JPH03109450A - Production of copolymer latex - Google Patents
Production of copolymer latexInfo
- Publication number
- JPH03109450A JPH03109450A JP32348289A JP32348289A JPH03109450A JP H03109450 A JPH03109450 A JP H03109450A JP 32348289 A JP32348289 A JP 32348289A JP 32348289 A JP32348289 A JP 32348289A JP H03109450 A JPH03109450 A JP H03109450A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polymerization
- copolymer latex
- coating
- paper
- 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
- 229920001577 copolymer Polymers 0.000 title claims abstract description 60
- 229920000126 latex Polymers 0.000 title claims abstract description 60
- 239000004816 latex Substances 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 49
- -1 diene compound Chemical class 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 32
- YHQGMYUVUMAZJR-UHFFFAOYSA-N α-terpinene Chemical compound CC(C)C1=CC=C(C)CC1 YHQGMYUVUMAZJR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 13
- YKFLAYDHMOASIY-UHFFFAOYSA-N γ-terpinene Chemical compound CC(C)C1=CCC(C)=CC1 YKFLAYDHMOASIY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 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 claims abstract description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract 3
- 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 15
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 12
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 6
- 229940125773 compound 10 Drugs 0.000 claims description 5
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 claims description 5
- 150000001993 dienes Chemical class 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 2
- 230000001804 emulsifying effect Effects 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 39
- 239000011248 coating agent Substances 0.000 abstract description 36
- 239000012986 chain transfer agent Substances 0.000 abstract description 26
- 239000008199 coating composition Substances 0.000 abstract description 26
- 239000011087 paperboard Substances 0.000 abstract description 14
- 229920000642 polymer Polymers 0.000 abstract description 11
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 abstract description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical class CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 abstract description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 abstract 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000000123 paper Substances 0.000 description 48
- 230000001070 adhesive effect Effects 0.000 description 24
- 239000000853 adhesive Substances 0.000 description 23
- 238000007639 printing Methods 0.000 description 19
- 230000007423 decrease Effects 0.000 description 18
- 239000000203 mixture Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000049 pigment Substances 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 239000011247 coating layer Substances 0.000 description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229960002447 thiram Drugs 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002985 plastic film Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000002019 disulfides Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000012488 sample solution Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 206010016807 Fluid retention Diseases 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000001023 inorganic pigment Substances 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 229930006978 terpinene Natural products 0.000 description 3
- 150000003507 terpinene derivatives Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-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 compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 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
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- 150000008360 acrylonitriles 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 persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000012736 aqueous medium 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
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical class NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 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
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000002036 drum drying Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 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
- KULVDYSXKPYRGX-UHFFFAOYSA-N 2,3,4,5-tetrahydroxypentyl prop-2-enoate Chemical compound OCC(O)C(O)C(O)COC(=O)C=C KULVDYSXKPYRGX-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
- QNDGQRJVVZJMJO-UHFFFAOYSA-N 2-(2-undecyl-4,5-dihydroimidazol-1-yl)ethanol Chemical class CCCCCCCCCCCC1=NCCN1CCO QNDGQRJVVZJMJO-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 class CCCCCCCCCCCCCCCCCC[N+](C)(C)CC([O-])=O HVYJSOSGTDINLW-UHFFFAOYSA-N 0.000 description 1
- BKTMEKOLXCZRFW-UHFFFAOYSA-N 3-(octadecylamino)propanoic acid Chemical class CCCCCCCCCCCCCCCCCCNCCC(O)=O BKTMEKOLXCZRFW-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- YGTVWCBFJAVSMS-UHFFFAOYSA-N 5-hydroxypentyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCO YGTVWCBFJAVSMS-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 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
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 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
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 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
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229940000635 beta-alanine Drugs 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 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
- 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
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- MRUAUOIMASANKQ-UHFFFAOYSA-O carboxymethyl-[3-(dodecanoylamino)propyl]-dimethylazanium Chemical class 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
- 239000002738 chelating agent Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- PGAXJQVAHDTGBB-UHFFFAOYSA-N dibutylcarbamothioylsulfanyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SSC(=S)N(CCCC)CCCC PGAXJQVAHDTGBB-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 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
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- ORTRWBYBJVGVQC-UHFFFAOYSA-N hexadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCS ORTRWBYBJVGVQC-UHFFFAOYSA-N 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
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient 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
- 229940094506 lauryl betaine Drugs 0.000 description 1
- 229910052744 lithium Inorganic materials 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 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
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035515 penetration Effects 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
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920006267 polyester film 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
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000002791 soaking Methods 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
- 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
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 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
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical compound CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 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
- 239000013053 water resistant agent Substances 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、特定の重合連鎖移動剤の存在下に、特定の単
量体を乳化重合する共重合体ラテックスの製造方法に関
し、さらに詳しくは高濃度塗工における塗工作業性に優
れ、微細凝固物の発生が少なく、かつ機械的安定性、接
着強度、印刷光沢。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a copolymer latex in which a specific monomer is emulsion polymerized in the presence of a specific polymerization chain transfer agent. Excellent coating workability in high-concentration coating, little generation of fine coagulation, mechanical stability, adhesive strength, and printing gloss.
着肉性、糊付性およびブリスターパック適性に優れ、板
紙用あるいはゲートロール塗工用の紙塗被組成物などに
有用な他、カーペットのパッキング材や接着剤などにも
使用できる共重合体ラテックスの製造方法に関する。A copolymer latex with excellent adhesion, adhesive properties, and suitability for blister packs, which is useful in paper coating compositions for paperboard and gate roll coating, and can also be used as carpet packing materials and adhesives. Relating to a manufacturing method.
［従来の技術］
近年、印刷物の急増によって、特にオフセット印刷での
高速印刷化の傾向がますます強まり、オフセット用顔料
塗被紙および顔料バインダーには、次のような性質が要
求されるようになっている。[Prior Art] In recent years, with the rapid increase in the number of printed materials, there has been an increasing trend towards high-speed printing, especially in offset printing, and the following properties are now required of pigment-coated papers and pigment binders for offset printing. It has become.
その一つは、印刷時の顔料塗被紙表面に対する機械的な
力に抗して顔料の脱落および塗被層の基紙からの剥離が
起こらずに美麗な印刷を可能にする性質である。このた
めには、顔料粒子相互ならびに顔料塗被層とその支持体
である基紙との間が強固に接着される必要がある。この
ような紙表面の破壊は印刷速度が大きくなればなるほど
、また、重ね刷り回数が多くなればなるほど激しくなり
、これに耐える顔料塗被紙が要求され、そのためには接
着強度の優れた顔料バインダーが要求される。One of these properties is that it resists the mechanical force applied to the surface of pigment-coated paper during printing, allowing beautiful printing without causing the pigment to fall off or the coating layer to peel from the base paper. For this purpose, it is necessary to firmly adhere the pigment particles to each other and the pigment coating layer to the base paper that is its support. Such damage to the paper surface becomes more severe as the printing speed increases and the number of overprints increases, so pigment-coated paper that can withstand this is required, and for this purpose pigment binders with excellent adhesive strength are required. is required.
