチレン４３．５部、マレイン酸２０．５部、マレイン酸のイソブチルアルコールモノエステル３６部およびトルエン１００部を仕込み、窒素気流下に撹拌しながら１１０℃まで昇温した。次いで、一の滴下ロートより、ｔ-ブチルパーオキシベンゾエート２．５部およびトルエン３４部からなる混合液を、約１．５時間を要して、反応容器内へと滴下し、還流下に約３．５時間保温した。その後トルエンを減圧留去した。次いで、反応系に、２８％アンモニア水１５．２部（共重合体中のカルボキシル基総モルの４０％中和）、４８％水酸化ナトリウム水溶液３１．４部（共重合体中のカルボキシル基総モルの６０％中和）、所定量の水からなる混合液を加えることにより、共重合体を中和した。次いで、水で希釈することにより、重量平均分子量が９５００の共重合体塩（Ａ−１１）成分を含む水溶液を得た。また当該水溶液は、不揮発分が２０％、２５℃の粘度が３０ｍＰａ・ｓ、およびｐＨが８．９であった。
Synthesis Example 11
In the same reaction vessel as in Synthesis Example 1, 43.5 parts of styrene, 20.5 parts of maleic acid, 36 parts of isobutyl alcohol monoester of maleic acid and 100 parts of toluene were charged, and the temperature was raised to 110 ° C. with stirring under a nitrogen stream. Warm up. Next, from one dropping funnel, a mixed solution consisting of 2.5 parts of t-butyl peroxybenzoate and 34 parts of toluene was dropped into the reaction vessel over about 1.5 hours, Incubated for 3.5 hours. Thereafter, toluene was distilled off under reduced pressure. Next, the reaction system was charged with 15.2 parts of 28% aqueous ammonia (40% neutralization of the total moles of carboxyl groups in the copolymer) and 31.4 parts of 48% aqueous sodium hydroxide solution (total of carboxyl groups in the copolymer). The copolymer was neutralized by adding a mixture of a predetermined amount of water. Subsequently, the aqueous solution containing the copolymer salt (A-11) component whose weight average molecular weight is 9500 was obtained by diluting with water. The aqueous solution had a nonvolatile content of 20%, a viscosity at 25 ° C. of 30 mPa · s, and a pH of 8.9.
比較合成例１
合成例１と同様の反応容器に、スチレン４３．５部、マレイン酸２０．５部、マレイン酸のイソブチルアルコールモノエステル３６部およびトルエン１００部を仕込み、窒素気流下に撹拌しながら１１０℃まで昇温した。次いで、一の滴下ロートより、ｔ-ブチルパーオキシベンゾエート０．５部およびトルエン３４部からなる混合液を、約１．５時間を要して、反応容器内へと滴下し、還流下に約３．５時間保温した。その後トルエンを減圧留去した。次いで、反応系に、２８％アンモニア水３８．１部（共重合体中のカルボキシル基総モルの１００％中和）、所定量の水からなる混合液を加えることにより、共重合体を中和した。次いで、水で希釈することにより、重量平均分子量が２５０００の共重合体塩（以下、（イ）成分という）を含む水溶液を得た。また当該水溶液は、不揮発分が１５％、２５℃の粘度が３０ｍＰａ・ｓ、およびｐＨが８．９であった。
Comparative Synthesis Example 1
In the same reaction vessel as in Synthesis Example 1, 43.5 parts of styrene, 20.5 parts of maleic acid, 36 parts of isobutyl alcohol monoester of maleic acid and 100 parts of toluene were charged, and the temperature was raised to 110 ° C. with stirring under a nitrogen stream. Warm up. Next, from one dropping funnel, a mixed solution consisting of 0.5 parts of t-butyl peroxybenzoate and 34 parts of toluene was dropped into the reaction vessel over about 1.5 hours, Incubated for 3.5 hours. Thereafter, toluene was distilled off under reduced pressure. Next, the copolymer was neutralized by adding a mixed solution consisting of 38.1 parts of 28% ammonia water (100% neutralization of the total moles of carboxyl groups in the copolymer) and a predetermined amount of water to the reaction system. did. Subsequently, by diluting with water, an aqueous solution containing a copolymer salt having a weight average molecular weight of 25000 (hereinafter referred to as “component (A)”) was obtained. The aqueous solution had a nonvolatile content of 15%, a viscosity at 25 ° C. of 30 mPa · s, and a pH of 8.9.
