JPH01280095A - Copolymer latex for coating paper - Google Patents
Copolymer latex for coating paperInfo
- Publication number
- JPH01280095A JPH01280095A JP10527288A JP10527288A JPH01280095A JP H01280095 A JPH01280095 A JP H01280095A JP 10527288 A JP10527288 A JP 10527288A JP 10527288 A JP10527288 A JP 10527288A JP H01280095 A JPH01280095 A JP H01280095A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- weight
- copolymer latex
- copolymer
- monomer mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 67
- 239000004816 latex Substances 0.000 title claims abstract description 54
- 229920000126 latex Polymers 0.000 title claims abstract description 54
- 239000011248 coating agent Substances 0.000 title claims description 17
- 238000000576 coating method Methods 0.000 title claims description 17
- 239000000178 monomer Substances 0.000 claims abstract description 74
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 27
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 15
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001993 dienes Chemical class 0.000 claims abstract description 7
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 3
- 125000005907 alkyl ester group Chemical group 0.000 abstract description 3
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 2
- 239000000123 paper Substances 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000000853 adhesive Substances 0.000 description 20
- 230000001070 adhesive effect Effects 0.000 description 20
- 239000011230 binding agent Substances 0.000 description 16
- -1 methacrylaterile Chemical compound 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000007639 printing Methods 0.000 description 9
- 239000008199 coating composition Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000010556 emulsion polymerization method Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical class NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 2
- 235000021240 caseins Nutrition 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000001254 oxidized starch Substances 0.000 description 2
- 235000013808 oxidized starch Nutrition 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 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
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- HADRUDTZSQDBIY-UHFFFAOYSA-O 2-(2-undecyl-1H-imidazol-1-ium-1-yl)ethanol Chemical class OCC[NH+]1C(=NC=C1)CCCCCCCCCCC HADRUDTZSQDBIY-UHFFFAOYSA-O 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- DTFFFOGZHBBKCX-UHFFFAOYSA-N 2-[bis(2-aminoethyl)amino]-2-octyldecanoic acid Chemical class CCCCCCCCC(C(O)=O)(N(CCN)CCN)CCCCCCCC DTFFFOGZHBBKCX-UHFFFAOYSA-N 0.000 description 1
- HVYJSOSGTDINLW-UHFFFAOYSA-N 2-[dimethyl(octadecyl)azaniumyl]acetate Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)CC([O-])=O HVYJSOSGTDINLW-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- AEDQNOLIADXSBB-UHFFFAOYSA-N 3-(dodecylazaniumyl)propanoate Chemical compound CCCCCCCCCCCCNCCC(O)=O AEDQNOLIADXSBB-UHFFFAOYSA-N 0.000 description 1
- BKTMEKOLXCZRFW-UHFFFAOYSA-N 3-(octadecylamino)propanoic acid Chemical compound CCCCCCCCCCCCCCCCCCNCCC(O)=O BKTMEKOLXCZRFW-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 108010073771 Soybean Proteins Proteins 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-L dioxidosulfate(2-) Chemical compound [O-]S[O-] HRKQOINLCJTGBK-UHFFFAOYSA-L 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229940094506 lauryl betaine Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical class CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- QUPCNWFFTANZPX-UHFFFAOYSA-M paramenthane hydroperoxide Chemical compound [O-]O.CC(C)C1CCC(C)CC1 QUPCNWFFTANZPX-UHFFFAOYSA-M 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- HLWRUJAIJJEZDL-UHFFFAOYSA-M sodium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC([O-])=O HLWRUJAIJJEZDL-UHFFFAOYSA-M 0.000 description 1
- 235000019710 soybean protein Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
- Paper (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は紙塗被用共重合体ラテックスに関し、詳しくは
印刷光沢、白紙光沢（以下、 「光沢」と総称する）、
接着強度、耐水性および耐ブリスター性などの性質がい
ずれもバランスよく優れ、特にこれら性質のうち光沢が
一段と優れた塗被紙（コート紙）を提供する紙塗被用バ
インダーとしての共重合体ラテックスに関する。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a copolymer latex for paper coating, and more specifically, printing gloss, white paper gloss (hereinafter collectively referred to as "gloss"),
A copolymer latex used as a binder for paper coating, which provides coated paper with excellent properties such as adhesive strength, water resistance, and blister resistance in a well-balanced manner, and which is particularly superior in gloss among these properties. Regarding.
（従来の技術）
脂肪族共役ジエン系単量体、エチレン系不飽和カルボン
酸などからなる単量体混合物を乳化重合して得られるカ
ルボキシル基変性共重合体ラテックスが単独あるいはカ
ゼイン、デンプン、蛋白質、セルロース、ポリビニルア
ルコールなどの天然もしくは合成のバインダーとともに
、紙塗被用バインダーとして用いられることはよく知ら
れている。(Prior art) A carboxyl group-modified copolymer latex obtained by emulsion polymerization of a monomer mixture consisting of an aliphatic conjugated diene monomer, an ethylenically unsaturated carboxylic acid, etc. can be used alone or with casein, starch, protein, It is well known that it can be used as a paper coating binder together with natural or synthetic binders such as cellulose and polyvinyl alcohol.
このカルボキシル基変性共重合体ラテックスを紙塗被用
バインダーとして含有する紙塗被組成物を塗布して得ら
れるコート紙は、接着強度、耐水性、光沢などが良好の
ため様々な用途に使用されている。Coated paper obtained by applying a paper coating composition containing this carboxyl group-modified copolymer latex as a paper coating binder has good adhesive strength, water resistance, gloss, etc., and is used for various purposes. ing.
近年、コート紙を用いた印刷物の需要は著しく、これに
伴い印刷の高速化と印刷方式の多様化の傾向がますます
強くなっている。このため、コート紙ひいては紙塗被用
バインダーには、従来にもまして諸物性の向上、特に光
沢、接着強度、耐水性および耐ブリスター性の全である
いはそのうちの複数項目を同時に向上させることが要求
されるようになっている。In recent years, there has been a significant demand for printed matter using coated paper, and as a result, there has been an increasingly strong trend toward faster printing and diversification of printing methods. For this reason, coated paper and, in turn, binders for paper coating, are required to have improved physical properties more than ever before, particularly in all or several of them at the same time: gloss, adhesive strength, water resistance, and blister resistance. It is now possible to do so.