さらに、板紙は包装用に用いられるためブリスターバッ
ク適性（品物を板紙とプラスチックフィルムまたはシー
トで挾んだパッケージにおける、板紙とプラスチックフ
ィルムまたはシートとの接着性）、糊付性（紙と紙との
糊付性）などの後加工性能が求められるが、従来のカル
ボキシル化スチレン／ブタジェン系ゴムラテックスは、
これらの点に関しても十分満足のいくものではながった
。Furthermore, since paperboard is used for packaging, it has blister-back suitability (adhesiveness between paperboard and plastic film or sheet in a package where an item is sandwiched between paperboard and plastic film or sheet), and sizing property (adhesiveness between paperboard and plastic film or sheet). However, conventional carboxylated styrene/butadiene rubber latex is
These points were also not fully satisfactory.
また、近年、塗工紙は各種雑誌類、包装紙、宣伝用印刷
紙等の高級化指向に対応して従来の塗工紙に比べ塗工量
の少くない軽量コート紙あるいは微量コート紙が急速に
普及している。この軽量塗工あるいは微量塗工方法とし
ては、ゲートロール塗工方法が採用されている。ゲート
ロール塗工の利点としては（１）紙の両面に同時塗工が
可能であること、（２）高濃度な塗工液・の高速塗工が
可能であること、（３）乾燥エネルギーが少なくてすむ
こと、（４）塗工液の原紙内部への浸透が少なく、紙表
面での歩留りが高いため、不透明度の高い平滑性に優れ
た塗工紙が得られることなどを挙げることができる。In addition, in recent years, coated paper has become increasingly popular for use in magazines, wrapping paper, advertising printing paper, etc., and lightweight coated paper or trace coated paper, which requires less coating than conventional coated paper, has rapidly become available. It is widespread. A gate roll coating method is adopted as this lightweight coating or small amount coating method. The advantages of gate roll coating are (1) simultaneous coating on both sides of the paper, (2) high-speed coating of highly concentrated coating liquid, and (3) low drying energy. (4) The penetration of the coating liquid into the inside of the base paper is small and the yield on the paper surface is high, so coated paper with high opacity and excellent smoothness can be obtained. can.
しかし、従来の一般的な共重合体ラテックスを顔料バイ
ンダーとして用いた塗被組成物をゲートロール塗工に使
用した場合、インナーゲートロールとアウターゲートロ
ール間あるいはアプリケータロールとインナーゲートロ
ール間で塗被組成物に強い剪断力がかかるため、ガムア
ップ現象が発生してロール表面をいためたり、あるいは
凝固物がロールの表面に付着して操業性およびコート層
の平滑性を低下させることがある。また、保水性が低す
ぎると、各ロール間で固着して操業性を著しく低下させ
る。一方、ゲートロール塗工後の塗工紙はドラム乾燥が
行われるのが一般的であり、紙塗被組成物の保水性が高
すぎるとドラム表面を汚し、またコート層表面の平滑性
も低下する。コート層に粘着性があると、ドラム表面に
付着してドラム表面を汚し、その結果、操業性が低下し
、さらにはコート層の平滑性を低下させる。However, when a coating composition using a conventional general copolymer latex as a pigment binder is used for gate roll coating, there is a gap between the inner gate roll and the outer gate roll or between the applicator roll and the inner gate roll. Since a strong shearing force is applied to the composition, a gum-up phenomenon may occur and damage the roll surface, or coagulum may adhere to the roll surface, reducing operability and the smoothness of the coat layer. In addition, if the water retention is too low, it will stick between the rolls, significantly reducing operability. On the other hand, coated paper after gate roll coating is generally drum-dried, and if the water retention of the paper coating composition is too high, it will stain the drum surface and also reduce the smoothness of the coated layer surface. do. If the coating layer is sticky, it will adhere to the drum surface and stain the drum surface, resulting in reduced operability and further reduced smoothness of the coating layer.
ゲートロール塗工は、軽量塗工あるいは微量塗工が可能
であるが、コート層が薄いと印刷光沢が低くなるという
問題がある。従って、ゲートロール塗工の塗被組成物は
、従来のブレード塗工における塗被組成物に比較して一
段と優れた印刷光沢が求められる。しかし、従来のカル
ボキシル化ブタジェン系ゴムラテックスを顔料バインダ
ーとする塗被組成物は、ゲートロール塗工に使用する場
合、コート層の平滑性、印刷光沢、接着強度、塗工乾燥
工程の操業性において、十分満足のいくものでなかった
。Gate roll coating allows for lightweight coating or small amount coating, but there is a problem in that if the coating layer is thin, the printing gloss will be low. Therefore, coating compositions for gate roll coating are required to have even better printing gloss than coating compositions for conventional blade coating. However, when using conventional coating compositions using carboxylated butadiene-based rubber latex as a pigment binder for gate roll coating, there are problems with the smoothness of the coating layer, printing gloss, adhesive strength, and operability of the coating drying process. , was not completely satisfactory.
さらに、最近は生産性の向上、高品質を得るために塗工
速度が上がり、その他の塗工条件が一段と厳しくなり、
これに対応するために、バインダーとして用いる共重合
体ラテックスとして、微細凝固物の含有量が少なくかつ
機械的安定性の優れた共重合体ラテックスが求められて
いるが、従来の共重合体ラテックスではこの点について
も十分でなかった。Furthermore, recently, coating speeds have increased in order to improve productivity and obtain high quality, and other coating conditions have become even more stringent.
In order to cope with this, there is a need for a copolymer latex that has a low content of fine coagulates and has excellent mechanical stability as a copolymer latex used as a binder, but conventional copolymer latex This was also not enough.
［発明が解決しようとする問題点］
本発明は、上記問題点を解決し、高濃度塗工による塗被
紙の製造において優れた塗工作業性を示し、さらには優
れた接着強度、印刷光沢２着肉性および糊付性、ブリス
ターパック適性等の後加工性を有する板紙塗工に好適な
、がっまたコート層表面の平滑性、印刷光沢、接着強度
に優れ、塗工時において塗布液のガムアップ現象および
ドラム乾燥時のドラム表面の汚染を生じることのない操
業性に優れたゲートロール塗工に好適な紙塗被組成物を
提供することを目的とするものである。[Problems to be Solved by the Invention] The present invention solves the above problems, exhibits excellent coating workability in the production of coated paper by high-concentration coating, and furthermore provides excellent adhesive strength and printing gloss. 2 Suitable for paperboard coating with post-processing properties such as ink adhesion, sizing properties, and suitability for blister packs.It has excellent surface smoothness, printing gloss, and adhesive strength of the bulk coating layer. The object of the present invention is to provide a paper coating composition suitable for gate roll coating, which has excellent operability and does not cause gum-up phenomenon or contamination of the drum surface during drum drying.