比較合成例２
合成例１と同様の反応容器に、軟水５０部とイソプロピルアルコール１００部を仕込み、窒素気流下に撹拌しながら加熱して８０℃まで昇温した。次いで、スチレン５０部、アクリル酸５０部を混合した単量体混合物と、過硫酸カリウム５部を水５０部に溶解した重合開始剤水溶液とを約３時間かけて系内に滴下し、更に２時間保温して反応を完結させた。次いで、イソプロピルアルコールを留去し、冷却後２８％アンモニア水溶液４６．４部（アクリル酸に対して１００モル％）を加え、共重合体を中和した。次いで、水で希釈することにより、重量平均分子量が１２０００の共重合体塩（以下、（ロ）成分という）を含む水溶液を得た。また当該水溶液は、不揮発分が２０％、２５℃の粘度が５０ｍＰａ・ｓ、およびｐＨが８．４であった。
Comparative Synthesis Example 2
In the same reaction vessel as in Synthesis Example 1, 50 parts of soft water and 100 parts of isopropyl alcohol were charged and heated to 80 ° C. with stirring under a nitrogen stream. Next, a monomer mixture obtained by mixing 50 parts of styrene and 50 parts of acrylic acid and an aqueous polymerization initiator solution prepared by dissolving 5 parts of potassium persulfate in 50 parts of water were dropped into the system over about 3 hours. The reaction was completed by incubating for a period of time. Then, isopropyl alcohol was distilled off, and after cooling, 46.4 parts of 28% aqueous ammonia solution (100 mol% with respect to acrylic acid) was added to neutralize the copolymer. Next, by diluting with water, an aqueous solution containing a copolymer salt having a weight average molecular weight of 12,000 (hereinafter referred to as (B) component) was obtained. The aqueous solution had a nonvolatile content of 20%, a viscosity at 25 ° C. of 50 mPa · s, and a pH of 8.4.
比較合成例３
合成例１と同様の反応容器に、スチレン４３．５部、マレイン酸２０．５部、マレイン酸イソブチルアルコールモノエステル３６部およびトルエン１００部を仕込み、窒素気流下に撹拌しながら１１０℃まで昇温した。次いで、一の滴下ロートより、ｔ-ブチルパーオキシベンゾエート２．５部およびトルエン３４部からなる混合液を、約１．５時間を要して、反応容器内へと滴下し、還流下に約３．５時間保温した。その後トルエンを減圧留去した。次いで、反応系に、４８％水酸化ナトリウム水溶液５２．３部（共重合体中のカルボキシル基総モルの１００％中和）、および所定量の水からなる混合液を加えることにより、共重合体を中和した。次いで、水で希釈することにより、重量平均分子量が９８００の共重合体塩（以下、（ハ）成分という）を含む水溶液を得た。また当該水溶液は、不揮発分が２０％、２５℃の粘度が２５ｍＰａ・ｓ、およびｐＨが９であった。
Comparative Synthesis Example 3
In the same reaction vessel as in Synthesis Example 1, 43.5 parts of styrene, 20.5 parts of maleic acid, 36 parts of isobutyl alcohol maleate monoester and 100 parts of toluene were charged, and the temperature was raised to 110 ° C. while stirring under a nitrogen stream. did. Next, from one dropping funnel, a mixed solution consisting of 2.5 parts of t-butyl peroxybenzoate and 34 parts of toluene was dropped into the reaction vessel over about 1.5 hours, Incubated for 3.5 hours. Thereafter, toluene was distilled off under reduced pressure. Next, a copolymer consisting of 52.3 parts of a 48% aqueous sodium hydroxide solution (100% neutralization of the total moles of carboxyl groups in the copolymer) and a predetermined amount of water was added to the reaction system. Neutralized. Subsequently, by diluting with water, an aqueous solution containing a copolymer salt having a weight average molecular weight of 9800 (hereinafter referred to as (C) component) was obtained. The aqueous solution had a nonvolatile content of 20%, a viscosity at 25 ° C. of 25 mPa · s, and a pH of 9.