このような要求にこたえるため、紙塗被用バインダーと
して使用する共重合体ラテックスに種々の改良がなされ
てきた０例えば、特開昭５４−３０９１０、同６０−２
１５８９５号公報には共重合体ラテックスの表面電荷状
態に工夫を加えることによって、また特開昭６１−１９
４２９６号公報には特殊な乳化剤を用いることによって
接着力を改良することが開示されている。しかし、これ
ら方法によっては、光沢、耐ブリスター性も同時に改良
されるに至っていない、更に、特開昭６１−２０７６９
４、同６１−６３７９４号公報には単量体や重合度調節
剤の添加方法に工夫を加えることによって、光沢、耐ブ
リスター性が改良されることが開示されている。また、
特開昭５０−９４０３４号公報にはシアン化ビニル系単
量体を用いることによって、特開昭５４−６４１１６号
公報には共重合体ラテックスに異層構造を付与すること
によって、また特開昭５６−３０４１８号公報には共重
合体ラテックスにアルカリ官能性を付与することによっ
て諸物性が改良されると記載されているが、上記のよう
な要求に十分こたえるほと改良されるに至っていない。In order to meet these demands, various improvements have been made to the copolymer latex used as a binder for paper coating.
No. 15895 discloses that by modifying the surface charge state of copolymer latex,
No. 4296 discloses improving adhesive strength by using a special emulsifier. However, depending on these methods, gloss and blister resistance have not been improved at the same time.
4, No. 61-63794 discloses that gloss and blister resistance can be improved by modifying the method of adding monomers and degree of polymerization regulators. Also,
JP-A No. 50-94034 uses a vinyl cyanide monomer, JP-A No. 54-64116 uses a copolymer latex with a different layer structure; Although Japanese Patent No. 56-30418 states that various physical properties are improved by imparting alkali functionality to copolymer latex, improvements have not yet been made to the extent that the above-mentioned demands can be fully met.
（発明が解決しようとするｒ５題）
上記の通り、従来の紙塗被用バインダーを用いて得られ
るコート紙は、光沢、接着強度、耐水性および耐ブリス
ター性のいずれかが劣り上記のような要求に十分こたえ
ることができないという問題があった。(R5 problems to be solved by the invention) As mentioned above, coated paper obtained using conventional paper coating binders is inferior in gloss, adhesive strength, water resistance, and blister resistance, and has the above-mentioned problems. There was a problem that it was not possible to fully meet the demands.
（課題を解決するための手段）
このような事情に鑑み、本出願人も、先に光沢、接着強
度、耐水性および耐ブリスター性のいずれにもバランス
よく優れたコート紙の製造を可能とする、紙塗被用バイ
ンダーとしての共重合体ラテックスの製造方法を提案し
た（特願昭６ｌ−２５９９１９）。(Means for Solving the Problems) In view of the above circumstances, the present applicant has first made it possible to manufacture coated paper that is excellent in gloss, adhesive strength, water resistance, and blister resistance in a well-balanced manner. proposed a method for producing copolymer latex as a binder for paper coating (Japanese Patent Application No. 61-259919).
本発明者らは、更に研究を重ねた結果、特定の組成を有
する単量体混合物を無機重合開始剤と有８１重合開始剤
とを用いて２段階乳化重合法によって得られ、かつ特定
範囲のトルエン不溶分を有する共重合体ラテックスを紙
塗被用バインダーとして使用して得られるコート紙は、
光沢、接着強度、耐水性および耐ブリスター性のいずれ
にも優れ、特にこれら性質のうち光沢が一段と優れてい
ることを見いだし、この知見に基づいて本発明を完成す
るに至った。As a result of further research, the present inventors found that a monomer mixture having a specific composition was obtained by a two-step emulsion polymerization method using an inorganic polymerization initiator and an organic polymerization initiator, and within a specific range. Coated paper obtained by using a copolymer latex with toluene-insoluble content as a paper coating binder is
It has been found that it is excellent in all of gloss, adhesive strength, water resistance, and blister resistance, and that among these properties, gloss is particularly excellent, and based on this knowledge, the present invention has been completed.
即ち、本発明は、共役ジエン系単量体２０〜８０重量％
、エチレン系不飽和カルボン酸単量体０．５〜１０ｆｆ
ｉｆｆｉ％、芳香族ビニル系単量体１０〜５０重量％、
シアン化ビニル系単量体３〜４０重量％およびこれらと
共重合可能な他の単量体とからなる単量体混合物を乳化
重合して得られる共重合体ラテックスにおいて、該共重
合体ラテックスが、まず、単量体混合物の１０〜５０重
量％を無機重合開始剤を用いて重合させ、次いで、得ら
れた共重合体の存在下に残りの単量体を重合させて得ら
れたものであり、かつ該共重合体ラテックス中の共重合
体のトルエン不溶分が２０〜９５重量％であることを特
徴とする紙塗被用共重合体ラテックスに関する。That is, in the present invention, the conjugated diene monomer is 20 to 80% by weight.
, ethylenically unsaturated carboxylic acid monomer 0.5 to 10ff
iffi%, aromatic vinyl monomer 10 to 50% by weight,
A copolymer latex obtained by emulsion polymerization of a monomer mixture consisting of 3 to 40% by weight of a vinyl cyanide monomer and another monomer copolymerizable with these, the copolymer latex is obtained by first polymerizing 10 to 50% by weight of the monomer mixture using an inorganic polymerization initiator, and then polymerizing the remaining monomers in the presence of the obtained copolymer. The present invention relates to a copolymer latex for paper coating, characterized in that the toluene insoluble content of the copolymer in the copolymer latex is 20 to 95% by weight.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の共重合体ラテックスの製造に使用する単量体の
うち、共役ジエン系単量体の具体例としては、ブタジェ
ン、イソプレン、２−クロル−１゜３−ブタジェン、２
−メチル−１，３−ブタジェンなどを挙げることができ
る。これらは単独でも、あるいは２種以上を組み合わせ
て使用することができる。これらのうち、特にブタジェ
ンが好ましい。Among the monomers used in the production of the copolymer latex of the present invention, specific examples of conjugated diene monomers include butadiene, isoprene, 2-chloro-1°3-butadiene,
-methyl-1,3-butadiene and the like. These can be used alone or in combination of two or more. Among these, butadiene is particularly preferred.