［問題点を解決するための手段］
本発明の第１の発明は、
（ａ）共役ジエン系化合物 １０〜６０重量％、（
ｂ）芳香族ビニル化合物 １０〜６５重量％、（ｅ
）アミド系ビニル化合物およびヒドロキシ（メタ）アク
リートから選ばれる少なくとも１種０．１〜１０重量％
、
（ｄ）エチレン系不飽和カルボン酸
０．５〜１０重量％、
（ｅ）他の共重合可能な単量体 ０〜４０重量％、を
含む単量体を、α−メチルスチレンダイマーの存在下、
乳化重合することを特徴とする共重合体ラテックスの製
造方法に関する。[Means for solving the problems] The first invention of the present invention comprises: (a) 10 to 60% by weight of a conjugated diene compound;
b) Aromatic vinyl compound 10-65% by weight, (e
) 0.1 to 10% by weight of at least one selected from amide vinyl compounds and hydroxy (meth)acrylates
(d) 0.5 to 10% by weight of an ethylenically unsaturated carboxylic acid, and (e) 0 to 40% by weight of other copolymerizable monomers in the presence of α-methylstyrene dimer. under,
The present invention relates to a method for producing a copolymer latex characterized by emulsion polymerization.
本発明の第２の発明は、
（ａ）共役ジエン系化合物 １０〜６０重量％、（
ｂ）芳香族ビニル化合物 １０〜６５重量％、（ｃ
）アミド系ビニル化合物およびヒドロキシ（メタ）アク
リートから選ばれる少なくとも１種０．１〜１０重量％
、
（ｄ）エチレン系不飽和カルボン酸
０．５〜１０重量％、
（ｅ）他の共重合可能な単量体 ０〜４０重量％、を
含む単量体を、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
種の化合物の存在下、乳化重合することを特徴とする共
重合体ラテックスの製造方法に関する。The second invention of the present invention is as follows: (a) conjugated diene compound 10 to 60% by weight, (
b) Aromatic vinyl compound 10-65% by weight, (c
) 0.1 to 10% by weight of at least one selected from amide vinyl compounds and hydroxy (meth)acrylates
, (d) ethylenically unsaturated carboxylic acid 0.5 to 10% by weight, (e) other copolymerizable monomers 0 to 40% by weight, and turbinolene, α-terpinene, γ −
At least one selected from terpinene and dipentene
The present invention relates to a method for producing a copolymer latex, which is characterized by carrying out emulsion polymerization in the presence of a seed compound.
以下に、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（ａ）共
役ジエン系化合物の代表例としては、ブタジェン、イソ
プレン、２−クロル−１，３−ブタジェン等を挙げるこ
とができる。この成分（ａ）の使用割合は、共重合体に
適度な弾性および膜の硬さを付与するために１０〜６０
重量％の範囲になくてはならず、好ましくは２０〜５５
重量％、さらに好ましくは２５〜５０重量％である。成
分（ａ）の使用割合が１０重量％未満では得られる共重
合体は硬くてもろく、一方６０重量％を越えると柔らか
くなりすぎ、耐水性が低下し、粘着性が増加するので乾
燥機のドラム汚染が発生し、操業性が低下する。Representative examples of the conjugated diene compound (a) used in the production of the copolymer latex of the present invention include butadiene, isoprene, 2-chloro-1,3-butadiene, and the like. The proportion of component (a) used is 10 to 60% in order to impart appropriate elasticity and film hardness to the copolymer.
Must be in the range of % by weight, preferably 20-55
% by weight, more preferably 25 to 50% by weight. If the proportion of component (a) used is less than 10% by weight, the resulting copolymer will be hard and brittle, while if it exceeds 60% by weight, it will become too soft, its water resistance will decrease, and its tackiness will increase, resulting in dryer drums. Contamination occurs and operational efficiency is reduced.
（ｂ）芳香族ビニル化合物の代表例としては、スチレン
、α−メチルスチレン、ビニルトルエン。(b) Typical examples of aromatic vinyl compounds include styrene, α-methylstyrene, and vinyltoluene.
ｐ−メチルスチレン等を挙げることができる。この成分
（ｂ）の使用割合は１０〜６５重量％、好ましくは３０
〜６０重量％である。成分（ｂ）の使用割合が１０重量
％未満では得られる共重合体の耐水性、接着強度が劣り
、一方６５重量％を越えると重合安定性が低下し、塗工
操業性が低下する。Examples include p-methylstyrene. The proportion of component (b) used is 10 to 65% by weight, preferably 30% by weight.
~60% by weight. If the proportion of component (b) used is less than 10% by weight, the resulting copolymer will have poor water resistance and adhesive strength, while if it exceeds 65% by weight, polymerization stability will decrease and coating operability will decrease.
（ｃ）アミド系ビニル化合物の代表例としては、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、ジアセトンアクリルアミド、クロトンアミド、
イタコンアミド、メチルイタコンアミド、マレイン酸モ
ノアミド、メチレンジアクリルアミド、ジメチルアクリ
ルアミド、ジエチルアクリルアミド、ジメチルメタクリ
ルアミド、ジエチルメタクリルアミド等のジアルキル（
メタ）アクリルアミド等が挙げられ、このうちアクリル
アミド、メタクリルアミド、Ｎ−メチロールアクリルア
ミド、Ｎ、Ｎ’−ジメチルアクリルアミドが好ましい。(c) Representative examples of amide vinyl compounds include acrylamide, methacrylamide, N-methylolacrylamide, diacetone acrylamide, crotonamide,
Dialkyl (
Examples include meth)acrylamide, among which acrylamide, methacrylamide, N-methylolacrylamide, and N,N'-dimethylacrylamide are preferred.