比較合成例４
合成例１と同様の反応容器に、スチレン４３．５部、マレイン酸２０．５部、マレイン酸イソブチルアルコールモノエステル３６部、およびトルエン１００部を仕込み、窒素気流下に撹拌しながら１１０℃まで昇温した。次いで、一の滴下ロートより、ｔ-ブチルパーオキシベンゾエート４．０部およびトルエン３４部からなる混合液を、約１．５時間を要して、反応容器内へと滴下し、還流下に約３．５時間保温した。その後トルエンを減圧留去した。次いで、反応系に、２８％アンモニア水３８．１部（共重合体中のカルボキシル基総モルの１００％中和）、および所定量の水からなる混合液を加えることにより、共重合体を中和した。次いで、水で希釈することにより、重量平均分子量が４０００の共重合体塩（以下、（ニ）成分という）を含む水溶液を得た。また当該水溶液は、不揮発分が２０％、２５℃の粘度が２０ｍＰａ・ｓ、およびｐＨが８．５であった。
Comparative Synthesis Example 4
In a reaction vessel similar to Synthesis Example 1, 43.5 parts of styrene, 20.5 parts of maleic acid, 36 parts of isobutyl alcohol maleate monoester, and 100 parts of toluene were charged, and the temperature was raised to 110 ° C. with stirring under a nitrogen stream. Warm up. Next, from one dropping funnel, a mixed solution consisting of 4.0 parts of t-butyl peroxybenzoate and 34 parts of toluene was dropped into the reaction vessel over about 1.5 hours, Incubated for 3.5 hours. Thereafter, toluene was distilled off under reduced pressure. Next, a mixed solution consisting of 38.1 parts of 28% ammonia water (100% neutralization of the total moles of carboxyl groups in the copolymer) and a predetermined amount of water was added to the reaction system, thereby adding the copolymer to the inside. It was summed up. Next, by diluting with water, an aqueous solution containing a copolymer salt having a weight average molecular weight of 4000 (hereinafter referred to as “component (D)”) was obtained. The aqueous solution had a nonvolatile content of 20%, a viscosity at 25 ° C. of 20 mPa · s, and a pH of 8.5.
表１中、各記号は以下の通りである。
Ｓｔ：スチレン
αＭｅＳt：αメチルスチレン
ＭＡｎ：マレイン酸
ＭＡｎ−ｍＩＢＡ：マレイン酸イソブチルアルコールモノエステル
ＭＡｎ−ｄｉＩＢＡ：マレイン酸イソブチルアルコールジエステル
ＭＡｎ−２ＥＨＡ：マレイン酸２エチルヘキシルアルコールモノエステル
ＡＡ：アクリル酸
ｎＭＡ：モノメチルアミン
Ｍｗ：重量平均分子量
ＮＶ：不揮発分
Ｖｉｓ：粘度
In Table 1, each symbol is as follows.