共役ジエン系単量体は共重合体に適当な弾性および膜の
硬さを与えるために単量体混合物の２０〜８０重量％、
好ましくは２０〜７０重量％の割合で使用する。その使
用割合が２０重量％未満では、十分な接着強度を得るこ
とができず、一方８０重量％を超えると耐水性が低下す
る。The conjugated diene monomer is used in an amount of 20 to 80% by weight of the monomer mixture in order to give the copolymer appropriate elasticity and film hardness.
It is preferably used in a proportion of 20 to 70% by weight. If the proportion used is less than 20% by weight, sufficient adhesive strength cannot be obtained, while if the proportion exceeds 80% by weight, water resistance decreases.
エチレン系不飽和カルボン酸単量体の具体例としては、
アクリル酸、メタクリル酸、クロトン酸、マレイン酸、
フマール酸、イタコン酸などのモノまたはジカルボン酸
などを挙げることができる。Specific examples of ethylenically unsaturated carboxylic acid monomers include:
Acrylic acid, methacrylic acid, crotonic acid, maleic acid,
Examples include mono- or dicarboxylic acids such as fumaric acid and itaconic acid.
更に、ジカルボン酸の無水物も使用することができる。Furthermore, anhydrides of dicarboxylic acids can also be used.
これらは単独でも、あるいは２種以上を組み合わせて使
用することができる。These can be used alone or in combination of two or more.
エチレン系不飽和カルボン酸単量体の使用割合は単量体
混合物の０．５〜１０重量％、好ましくは１〜７重量％
である。この使用割合が０．５重量％未満では接着強度
のほか、共重合体ラテックスの機械的安定性が低下し、
一方１０重量％を越えると共重合体ラテックスの粘度が
高くなり、その取扱い（ハンドリング）が困難となり、
操作性が低下する。The proportion of the ethylenically unsaturated carboxylic acid monomer used is 0.5 to 10% by weight, preferably 1 to 7% by weight of the monomer mixture.
It is. If the proportion used is less than 0.5% by weight, not only the adhesive strength but also the mechanical stability of the copolymer latex will decrease.
On the other hand, if it exceeds 10% by weight, the viscosity of the copolymer latex increases, making it difficult to handle.
Operability deteriorates.
芳香族ビニル系単量体はオフセット印刷時に重要な性能
である耐水性を付与する機能を有し、その具体例として
は、スチレン、α−メチルスチレン、ビニルトルエン、
ｐ−メチルスチレンなどを挙げることができる。これら
のうち、特にスチレンが好ましい。Aromatic vinyl monomers have the function of imparting water resistance, which is an important performance during offset printing, and specific examples include styrene, α-methylstyrene, vinyltoluene,
Examples include p-methylstyrene. Among these, styrene is particularly preferred.
芳香族ビニル系単量体の使用割合は単量体混合物の１０
〜５０重量％、好ましくは１０〜４５重堡％である。こ
の使用割合がｌＯ１屓％未満ては耐水性が低下し、一方
５０重世％を超えるとドライ強度が低下する。The ratio of aromatic vinyl monomer used is 10% of the monomer mixture.
-50% by weight, preferably 10-45% by weight. If the usage rate is less than 1% by weight, the water resistance will decrease, while if it exceeds 50% by weight, the dry strength will decrease.
シアン化ビニル系単量体の具体例としては、アクリロニ
トリル、メタクリレートリル、α−クロルアクリロニト
リルなどを挙げることができる。Specific examples of vinyl cyanide monomers include acrylonitrile, methacrylaterile, α-chloroacrylonitrile, and the like.
これらは単独でも、あるいは２種以上を混合して使用す
ることができる。これらのうち、特にアクリロニトリル
が好ましい。These can be used alone or in combination of two or more. Among these, acrylonitrile is particularly preferred.
シアン化ビニル系単量体の使用割合は単量体混合物の３
〜４０重量％、好ましくは３〜３５重塁％である。この
使用割合が３重量％未満では優れた印刷光沢を得ること
ができない、一方、４０重量％を超えると接着強度、耐
水性が劣る。従来、シアン化ビニル系単量体を用いると
得られる共重合体ラテックスが着色しやすくなる傾向に
あるが、本発明の共重合体ラテックスは、シアン化ビニ
ル系単量体を用いて得られるものの、従来の重合方法で
得られる共重合体ラテックスと比較して、ラテックス自
体が着色しにくく、更には印刷光沢の向上効果が大きい
などの利点を有する。The usage ratio of vinyl cyanide monomer is 3% of the monomer mixture.
~40% by weight, preferably 3~35% by weight. If this proportion is less than 3% by weight, excellent printing gloss cannot be obtained, while if it exceeds 40% by weight, adhesive strength and water resistance will be poor. Conventionally, when a vinyl cyanide monomer is used, the copolymer latex obtained tends to be easily colored. Compared to copolymer latex obtained by conventional polymerization methods, the latex itself has advantages such as being less likely to be colored and furthermore having a large effect of improving printing gloss.
上記単量体と共重合可能な他の単量体の具体例としては
、アクリル酸メチル、アクリル酸エチル、アクリル酸ブ
チル、メタクリル酸メチル、２−ヒドロキシエチルアク
リレート、２−ヒドロキシメタクリレート、グリシジル
メタクリレートなどのアクリル酸あるいはメタクリル酸
のアルキルエステル類、アクリルアミド、メタクリルア
ミド、Ｎ−メチロールアクリルアミドなどのエチレン系
不飽和カルボン酸のアクリルアミド類、酢酸ビニルなど
のカルボン酸ビニルエステルなどを挙げることができる
。これらは単独でも、あるいは２種以上を紺み合わせて
使用することができる。これらの単量体は、共重合体に
適度の硬さ、弾性および耐水性を付与するため、単量体
混合物のＯ〜６６．５重量％、好ましくは０−４９重量
％の割合で使用する。Specific examples of other monomers copolymerizable with the above monomers include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxymethacrylate, glycidyl methacrylate, etc. Examples include alkyl esters of acrylic acid or methacrylic acid, acrylamides of ethylenically unsaturated carboxylic acids such as acrylamide, methacrylamide, and N-methylolacrylamide, and carboxylic acid vinyl esters such as vinyl acetate. These can be used alone or in combination of two or more. These monomers are used in a proportion of 0 to 66.5% by weight, preferably 0 to 49% by weight of the monomer mixture, in order to impart appropriate hardness, elasticity and water resistance to the copolymer. .
