JPH03113096A - Paper coating composition - Google Patents
Paper coating compositionInfo
- Publication number
- JPH03113096A JPH03113096A JP1273003A JP27300389A JPH03113096A JP H03113096 A JPH03113096 A JP H03113096A JP 1273003 A JP1273003 A JP 1273003A JP 27300389 A JP27300389 A JP 27300389A JP H03113096 A JPH03113096 A JP H03113096A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- copolymer latex
- monomer
- pts
- 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.)
- Granted
Links
- 239000008199 coating composition Substances 0.000 title claims description 33
- 239000000178 monomer Substances 0.000 claims abstract description 50
- 229920001577 copolymer Polymers 0.000 claims abstract description 49
- 239000004816 latex Substances 0.000 claims abstract description 45
- 229920000126 latex Polymers 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 34
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 150000001993 dienes Chemical class 0.000 claims abstract description 8
- 239000000049 pigment Substances 0.000 claims abstract description 8
- 239000012736 aqueous medium Substances 0.000 claims abstract description 7
- -1 alkyl mercaptans Chemical class 0.000 claims description 34
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 14
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 12
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 10
- YKFLAYDHMOASIY-UHFFFAOYSA-N γ-terpinene Chemical compound CC(C)C1=CCC(C)=CC1 YKFLAYDHMOASIY-UHFFFAOYSA-N 0.000 claims description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- YHQGMYUVUMAZJR-UHFFFAOYSA-N α-terpinene Chemical compound CC(C)C1=CC=C(C)CC1 YHQGMYUVUMAZJR-UHFFFAOYSA-N 0.000 claims description 9
- 150000002019 disulfides Chemical class 0.000 claims description 7
- 229930006978 terpinene Natural products 0.000 claims description 4
- 150000003507 terpinene derivatives Chemical class 0.000 claims description 4
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 21
- 230000001070 adhesive effect Effects 0.000 abstract description 21
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 14
- 238000007639 printing Methods 0.000 abstract description 5
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical class CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 abstract description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 abstract description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 abstract description 2
- 239000011976 maleic acid Substances 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract 2
- 238000006116 polymerization reaction Methods 0.000 description 39
- 238000000034 method Methods 0.000 description 22
- 239000003505 polymerization initiator Substances 0.000 description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 239000003995 emulsifying agent Substances 0.000 description 7
- 229960002447 thiram Drugs 0.000 description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 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 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 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 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- WSTYNZDAOAEEKG-UHFFFAOYSA-N Mayol Natural products CC1=C(O)C(=O)C=C2C(CCC3(C4CC(C(CC4(CCC33C)C)=O)C)C)(C)C3=CC=C21 WSTYNZDAOAEEKG-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000001023 inorganic pigment Substances 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 150000003871 sulfonates Chemical class 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 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 compound NCC(O)=O DHMQDGOQFOQNFH-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
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 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
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 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
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 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
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- PGAXJQVAHDTGBB-UHFFFAOYSA-N dibutylcarbamothioylsulfanyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SSC(=S)N(CCCC)CCCC PGAXJQVAHDTGBB-UHFFFAOYSA-N 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
- 229920001971 elastomer Polymers 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- ORTRWBYBJVGVQC-UHFFFAOYSA-N hexadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCS ORTRWBYBJVGVQC-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical compound CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- ZUDLIFVTNPYZJH-UHFFFAOYSA-N 1,1,2,2-tetraphenylethylbenzene Chemical compound C1=CC=CC=C1C(C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 ZUDLIFVTNPYZJH-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-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
- 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
- DTFFFOGZHBBKCX-UHFFFAOYSA-N 2-[bis(2-aminoethyl)amino]-2-octyldecanoic acid Chemical compound CCCCCCCCC(C(O)=O)(N(CCN)CCN)CCCCCCCC DTFFFOGZHBBKCX-UHFFFAOYSA-N 0.000 description 1
- PTFSLTXIXFNFSI-UHFFFAOYSA-N 2-[bis(2-aminoethyl)amino]tetradecanoic acid Chemical class CCCCCCCCCCCCC(C(O)=O)N(CCN)CCN PTFSLTXIXFNFSI-UHFFFAOYSA-N 0.000 description 1
- HVYJSOSGTDINLW-UHFFFAOYSA-N 2-[dimethyl(octadecyl)azaniumyl]acetate Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CC([O-])=O HVYJSOSGTDINLW-UHFFFAOYSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- IZFHMLDRUVYBGK-UHFFFAOYSA-N 2-methylene-3-methylsuccinic acid Chemical compound OC(=O)C(C)C(=C)C(O)=O IZFHMLDRUVYBGK-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
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- FVCPXLWAKNJIKK-UHFFFAOYSA-N Dimexano Chemical compound COC(=S)SSC(=S)OC FVCPXLWAKNJIKK-UHFFFAOYSA-N 0.000 description 1
- FVIGODVHAVLZOO-UHFFFAOYSA-N Dixanthogen Chemical compound CCOC(=S)SSC(=S)OCC FVIGODVHAVLZOO-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
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical class C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 108010073771 Soybean Proteins Proteins 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 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
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000007664 blowing Methods 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
- 239000004202 carbamide Substances 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
- MRUAUOIMASANKQ-UHFFFAOYSA-O carboxymethyl-[3-(dodecanoylamino)propyl]-dimethylazanium Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC(O)=O MRUAUOIMASANKQ-UHFFFAOYSA-O 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000002301 combined 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
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 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
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- 229940096818 dipentamethylenethiuram disulfide Drugs 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229960002377 dixanthogen Drugs 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-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
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 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
- 238000010438 heat treatment Methods 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 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
- 125000000400 lauroyl group Chemical group O=C([*])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 1
- 229940094506 lauryl betaine Drugs 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- ZWWQICJTBOCQLA-UHFFFAOYSA-N o-propan-2-yl (propan-2-yloxycarbothioyldisulfanyl)methanethioate Chemical compound CC(C)OC(=S)SSC(=S)OC(C)C ZWWQICJTBOCQLA-UHFFFAOYSA-N 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 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
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- KNBRWWCHBRQLNY-UHFFFAOYSA-N piperidine-1-carbothioylsulfanyl piperidine-1-carbodithioate Chemical compound C1CCCCN1C(=S)SSC(=S)N1CCCCC1 KNBRWWCHBRQLNY-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 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
- 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
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 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
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 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
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate 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
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 235000019710 soybean protein Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 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
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Paper (AREA)
- Polymerisation Methods In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は紙塗被組成物に関し、詳しくは接着強度および
耐ブリスター性がともに一段と優れた紙塗被組成物に関
する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a paper coating composition, and more particularly to a paper coating composition that has improved adhesive strength and blister resistance.
（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うテ・ソクスが、単独で、あ
るいはガゼイン、デンプン、タンパク質、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) Carboxyl group-modified copolymer Ute Sox, which is 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 casein, starch, protein, cellulose,
It is well known that it can be used as a paper coating binder together with natural or synthetic binders such as 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被して得ら
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。The coated paper obtained by coating a paper coating composition containing this carboxyl group-modified copolymer latex as a binder for paper coating has good adhesive strength, water resistance, gloss, etc., and is suitable for various uses. It is used.
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、印刷強度、耐水性および耐ブリスター性の全て、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。特に、オフセット輪転印刷
用コート紙に対しては、接着強度と耐ブリスター性の向
上要求がますます高まっている。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 improve various physical properties more than ever before, especially to improve gloss, printing strength, water resistance, and blister resistance, or all or several of them at the same time. It is now possible to do so. In particular, there is an increasing demand for improved adhesive strength and blister resistance for coated paper for rotary offset printing.
このような要求に応えるため、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。例えば、特開昭５７−１５３０１２号公報、同６
１−６３７９４号公報には、重合連鎖移動剤の添加方法
に工夫を加えることによって接着強度あるいは耐ブリス
ター性が改良されることが開示されている。その他、特
開昭５０−１０７０３０号公報、同５５−９０６９７号
公報、同６０−３８４１５号公報、同６１−２０７６９
４号公報などにも改良された紙塗被組成物あるいはその
製造方法が開示されている。In order to meet these demands, various improvements have been made to copolymer latexes used as paper coating binders. For example, Japanese Unexamined Patent Publication No. 57-153012, No. 6
1-63794 discloses that adhesive strength or blister resistance can be improved by adding a method of adding a polymer chain transfer agent. In addition, JP-A No. 50-107030, JP-A No. 55-90697, JP-A No. 60-38415, JP-A No. 61-20769.
Publication No. 4 and the like also disclose improved paper coating compositions and methods for producing the same.