St: styrene αMeSt: α-methylstyrene MAn: maleic acid MAn-mIBA: maleic acid isobutyl alcohol monoester MAn-diIBA: maleic acid isobutyl alcohol diester MAn-2EHA: maleic acid 2-ethylhexyl alcohol monoester AA: acrylic acid nMA: monomethylamine Mw: weight average molecular weight NV: nonvolatile content Vis: viscosity
製造例１
撹拌器、還流冷却管、窒素導入管付きの反応器に、窒素雰囲気下、軟水１８０部、前記（Ａ−１）の水溶液１００部、非反応性のアニオン性界面活性剤（商品名「ハイテノールＬＡ１０」、第一工業製薬（株）製）１部、およびメタリルスルホン酸ナトリウム０．５部を仕込み、さらに、アクリルアミド５部、メタクリル酸５部、スチレン４０部、α−メチルスチレン１０部、メタクリル酸ブチル４０部を仕込んだ（なお、単量体全量に対し、（Ａ−１）は２０重量部である。）次いで、４８％水酸化ナトリウム水溶液４．８部（メタクリル酸に対して１００モル％）を加え、撹拌下に系を加熱し、８０℃まで上昇させた。次いで、過硫酸アンモニウム３部を仕込み、系を３時間保温して、（Ａ−１）成分の存在下で、乳化重合反応を完結させた。その後、得られた組成物を、共重合体の濃度が３０％になるように水で希釈した。こうして得られたエマルジョンは、２５℃における粘度測定値が３０ｍＰａ・ｓ、ｐＨが７．６、光散乱粒子径が９０ｎｍであった。該エマルジョンの組成と物性を表２に示す。
Production Example 1
In a reactor equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube, under a nitrogen atmosphere, 180 parts of soft water, 100 parts of an aqueous solution of the above (A-1), a non-reactive anionic surfactant (trade name “Hitenol”) LA10 "(manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 0.5 part of sodium methallyl sulfonate, 5 parts of acrylamide, 5 parts of methacrylic acid, 40 parts of styrene, 10 parts of α-methylstyrene, Then, 40 parts of butyl methacrylate was charged (note that (A-1) is 20 parts by weight with respect to the total amount of monomers.) Next, 4.8 parts of 48% aqueous sodium hydroxide solution (100 parts with respect to methacrylic acid). Mol%) was added and the system was heated to 80 ° C. with stirring. Subsequently, 3 parts of ammonium persulfate was charged, and the system was kept warm for 3 hours to complete the emulsion polymerization reaction in the presence of the component (A-1). Thereafter, the obtained composition was diluted with water so that the concentration of the copolymer was 30%. The emulsion thus obtained had a measured viscosity at 25 ° C. of 30 mPa · s, a pH of 7.6, and a light scattering particle diameter of 90 nm. Table 2 shows the composition and physical properties of the emulsion.
製造例２〜２１、比較製造例１〜６
（Ａ）成分〜（Ｃ）成分、乳化剤の種および使用量を表２に示すように変更した他は、製造例１と同様にして、実施例用および比較例用のエマルジョンを得た。
Production Examples 2 to 21 and Comparative Production Examples 1 to 6
The emulsions for Examples and Comparative Examples were obtained in the same manner as in Production Example 1 except that the components (A) to (C), the type of emulsifier , and the amounts used were changed as shown in Table 2.
表２中、各記号は以下の通りである。
ＬＡ：ハイテノールＬＡ１０
ＫＨ：反応性乳化剤（製品名「アクアロンＫＨ−０５」、第一工業製薬（株）製）
ＳＭＡＳ：メタリルスルホン酸ナトリウム
ＮＤＭ：ノルマルドデシルメルカプタン
ＡＭ：アクリルアミド
ＭＡＡ：メタクリル酸
２ＨＥＭＡ：２−ヒドロキシエチルメタクリレート
Ｓｔ：スチレン
αＭｅＳｔ：α−メチルスチレン
ＢＭＡ：ノルマルブチルメタクリレート
ＭＢＡＡ：Ｎ，Ｎ'−メチレンビスアクリルアミド
Ｖｉｓ：粘度
In Table 2, each symbol is as follows.