本発明の共重合体ラテックスは、２段階乳化重合法によ
って製造される。まず、第１工程では、上記単量体混合
物の１０〜５０重量％、好ましくは１５〜４５重量％を
無機系重合開始剤を用いて乳化重合する０次に、第２工
程では、上記第１工程で得られた共重合体の存在下に、
残りの単量体混合物を有機系重合閉始剤を用いて乳化重
合する。The copolymer latex of the present invention is produced by a two-step emulsion polymerization method. First, in the first step, 10 to 50% by weight, preferably 15 to 45% by weight of the monomer mixture is emulsion polymerized using an inorganic polymerization initiator. In the presence of the copolymer obtained in the process,
The remaining monomer mixture is subjected to emulsion polymerization using an organic polymerization initiator.
第１工程における単量体混合物の使用割合が、上記範囲
未満であったり、あるいはこの範囲を超えると、例えば
光沢が低下して好ましくない、即ち、上記条件下での２
段階乳化重合法によってのみ、本発明の目的とする共重
合体ラテックスを得ることができる。If the proportion of the monomer mixture used in the first step is less than the above-mentioned range or exceeds this range, for example, the gloss will decrease, which is undesirable.
Only by the step emulsion polymerization method can the copolymer latex targeted by the present invention be obtained.
上記２段階乳化重合法の第１工程で使用する無機系重合
開始剤の具体例としては、過硫酸カリウム、過ｆＩＲ酸
アンモニウム、過硫酸ナトリウム、過酸化水素などを挙
げることができる。２５℃の水に対する溶解度が１重量
％以上のものが好ましく、特に過硫酸塩が好ましい。無
機系重合開始剤の使用量は、使用単量体１００重量部に
対し０．０５〜５重量部とするのが好ましい。Specific examples of the inorganic polymerization initiator used in the first step of the two-step emulsion polymerization method include potassium persulfate, ammonium perfIRate, sodium persulfate, and hydrogen peroxide. Those having a solubility in water at 25° C. of 1% by weight or more are preferred, and persulfates are particularly preferred. The amount of the inorganic polymerization initiator used is preferably 0.05 to 5 parts by weight per 100 parts by weight of the monomer used.
第２工程で使用する有機系重合開始剤の具体例としては
、クメンハイドロパーオキサイド、ジイソプロピルベン
ゼンハイドロパーオキサイド、パラメンタンハイドロパ
ーオキサイド、ベンゾイルパーオキサイドなどの有機過
酸化物、アゾビスイソブチロニトリルなどのアゾ化合物
などを挙げることができる。これらは単独でも、あるい
は２種以上を組み合わせて使用することもできる。有機
過酸化物は単独でも使用できるが、触媒活性を高めるた
めに含糖ピロリン酸処方、スルホキシレート処方などで
代表される還元剤との絹合せによるレドックス系で使用
することができる。有機系重合開始剤の使用量は、使用
単量体１００重量部に対し０．０１〜２ＭＩｋ部とする
のが好ましい。Specific examples of the organic polymerization initiator used in the second step include organic peroxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, para-menthane hydroperoxide, and benzoyl peroxide, and azobisisobutyronitrile. Examples include azo compounds such as. These can be used alone or in combination of two or more. Organic peroxides can be used alone, but in order to increase the catalytic activity, they can be used in a redox system by combining them with reducing agents, such as sugar-containing pyrophosphoric acid formulations and sulfoxylate formulations. The amount of the organic polymerization initiator used is preferably 0.01 to 2 MIk parts per 100 parts by weight of the monomers used.
上記２段階乳化重合は、具体的には、例えば次の方法に
よって実施することができる。Specifically, the two-stage emulsion polymerization described above can be carried out, for example, by the following method.
（１） 第１工程では、単量体混合物の１０〜５０重塁
％、あるいはこれと無機系重合開始剤とを反応容器に仕
込んで乳化重合を行う、単量体混合物のみを予め仕込ん
だ場合には、無機系重合開始剤を連続的、回分的、逐次
的、あるいはこれらの紺合せによって添加して乳化重合
を行う０次に、第２工程では、残りの単量体混合物と有
機系重合開始剤とを反応容器に添加して乳化重合を行い
、反応を完結させる。この残りの単量体混合物と有機系
重合開始剤とは、連続的、回分的、逐次的あるいはこれ
らの組合せによって、あるいは−括して添加することが
できる。(1) In the first step, emulsion polymerization is carried out by charging 10 to 50% of the monomer mixture, or this and an inorganic polymerization initiator, into a reaction vessel. In the case where only the monomer mixture is charged in advance. In this step, emulsion polymerization is carried out by adding an inorganic polymerization initiator continuously, batchwise, sequentially, or by a combination of these.Next, in the second step, organic polymerization is carried out with the remaining monomer mixture. An initiator is added to the reaction vessel to perform emulsion polymerization and complete the reaction. The remaining monomer mixture and the organic polymerization initiator can be added continuously, batchwise, sequentially, a combination thereof, or all at once.
（２） 第１工程では、無機系重合開始剤のみを予め反
応容器に仕込んだ後、単量体混合物の１０〜５０重量％
に相当する単量体を連続的、回分的、逐次的あるいはこ
れらを絹み合わせて、あるいは−括して添加して乳化重
合を行うか、あるいは単量体混合物の１０〜５０重量％
のうちの一部を無機系重合開始剤と共に予め反応容器に
仕込んだ後、残りの単量体を上記と同じように連続的、
回分的、逐次的あるいはこれらを紺み合わせて、あるい
は−括して添加して乳化重合を行う０次いで、第２工程
では、残りの単量体混合物と有機系重合開始剤とを上記
（１）と同様にして添加して乳化重合を行い、反応を完
結させる。(2) In the first step, after charging only the inorganic polymerization initiator into the reaction vessel in advance, 10 to 50% by weight of the monomer mixture is added.
Emulsion polymerization is carried out by adding monomers corresponding to 10 to 50% by weight of the monomer mixture continuously, batchwise, sequentially, or in combination or all at once.
After charging some of the monomers together with an inorganic polymerization initiator into a reaction vessel, the remaining monomers were added continuously in the same manner as above.
Emulsion polymerization is carried out batchwise, sequentially, or by adding them together or all at once.Next, in the second step, the remaining monomer mixture and organic polymerization initiator are added as described above (1). ) to perform emulsion polymerization and complete the reaction.