（発明が解決しようとする課題）
しかしながら、これら従来の紙塗被組成物は、なお接着
強度、耐ブリスター性が十分でなく、上記のような要求
に十分応えるには至っていないのが実状である。本発明
は、これら従来の紙塗被組成物の問題点を解決し、接着
強度および耐ブリスター性がともに一段と改良された紙
塗被組成物を提供することを目的とするものである。(Problems to be Solved by the Invention) However, these conventional paper coating compositions still lack sufficient adhesive strength and blister resistance, and the reality is that they have not yet fully met the above requirements. . The object of the present invention is to solve these problems of conventional paper coating compositions and to provide a paper coating composition that has further improved adhesive strength and blister resistance.
（課題を解決するための手段）
本発明者らは、鋭意検討の結果、単量体混合物を特定の
重合連鎖移動剤の存在下に乳化重合して得られる共重合
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
被組成物は、接着強度および耐ブリスター性がともに一
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。(Means for Solving the Problems) As a result of extensive studies, the present inventors have developed a copolymer latex obtained by emulsion polymerization of a monomer mixture in the presence of a specific polymerization chain transfer agent for paper coating. It was discovered that the paper coating composition contained as a binder has much better adhesive strength and blister resistance, and based on this knowledge, the present invention was completed.
すなわち、本発明は、顔料およびバインダーとしての共
重合体ラテックスを含有する紙塗被組成物において、該
共重合体が、
（ａ）共役ジエン系単量体
１０〜６０重量部
（ｂ）エチレン系不飽和単量体
３０〜８９６５重量部
（ｃ）エチレン系不飽和カルボン酸単量体０．５〜１０
重量部
からなる単量体混合物（合計１００重量部）を、該混合
物１００重量部当り、α−メチルスチレンダイマー２〜
１００重量％と他の重合連鎖移動剤９８〜０重量％とか
らなる重合連鎖移動剤０．３〜１０重量部の存在下にお
いて、水性媒体中で乳化重合して得られる共重合体ラテ
ックスであることを特徴とする紙塗被組成物に関する。That is, the present invention provides a paper coating composition containing a pigment and a copolymer latex as a binder, in which the copolymer contains (a) 10 to 60 parts by weight of a conjugated diene monomer, and (b) an ethylene monomer. Unsaturated monomer 30-8965 parts by weight (c) Ethylenically unsaturated carboxylic acid monomer 0.5-10
A monomer mixture consisting of parts by weight (total 100 parts by weight) is mixed with 2 to 10 parts by weight of α-methylstyrene dimer per 100 parts by weight of the mixture.
It is a copolymer latex obtained by emulsion polymerization in an aqueous medium in the presence of 0.3 to 10 parts by weight of a polymer chain transfer agent consisting of 100 weight % and 98 to 0 weight % of another polymer chain transfer agent. The present invention relates to a paper coating composition characterized in that:
さらに、本発明は、顔料およびバインダーとしての共重
合体ラテックスを含有する紙塗被組成物において、該共
重合体ラテックスが、
（ａ）共役ジエン系単量体
１０〜６０重量部
（ｂ）エチレン系不飽和単量体
３０〜８９．５重量部
（ｃ）エチレン系不飽和カルボン酸単量体０．５〜１０
重量部
からなる単量体混合物（合計１００重量部）を、該混合
物１００重量部当り、（イ）タービノーレン、α−テル
ピネン、γ−テルピネンおよびジペンテンから選ばれる
少なくとも１種の化合物５〜９５重量％と（ロ）アルキ
ルメルカプタン類、四塩化炭素、キサントゲンジスルフ
ィド類およびチウラムジスルフィド類から選ばれる少な
くとも１種の化合物９５〜５重量％とからなる重合連鎖
移動剤０．３〜１０重量部の存在下において、水性媒体
中で乳化重合して得られる共重合体ラテックスであるこ
とを特徴とする紙塗被組成物に関する。Furthermore, the present invention provides a paper coating composition containing a copolymer latex as a pigment and a binder, in which the copolymer latex contains (a) 10 to 60 parts by weight of a conjugated diene monomer (b) ethylene Systemically unsaturated monomer 30-89.5 parts by weight (c) Ethylenically unsaturated carboxylic acid monomer 0.5-10
(a) 5 to 95% by weight of at least one compound selected from terbinolene, α-terpinene, γ-terpinene, and dipentene, per 100 parts by weight of the monomer mixture (total 100 parts by weight); and (b) 95 to 5% by weight of at least one compound selected from alkyl mercaptans, carbon tetrachloride, xanthogen disulfides, and thiuram disulfides in the presence of 0.3 to 10 parts by weight of a polymerization chain transfer agent. , relates to a paper coating composition characterized in that it is a copolymer latex obtained by emulsion polymerization in an aqueous medium.
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共役ジエ
ン系単量体（ａ）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、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。Specific examples of the conjugated diene monomer (a) used in the production of the copolymer latex of the present invention include butadiene, isoprene, 2-chloro-1,3-butadiene, 2-methyl-1,3-butadiene. etc. can be mentioned. 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、得られる共重合体に適当な弾性
および膜の硬さを付与するために使用するが、その使用
量は、単量体混合物の全量が１００重量部となるように
、１０〜６０重量部、好ましくは２０〜６０重量部の範
囲から選ばれる。この使用量が１０重量部未満では十分
な接着強度を得ることができず、一方６０重量部を越え
ると耐水性および接着強度が低下して好ましくない。The conjugated diene monomer is used to impart appropriate elasticity and film hardness to the resulting copolymer, and the amount used is such that the total amount of the monomer mixture is 100 parts by weight. , 10 to 60 parts by weight, preferably 20 to 60 parts by weight. If the amount used is less than 10 parts by weight, sufficient adhesive strength cannot be obtained, while if it exceeds 60 parts by weight, water resistance and adhesive strength will decrease, which is not preferred.
エチレン系不飽和単量体（ｂ）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
ルスチレンなどの芳香族ビニル化合物、アクリル酸メチ
ル、アクリル酸エチル、アクリル酸ブチル、アクリル酸
２−ヒドロキシエチル、メタクリル酸２−ヒドロキシエ
チル、メタクリル酸グリシジルなどのアクリル酸または
メタクリル酸のアルキルエステル化合物、アクリルアミ
ド、メタクリルアミド、Ｎ、Ｎ−ジメチルアクリルアミ
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またはメタクリルアミ
ド化合物、酢酸ビニルなどのカルボン酸ビニルエステル
類、アクリロニトリル、メタクリロニトリル、α−クロ
ルアクリロニトリルなどのシアン化ビニル化合物などを
挙げることができる。これらは単独で、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
、特に芳香族ビニル化合物としてはスチレンが、アルキ
ルエステル化合物としてはメタクリル酸メチルが、また
シアン化ビニル化合物としてはアクリロニトリルが好適
に使用される。Specific examples of the ethylenically unsaturated monomer (b) include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, p-methylstyrene, methyl acrylate, ethyl acrylate, butyl acrylate, and acrylic. Alkyl ester compounds of acrylic acid or methacrylic acid such as 2-hydroxyethyl acid, 2-hydroxyethyl methacrylate, glycidyl methacrylate, ethylenically unsaturated compounds such as acrylamide, methacrylamide, N,N-dimethylacrylamide, N-methylolacrylamide, etc. Examples include acrylamide or methacrylamide compounds of carboxylic acids, vinyl carboxylic esters such as vinyl acetate, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile. These can be used alone or in combination of two or more. Among these, styrene is particularly preferably used as the aromatic vinyl compound, methyl methacrylate as the alkyl ester compound, and acrylonitrile as the vinyl cyanide compound.
エチレン系不飽和単量体は、得られる共重合体に適度の
硬さ、弾性および耐水性を付与するために使用するが、
その使用量は、単量体混合物の全量が１００重量部にな
るように、３０〜８９．５重量部、好ましくは３０〜７
９．５重量部の範囲から選ばれる。この使用量が、３０
重量部未満では耐水性が劣り、一方８９．５重量部を越
えると共重合体が硬くなりすぎ、接着強度が低下して好
ましくない。The ethylenically unsaturated monomer is used to impart appropriate hardness, elasticity, and water resistance to the resulting copolymer.
The amount used is 30 to 89.5 parts by weight, preferably 30 to 7 parts by weight, so that the total amount of the monomer mixture is 100 parts by weight.
selected from a range of 9.5 parts by weight. This usage amount is 30
If it is less than 89.5 parts by weight, the water resistance will be poor, while if it exceeds 89.5 parts by weight, the copolymer will become too hard and the adhesive strength will decrease, which is not preferable.