LA: Haitenol LA10
KH: Reactive emulsifier (Product name “AQUALON KH-05”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
SMAS: sodium methallyl sulfonate NDM: normal dodecyl mercaptan AM: acrylamide MAA: methacrylic acid 2HEMA: 2-hydroxyethyl methacrylate St: styrene αMeSt: α-methylstyrene BMA: normal butyl methacrylate MBAA: N, N′-methylenebisacrylamide Vis: viscosity
実施例１〜２１、比較例１〜６
＜表面サイズ液の調製＞
製造例１のエマルジョン、１０％で糊化を行った酸化澱粉（商品名「王子エースＡ」：王子コンスターチ（株）製）、および水を混合し、該酸化澱粉にもとづく不揮発分が約２．５％、該エマルジョンにもとづく不揮発分が約０．１％となる表面サイズ液を調製した。他の製造例および比較製造例のエマルジョンについても同様にして表面サイズ液を調製した。
Examples 1-21, Comparative Examples 1-6
<Preparation of surface sizing solution>
Oxidized starch gelatinized with the emulsion of Production Example 1 (trade name “Oji Ace A” manufactured by Oji Constarch Co., Ltd.) and water were mixed, and the nonvolatile content based on the oxidized starch was about 2. A surface sizing solution having 5% non-volatile content based on the emulsion of about 0.1% was prepared. Surface emulsions were prepared in the same manner for the emulsions of other production examples and comparative production examples.
＜試験用紙の作製＞
２ロールサイズプレス塗工機（熊谷理機工業（株）製）を用いて、各表面サイズ液をそれぞれ、中性上質用紙（坪量６０ｇ／ｍ２、ステキヒトサイズ度０秒）に塗工した。次いで、各塗工紙を回転式ドライヤーにて乾燥（１０５℃、１分間）させ、試験紙を得た。
<Preparation of test paper>
Using a two-roll size press coater (manufactured by Kumagai Riki Kogyo Co., Ltd.), each surface size liquid is applied to neutral high-quality paper (basis weight 60 g / m 2 , steecht size degree 0 seconds). did. Next, each coated paper was dried with a rotary dryer (105 ° C., 1 minute) to obtain a test paper.
＜ステキヒトサイズ度の測定＞
前記方法で得られた各試験用紙を用い、ＪＩＳ Ｐ−８１２２に準拠して、ステキヒトサイズ度（秒）を測定した。数値が大きいほど良好なサイズ度を表す。結果を表３に示す。
<Measurement of squeecht size>
Using each test paper obtained by the above-mentioned method, the Steecht sizing degree (second) was measured according to JIS P-8122. The larger the value, the better the sizing degree. The results are shown in Table 3.
＜ペン書きサイズ度の測定＞
前記方法で得られた各塗工紙を用い、J．Ｔａｐｐｉ Ｎｏ．１２に準拠して、ペン書きサイズ度を測定した。数字が大きいほど当該サイズ効果に優れることを意味する。結果を表３に示す。
<Measurement of pen writing size>
Using each coated paper obtained by the above method, Tappi No. 12 was used to measure the pen writing size. The larger the number, the better the size effect. The results are shown in Table 3.
＜発泡性の試験＞
各表面サイズ液にシリコン系消泡剤（商品名「ＤＫＱ１−０７１」：東レ・ダウコーニング（株）製）を５０ｐｐｍ添加した後、５０℃に加温し、家庭用ミキサーで２分間処理した後に、処理直後の液面の高さの増加量を測定した。結果を表３に示す。
<Foaming test>
After adding 50 ppm of a silicon-based antifoaming agent (trade name “DKQ1-071” manufactured by Toray Dow Corning Co., Ltd.) to each surface size liquid, heating to 50 ° C. and treating with a home mixer for 2 minutes The amount of increase in the liquid level immediately after the treatment was measured. The results are shown in Table 3.