（３） 全単量体混合物を反応容器に仕込み、第１工程
として、無機系重合開始剤を用いて全単量体混合物の１
０〜５０重量％を反応させ、次いで第２工程として、残
りの単量体混合物を有機系重合開始剤を用いて乳化重合
させて、反応を完結させる。(3) Charge the entire monomer mixture into a reaction vessel, and in the first step, add 1 part of the total monomer mixture using an inorganic polymerization initiator.
0 to 50% by weight is reacted, and then, as a second step, the remaining monomer mixture is emulsion polymerized using an organic polymerization initiator to complete the reaction.
上記乳化重合は常圧または加圧下に３０〜９０℃程度の
温度で行うことができる。The above emulsion polymerization can be carried out at a temperature of about 30 to 90° C. under normal pressure or increased pressure.
また、上記乳化重合は、一般の乳化重合に用いられる乳
化剤、重合連鎖移動剤などを用いて行うことができる。Further, the emulsion polymerization can be carried out using an emulsifier, a polymerization chain transfer agent, etc. that are used in general emulsion polymerization.
乳化剤としては、両性界面活性剤、アニオン性界面活性
剤あるいはノニオン性界面活性剤を使用することができ
る０両性界面活性剤としては、アニオン部分としてカル
ボン酸塩、硫酸エステル塩、スルホン酸塩、リン酸エス
テル塩を、またカチオン部分としてアミン塩、第４級ア
ンモニウム塩を有するものを挙げることができる。その
具体例としては、アルキルベタインの塩としてラウリル
ベタイン、ステアリルベタイン、２−ウンデシル−ヒド
ロキシエチルイミダゾリウムベタインの各々の塩を、ア
ミン酸タイプのものとしてラウリル−β−アラニン、ス
テアリル−β−アラニン、ラウリルジ（アミノエチル）
グリシン、ジオクチルジ（アミノエチル）グリシンの各
々の塩を挙げることができる。アニオン性界面活性剤の
具体例としては、高級アルコールの＠酸エステル、アル
キルベンゼンスルホン酸塩、脂肪族スルホン酸塩、ジア
ルキルスルホコハク酸塩、アルキルナフタレンスルホン
酸塩などを挙げることができる。ノニオン性界面活性剤
としては、一般のポリエチレングリコールのアルキルエ
ステル型、アルキルエーテル型、アルキルフェニルエー
テル型界面活性剤などを挙げることができる。As the emulsifier, an amphoteric surfactant, an anionic surfactant or a nonionic surfactant can be used.Ampholytic surfactants include carboxylates, sulfate ester salts, sulfonates, phosphates as anionic moieties. Examples include acid ester salts, and those having amine salts and quaternary ammonium salts as cation moieties. Specific examples include salts of lauryl betaine, stearyl betaine, and 2-undecyl-hydroxyethylimidazolium betaine as alkyl betaine salts, and lauryl-β-alanine, stearyl-β-alanine, and amino acid type salts. Lauryl di(aminoethyl)
Examples include salts of glycine and dioctyldi(aminoethyl)glycine. Specific examples of the anionic surfactant include higher alcohol esters, alkylbenzene sulfonates, aliphatic sulfonates, dialkyl sulfosuccinates, alkylnaphthalene sulfonates, and the like. Examples of nonionic surfactants include general polyethylene glycol alkyl ester type, alkyl ether type, and alkylphenyl ether type surfactants.
また、重合連鎖移動剤の具体例としては、１−ドデシル
メルカプタン、ｎ−ドデシルメル力ブタン、メルカプト
エタノールなとのメルカプタン類、タービノーレン、ジ
ペンテン、ｔ−テルピンおよび少量の他の環状テルペン
類よりなるテルペン混合物やクロロホルム、四塩化炭素
などのハロゲン化炭化水素を挙げることができる。Further, specific examples of polymerization chain transfer agents include mercaptans such as 1-dodecylmercaptan, n-dodecylmercaptan, and mercaptoethanol, terpene mixtures consisting of turbinolene, dipentene, t-terpine, and small amounts of other cyclic terpenes. Examples include halogenated hydrocarbons such as chlorine, chloroform, and carbon tetrachloride.
本発明の共重合体ラテックス中の共重合体のトルエン不
溶分は２０〜９５重量％、好ましくは８０〜９０重量％
である。トルエン不溶分が２０重置火未満では接着強度
が低下し、一方９５重量％を超えると接着強度、耐ブリ
スター性が低下する。The toluene insoluble content of the copolymer in the copolymer latex of the present invention is 20 to 95% by weight, preferably 80 to 90% by weight.
It is. If the toluene-insoluble content is less than 20% by weight, the adhesive strength will decrease, while if it exceeds 95% by weight, the adhesive strength and blister resistance will decrease.
なお、本発明における共重合体のトルエン不溶分は、次
の方法によって測定したものである。Note that the toluene insoluble content of the copolymer in the present invention was measured by the following method.
共重合体ラテックス試料をｐＨ８に調整し、ラテックス
中の共重合体をイソプロパツールで凝固した後、得られ
た固形分を洗浄、乾燥した。この固形公約０．３ｇ（全
固形分１ｉＡ）をトルエン１００ｍ１に室温で２０時間
浸漬した後、Ｎｏ、２定性ろ紙を用いてろ過した。ろ液
の一部（Ｃ＃Ｊ）を正確に採取して、蒸発乾固させ、得
られた残存固形分（トルエン可溶分）（トルエン可溶分
子ｆｉＢ）を秤量し、下記式によってトルエン不溶分を
決定した。After adjusting the pH of the copolymer latex sample to 8 and coagulating the copolymer in the latex with isopropanol, the obtained solid content was washed and dried. Approximately 0.3 g of this solid (total solid content: 1 iA) was immersed in 100 ml of toluene at room temperature for 20 hours, and then filtered using No. 2 qualitative filter paper. A part of the filtrate (C#J) is accurately collected, evaporated to dryness, the resulting residual solid content (toluene soluble content) (toluene soluble molecule fiB) is weighed, and the toluene insoluble content is determined by the following formula. decided on the minutes.
共重合体のトルエン不溶分は、重合連鎖移動剤の種類お
よび使用量、エチレン系不飽和カルボン酸単量体の種類
および使用量、重合開始剤の種類および使用量、重合温
度などを適宜決定することによってｔＡ！！することが
できる。The toluene-insoluble content of the copolymer is determined by appropriately determining the type and amount of the polymerization chain transfer agent, the type and amount of the ethylenically unsaturated carboxylic acid monomer, the type and amount of the polymerization initiator, and the polymerization temperature. By doing so, tA! ! can do.