エチレン系不飽和カルボン酸単量体（ｃ）の具体例とし
ては、アクリル酸、メタクリル酸、クロトン酸などのモ
ノカルボン酸類、マレイン酸、フマル酸、イタコン酸な
どのジカルボン酸類、さらにマレイン酸メチル、イタコ
ン酸メチル、β−メタアクリルオキシエチルアシッドヘ
キサハイドロフタレート等のハーフエステル類等を挙げ
ることができる。また、ジカルボン酸の無水物も使用す
ることができる。これらは単独でも、あるいは２種以上
を組合せて使用することもできる。エチレン系不飽和カ
ルボン酸単量体（ｃ）としては、ジカルボン酸、そのハ
ーフエステル類およびジカルことが好ましい。そして、
ジカルボン酸、ハーフエステル類およびジカルボン酸無
水物から選ばれる少なくとも１種（α）とモノカルボン
酸（β）との比率（α）／（β）が、５〜１００／９５
〜０、さらに好ましくは１０〜９５／９０〜５である。Specific examples of the ethylenically unsaturated carboxylic acid monomer (c) include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, and methyl maleate. Half esters such as methyl itaconate and β-methacryloxyethyl acid hexahydrophthalate can be mentioned. Anhydrides of dicarboxylic acids can also be used. These can be used alone or in combination of two or more. As the ethylenically unsaturated carboxylic acid monomer (c), dicarboxylic acids, half esters thereof, and radicals are preferred. and,
The ratio (α)/(β) of at least one selected from dicarboxylic acids, half esters and dicarboxylic anhydrides (α) and monocarboxylic acid (β) is 5 to 100/95.
-0, more preferably 10-95/90-5.
この比率範囲で用いると、接着強度、ラテックスならび
に塗被組成物の機械的安定性が優れる。When used within this ratio range, the adhesive strength, latex, and mechanical stability of the coating composition are excellent.
エチレン系不飽和カルボン酸単量体の使用量は、単量体
混合物の全量が１００重量部になるように０．５〜１０
重量部、好ましくは１〜７重量部の範囲から選ばれる。The amount of the ethylenically unsaturated carboxylic acid monomer used is 0.5 to 10 parts by weight so that the total amount of the monomer mixture is 100 parts by weight.
Parts by weight, preferably from 1 to 7 parts by weight.
この使用量が０．５重量部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
量部を越えると共重合体ラテックスの粘度が高くなって
、取扱い（ハンドリング）が困難となり、操作性が低下
して好ましくない。If the amount used is less than 0.5 parts by weight, the adhesive strength and mechanical stability of the copolymer latex will decrease, while if it exceeds 10 parts by weight, the viscosity of the copolymer latex will increase, making it difficult to handle. ) becomes difficult and the operability deteriorates, which is undesirable.
本発明における共重合体ラテックスは、上記単量体混合
物を水性媒体中で乳化重合することによって得られるが
、本発明の特徴はこの乳化重合を特定の重合連鎖移動剤
の存在下に行なう点にある。The copolymer latex in the present invention is obtained by emulsion polymerization of the above monomer mixture in an aqueous medium, but the feature of the present invention is that this emulsion polymerization is carried out in the presence of a specific polymerization chain transfer agent. be.
すなわち、本発明の第一の発明においては、α−メチル
スチレンダイマー２〜１００重量％と他の重合連鎖移動
剤０〜９８重量％とからなる重合連鎖移動剤の存在下に
、また本発明の第二の発明においては、（イ）ターピノ
ーレン、α−テルピネン、γ−テルピネンおよびジペン
テンから選ばれる少なくとも１種の化合物５〜９５重量
％と、（ロ）アルキルメルカプタン類、四塩化炭素、キ
サントゲンジスルフィド類およびチウラムジスルフィド
類から選ばれる少なくとも１種の化合物９５〜５重量％
とからなる重合連鎖移動剤の存在下に乳化重合を行う。That is, in the first invention of the present invention, in the presence of a polymerization chain transfer agent consisting of 2 to 100% by weight of α-methylstyrene dimer and 0 to 98% by weight of another polymerization chain transfer agent; In the second invention, (a) 5 to 95% by weight of at least one compound selected from terpinene, α-terpinene, γ-terpinene, and dipentene, and (b) alkylmercaptans, carbon tetrachloride, and xanthogen disulfides. and 95 to 5% by weight of at least one compound selected from thiuram disulfides
Emulsion polymerization is carried out in the presence of a polymerization chain transfer agent consisting of.
これら第一発明および第二発明について、以下に詳しく
説明する。The first invention and the second invention will be explained in detail below.
第一発明において使用する重合連鎖移動剤（以下、重合
連鎖移動剤（Ｉ）という）は、α−メチルスチレンダイ
マー２〜１００重量％と他の重合連鎖移動剤０〜９８重
量％とからなる。The polymeric chain transfer agent (hereinafter referred to as polymeric chain transfer agent (I)) used in the first invention consists of 2 to 100% by weight of α-methylstyrene dimer and 0 to 98% by weight of another polymeric chain transfer agent.
α−メチルスチレンダイマーとしては、異性体として、
（イ）２−４−ジフェニル−４−メチル−１−ベノアノ
、
（ロ）２−４−ジフェニル−４−メチル−２−ペンテン
、および
（ハ）１−１−３−トリメチル−３−フェニルインダン
がある。α−メチルスチレンダイマーとして好ましい組
成は、（イ）成分が４０重量％以上、（ロ）成分および
／または（ハ）成分が６０重量％以下、さらに好ましく
は、（イ）成分が５０重量％以上、（ロ）成分および／
または（ハ）成分が５０重量％以下、特に好ましくは、
（イ）成分が７０重量％以上、（ロ）成分および／また
は（ハ）成分が３０重量％以下である。（イ）成分の組
成比率が高くなるに従って、連鎖移動効果に優れる。The isomers of the α-methylstyrene dimer include (a) 2-4-diphenyl-4-methyl-1-benoano, (b) 2-4-diphenyl-4-methyl-2-pentene, and (c) There is 1-1-3-trimethyl-3-phenylindan. A preferred composition of the α-methylstyrene dimer is that component (a) is 40% by weight or more, component (b) and/or component (c) is 60% by weight or less, and more preferably component (a) is 50% by weight or more. , (b) component and/
or (c) component is 50% by weight or less, particularly preferably,
The content of component (a) is 70% by weight or more, and the content of component (b) and/or component (c) is 30% by weight or less. (a) As the composition ratio of the components increases, the chain transfer effect becomes better.
α−メチルスチレンダイマーは、本発明の目的を損なわ
ない範囲で、不純物、例えば未反応のα−メチルスチレ
ン、前記（イ）、（ロ）、（ハ）成分以外のα−メチル
スチレンオリゴマー α−メチルスチレンボリマーを含
むものであってもよい。The α-methylstyrene dimer may contain impurities, such as unreacted α-methylstyrene, α-methylstyrene oligomers other than the components (a), (b), and (c), to the extent that the purpose of the present invention is not impaired. It may also contain methylstyrene polymer.
α−メチルスチレンダイマーを使用する場合、その目的
を損なわないものであれば、α−メチルスチレンダイマ
ー合成後、これを未精製の状態で使用することもできる
。When α-methylstyrene dimer is used, it can be used in an unpurified state after synthesizing α-methylstyrene dimer, as long as the purpose is not impaired.
α−メチルスチレンダイマーと併用する他の重合連鎖移
動剤としては、一般の乳化重合に使用されている公知の
重合連鎖移動剤を使用することができる。具体的には、
例えば、オクチルメルカプタン、ｎ−ドデシルメルカプ
タン、ｔ−ドデシルメルカプタン、ｎ−ヘキサデシルメ
ルカプタン、ｎ−テトラデシルメルカプタン、ｔ−テト
ラデシルメルカプタンなどのメルカプタン類；ジメチル
キサントゲンジスルフィド、ジエチルキサントゲンジス
ルフィド、ジイソプロピルキサントゲンジスルフィドな
どのキサントゲンジスルフィド類；テトラメチルチウラ
ムジスルフィド、テトラエチルチウラムジスルフィド、
テトラブチルチウラムジスルフィドなどのチウラムジス
ルフィド類；四塩化炭素、臭化エチレンなどのハロゲン
化炭化水素類；ペンタフェニルエタンなどの炭化水素類
；およびアクロレイン、メタクロレイン、アリルアルコ
ール、２−エチルへキシルチオグリコレート、ターピノ
ーレン、α−テルピネン、γ−テルピネン、ジペンテン
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種以上組み合わせて使用することもできる。これら
のうち、メルカプタン類、キサントゲンジスルフィド類
、チウラムジスルフィド類、四塩化炭素などが好適に使
用される。As other polymerization chain transfer agents used in combination with the α-methylstyrene dimer, known polymerization chain transfer agents used in general emulsion polymerization can be used. in particular,
For example, mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, and t-tetradecyl mercaptan; Xanthogen disulfides; tetramethylthiuram disulfide, tetraethylthiuram disulfide,
Thiuram disulfides such as tetrabutylthiuram disulfide; halogenated hydrocarbons such as carbon tetrachloride and ethylene bromide; hydrocarbons such as pentaphenylethane; and acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglyco Examples include ester, terpinene, α-terpinene, γ-terpinene, and dipentene. These can be used alone or in combination of two or more. Among these, mercaptans, xanthogen disulfides, thiuram disulfides, carbon tetrachloride and the like are preferably used.