ヒドロキシ（メタ）アクリレートは、ヒドロキシ含有ア
クリレートまたはメタクリレートであり、その代表例と
しては、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、３〜ヒドロキシプロピルアクレ
ート、３−ヒドロキシプロピルメタクリレート、２．３
．４．５．６−ペンタヒドロキシへキシルアクリレート
、２，３゜４．５．６−ペンタヒドロキシへキシルメタ
クリレート、２，３．４．５−テトラヒドロキシペンチ
ルアクリレート、２，３，４．５−テトラヒドロキシペ
ンチルメタクリレート等が挙げられ、このうち２−ヒド
ロキシエチルアクリレート、２〜ヒドロキシエチルメタ
クリレートが好ましく使用される。Hydroxy (meth)acrylate is a hydroxy-containing acrylate or methacrylate, typical examples of which are 2-hydroxyethyl acrylate, 2-hydroxy methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2.3
．． 4.5.6-pentahydroxyhexyl acrylate, 2,3゜4.5.6-pentahydroxyhexyl methacrylate, 2,3.4.5-tetrahydroxypentyl acrylate, 2,3,4.5-tetra Examples include hydroxypentyl methacrylate, among which 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferably used.
成分（ｃ）としては、上記アミド系ビニル単量体とヒド
ロキシ（メタ）アクリレートから選ばれた少なくとも１
種の化合物が使用されるが、もちろんアミド系ビニル化
合物とヒドロキシ（メタ）アクリレートをそれぞれ単独
または組合せて使用してもよく、またそれぞれ２種以上
を組合せて使用してもよい。特に、成分（ｃ）としては
、アミド系ビニル化合物を単独またはその２種以上から
なる混合物として使用するのが好ましい。Component (c) is at least one selected from the above amide vinyl monomers and hydroxy (meth)acrylates.
Of course, amide vinyl compounds and hydroxy (meth)acrylates may be used alone or in combination, or two or more of them may be used in combination. In particular, as component (c), it is preferable to use an amide vinyl compound alone or as a mixture of two or more thereof.
成分（ｃ）の使用割合は、０．１〜１０重量％、好まし
くは１〜８重量％である。成分（ｃ）の使用割合が０．
１重量％未満では、適切な粘度が得られず、塗工操業性
が劣り、ブリスターパック適性。The proportion of component (c) used is 0.1 to 10% by weight, preferably 1 to 8% by weight. The usage ratio of component (c) is 0.
If it is less than 1% by weight, an appropriate viscosity cannot be obtained, coating operability is poor, and blister pack suitability is not achieved.
糊付性等の後加工性能の改良効果ならびに印刷光沢が十
分ではなく、一方、１０重量％を越えると、組成物の粘
度が高くなりすぎて操業性が低下するので好ましくない
。The effect of improving post-processing performance such as pastiness and printing gloss is not sufficient. On the other hand, if it exceeds 10% by weight, the viscosity of the composition becomes too high and the operability deteriorates, which is not preferable.
（ｄ）エチレン系不飽和カルボン酸の代表例としては、
アクリル酸、メタクリル酸、クロトン酸。(d) Representative examples of ethylenically unsaturated carboxylic acids include:
Acrylic acid, methacrylic acid, crotonic acid.
マレイン酸、フマール酸２イタコン酸等のモノまたはジ
カルボン酸を挙げることができる。さらに、ジカルボン
酸無水物も使用することができる。成分（ｄ）の使用割
合は０．５〜１０重量％、好ましくは１〜７重量％であ
る。成分（ｄ）の使用割合が０．５重量％未満では、得
られる共重合体の接着強度が低下し、機械的安定性が低
くなるので操業性が低下し、一方、１０重量％を越える
とラテックスの粘度が高くなりすぎ、ハンドリングが難
しくなる。Mention may be made of mono- or dicarboxylic acids such as maleic acid, fumaric acid and diitaconic acid. Furthermore, dicarboxylic acid anhydrides can also be used. The proportion of component (d) used is 0.5 to 10% by weight, preferably 1 to 7% by weight. If the proportion of component (d) used is less than 0.5% by weight, the adhesive strength of the resulting copolymer will decrease, and the mechanical stability will decrease, resulting in a decrease in operability; on the other hand, if it exceeds 10% by weight, The viscosity of the latex becomes too high, making it difficult to handle.
本発明においては、さらに前記成分（ａ）〜（ｄ）と共
重合可能なその他の単量体（以下、「成分（ｅ）」とい
う）を使用することもでき、例えばエチレン系不飽和カ
ルボン酸エステル、シアン化ビニル化合物等を挙げるこ
とができる。In the present invention, other monomers copolymerizable with the components (a) to (d) (hereinafter referred to as "component (e)") may also be used, such as ethylenically unsaturated carboxylic acid. Examples include esters and vinyl cyanide compounds.
エチレン系不飽和カルボン酸エステルの具体例としては
、メチルアクリレート、メチルメタクリレート、エチル
アクレート、エチルメタクリレート、ブチルアクリレー
ト、ブチルメタクリレート等のアルキルアクリレートお
よびアルキルメタクリレート等であり、シアン化ビニル
化合物の具体例としては、アクリロニトリル、メタクリ
レートリル等がある。これらのうち、メチルメタクリレ
ート、アクリロニトリルが好適に使用される。成分（ｅ
）の使用割合は０〜４０重量％、好ましくは５〜３０重
量％である。成分（ｅ）が４０重量％を越えると、上記
成分（ａ）〜（ｄ）の使用割合が規定範囲外となって、
本発明の目的を達成することはできない。Specific examples of ethylenically unsaturated carboxylic acid esters include alkyl acrylates and alkyl methacrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate; specific examples of vinyl cyanide compounds include Examples include acrylonitrile and methacrylate trile. Among these, methyl methacrylate and acrylonitrile are preferably used. Component (e
) is used in an amount of 0 to 40% by weight, preferably 5 to 30% by weight. If component (e) exceeds 40% by weight, the proportion of the components (a) to (d) used will be outside the specified range,
The purpose of the invention cannot be achieved.
本発明によって得られる共重合体ラテックスをゲートロ
ール塗工用塗被組成物のバインダーとして用いる場合に
は、（ｃ）成分としては少なくともアミド系ビニル化合
物を用いることが好ましく、従ってアミド系ビニル化合
物単独またはアミド系ビニル単量体とヒドロキシ（メタ
）アクリレートとを組合せて使用する。When the copolymer latex obtained by the present invention is used as a binder for a coating composition for gate roll coating, it is preferable to use at least an amide vinyl compound as the component (c), and therefore an amide vinyl compound alone. Alternatively, an amide vinyl monomer and hydroxy (meth)acrylate are used in combination.