本発明の共重合体ラテックスにおいて、ラテックスの平
均粒子径は６００〜３０００Ａの範囲にあるのが好まし
い。In the copolymer latex of the present invention, the average particle diameter of the latex is preferably in the range of 600 to 3000A.
本発明の共重合体ラテックスは、紙塗被用バインダーと
して使用されるが、紙塗被用組成物はこの共重合体ラテ
ックスを無ｎａ料あるいは有８！顔料、好ましくは無機
顔料と、必要に応じてその他の結合剤と共に混合して、
水性分散液として調製される。The copolymer latex of the present invention is used as a paper coating binder, and the paper coating composition may contain this copolymer latex free of or containing 8% or more. mixed with a pigment, preferably an inorganic pigment, optionally with other binders,
Prepared as an aqueous dispersion.
紙塗被用組成物における各成分の配合量については、固
形分換算で顔料１００重量部に対し本発明の共重合体ラ
テックスが５〜４０重量部、好ましくは９〜３０重量部
であり、その他の結合剤が０〜３０重量部、好ましくは
２〜ｌＯ重量部である。The amount of each component in the paper coating composition is 5 to 40 parts by weight, preferably 9 to 30 parts by weight, of the copolymer latex of the present invention per 100 parts by weight of pigment in terms of solid content, and other ingredients. of binder in an amount of 0 to 30 parts by weight, preferably 2 to 10 parts by weight.
上記無機顔料の具体例としては、カオリンクレー、タル
ク、硫酸バリウム、酸化チタン（ルチルアナターゼ）、
炭酸カルシウム、水酸化アルミニウム、酸化亜鉛、サテ
ンホワイトなどを挙げることができる。また、有ｊａＭ
科の具体例としては、ポリスチレンラテックスなどを挙
げることができる。Specific examples of the above inorganic pigments include kaolin clay, talc, barium sulfate, titanium oxide (rutile anatase),
Examples include calcium carbonate, aluminum hydroxide, zinc oxide, and satin white. Also, there is
Specific examples of this family include polystyrene latex and the like.
また、その他の結合剤としては、でんぷん、酸化でんぷ
ん、大豆蛋白、カゼインなどの天然バインダー、あるい
はポリビニルアルコール、ポリ酢酸ビニルラテックス、
アクリル系ラテックス、ブタジェン−メチルメタクリレ
ートラテックスなとの合成ラテックスを使用することが
できる。Other binders include starch, oxidized starch, soybean protein, natural binders such as casein, polyvinyl alcohol, polyvinyl acetate latex,
Synthetic latexes such as acrylic latexes and butadiene-methyl methacrylate latexes can be used.
紙塗被用組成物の調製に際しては、他の助剤、例えば分
散剤（ビロリン酸ナトリウム、ヘキサメタリン酸ナトリ
ウムなど）、消泡剤（ポリグリコール、脂肪酸エステル
、リン酸エステル、シリコンオイルなど）、レベリング
剤（ロート油、ジシアンジアミド、尿素など）、防腐剤
、耐水化剤（ホルマリン、ヘキサミン、メラミン樹脂、
尿素梅脂１．グリオキサルなど）、離型剤（ステアリン
酸カルシウム、パラフィンエマルジョンなと）、蛍光染
料、カラー保水性向上剤（カルボキシメチルセルローズ
、アルギン酸ナトリウムなど）などを必要に応じて添加
することができる。When preparing the paper coating composition, other auxiliary agents, such as dispersants (sodium birophosphate, sodium hexametaphosphate, etc.), antifoaming agents (polyglycols, fatty acid esters, phosphate esters, silicone oil, etc.), leveling agents, etc. agents (funnel oil, dicyandiamide, urea, etc.), preservatives, waterproofing agents (formalin, hexamine, melamine resin,
Urea plum fat 1. Glyoxal, etc.), mold release agents (calcium stearate, paraffin emulsion, etc.), fluorescent dyes, color water retention improvers (carboxymethyl cellulose, sodium alginate, etc.), etc. can be added as necessary.
紙塗被用組成物の塗工用紙への塗布は、公知の技術、例
えばエアーナイフコーター、ブレードコーター、ゲート
ロールコータ−、ロールコータ−などを用いて行うこと
ができる。塗布後、表面を乾燥し、カレンダーリングな
どにより仕上げる。The paper coating composition can be applied to the coated paper using known techniques such as an air knife coater, a blade coater, a gate roll coater, a roll coater, and the like. After application, the surface is dried and finished by calendering, etc.
このように上記紙塗被用組成物を塗布して得られた塗工
紙は、アート紙、コート紙、軽量塗工紙、１１ｆｉｆｆ
ｉ塗工紙、コート板紙などとして使用される。The coated paper obtained by applying the above-mentioned paper coating composition can be used as art paper, coated paper, lightweight coated paper, 11fiff paper, etc.
Used as coated paper, coated paperboard, etc.
（実施例）
以下、実施例を挙げて本発明を更に詳細に説明する。な
お、以下の実施例における部および％は、それぞれ、重
量部および重量％を意味する。(Example) Hereinafter, the present invention will be explained in more detail by giving examples. Note that parts and % in the following examples mean parts by weight and % by weight, respectively.
実施例
（共重合体ラテックスの！！造）
次の共重合体ラテックスを製造した。なお、共重合体ラ
テックス（Ａ−１）〜（Ａ−１）は本発明の共重合体ラ
テックスであり、共重合体ラテックス（Ｂ−１）〜（Ｂ
−１０）は比較用共重合体ラテックスである。Example (Preparation of copolymer latex) The following copolymer latex was produced. In addition, copolymer latex (A-1) to (A-1) are copolymer latexes of the present invention, and copolymer latexes (B-1) to (B
-10) is a comparative copolymer latex.