重合連鎖移動剤（１）中のα−メチルスチレンダイマー
の割合は２〜１００重量％、好ましくは３〜１００重量
％、さらに好ましくは５〜９５重量％である。The proportion of α-methylstyrene dimer in the polymerization chain transfer agent (1) is 2 to 100% by weight, preferably 3 to 100% by weight, and more preferably 5 to 95% by weight.
このα−メチルスチレンダイマーの割合が２重量％未満
では接着強度と耐ブリスター性に優れた共重合体ラテッ
クスを得ることができない。また、α−メチルスチレン
ダイマーと他の重合連鎖移動剤との併用により、重合時
における反応性を高めることができる。If the proportion of α-methylstyrene dimer is less than 2% by weight, a copolymer latex with excellent adhesive strength and blister resistance cannot be obtained. Further, by using the α-methylstyrene dimer in combination with another polymerization chain transfer agent, the reactivity during polymerization can be increased.
重合連鎖移動剤（１）の使用量は、単量体混合物１００
重量部当り、０．３〜１０重量部、好ましくは０．５〜
７重量部である。この重合連鎖移動剤（１）の使用量が
０１．３重量部未満では耐ブリスター性が劣り、一方１
０重量部を越えると接着強度が低下して好ましくない。The amount of polymerization chain transfer agent (1) used is 100% of the monomer mixture.
0.3 to 10 parts by weight, preferably 0.5 to 10 parts by weight
7 parts by weight. If the amount of the polymerization chain transfer agent (1) used is less than 01.3 parts by weight, the blister resistance will be poor;
If it exceeds 0 parts by weight, the adhesive strength will decrease, which is not preferable.
なお、α−メチルスチレンダイマーの使用量については
、単量体混合物の１００重量部当り、０゜１〜５重量部
の範囲で使用するのが好ましい。The amount of α-methylstyrene dimer used is preferably in the range of 0.1 to 5 parts by weight per 100 parts by weight of the monomer mixture.
次に、第二発明において使用する重合連鎖移動剤（以下
、重合連鎖移動剤（ＩＩ）という）は、（イ）ターピノ
ーレン、α−テルピネン、γ−テルピネンおよびジペン
テンから選ばれる少なくとも１種の化合物（以下、「成
分（イ）」という）と、（ロ）アルキルメルカプタン類
、四塩化炭素、キサントゲンジスルフィド類およびチウ
ラムジスルフィド類から選ばれる少なくとも１種の化合
物（以下、「成分（ロ）」という）とからなる。Next, the polymerization chain transfer agent (hereinafter referred to as polymerization chain transfer agent (II)) used in the second invention is (a) at least one compound selected from terpinene, α-terpinene, γ-terpinene, and dipentene ( (hereinafter referred to as "component (a)"); and (b) at least one compound selected from alkyl mercaptans, carbon tetrachloride, xanthogen disulfides, and thiuram disulfides (hereinafter referred to as "component (b)"). Consisting of
成分（ロ）のアルキルメルカプタン類の具体例としては
、オクチルメルカプタン、ｎ−ドデシルメルカプタン、
ｔ−ドデシルメルカプタン、ｎ−テトラデシルメルカプ
タン、ｔ−テトラデシルメルカプタン、ｎ−ヘキサデシ
ルメルカプタンなどを挙げることができる。これらのう
ち、ｔ−ドデシルメルカプタンが好ましく使用される。Specific examples of the alkyl mercaptans of component (b) include octyl mercaptan, n-dodecyl mercaptan,
Examples include t-dodecylmercaptan, n-tetradecylmercaptan, t-tetradecylmercaptan, and n-hexadecylmercaptan. Among these, t-dodecyl mercaptan is preferably used.
キサントゲンジスルフィド類の具体例としては、ジエチ
ルキサントゲンジスルフィド、ジメチルキサントゲンジ
スルフィド、ジイソプロピルキサントゲンジスルフィド
などを挙げることができる。Specific examples of xanthogen disulfides include diethylxanthogen disulfide, dimethylxanthogen disulfide, diisopropylxanthogen disulfide, and the like.
チウラムジスルフィド類の具体例としては、テトラメチ
ルチウラムモノスルフィド、テトラエチルチウラムジス
ルフィド、テトラブチルチウラムジスルフィド、ジペン
タメチレンチウラムジスルフィドなどを挙げることがで
きる。Specific examples of thiuram disulfides include tetramethylthiuram monosulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram disulfide, and the like.
重合連鎖移動剤（ＩＩ）中の成分（イ）の割合は５〜９
５重量％、好ましくは１０〜９０重量％である。この重
合連鎖移動剤中の成分（イ）の割合が５重量％未満ある
いは９５重量％を越えると、成分（イ）、（ロ）の併用
効果が得られず、本発明の目的とする接着強度および耐
ブリスター性がともに優れた紙塗被組成物を得ることが
できない。The ratio of component (a) in polymerization chain transfer agent (II) is 5 to 9
5% by weight, preferably 10-90% by weight. If the proportion of component (a) in this polymer chain transfer agent is less than 5% by weight or exceeds 95% by weight, the combined effect of components (i) and (b) cannot be obtained, and the adhesive strength targeted by the present invention cannot be obtained. It is not possible to obtain a paper coating composition that is excellent in both blister resistance and blister resistance.
重合連鎖移動剤（ＩＩ）の使用量は、単量体混合物１０
０重量部当り、０．３〜１０重量部、好ましくは０．５
〜７重量部である。重合連鎖移動剤（ＩＩ）の使用量が
０．３重量部未満では耐ブリスター性が劣り、また１０
重量部を越えると接着強度が低下して好ましくない。The amount of polymerization chain transfer agent (II) used is 10% of the monomer mixture.
0 parts by weight, 0.3 to 10 parts by weight, preferably 0.5 parts by weight
~7 parts by weight. If the amount of the polymerization chain transfer agent (II) used is less than 0.3 parts by weight, the blister resistance will be poor;
If the amount exceeds 1 part by weight, the adhesive strength decreases, which is undesirable.
なお、成分（イ）の使用量については、単量体混合物１
００重量部当り、０．１〜５重量部の範囲で使用するの
が好ましい。Regarding the usage amount of component (a), monomer mixture 1
It is preferably used in an amount of 0.1 to 5 parts by weight per 00 parts by weight.
本発明における共重合体ラテックスは、上記の単量体混
合物および重合連鎖移動剤を使用する点を除けば、従来
公知の乳化重合方法によって製造することができる。す
なわち、水性媒体（通常、水）に単量体混合物ならびに
重合開始剤、乳化剤、重合連鎖移動剤などを加えて乳化
重合を行なうことによって得られる。The copolymer latex in the present invention can be produced by a conventionally known emulsion polymerization method, except that the monomer mixture and polymerization chain transfer agent described above are used. That is, it is obtained by adding a monomer mixture, a polymerization initiator, an emulsifier, a polymerization chain transfer agent, etc. to an aqueous medium (usually water) and carrying out emulsion polymerization.
本発明における乳化重合に使用する重合開始剤について
は特に制限はなく、例えばクメンハイドロパーオキサイ
ド、ジイソブロピルベンゼンノ＼イドロバ−オキサイド
、パラメンタンハイドロパーオキサイドなどのハイドロ
パーオキサイド類、ベンゾイルパーオキサイド、ラウロ
イルバーオギサイドなどのパーオキサイド類およびアゾ
ビスイソブチロニトリルなどのアゾ化合物類などの有機
系重合開始剤、ならびに過硫酸カリウム、過硫酸ナトリ
ウム、過硫酸アンモニウムなどの過硫酸塩などの無機系
重合開始剤を使用することができる。There are no particular limitations on the polymerization initiator used in the emulsion polymerization in the present invention, and examples thereof include hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, para-menthane hydroperoxide, benzoyl peroxide, Organic polymerization initiators such as peroxides such as lauroyl baroxide and azo compounds such as azobisisobutyronitrile, and inorganic polymerizations such as persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate. Initiators can be used.