本発明における共重合体ラテックスは、上記単量体を水
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
下に行う点にある。すなわち、本発明の第１の発明にお
いては、α−メチルスチレンダイマーの存在下、好まし
くはα−メチルスチレンダイマー１〜１００重量％と他
の重合連鎖移動剤９９〜０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２の発明においては、
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種の化合物の存
在下、好ましくは（Ａ）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１〜１００重量％と、（Ｂ）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９９〜０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。The copolymer latex in the present invention is obtained by emulsion polymerization of the above monomers in an aqueous medium, and the feature of the present invention is that this emulsion polymerization is carried out in the presence of a specific polymerization chain transfer agent. . That is, in the first aspect of the present invention, in the presence of an α-methylstyrene dimer, a polymerization chain preferably consisting of 1 to 100% by weight of α-methylstyrene dimer and 99 to 0% by weight of another polymerization chain transfer agent is formed. In the presence of a transfer agent, and in the second aspect of the present invention,
In the presence of at least one compound selected from terpinene, α-terpinene, γ-terpinene and dipentene, preferably (A) at least one compound selected from terpinene, α-terpinene, γ-terpinene and dipentene 1 to 100 Emulsion polymerization is carried out in the presence of a polymerization chain transfer agent consisting of 99% to 0% by weight of at least one compound selected from (B) alkyl mercaptans, carbon tetrachloride, xanthogen disulfides, and thiuram disulfides. .
これら第１の発明および第２の発明で使用する重合連鎖
移動剤について、以下に詳しく説明する。The polymer chain transfer agent used in the first invention and the second invention will be explained in detail below.
第１の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（１）という）は、α−メチルスチレンダ
イマーと必要に応じて用いられる他の重合連鎖移動剤と
からなる。The polymer chain transfer agent used in the first invention (hereinafter referred to as polymer chain transfer agent (1)) consists of an α-methylstyrene dimer and other polymer chain transfer agents used as necessary.
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−メチルスチレンポリマーを含
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、タービノ
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, turbinolene, 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、好ましくは１〜１００重量％、より好ましく
は３〜１００重量％、特に好ましくは５〜９５重量％で
ある。The proportion of α-methylstyrene dimer in the polymerization chain transfer agent (1) is preferably 1 to 100% by weight, more preferably 3 to 100% by weight, particularly preferably 5 to 95% by weight.
このα−メチルスチレンダイマーの割合が１重量％未満
では、微細凝固物が少なくかつ機械的安定性に優れた共
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 1% by weight, it is impossible to obtain a copolymer latex with few fine coagulums and excellent mechanical stability. 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、全単量体１００重量
部当り、通常０．０５〜２０重量部、好ましくは０．１
〜１０重量部、より好ましくは０．３〜７重量部である
。この重合連鎖移動剤（Ｉ）の使用量が０．０５重量部
未満では接着強度が劣り、一方２０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 usually 0.05 to 20 parts by weight, preferably 0.1 parts by weight per 100 parts by weight of total monomers.
~10 parts by weight, more preferably 0.3 to 7 parts by weight. If the amount of the polymer chain transfer agent (I) used is less than 0.05 parts by weight, the adhesive strength will be poor, while if it exceeds 20 parts by weight, the adhesive strength will decrease, which is not preferred.
なお、α−メチルスチレンダイマーの使用量については
、全単量体の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 0.1 to 5 parts by weight per 100 parts by weight of the total monomers.
次に、第２の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（ｎ）という）は、（Ａ）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（以下、「成
分（Ａ）」という）と、（Ｂ）必要に応じて用いられる
他の重合連鎖移動剤、好ましくは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（Ｂ）」という）とからなる。Next, the polymer chain transfer agent used in the second invention (hereinafter referred to as polymer chain transfer agent (n)) is (A) at least one compound selected from terbinolene, α-terpinene, γ-terpinene, and dipentene. (hereinafter referred to as "component (A)"), and (B) another polymerization chain transfer agent used as necessary, preferably at least one selected from alkyl mercaptans, carbon tetrachloride, xanthogen disulfides, and thiuram disulfides. It consists of one type of compound (hereinafter referred to as "component (B)").
成分（Ｂ）のアルキルメルカプタン類の具体例としては
、既述のアルキルメルカプタン類と同様の化合物を挙げ
ることができ、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 the same compounds as the alkyl mercaptans described above, and among these, t-dodecyl mercaptan is preferably used.
また、キサントゲンジスルフィド類およびチウラムジス
ルフィド類の具体例としては、既述のメルカプタン類お
よびチウラムジスルフィド類と同様の化合物を挙げるこ
とができる。Furthermore, specific examples of xanthogen disulfides and thiuram disulfides include compounds similar to the mercaptans and thiuram disulfides described above.
重合連鎖移動剤（ｎ）中の成分（Ａ）の割合は、好まし
くは１〜１００重量％、より好ましくは３〜１００重量
％、特に好ましくは５〜９５重量％である。成分（Ａ）
と成分（Ｂ）とを併用することにより、重合時におけ反
応性を高めることができる。The proportion of component (A) in the polymerization chain transfer agent (n) is preferably 1 to 100% by weight, more preferably 3 to 100% by weight, particularly preferably 5 to 95% by weight. Ingredient (A)
By using Component (B) and Component (B) together, reactivity can be increased during polymerization.
重合連鎖移動剤（ｎ）の使用量は、全単量体１００重量
部当り、通常０．０５〜２０重量部、好ましくは０．１
〜１０重量部、より好ましくは０．５〜７重量部である
。重合連鎖移動剤（ｎ）の使用量が０．０５重量部未満
では接着強度が劣り、また２０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 (n) used is usually 0.05 to 20 parts by weight, preferably 0.1 parts by weight, per 100 parts by weight of total monomers.
~10 parts by weight, more preferably 0.5 to 7 parts by weight. If the amount of the polymer chain transfer agent (n) used is less than 0.05 parts by weight, the adhesive strength will be poor, and if it exceeds 20 parts by weight, the adhesive strength will decrease, which is not preferred.
なお、成分（Ａ）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.
本発明においては、下記に示す特定な条件の多段重合法
によって共重合ラテックスを合成することが好ましい。In the present invention, it is preferable to synthesize the copolymer latex by a multi-stage polymerization method under the specific conditions shown below.
詳しくは、まず、前記単量体成分（ｃ）以外の成分から
なる単量体を全単量体の重量基準で、通常５〜４０重量
％、好ましくは１０〜３５重量％重合させて、好ましく
はガラス転移温度が５０℃以下、さらに好ましくは４０
℃以下の共重合体を得る。次いで、この共重合体の存在
下に、成分（ｃ）および成分（ｃ）以外の成分の残りか
らなる単量体を重合させて得られる。−段目の重合にお
け−る単量体重合割合が５重量％未満では接着強度が低
下して本発明の目的を達成できず、一方４０重量％を越
えると重合安定性が悪く好ましくない。また、−段目の
重合によって得られる重合体のガラス転移温度が５０℃
以下であゐと、組成物の塗被工程においてロール汚れ耐
性および塗工作業性に優れるので好ましい。Specifically, first, a monomer consisting of a component other than the monomer component (c) is polymerized in an amount of usually 5 to 40% by weight, preferably 10 to 35% by weight, based on the weight of all monomers. has a glass transition temperature of 50°C or less, more preferably 40°C.