ｌＯ撹拌器付オートクレーブに水２００部、ドデシルベ
ンゼンスルホン酸ナトリウム０ 、５８Ｂおよび表に示
した第１工程の単量体、分子ＷｌｙＪ４整剤および重合
開始剤を仕込み、７０℃にて３時間反応させた。引続き
、表に示した第２工程の単量体および重合開始剤を１０
時間にわたって連続的に添加し、その後更に５時間反応
させて重合転化率９８％以上で目的の共重合体ラテック
スを得た。200 parts of water, sodium dodecylbenzenesulfonate 0, 58B, the monomer of the first step shown in the table, molecular WlyJ4 stabilizer and polymerization initiator were placed in an autoclave equipped with a 1O stirrer, and the mixture was allowed to react at 70°C for 3 hours. Ta. Subsequently, 10% of the monomers and polymerization initiator for the second step shown in the table were added.
The mixture was added continuously over a period of time, and then reacted for an additional 5 hours to obtain the desired copolymer latex with a polymerization conversion rate of 98% or more.
八 −一２、 − −
第１工程は、上記と同様に実施した後、反応活性剤とし
ての硫酸第一鉄０．０１部、エチレンジアミン４酢酸ナ
トリウム塩０．０５部およびナトリウムホルムアルデヒ
ドスルホキシレート０．０５部を水１０部に溶解させた
水溶液を添加し、その後表に示した第２工程の単重体お
よび重合開始剤を３５℃で１０時間にわたって連続的に
添加し、その後更に５時間反応させて重合転化率９８％
以上で目的の共重合体ラテックスを得た。8-12, - - The first step is carried out in the same manner as above, and then 0.01 part of ferrous sulfate as a reaction activator, 0.05 part of ethylenediaminetetraacetic acid sodium salt and 0 sodium formaldehyde sulfoxylate are added. An aqueous solution of 0.05 parts dissolved in 10 parts of water was added, then the monomer and polymerization initiator of the second step shown in the table were added continuously at 35°C for 10 hours, and then the reaction was continued for an additional 5 hours. Polymerization conversion rate of 98%
The desired copolymer latex was thus obtained.
上記のようにして得られた共重合体ラテックスは全て苛
性ソーダを用いてｐＨ８に調整した後、水蒸気を吹き込
んで未反応単量体を除去し、更に減圧蒸留によって固形
分を５０％に調整した。All of the copolymer latexes obtained as described above were adjusted to pH 8 using caustic soda, then steam was blown into them to remove unreacted monomers, and the solid content was further adjusted to 50% by vacuum distillation.
（共重合体ラテックスの性能評価）
上記共重合体ラテックスを用いて下記処方により紙塗被
用組成物を：Ａ製した。(Performance evaluation of copolymer latex) A paper coating composition was prepared using the above copolymer latex according to the following formulation.
共重合体ラテックス １０部
クレー（分散剤としてビロリン酸ナトリウムを０．５％
含む） ８０部炭酸カルシウム
１０部
酸化でんぷん ５部
水（固形分が６０％になるように添加した）得られた組
成物を６４ｇ／ｍ２のコート原紙にコーティング用ブレ
ードを用い、塗工ｆ１２０ｇ／ｍ２となるように塗工し
、コート紙を得た。このコート紙の性能を下記試験方法
によって評価した。Copolymer latex 10 parts clay (0.5% sodium birophosphate as a dispersant)
) 80 parts calcium carbonate
10 parts oxidized starch 5 parts water (added so that the solid content was 60%) The obtained composition was coated on 64 g/m2 coated base paper using a coating blade so that the coating f1 was 120 g/m2. A coated paper was obtained. The performance of this coated paper was evaluated by the following test method.
トライ強度：接着強度の指標
Ｒ１印刷機で印刷したときのピッキングの程度を肉眼で
判定し、５段階法で評価した０点数の高いものほと接着
力が高い、測定回数６回の平均値を示した。Try strength: Indicator of adhesive strength The degree of picking when printing with the R1 printing machine is visually judged, and the higher the 0 score, the higher the adhesive strength, evaluated using a 5-step method.The average value of 6 measurements is taken. Indicated.
ウェット強度：耐水性の指標
Ｒ１印刷機でモルトンロールを用いて湿し水を与えたと
きのビックングの程度を肉眼で判定し、５段階法で評価
した０点数の高いものほど耐水性が良好である。測定回
数６回の平均値を示した。Wet strength: Water resistance index R1 The degree of bickling when dampening water is applied using a Molton roll on a printing machine is judged with the naked eye, and the higher the 0 score evaluated on a 5-point scale, the better the water resistance. be. The average value of 6 measurements is shown.
耐ブリスター性
両面塗工した紙を調ｆＡ＜約６％）し、加熱したオイル
バスに投げ込み、ブリスターが発生するときの最低温度
を示した。温度が高いほど耐ブリスター性が良好である
。Blister resistance A paper coated on both sides was adjusted to fA<about 6%) and thrown into a heated oil bath to indicate the lowest temperature at which blistering occurred. The higher the temperature, the better the blister resistance.
白紙光沢 村上式光沢計を使用して測定した（７５°−７５°）。white paper gloss Measurements were made using a Murakami gloss meter (75°-75°).
印刷光沢
Ｒｒ印刷機を使用してウェブオフセット用インキをベタ
塗りし、村上式光沢計を使用して測定した（６０°−６
０°）。Print gloss Rr printing machine was used to apply web offset ink, and Murakami type gloss meter was used to measure (60°-6
0°).
結果を表に示す、（以下余白） 表の結果から次のことが理解される。The results are shown in the table (margin below) The following can be understood from the results in the table.
本発明の共重合体ラテックス（Ａ−１）〜（Ａ−１１）
は、各種特性のバランスが良好であり、特に光沢が優れ
ている。Copolymer latex (A-1) to (A-11) of the present invention
has a good balance of various properties, and is particularly excellent in gloss.
比較用共重合体ラテックス（Ｂ−１）、 （Ｂ−２）は
、それぞれ、シアン化ビニル系単量体の使用割合が本発
明の範囲未満およびこの範囲を超える例であり、 （Ｂ
−１）では光沢が劣り、 （Ｂ−２）では接着強度、耐
水性および光沢が劣る。Comparative copolymer latexes (B-1) and (B-2) are examples in which the proportion of vinyl cyanide monomer used is below and above the range of the present invention, respectively, and (B
-1) has poor gloss, and (B-2) has poor adhesive strength, water resistance, and gloss.
比較用共重合体ラテックス（Ｂ−３）、 （Ｂ−４）は
、それぞれ、共役ジエン系単量体の使用割合が本発明の
範囲未満およびこの範囲を超える例であり、 （Ｂ−３
）、 （Ｂ−４）とも接着強度、耐水性および光沢が劣
る。Comparative copolymer latexes (B-3) and (B-4) are examples in which the proportion of conjugated diene monomer used is below and above the range of the present invention, respectively.