本発明においては、有機系重合開始剤を単独で使用する
と得られる共重合体ラテックスの機械的安定性が劣り、
また重合中に多量の凝固物が発生することから、無機系
重合開始剤を単独で、あるいは有機系重合開始剤と組み
合わせて使用するのが好ましい。In the present invention, when an organic polymerization initiator is used alone, the mechanical stability of the copolymer latex obtained is poor;
Furthermore, since a large amount of coagulated material is generated during polymerization, it is preferable to use an inorganic polymerization initiator alone or in combination with an organic polymerization initiator.
なお、上記重合開始剤は重亜硫酸ナトリウムなどの還元
剤と組み合わせた、いわゆるレドックス系重合開始剤と
しても使用することができる。The above polymerization initiator can also be used as a so-called redox polymerization initiator in combination with a reducing agent such as sodium bisulfite.
これら重合開始剤のうち、過硫酸カリウム、過硫酸アン
モニウムなどの過硫酸塩、またはこれとアゾビスイソブ
チロニトリルあるいはベンゾイルパーオキサイドとの組
合せ、さらにはこれらと還元剤とを組み合わせたものが
好ましく使用される。Among these polymerization initiators, persulfates such as potassium persulfate and ammonium persulfate, a combination of these with azobisisobutyronitrile or benzoyl peroxide, and further a combination of these with a reducing agent are preferably used. be done.
本発明における重合開始剤の使用量は、単量体混合物１
００重量部当り、通常０．１〜５重量部であり、好まし
くは０゜５〜２重量部である。無機系重合開始剤と有機
系重合開始剤とを併用する場合には、有機系重合開始剤
の割合は、好ましくは全重合開始剤の７０重量％以下、
さらに好ましくは５０重量％以下である。有機系重合開
始剤の割合が７０重量％を越えると、有機系重合開始剤
を単独で使用した場合のような問題が生じて好ましくな
い。The amount of the polymerization initiator used in the present invention is as follows:
It is usually 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight per 0.00 parts by weight. When an inorganic polymerization initiator and an organic polymerization initiator are used together, the proportion of the organic polymerization initiator is preferably 70% by weight or less of the total polymerization initiator,
More preferably, it is 50% by weight or less. If the proportion of the organic polymerization initiator exceeds 70% by weight, problems similar to those caused when the organic polymerization initiator is used alone are undesirable.
本発明における乳化重合に使用する乳化剤については特
に制限はなく、アニオン型、ノニオン型および両性型界
面活性剤のいずれも使用することができる。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もで
きる。例えば、ラウリル硫酸ナトリウムなどの高級アル
コールの硫酸エステル塩、ドデシルベンゼンスルホン酸
ナトリウムなどのアルキルベンゼンスルホン酸塩、ジオ
クチルスルホコハク酸ナトリウムなどの脂肪族カルボン
酸エステルのスルホン酸塩などのアニオン型界面活性剤
、ポリエチレングリコールのアルキルエステル型、アル
キルフェニルエーテル型、アルキルエーテル型などのノ
ニオン型界面活性剤などを使用することができる。また
、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、りん酸塩、り
ん酸エステル塩を、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もつものを挙げることができる
。具体的には、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、ココアミドプロピルベタ
イン、２−ウンデシルヒドロキシエチルイミダゾリウム
ベタインの塩が、またアミノ酸タイプのものとしてはラ
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、オクチルジ（アミ
ノエチル）グリシン、ジオクチルジ（アミノエチル）グ
リシンの塩を挙げることができる。The emulsifier used in the emulsion polymerization in the present invention is not particularly limited, and any of anionic, nonionic and amphoteric surfactants can be used. These can be used alone or in combination of two or more. For example, anionic surfactants such as sulfate ester salts of higher alcohols such as sodium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, sulfonates of aliphatic carboxylic acid esters such as sodium dioctyl sulfosuccinate, polyethylene Nonionic surfactants such as glycol alkyl ester type, alkylphenyl ether type, and alkyl ether type can be used. In addition, as amphoteric surfactants, carboxylates, sulfate ester salts, sulfonates, phosphates, phosphate ester salts are used as anionic moieties, and amine salts, phosphate ester salts are used as cationic moieties.
Examples include those having quaternary ammonium salts. Specifically, alkyl betaine salts include lauryl betaine, stearyl betaine, cocoamidopropyl betaine, and 2-undecylhydroxyethylimidazolium betaine salts, and amino acid types include lauryl-β-alanine and stearyl-β. - Mention may be made of the salts of alanine, lauryl di(aminoethyl)glycine, octyldi(aminoethyl)glycine, dioctyldi(aminoethyl)glycine.
これら乳化剤のうち、特にアルキルベンゼンスルホン酸
塩が好ましく使用される。さらに具体的には、ドデシル
ベンゼンスルホン酸ナトリウムなどが特に好ましく使用
される。このアルキルベンゼンスルホン酸塩は、他の界
面活性剤、例えば高級アルコールの硫酸エステル塩、脂
肪族カルボン酸エステルのスルホン酸塩などのアニオン
型界面活性剤あるいは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
エーテル型などのノニオン型界面活性剤などと併用して
もよい。Among these emulsifiers, alkylbenzene sulfonates are particularly preferably used. More specifically, sodium dodecylbenzenesulfonate and the like are particularly preferably used. This alkylbenzene sulfonate can be used with other surfactants, such as anionic surfactants such as higher alcohol sulfate ester salts, aliphatic carboxylic acid ester sulfonates, or polyethylene glycol alkyl ester, alkyl ether, and alkyl esters. It may be used in combination with a nonionic surfactant such as a phenyl ether type surfactant.
乳化剤の使用量は、単量体混合物１００重量部当り、通
常０．０５〜２重量部であり、好ましくは０．０５〜１
重量部である。乳化剤の使用量が２重量部を越えると、
耐水性が劣り、紙塗被組成物の泡立ちが著しくなって塗
工時に問題となる。The amount of emulsifier used is usually 0.05 to 2 parts by weight, preferably 0.05 to 1 part by weight, per 100 parts by weight of the monomer mixture.
Parts by weight. If the amount of emulsifier used exceeds 2 parts by weight,
Water resistance is poor, and the paper coating composition foams significantly, causing problems during coating.
なお、アルキルベンゼンスルホン酸塩を他のアニオン型
あるいはノニオン型界面活性剤と併用する場合、アルキ
ルベンゼンスルホン酸塩の使用割合は全乳化剤の５０重
量％以上とするのが好ましい。In addition, when an alkylbenzene sulfonate is used in combination with another anionic or nonionic surfactant, the proportion of the alkylbenzene sulfonate used is preferably 50% by weight or more of the total emulsifier.
本発明における乳化重合方法およびその条件については
特に制限はなく、従来公知の方法および条件下において
実施することができる。There are no particular limitations on the emulsion polymerization method and conditions in the present invention, and the emulsion polymerization can be carried out under conventionally known methods and conditions.
例えば、重合連鎖移動剤の添加方法については、−括添
加方式、分割添加方式、連続添加方式あるいはこれらの
組合わせのいずれでもよい。For example, the method of adding the polymer chain transfer agent may be a batch addition method, a divided addition method, a continuous addition method, or a combination thereof.
また、単量体混合物の添加方法については、括添加方式
、分割添加方式、連続添加方式あるいはこれらの組合せ
のいずれでもよい。これらの方式のうち、凝固物の生成
の減少、反応熱の除去などの点からは、分割添加方式ま
たは連続添加方式が好ましい。さらに、エチレン系不飽
和カルボン酸単量体の全量または一部を含む単量体混合
物の１０〜５０重量％を１段目で重合し、２段目では残
りの単量体混合物５０〜９０重量％を連続的に添加して
乳化重合する２段重合方法によれば、重合工程における
凝固物の生成がより一層減少でき、本発明が目的とする
紙塗被組成物が効果的に得られることから、この２段重
合方法によって本発明の乳化重合を実施するのが好まし
い。なお、この方法において、重合連鎖移動剤は１段目
、２段目のいずれか一方に添加してもよく、あるいは両
方に添加してもよい。重合連鎖移動剤を２段目に使用す
る場合には、連続的に添加するのが好ましい。The method of adding the monomer mixture may be a batch addition method, a divided addition method, a continuous addition method, or a combination thereof. Among these methods, the divided addition method or the continuous addition method is preferable from the viewpoint of reducing the formation of coagulum and removing the heat of reaction. Furthermore, 10 to 50% by weight of the monomer mixture containing all or a part of the ethylenically unsaturated carboxylic acid monomer is polymerized in the first stage, and 50 to 90% by weight of the remaining monomer mixture is polymerized in the second stage. According to the two-stage polymerization method in which emulsion polymerization is carried out by continuously adding % of the coagulate, the formation of coagulum in the polymerization process can be further reduced, and the paper coating composition targeted by the present invention can be effectively obtained. Therefore, it is preferable to carry out the emulsion polymerization of the present invention by this two-stage polymerization method. In this method, the polymer chain transfer agent may be added to either the first stage or the second stage, or to both stages. When a polymer chain transfer agent is used in the second stage, it is preferably added continuously.