A copolymer with a temperature below ℃ is obtained. Next, in the presence of this copolymer, a monomer consisting of component (c) and the remainder of components other than component (c) is polymerized. If the monomer polymerization ratio in the second stage polymerization is less than 5% by weight, the adhesive strength will decrease and the object of the present invention cannot be achieved, while if it exceeds 40% by weight, polymerization stability will be poor and undesirable. Furthermore, the glass transition temperature of the polymer obtained by the -stage polymerization is 50°C.
The following is preferable because it provides excellent roll stain resistance and coating workability in the coating process of the composition.
−段目の重合の後の成分（ｃ）および成分（ｃ）以外の
成分の残りの重合は一段反応に限定されるものではなく
、複数段反応でもよい。すなわち−段目以降の重合回数
には特に制限はない。また、二段目以降の重合における
上記成分の組み合わせ、添加順序等についても特に制限
はない。具体的には、例えば、−段目の重合の後、成分
（ｃ）を加えて重合を行い、次いで成分（ｃ）以外の成
分の残りを加えて重合を完結させてもよいし、あるいは
成分（ｃ）と成分（ｃ）以外の成分の残りとを同時に加
えて重合を行なってもよい。また、−段目あるいは二段
目以降の重合において、使用する単量体は一括して反応
器に仕込み重合させてもよく、また反応器に連続的ある
いは逐次的に添加しながら重合させることもできる。成
分（ｃ）については、本発明の目的を損なわない範囲で
あれば、−段目に少量添加することも可能である。The remaining polymerization of component (c) and components other than component (c) after the -stage polymerization is not limited to a single-stage reaction, but may be a multi-stage reaction. That is, there is no particular restriction on the number of polymerizations after the -th stage. Furthermore, there are no particular limitations on the combination of the above components, the order of addition, etc. in the second and subsequent polymerizations. Specifically, for example, after the -th stage polymerization, component (c) may be added and polymerized, and then the remainder of the components other than component (c) may be added to complete the polymerization, or the component (c) may be added to complete the polymerization. (c) and the rest of the components other than component (c) may be added simultaneously to carry out the polymerization. In addition, in the -stage or second-stage polymerization and subsequent stages, the monomers used may be charged into the reactor all at once and polymerized, or may be polymerized while being added to the reactor continuously or sequentially. can. Component (c) can be added in a small amount to the - stage as long as it does not impair the purpose of the present invention.
本発明における共重合体ラテックスは、前記単量体成分
および重合連鎖移動剤を使用する点を満たすかぎり、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。The copolymer latex in the present invention can be produced by a conventionally known emulsion polymerization method as long as the above-mentioned monomer components and polymerization chain transfer agent are used.
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、重合連鎖移動剤等を加えて乳化
重合を行うことによって得られる。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.
ここで、乳化剤としては、例えば両性界面活性剤、アニ
オン性界面活性剤、あるいはノニオン性界面活性剤が使
用できる。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、カチオン部分としてはアミン塩、第４
級アンモニウム塩を持つものが挙げられ、具体的にはア
ルキルベタインの塩としてはラウリルベタイン、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ニウムベタインの
各々の塩が、アミノ酸タイプのものとしではラウリル−
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
各々の塩が挙げられる。また、アニオン性界面活性剤と
しては、例えば高級アルコールの硫酸エステル、アルキ
ルベンゼンスルホン酸塩、脂肪族スルホン酸塩などが挙
げられる。さらに、ノニオン性界面活性剤としては、通
常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などが
用いられる。Here, as the emulsifier, for example, an amphoteric surfactant, an anionic surfactant, or a nonionic surfactant can be used. The amphoteric surfactants include carboxylates, sulfate ester salts, sulfonates, and phosphate ester salts as anionic moieties, and amine salts and quaternary ester salts as cationic moieties.
Specific examples of alkyl betaine salts include salts of lauryl betaine, stearyl betaine, cocoamidopropyl betaine, and 2-undecyl-hydroxyethylimidazolinium betaine, which are amino acid-type salts. As a matter of fact, Lauryl-
Examples include salts of β-alanine, stearyl-β-alanine, lauryl di(aminoethyl)glycine, octyldi(aminoethyl)glycine, and dioctyldi(aminoethyl)glycine. Further, examples of the anionic surfactant include sulfuric esters of higher alcohols, alkylbenzene sulfonates, aliphatic sulfonates, and the like. Further, as the nonionic surfactant, ordinary polyethylene glycol alkyl ester type, alkyl ether type, alkylphenyl ether type, etc. are used.
重合開始剤としては、過硫酸ナトリウム、過硫酸カリウ
ム、過硫酸アンモニウムなどの水溶性開始剤；過酸化ベ
ンゾイル、クメンｌ−イドコノく−オキサイド、アゾビ
スイソブチロニトリルなどの油溶性開始剤；あるいはレ
ドックス系開始剤のいずれでも使用できる。Examples of polymerization initiators include water-soluble initiators such as sodium persulfate, potassium persulfate, and ammonium persulfate; oil-soluble initiators such as benzoyl peroxide, cumene l-idoconoku-oxide, and azobisisobutyronitrile; or redox. Any system initiator can be used.
キレート剤、無機塩なども、乳化重合として公知のもの
が用いられる。As chelating agents, inorganic salts, etc., those known for emulsion polymerization are used.
本発明によって得られた共重合体ラテ・ソクスは、例え
ば板紙用あるいはゲートロール塗工用の紙塗被組成物と
して有用であり、このような紙塗被組成物は、かかる共
重合体ラテックスに、無機顔料あるいは有機顔料、好ま
しくは無機顔料、さらに必要に応じてその他の結合剤と
共に水性分散液として調整される。The copolymer latex obtained by the present invention is useful as a paper coating composition for, for example, paperboard or gate roll coating, and such a paper coating composition can be applied to such copolymer latex. , an inorganic pigment or an organic pigment, preferably an inorganic pigment, and if necessary, prepared as an aqueous dispersion together with other binders.
この際、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、通常５〜４０重量部、好まし
くは９〜３０重量部、その他の結合剤が、通常０〜３０
重量部、好ましくは２〜１０重量部使用される。共重合
体ラテックスが５重量部未満であると十分な接着強度が
得られず、一方４０重量部を越えると塗被組成物の粘度
が上昇し流動性が低下するので、塗工作業性が低下する
。At this time, the copolymer latex of the present invention is usually 5 to 40 parts by weight, preferably 9 to 30 parts by weight, and the other binder is usually 0 to 30 parts by weight, based on 100 parts by weight of the pigment in terms of solid content.