) and (B-4) are both inferior in adhesive strength, water resistance, and gloss.
比較用共重合体ラテックス（Ｂ−５）、 （Ｂ−６）は
、それぞれ、第１工程で使用する単量体混合物の割合が
本発明の範囲未満およびこの範囲を超える例であり、
（Ｂ−５）、 （Ｂ−６）とも光沢が劣る。Comparative copolymer latexes (B-5) and (B-6) are examples in which the proportion of the monomer mixture used in the first step is below and above the range of the present invention, respectively,
Both (B-5) and (B-6) are inferior in gloss.
比較用共重合体ラテックス（Ｂ−７）、 （Ｂ−８）は
、それぞれ、第１工程および第２工程で使用する重合開
始剤が本発明のそれと異なる例であり、 （Ｂ−７）は
耐ブリスター性および光沢が劣り、 （Ｂ−８）は接着
強度および光沢が劣る。Comparative copolymer latex (B-7) and (B-8) are examples in which the polymerization initiator used in the first step and the second step is different from that of the present invention, and (B-7) is Blister resistance and gloss are poor, and (B-8) is poor in adhesive strength and gloss.
比較用共重合体ラテックス（Ｂ−９）、 （Ｂ−１０）
は、それぞれ、共重合体のトルエン不溶分が本発明の範
囲未満およびこの範囲を超えた例であり、 （Ｂ−９）
では接着強度、耐水性および光沢が劣り、 （Ｂ−１０
）は接着強度、耐水性、耐ブリスター性および光沢が劣
る。Comparative copolymer latex (B-9), (B-10)
are examples in which the toluene insoluble content of the copolymer is less than the range of the present invention and exceeds this range, respectively, (B-9)
(B-10) has poor adhesive strength, water resistance, and gloss.
) has poor adhesive strength, water resistance, blister resistance, and gloss.
（発明の効果）
本発明の紙塗被用共重合体ラテックスをバインダーとし
て使用して得られるコート紙は、光沢、接着強度、耐水
性および耐ブリスター性などの性質のいずれもが優れ、
特にこれら性質のうちでも光沢が一段と優れていること
から、本発明の共重合体ラテックスは紙塗被バインダー
として極めて有用なものである。(Effects of the Invention) The coated paper obtained by using the copolymer latex for paper coating of the present invention as a binder has excellent properties such as gloss, adhesive strength, water resistance, and blister resistance.
Among these properties, the copolymer latex of the present invention is extremely useful as a paper coating binder because it has excellent gloss.
特許出願人 日本合成ゴム株式会社Patent applicant: Japan Synthetic Rubber Co., Ltd.
Claims (1)
系不飽和カルボン酸単量体０．５〜１０重量％、芳香族
ビニル系単量体１０〜５０重量％、シアン化ビニル系単
量体３〜４０重量％およびこれらと共重合可能な他の単
量体０〜６６．５重量％とからなる単量体混合物を乳化
重合して得られる共重合体ラテックスにおいて、該共重
合体ラテックスが、まず、単量体混合物の１０〜５０重
量％を無機系重合開始剤を用いて重合させ、次いで、得
られた共重合体の存在下に残りの単量体を有機系重合開
始剤を用いて重合させて得られたものであり、かつ該共
重合体ラテックス中の共重合体のトルエン不溶分が２０
〜９５重量％であることを特徴とする紙塗被用共重合体
ラテックス。(1) Conjugated diene monomer 20-80% by weight, ethylenically unsaturated carboxylic acid monomer 0.5-10% by weight, aromatic vinyl monomer 10-50% by weight, vinyl cyanide monomer In a copolymer latex obtained by emulsion polymerization of a monomer mixture consisting of 3 to 40% by weight of a monomer and 0 to 66.5% by weight of another monomer copolymerizable with these, the copolymer The latex is produced by first polymerizing 10 to 50% by weight of the monomer mixture using an inorganic polymerization initiator, and then adding the remaining monomers to the organic polymerization initiator in the presence of the resulting copolymer. The toluene insoluble content of the copolymer in the copolymer latex is 20%.
A copolymer latex for paper coating, characterized in that the content is 95% by weight.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10527288A JPH01280095A (en) | 1988-04-27 | 1988-04-27 | Copolymer latex for coating paper |
| KR1019890005422A KR900016286A (en) | 1988-04-27 | 1989-04-25 | Paper coating latex |
| DE3913777A DE3913777A1 (en) | 1988-04-27 | 1989-04-26 | Paper coating latex |
| FR898905553A FR2630761B1 (en) | 1988-04-27 | 1989-04-26 | PAPER COATING LATEX |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10527288A JPH01280095A (en) | 1988-04-27 | 1988-04-27 | Copolymer latex for coating paper |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01280095A true JPH01280095A (en) | 1989-11-10 |
Family
ID=14403031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10527288A Pending JPH01280095A (en) | 1988-04-27 | 1988-04-27 | Copolymer latex for coating paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01280095A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06192998A (en) * | 1992-12-25 | 1994-07-12 | Mitsui Toatsu Chem Inc | Composition for paper coating and coated paper obtained by applying the same composition |
| JP2002220405A (en) * | 2001-01-25 | 2002-08-09 | Asahi Kasei Corp | Copolymer latex and paper coating composition |
| US20160333189A1 (en) * | 2014-01-10 | 2016-11-17 | Asahi Kasei Kabushiki Kaisha | Aqueous composite particle dispersion |
-
1988
- 1988-04-27 JP JP10527288A patent/JPH01280095A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06192998A (en) * | 1992-12-25 | 1994-07-12 | Mitsui Toatsu Chem Inc | Composition for paper coating and coated paper obtained by applying the same composition |
| JP2002220405A (en) * | 2001-01-25 | 2002-08-09 | Asahi Kasei Corp | Copolymer latex and paper coating composition |
| US20160333189A1 (en) * | 2014-01-10 | 2016-11-17 | Asahi Kasei Kabushiki Kaisha | Aqueous composite particle dispersion |
| US10214650B2 (en) * | 2014-01-10 | 2019-02-26 | Asahi Kasei Kabushiki Kaisha | Aqueous composite particle dispersion |
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