得られた共重合体ラテックスのゲル含量は、好ましくは
５．０％以上、さらに好ましくは１０〜９８％である。The gel content of the obtained copolymer latex is preferably 5.0% or more, more preferably 10 to 98%.
ゲル含量が５％未満では、接着強度および機械的安定性
の低下が大きく、さらにはラテックスフィルムの粘着性
の増大に伴いバッキングロール汚れ等の問題が生じるの
で好ましくない。また、ゲル含量が９８％を越えると、
接着強度が低下する傾向を示すので好ましくない。If the gel content is less than 5%, the adhesive strength and mechanical stability will be significantly reduced, and problems such as backing roll stains will occur as the tackiness of the latex film increases, which is not preferable. In addition, when the gel content exceeds 98%,
This is not preferable because it tends to reduce adhesive strength.
本発明の紙塗被組成物は、無機顔料あるいは有機顔料、
好ましくは無機顔料に上記共重合体ラテックスを単独で
、あるいは必要に応じて他のバインダーとともに配合す
ることによって得られる。The paper coating composition of the present invention contains an inorganic pigment or an organic pigment,
Preferably, the above-mentioned copolymer latex is blended with an inorganic pigment alone or, if necessary, with other binders.
本発明の紙塗被組成物における上記共重合体ラテックス
の配合量は、固形分換算で、顔料１００重量部に対し通
常５〜３０重量部であり、好ましくは５〜２０重量部で
ある。また、必要に応じて添加される他のバインダーの
配合量は、固形分換算で、顔料１００重量部に対し通常
１０重量部以下であり、好ましくは２〜５重量部である
。The amount of the copolymer latex in the paper coating composition of the present invention is generally 5 to 30 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the pigment, in terms of solid content. Further, the amount of other binders added as necessary is usually 10 parts by weight or less, preferably 2 to 5 parts by weight, based on 100 parts by weight of the pigment, in terms of solid content.
無機顔料としては、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
どが、また有機顔料としてはポリスチレンラテックスな
どを使用することができる。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もできる。Examples of inorganic pigments that can be used include kaolin clay talc, barium sulfate, titanium oxide (rutyl anatase), calcium carbonate, aluminum hydroxide, zinc oxide, and satin white. Examples of organic pigments that can be used include polystyrene latex. These can be used alone or in combination of two or more.
他のバインダーとしては、デンプン、酸化デンプン、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
系ラテックスなどの合成ラテックスを挙げることができ
る。Other binders include natural binders such as starch, oxidized starch, soybean protein, and casein, and synthetic latexes such as polyvinyl alcohol, polyvinyl acetate latex, and acrylic latex.
本発明の紙塗被組成物には、さらに一般に使用されてい
る種々の助剤、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、尿素樹脂、グリオキサルなど）
、離型剤（ステアリン酸カリシウム、パラフィンエマル
ジジンなど）、螢光染料、カラー保持性向上剤（カルボ
キシメチルセルロース、アルギン酸ナトリウムなど）な
どを必要に応じて配合することができる。The paper coating composition of the present invention may further contain various commonly used auxiliaries, such as dispersants (sodium birophosphate,
(sodium hexametaphosphate, etc.), antifoaming agents (polyglycol, fatty acid ester, phosphate ester, silicone oil, etc.), leveling agents (funnel oil, dicyandiamide, urea, etc.), preservatives, water resistance agents (formalin, hexamine, melamine resin, etc.) , urea resin, glyoxal, etc.)
, a mold release agent (calcium stearate, paraffin emulzidine, etc.), a fluorescent dye, a color retention improver (carboxymethyl cellulose, sodium alginate, etc.), etc. can be blended as necessary.
本発明の紙塗被組成物は、従来公知の方法にょって、例
えばエアーナイフコーター ブレードコーター ロール
コータ−、アプリケーターなどを用いて塗布することが
できる。The paper coating composition of the present invention can be applied by a conventionally known method, for example, using an air knife coater, blade coater, roll coater, applicator, or the like.
（実施例）
以下、実施例を挙げて本発明をさらに具体的に説明する
。なお、実施例中の「％」および「部」は重量基準であ
る。(Example) Hereinafter, the present invention will be described in more detail with reference to Examples. Note that "%" and "part" in the examples are based on weight.
実施例１
（共重合体ラテックスの製造）
１００！の耐圧容器に、表１に示すように、１段目の単
量体混合物としてイタコン酸２部、アクリル酸１部、ブ
タジェン１０部、スチレン１８部、メタクリル酸メチル
１ｏ部およびアクリロニトリル５部を仕込み、さらに水
１５０部、α−メチルスチレンダイマー１．５部、ドデ
シルベンゼンスルホン酸ナトリウム０．３部および過硫
酸カリウム１．０部を仕込んだ後、窒素雰囲気中で温度
７０℃で２時間重合を行なった。次に、２段目の単量体
混合物として、ブタジェン１５部、スチレン３１部、ア
クリロニトリル３部およびメタクリル酸メチル５部を、
またα−メチルスチレンダイマー１．５部を８時間かけ
て連続的に添加して重合を行なった。その後、重合を完
結させるため、さらに３時間反応を継続し、重合添加率
９８％で重合を終了した。Example 1 (Production of copolymer latex) 100! As shown in Table 1, 2 parts of itaconic acid, 1 part of acrylic acid, 10 parts of butadiene, 18 parts of styrene, 1 part of methyl methacrylate, and 5 parts of acrylonitrile were charged into a pressure-resistant container as shown in Table 1. After further charging 150 parts of water, 1.5 parts of α-methylstyrene dimer, 0.3 parts of sodium dodecylbenzenesulfonate and 1.0 parts of potassium persulfate, polymerization was carried out at a temperature of 70°C for 2 hours in a nitrogen atmosphere. I did it. Next, as a second-stage monomer mixture, 15 parts of butadiene, 31 parts of styrene, 3 parts of acrylonitrile, and 5 parts of methyl methacrylate were added.
Further, 1.5 parts of α-methylstyrene dimer was continuously added over 8 hours to carry out polymerization. Thereafter, in order to complete the polymerization, the reaction was continued for an additional 3 hours, and the polymerization was completed at a polymerization addition rate of 98%.
得られた共重合体ラテックスを水酸化ナトリウムを用い
てｐＨ７，５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、さらに加熱減圧蒸溜によって固形分濃
度５０％の共重合体ラテックス（１−１）を得た。After adjusting the pH of the obtained copolymer latex to 7.5 using sodium hydroxide, unreacted monomers were removed by blowing in water vapor, and then a copolymer latex with a solid content concentration of 50% was obtained by heating and vacuum distillation. (1-1) was obtained.
なお、ここで使用したα−メチルスチレンダイマーおよ
び、以下の実施例、比較例で使用するα−メチルスチレ
ンダイマーは、下記のものである。The α-methylstyrene dimer used here and the α-methylstyrene dimer used in the following Examples and Comparative Examples are as follows.
商品名：ノフマーＭＳＤ （日本油脂株式会社製）組成
組成名
２−４−ジフェニル−４−メチル−１−ペンテン２−４
−ジフェニル−４−メチル−２−ペンテン１−！−３−
トリメチルー３−フェニルインダン２−メチルスチレン
組成（重量％）
９２．０％以上
５．０％以下
１．５％以下
１．０％以下
この共重合体ラテックス（１−１）のゲル含量は下記の
方法で測定した。Product name: Nofumar MSD (manufactured by NOF Corporation) Composition name 2-4-diphenyl-4-methyl-1-pentene 2-4
-diphenyl-4-methyl-2-pentene 1-! -3-
Trimethyl-3-phenylindan 2-methylstyrene composition (wt%) 92.0% or more and 5.0% and below 1.5% and 1.0% The gel content of this copolymer latex (1-1) is as follows: It was measured by the method.