Parts by weight are used, preferably 2 to 10 parts by weight. If the amount of copolymer latex is less than 5 parts by weight, sufficient adhesive strength will not be obtained, while if it exceeds 40 parts by weight, the viscosity of the coating composition will increase and fluidity will decrease, resulting in a decrease in coating workability. do.
ここで、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、サチンホワ
イトなどの無機顔料、あるいはポリスチレンラテックス
のような有機顔料が挙げられ、これらは単独または混合
して使用される。Examples of pigments include inorganic pigments such as kaolin clay talc, barium sulfate, lithium, titanium oxide (rutyl anatase), calcium carbonate, aluminum hydroxide, zinc oxide, and satin white, and organic pigments such as polystyrene latex. These can be used alone or in combination.
また、その他の結合剤としては、澱粉、酸化澱粉、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、カルボキシ変性ＳＢラテックス、ブタジェ
ン・メチルメタクリレートなどの合成ラテックスが使用
される。Other binders used include natural binders such as starch, oxidized starch, soybean protein, and casein, or synthetic latexes such as polyvinyl alcohol, polyvinyl acetate latex, acrylic latex, carboxy-modified SB latex, and butadiene/methyl methacrylate. be done.
紙塗被組成物を調整するには、さらにその他の助剤、例
えば分散剤（ピ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、シリコーンオイルなど）、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
アリン酸カルシウム、パラフィンエマルジョンなど）、
螢光染料、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）が必要に応じて添
加される。In order to prepare the paper coating composition, further auxiliary agents such as dispersants (sodium pyrophosphate, sodium hexametaphosphate, etc.), antifoaming agents (polyglycols, fatty acid esters, phosphoric acid esters, silicone oils, etc.), Leveling agents (funnel oil, dicyandiamide, urea, etc.)
, preservatives, water-resistant agents (formalin, hexamine, melamine resin, urea resin, glyoxal, etc.), mold release agents (calcium stearate, paraffin emulsion, etc.),
Fluorescent dyes and color water retention improvers (carboxymethyl cellulose, sodium alginate, etc.) are added as necessary.
紙塗被組成物は塗布後、表面を乾燥し、カレンダーリン
グなどにより仕上げられる。After the paper coating composition is applied, the surface is dried and finished by calendering or the like.
なお、紙塗被組成物をゲートロール塗工用紙塗被組成物
として使用する場合、バインダーとして使用する共重合
体ラテックスの平均粒子径は好ましくは５００〜２５０
０人、より好ましくは６００〜２３００人、さらに好ま
しくは７００〜２０００人である。In addition, when the paper coating composition is used as a coating composition for gate roll coated paper, the average particle diameter of the copolymer latex used as a binder is preferably 500 to 250.
0 person, more preferably 600 to 2300 people, still more preferably 700 to 2000 people.
平均粒子が２５００人を越えるるとドライ強度が低下し
、ゲートロール塗工に適さなくなる。一方、５００人未
満では、共重合体ラテックスの粘度が高くなり、紙塗被
組成物の安定性が低下して、操業性が低下する。また、
共重合体のトルエン不溶分は、好ましくは２０〜９５重
量％、より好ましくは４０〜９０重量％である。トルエ
ン不溶分が２０重量％未満では、接着強度が低下し、ま
た共重合体ラテックスの安定性が低下するためガムアッ
プ現象が発生しやすくなり、操業性が低下する。If the average particle size exceeds 2,500 particles, the dry strength decreases, making it unsuitable for gate roll coating. On the other hand, if the number of people is less than 500, the viscosity of the copolymer latex increases, the stability of the paper coating composition decreases, and the operability decreases. Also,
The toluene-insoluble content of the copolymer is preferably 20 to 95% by weight, more preferably 40 to 90% by weight. If the toluene-insoluble content is less than 20% by weight, the adhesive strength will decrease and the stability of the copolymer latex will decrease, making it easy for gum-up phenomenon to occur, resulting in a decrease in operability.
一方、トルエン不溶分が９５重量％を越えると、接着強
度が低下する。On the other hand, when the toluene insoluble content exceeds 95% by weight, the adhesive strength decreases.
また、紙塗被組成物をゲートロール塗工用紙塗被組成物
として使用する場合、安定度（試験法は実施例の欄に示
す）は、０．９重量％以下、好ましくは０．６重量％以
下である。安定度が０．９重量％を越えるとガムアップ
現象が発生し易くなり、その結果平滑なコート層が得ら
れず、操業性も低下する。In addition, when the paper coating composition is used as a gate roll coated paper coating composition, the stability (test method is shown in the Examples column) is 0.9% by weight or less, preferably 0.6% by weight. % or less. If the stability exceeds 0.9% by weight, gum-up phenomenon tends to occur, and as a result, a smooth coating layer cannot be obtained and operability also deteriorates.
本発明に使用する共重合体ラテックスのガラス転移温度
は一５０℃〜＋４０℃の範囲にあるのが好ましい。ガラ
ス転移温度が一５０℃より低いと共重合体ラテックスの
粘着性が高くなり、操業性が低下し、一方、＋４０℃よ
り高いと接着強度が低下するので好ましくない。The glass transition temperature of the copolymer latex used in the present invention is preferably in the range of -50°C to +40°C. If the glass transition temperature is lower than 150°C, the copolymer latex will have high stickiness and operability will be reduced, while if it is higher than +40°C, the adhesive strength will be lowered, which is not preferable.
［実施例］
次に、実施例を挙げて本発明を説明するが、本発明はそ
の要旨を越えない限り、以下の実施例に制約されるもの
ではない。なお実施例において割合を示す「部」および
「％」はそれぞれ重量部および重量％を意味する。[Examples] Next, the present invention will be explained with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded. In the examples, "parts" and "%" indicating proportions mean parts by weight and % by weight, respectively.
実施例で用いる共重合体ラテックスの各種試験方法を以
下に示す。Various test methods for the copolymer latex used in the examples are shown below.
■平均粒子径
共重合体ラテックスをオスミウム酸で処理した後、電子
顕微鏡で観察し、５００個の粒子の粒子径を算術平均し
て平均粒子径をとした。(2) Average particle size After the copolymer latex was treated with osmic acid, it was observed with an electron microscope, and the average particle size was determined by taking the arithmetic average of the particle sizes of 500 particles.
■トルエン不溶分
共重合体ラテックスを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、洗浄、乾燥
して得られた固形分０．３ｇをトルエン１００１に室温
で２０時間浸漬し、その後１２０メツシユの金網でろ過
して得られる残存固形分の全固形分に対する重量割合で
示した。■Adjust the pH of the toluene-insoluble copolymer latex to 8, coagulate the copolymer in the latex with isopropanol, wash and dry, and add 0.3 g of the solid content to toluene 1001 at room temperature for 20 hours. The weight ratio of the residual solid content obtained by soaking and then filtering through a 120-mesh wire mesh to the total solid content is shown.