＜機械安定性の測定（硬水系）＞
硬度６０°ｄＨの水を用いて各表面サイズ液を２倍希釈し、それぞれ酸化澱粉の不揮発分が１．２５％、エマルジョンの不揮発分が０．０５％となる組成とした。次いで、当該組成の表面サイズ液を、２ロールサイズプレスにおいて一時間循環させ、凝集物の発生および２本のロールの汚れを以下の規準にて目視評価した。結果を表３に示す。
◎：機械的安定性に極めて優れる（凝集物は確認できず、ロールの汚れもない）
○：機械的安定性に優れる（凝集物は確認できないが、ロールが微妙に汚れる）
△：機械的安定性がやや劣る（少量の凝集物が確認でき、ロールが汚れる）
×：機械的安定性が劣る（多量の凝集物が確認でき、ロールが著しく汚れる）
<Mechanical stability measurement (hard water)>
Each surface sizing solution was diluted twice with water having a hardness of 60 ° dH to have a composition in which the nonvolatile content of the oxidized starch was 1.25% and the nonvolatile content of the emulsion was 0.05%. Subsequently, the surface sizing liquid having the composition was circulated for 1 hour in a two-roll size press, and the occurrence of aggregates and the contamination of the two rolls were visually evaluated according to the following criteria. The results are shown in Table 3.
A: Extremely excellent in mechanical stability (no agglomerates can be confirmed and there is no dirt on the roll)
○: Excellent in mechanical stability (Agglomerates cannot be confirmed, but the roll is slightly stained)
Δ: Slightly inferior in mechanical stability (a small amount of agglomerates can be confirmed and the roll becomes dirty)
X: Mechanical stability is inferior (a large amount of agglomerates can be confirmed, and the roll becomes extremely dirty)
Claims (18)
（式（１）中、Ｘ１、Ｘ２およびＸ３は水素または炭素数１〜３のアルキル基を表す。） A monomer group (a) containing an unsaturated dicarboxylic acid and styrene and not containing an unsaturated monocarboxylic acid is subjected to a polymerization reaction, and the carboxyl group is represented by the following general formula (1). Hydrophilic unsaturated monomers in the presence of a copolymer (A) having a salt with a nitrogen compound and having a weight average molecular weight of 5000 to 20000 and a water-soluble chain transfer agent (B) And a surface sizing agent for papermaking, comprising an emulsion obtained by emulsion polymerization of a monomer group (C) containing hydrophobic unsaturated monomers.
(In formula (1), X 1 , X 2 and X 3 represent hydrogen or an alkyl group having 1 to 3 carbon atoms.)
（式（２）中、Ｙ１は水素またはメチル基を、ｌは１〜４の整数を、Ｙ２は水素又はアルカリ金属原子を示す。） The surface sizing agent for papermaking according to any one of claims 1 to 7 , wherein the water-soluble chain transfer agent (B) is a compound represented by the following general formula (2).
(In formula (2), Y 1 represents hydrogen or a methyl group, l represents an integer of 1 to 4, and Y 2 represents hydrogen or an alkali metal atom.)
（式（３）中、Ｒ１は炭素数１〜２０の炭化水素基、または、炭素数１〜２０の炭化水素基を有する芳香環を示す。ｍは０または１の整数を示す。（ＡＯ）のうちＡは炭素数２〜４のアルキレン基もしくは置換アルキレン基を示す。ｎは１〜１００の整数を示す。Ｚ１は炭素−炭素二重結合を有する共重合性の官能基を示す。Ｚ２は水素、スルホン酸基、リン酸基、スルホコハク酸基およびこれらの塩ならびにスルホコハク酸基エステルから選ばれる１種を示す。） The surface sizing agent for papermaking of Claim 15 in which an emulsifier contains the reactive emulsifier represented by following General formula (3).
(In Formula (3), R 1 represents an aromatic ring having a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms. M represents an integer of 0 or 1 (AO). A represents an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, n represents an integer of 1 to 100, and Z 1 represents a copolymerizable functional group having a carbon-carbon double bond. Z 2 represents one selected from hydrogen, sulfonic acid group, phosphoric acid group, sulfosuccinic acid group and salts thereof, and sulfosuccinic acid group ester.)
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