共重合体ラテックスをｐＨ８，０に調整した後、イソプ
ロパツールで凝固し、洗浄した後、乾燥した。次に、約
０．３ｇの試料を採取し、これを１００ ｍｌのトルエ
ンに２０時間浸漬した後、トルエン不溶分を測定し、試
料に対する割合（％）を求めてゲル含量とした。After adjusting the copolymer latex to pH 8.0, it was coagulated with isopropanol, washed, and then dried. Next, about 0.3 g of a sample was taken and immersed in 100 ml of toluene for 20 hours, and the toluene insoluble content was measured, and the ratio (%) to the sample was calculated as the gel content.
（紙塗被組成物の調整）
上記共重合体ラテックス（Ｉ−１）を用いて下記の処方
により紙塗被組成物（カラー）を調整した。(Preparation of paper coating composition) A paper coating composition (color) was prepared using the copolymer latex (I-1) according to the following formulation.
クレー ８０部
炭酸カルシウム ２０部
共重合体ラテックス １０部
酸化デンプン ５部
ピロリン酸ナトリウム ０．５部水
全固形分が６０％になる量
得られたカラーは、下記試験方法で評価した。Clay 80 parts Calcium carbonate 20 parts Copolymer latex 10 parts Starch oxide 5 parts Sodium pyrophosphate 0.5 parts Water
The color obtained in an amount with a total solids content of 60% was evaluated by the following test method.
なお、試験に使用したコート紙は、カラーを坪量６４
ｇ／ｒ＆の原紙にコーティングブレードを用いて塗被量
２０ｇ／ｒｒｉｌ′で塗工して得た。The coated paper used in the test had a color basis weight of 64
It was obtained by coating g/r& base paper using a coating blade at a coating amount of 20 g/ril'.
■Ｒ１ドライピック：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。点数の高いものほど良好
である。点数は測定回数６回の平均値で示した。(2) R1 Dry Pick: Indicator of Adhesive Strength The degree of picking when printed with the R1 printing machine was visually judged and evaluated using a 5-step method. The higher the score, the better. The score was expressed as the average value of 6 measurements.
■耐ブリスター性
両面印刷塗工紙を調湿（約６％）した後、加熱オイルバ
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。■Blister resistance After controlling the humidity of double-sided printed coated paper (approximately 6%), it was thrown into a heated oil bath, and the lowest temperature at which blistering occurred was determined.
■機械的安定性
カラーをガムアップテスターを用いてゴムロール間で練
り、機械的剪断をかけてゴムロール上に凝固物が発生す
るまでの時間（分）を測定し、下記の３段階で評価した
。(2) Mechanical stability The color was kneaded between rubber rolls using a gum-up tester, and the time (minutes) until coagulation appeared on the rubber roll by mechanical shearing was measured and evaluated on the following three scales.
Ｑ：２０分以上 △：１０〜２０分 Ｘ：１０分以下 結果を表２に示す。Q: More than 20 minutes △: 10-20 minutes X: 10 minutes or less The results are shown in Table 2.
実施例２〜１０、比較例１〜７
実施例１において、単量体混合物、重合連鎖移動剤、重
合開始剤および乳化剤を表１に示すように変更した以外
は、実施例１と同様にして共重合体ラテックス（１−２
）〜（１−１０）および比較用共重合体ラテックス（Ｉ
−１１）〜（１−１７）を得た。なお、共重合体ラテッ
クス（１−１０）においては、１段目の重合を６時間、
２段目の重合を２時間かけて行なった点で、実施例１と
異なる。Examples 2 to 10, Comparative Examples 1 to 7 The same procedure as in Example 1 was carried out except that the monomer mixture, polymerization chain transfer agent, polymerization initiator, and emulsifier were changed as shown in Table 1. Copolymer latex (1-2
) to (1-10) and comparative copolymer latex (I
-11) to (1-17) were obtained. In addition, in the copolymer latex (1-10), the first stage polymerization was carried out for 6 hours,
This example differs from Example 1 in that the second stage polymerization was carried out over 2 hours.
これらの共重合体ラテックスを用い、実施例１と同様に
して、紙塗被組成物を調整し、その性能を評価した。Using these copolymer latexes, paper coating compositions were prepared in the same manner as in Example 1, and their performance was evaluated.
結果を表２に示す。The results are shown in Table 2.
実施例１１
１００１の耐圧容器に、表３に示すように、１段目の単
量体混合物としてイタコン酸２部、アクリル酸１部、ブ
タジェン１０部、スチレン１１部、メタクリル酸メチル
５部およびアクリロニトリル３部を仕込み、さらに水１
５０部、タービノーレン０．１部、ｔ−ドデシルメルカ
プタン０．１部、ドデシルベンゼンスルホン酸ナトリウ
ム０．２部および過硫酸カリウム１．０部を仕込んだ後
、窒素気流中で温度７０℃で２時間重合した。次に、２
段目の単量体混合物としてブタジェン１５部、スチレン
４４部、メタクリル酸メチル５部およびアクリロニトリ
ル３部、ならびにターピノーレン０．１部およびｔ−ド
デシルメルカプタン０．１部を８時間かけて連続的に添
加して重合を行なった。その後、重合を完結させるため
、さらに３時間反応を継続し重合添加率９８％で重合を
終了した。Example 11 As shown in Table 3, 2 parts of itaconic acid, 1 part of acrylic acid, 10 parts of butadiene, 11 parts of styrene, 5 parts of methyl methacrylate, and acrylonitrile were added to a 1001 pressure-resistant container as shown in Table 3. Prepare 3 parts and add 1 part of water.
After adding 50 parts of Turbinolene, 0.1 part of terbinolene, 0.1 part of t-dodecylmercaptan, 0.2 parts of sodium dodecylbenzenesulfonate and 1.0 part of potassium persulfate, the mixture was heated at 70°C for 2 hours in a nitrogen stream. Polymerized. Next, 2
Continuously add 15 parts of butadiene, 44 parts of styrene, 5 parts of methyl methacrylate, and 3 parts of acrylonitrile as a monomer mixture in the step, as well as 0.1 part of terpinolene and 0.1 part of t-dodecylmercaptan over 8 hours. Polymerization was carried out. Thereafter, in order to complete the polymerization, the reaction was continued for an additional 3 hours, and the polymerization was completed at a polymerization addition rate of 98%.
その後、実施例１と同様にして、共重合体ラテックス（
ロー１）を得た。Thereafter, in the same manner as in Example 1, the copolymer latex (
Low 1) was obtained.
次に、この共重合体ラテックスを用い、実施例１と同様
にして、紙塗被組成物を調製した。Next, a paper coating composition was prepared in the same manner as in Example 1 using this copolymer latex.
共重合体ラテックスのゲル含量の測定および紙塗被組成
物の特性評価を実施例１と同様にして行なった。Measurement of the gel content of the copolymer latex and evaluation of the properties of the paper coating composition were carried out in the same manner as in Example 1.
結果をそれぞれ表３および表４に示す。The results are shown in Tables 3 and 4, respectively.
実施例１２〜１６、比較例８〜１４
実施例１０において、単量体混合物、重合連鎖移動剤、
重合開始剤および乳化剤を表３に示すように変更した以
外は、実施例１０と同様にして共重合体ラテックス（Ｉ
Ｉ−２）〜（ＩＩ−６）および比較用共重合体ラテック
ス（ｎ−７）〜（■−１３）を得た。なお、共重合体ラ
テックス（ＩＩ−６）においては、１段目の重合を６時
間、２段目の重合を２時間かけた点で、実施例１１と異
なる。Examples 12 to 16, Comparative Examples 8 to 14 In Example 10, the monomer mixture, the polymerized chain transfer agent,
A copolymer latex (I
I-2) to (II-6) and comparative copolymer latexes (n-7) to (■-13) were obtained. The copolymer latex (II-6) differs from Example 11 in that the first stage polymerization took 6 hours and the second stage polymerization took 2 hours.
これら共重合体ラテックスを用い、実施例１１と同様に
して、紙塗被組成物を調製し、その性能を評価した。Paper coating compositions were prepared using these copolymer latexes in the same manner as in Example 11, and their performance was evaluated.
結果を表４に示す。The results are shown in Table 4.
（発明の効果）
本発明の紙塗被組成物は、接着強度および耐ブリスター
性がともに一段と優れている。このため、本発明の紙塗
被組成物は、コート紙、特にオフセット輪転印刷用コー
ト紙の製造に好適に使用することができる。(Effects of the Invention) The paper coating composition of the present invention has even better adhesive strength and blister resistance. Therefore, the paper coating composition of the present invention can be suitably used for producing coated paper, particularly coated paper for rotary offset printing.
Claims (1)
スを含有する紙塗被組成物において、該共重合体ラテッ
クスが、 （ａ）共役ジエン系単量体 １０〜６０重量部 （ｂ）エチレン系不飽和単量体 ３０〜８９．５重量部 （ｃ）エチレン系不飽和カルボン酸単量体 ０．５〜１０重量部 からなる単量体混合物（合計１００重量部）を、該混合
物１００重量部当り、α−メチルスチレンダイマー２〜
１００重量％と他の重合連鎖移動剤９８〜０重量％とか
らなる重合連鎖移動剤０．３〜１０重量部の存在下にお
いて、水性媒体中で乳化重合して得られる共重合体ラテ
ックスであることを特徴とする紙塗被組成物。 （２）顔料およびバインダーとしての共重合体ラテック
スを含有する紙塗被組成物において、該共重合体ラテッ
クスが、 （ａ）共役ジエン系単量体 １０〜６０重量部 （ｂ）エチレン系不飽和単量体 ３０〜８９．５重量部 （ｃ）エチレン系不飽和カルボン酸単量体 ０．５〜１０重量部 からなる単量体混合物（１００重量部）を、該混合物１
００重量部当り、（イ）ターピノーレン、ａ−テルピネ
ン、γ−テルピネンおよびジペンテンから選ばれる少な
くとも１種の化合物５〜９５重量％と（ロ）アルキルメ
ルカプタン類、四塩化炭素、キサントゲンジスルフィド
類およびチウラムジスルフィド類から選ばれる少なくと
も１種の化合物９５〜５重量％とからなる重合連鎖移動
剤０．３〜１０重量部の存在下において、水性媒体中で
乳化重合して得られる共重合体ラテックスであることを
特徴とする紙塗被組成物。Scope of Claims: (1) A paper coating composition containing a pigment and a copolymer latex as a binder, wherein the copolymer latex contains (a) 10 to 60 parts by weight of a conjugated diene monomer ( b) 30 to 89.5 parts by weight of an ethylenically unsaturated monomer (c) 0.5 to 10 parts by weight of an ethylenically unsaturated carboxylic acid monomer (100 parts by weight in total), α-methylstyrene dimer 2 to 100 parts by weight of the mixture
It is a copolymer latex obtained by emulsion polymerization in an aqueous medium in the presence of 0.3 to 10 parts by weight of a polymer chain transfer agent consisting of 100 weight % and 98 to 0 weight % of another polymer chain transfer agent. A paper coating composition characterized by: (2) In a paper coating composition containing a pigment and a copolymer latex as a binder, the copolymer latex contains (a) 10 to 60 parts by weight of a conjugated diene monomer (b) ethylenically unsaturated A monomer mixture (100 parts by weight) consisting of 30 to 89.5 parts by weight of a monomer (c) and 0.5 to 10 parts by weight of an ethylenically unsaturated carboxylic acid monomer is added to the mixture 1
00 parts by weight, (a) 5 to 95 wt% of at least one compound selected from terpinene, a-terpinene, γ-terpinene, and dipentene; and (b) alkyl mercaptans, carbon tetrachloride, xanthogen disulfides, and thiuram disulfide. It is a copolymer latex obtained by emulsion polymerization in an aqueous medium in the presence of 0.3 to 10 parts by weight of a polymer chain transfer agent consisting of 95 to 5% by weight of at least one compound selected from the following. A paper coating composition characterized by:
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1-169142 | 1989-06-30 | ||
| JP16914289 | 1989-06-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03113096A true JPH03113096A (en) | 1991-05-14 |
| JP2555294B2 JP2555294B2 (en) | 1996-11-20 |
Family
ID=15881066
Family Applications (5)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1273003A Expired - Fee Related JP2555294B2 (en) | 1989-06-30 | 1989-10-20 | Paper coating composition |
| JP1320952A Expired - Lifetime JP2541324B2 (en) | 1989-06-30 | 1989-12-11 | Gravure printing paper coating composition |
| JP1323482A Expired - Lifetime JP2792165B2 (en) | 1989-06-30 | 1989-12-13 | Method for producing copolymer latex |
| JP32347989A Expired - Lifetime JPH0776324B2 (en) | 1989-06-30 | 1989-12-13 | Composition for coating |
| JP1327973A Expired - Lifetime JP2792166B2 (en) | 1989-06-30 | 1989-12-18 | Method for producing copolymer latex |
Family Applications After (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1320952A Expired - Lifetime JP2541324B2 (en) | 1989-06-30 | 1989-12-11 | Gravure printing paper coating composition |
| JP1323482A Expired - Lifetime JP2792165B2 (en) | 1989-06-30 | 1989-12-13 | Method for producing copolymer latex |
| JP32347989A Expired - Lifetime JPH0776324B2 (en) | 1989-06-30 | 1989-12-13 | Composition for coating |
| JP1327973A Expired - Lifetime JP2792166B2 (en) | 1989-06-30 | 1989-12-18 | Method for producing copolymer latex |
Country Status (1)
| Country | Link |
|---|---|
| JP (5) | JP2555294B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07166496A (en) * | 1993-12-14 | 1995-06-27 | Sumitomo Dow Ltd | Double coated paper |
| JP2002348309A (en) * | 2001-05-28 | 2002-12-04 | Mitsubishi Rayon Co Ltd | Process for producing methacrylic resin composition and methacrylic resin molding |
| JP4606517B1 (en) * | 2010-09-03 | 2011-01-05 | 香代子 吉田 | Shelf lifting device |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2777620B2 (en) * | 1991-07-15 | 1998-07-23 | 旭化成工業株式会社 | Diene polymer latex |
| JPH0616708A (en) * | 1992-04-28 | 1994-01-25 | Sumitomo Dow Ltd | Production of polymer latex |
| US6784253B2 (en) * | 2001-07-24 | 2004-08-31 | General Electric Company | Enhanced polymerization process |
| DE10148511A1 (en) * | 2001-10-01 | 2003-04-10 | Basf Ag | Process for the preparation of aqueous styrene-butadiene polymer dispersions-IV |
| AU2003223117A1 (en) | 2002-04-23 | 2003-11-10 | Nippon Shokubai Co., Ltd. | Emulsion polymer resin composition |
| JP5162115B2 (en) * | 2005-08-31 | 2013-03-13 | 関西ペイント株式会社 | Method for producing granular gel and coating composition containing the granular gel |
| JP2009150012A (en) * | 2007-12-20 | 2009-07-09 | Daio Paper Corp | Coated paper for gravure printing |
| WO2010001964A1 (en) | 2008-07-04 | 2010-01-07 | 旭化成ケミカルズ株式会社 | Copolymer latex and method for producing the same |
| KR102122440B1 (en) | 2017-08-30 | 2020-06-12 | 주식회사 엘지화학 | Method for preparing conjugated diene copolymer, conjugated diene copolymer by prepared the method and rubber composition comprising the copolymer |
| RU2676609C1 (en) * | 2017-12-12 | 2019-01-09 | Публичное акционерное общество "СИБУР Холдинг" | Method of obtaining latex |
| CN116157425A (en) * | 2020-06-05 | 2023-05-23 | 日本瑞翁株式会社 | Acrylic rubber bag excellent in storage stability and Banbury processability |
| CN116057075A (en) * | 2020-06-05 | 2023-05-02 | 日本瑞翁株式会社 | Acrylic rubber sheet excellent in roll processability and banbury processability |
| JPWO2021246515A1 (en) * | 2020-06-05 | 2021-12-09 | ||
| JPWO2021261214A1 (en) * | 2020-06-23 | 2021-12-30 |
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- 1989-12-13 JP JP1323482A patent/JP2792165B2/en not_active Expired - Lifetime
- 1989-12-13 JP JP32347989A patent/JPH0776324B2/en not_active Expired - Lifetime
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| JPH07166496A (en) * | 1993-12-14 | 1995-06-27 | Sumitomo Dow Ltd | Double coated paper |
| JP2002348309A (en) * | 2001-05-28 | 2002-12-04 | Mitsubishi Rayon Co Ltd | Process for producing methacrylic resin composition and methacrylic resin molding |
| JP4606517B1 (en) * | 2010-09-03 | 2011-01-05 | 香代子 吉田 | Shelf lifting device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2541324B2 (en) | 1996-10-09 |
| JP2792165B2 (en) | 1998-08-27 |
| JP2792166B2 (en) | 1998-08-27 |
| JPH03109470A (en) | 1991-05-09 |
| JPH0776324B2 (en) | 1995-08-16 |
| JP2555294B2 (en) | 1996-11-20 |
| JPH03109450A (en) | 1991-05-09 |
| JPH03113097A (en) | 1991-05-14 |
| JPH03109451A (en) | 1991-05-09 |
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