■安定度
共重合体ラテックス１５重合部（固形分換算）、クレー
８０部、炭酸カルシウム２０部およびスターチ７部とを
混合し、これに水を添加して固形分濃度が３０％になる
ように調整した。■Stability Mix 15 polymerized parts of copolymer latex (solid content equivalent), 80 parts of clay, 20 parts of calcium carbonate, and 7 parts of starch, and add water to make the solid content concentration 30%. It was adjusted.
この試料液１００ｇをＪ Ｉ Ｓ Ｋ２ＳＯ３に準す
るマロン式安定度測定試験機の測定容器に採取し、温水
を用いて試料液を７０℃に加温し、温水は７０℃一定と
した。試料液は圧力２ ｋｇ ／ ｃｄ 、撹拌速度１
１０００ｒｐ 、撹拌時間１０分の条件で撹拌し、その
後試料液を１２０メツシユの金網でろ過し、金網上の残
金量を測定し、次の式に従って安定度を求めた。100 g of this sample liquid was collected into a measuring container of a Maron type stability measurement tester conforming to JIS K2SO3, and the sample liquid was heated to 70°C using hot water, and the hot water was kept constant at 70°C. The sample solution had a pressure of 2 kg/cd and a stirring speed of 1.
The sample solution was stirred at 1000 rpm for 10 minutes, and then the sample solution was filtered through a 120-mesh wire mesh, the amount of metal remaining on the wire mesh was measured, and the stability was determined according to the following formula.
安定度（％）−
残金量（ｇ）
測定前の試料液中の全固形分（ｇ）
■微細凝固物
共重合体ラテックス１ｋｇを試料として採取し、これを
４００メツシユの金網でろ過し、金網上に残った凝固物
量を測定し、試料（固形分換算）に対する割合を求め、
下記の３段階で評価した。Stability (%) - Remaining amount (g) Total solid content in the sample solution before measurement (g) ■Collect 1 kg of fine coagulated copolymer latex as a sample, filter it through a 400-mesh wire mesh, and Measure the amount of coagulation remaining on the top, calculate the proportion to the sample (solid content equivalent),
Evaluation was made on the following three levels.
０ ： ０．０５％以下（少ない）
Δ： ０．０５％〜０．１％（やや多い）Ｘ ： ０．
１％以上（かなり多い）
実施例１〜６
オートクレーブ中に、水２００部、ドデシルベンゼンス
ルホン酸ナトリウム０．５部、過硫酸カリウム１．５部
、および第１表に示す一段目の単量体成分と重合連鎖移
動剤を仕込み、６５℃にて３時間反応させ、重合転化率
９８％以上で共重合体ラテックスを得た。引き続き、重
合温度を７０℃にあげ、第１表に示す二段目の単量体成
分と重合連鎖移動剤を混合し、１０時間かけて連続的に
添加して重合を行った。さらに３時間重合を継続し、重
合転化率９８％以上で、実施例にかかる６種の共重合体
ラテックス（Ａ）〜（Ｆ）を得た。0: 0.05% or less (less) Δ: 0.05% to 0.1% (slightly more) X: 0.
1% or more (quite a lot) Examples 1 to 6 In an autoclave, 200 parts of water, 0.5 parts of sodium dodecylbenzenesulfonate, 1.5 parts of potassium persulfate, and the first stage monomer shown in Table 1. The components and a polymerization chain transfer agent were charged and reacted at 65° C. for 3 hours to obtain a copolymer latex with a polymerization conversion rate of 98% or more. Subsequently, the polymerization temperature was raised to 70° C., and the second-stage monomer components shown in Table 1 and a polymerization chain transfer agent were mixed and polymerized by continuous addition over 10 hours. Polymerization was continued for an additional 3 hours, and six types of copolymer latexes (A) to (F) according to Examples were obtained at a polymerization conversion rate of 98% or more.
比較例１〜４
オートクレーブ中に、水２００部、ドデシルベンゼンス
ルホン酸ナトリウム０．５部、過硫酸カリウム１．５部
および第１表に示す一段目の単量体成分と重合連鎖移動
剤を入れて、６０℃にて３時間反応させ、重合転化率７
８％以上で共重合体ラテックスを得た。引き続き、′！
Ｊ１表に示す二段目の単量体成分と重合連鎖移動剤を１
０時間連続的に添加し、重合を行った。さらに３時間反
応を継続し、重合転化率９８％以上で、比較例にかかる
４種の共重合体ラテックス（ａ）〜（ｄ）を得た。Comparative Examples 1 to 4 200 parts of water, 0.5 parts of sodium dodecylbenzenesulfonate, 1.5 parts of potassium persulfate, and the first stage monomer components shown in Table 1 and a polymerization chain transfer agent were placed in an autoclave. The reaction was carried out at 60°C for 3 hours, and the polymerization conversion rate was 7.
A copolymer latex with a concentration of 8% or more was obtained. continuation,'!
The second-stage monomer components and polymerization chain transfer agent shown in Table J1 were added to 1
The polymerization was carried out by continuously adding for 0 hours. The reaction was continued for an additional 3 hours, and four types of copolymer latexes (a) to (d) according to comparative examples were obtained at a polymerization conversion rate of 98% or more.
（板紙用塗被組成物の調整）
適用例１〜６．比較適用例１〜４
共重合体ラテックス（Ａ）〜（Ｆ）および（ａ）〜（ｄ
）を用い、下記の処方による板紙用塗被組成物を調整し
た。(Preparation of coating composition for paperboard) Application examples 1 to 6. Comparative Application Examples 1 to 4 Copolymer latex (A) to (F) and (a) to (d
) to prepare a coating composition for paperboard according to the following formulation.
配 合：
クレー ６０部炭酸カルシウム
４０部共重合体ラテックス（固形分）
１６部カゼイン ５部
水は固形分濃度が６０％になるように添加した。Blend: Clay 60 parts Calcium carbonate 40 parts Copolymer latex (solid content)
16 parts casein 5 parts water was added so that the solid content concentration was 60%.
この板紙用塗被組成物を次の条件で塗布して塗工紙を得
た。This paperboard coating composition was applied under the following conditions to obtain coated paper.
方 法二ロッド手塗り
乾 燥：ギャーオープン、１２０℃、３０秒カレンダー
ニゲロスカレンダー＋１２０℃。Method Two-rod hand-painted drying: Gear open, 120°C, 30 seconds Calendar Nigelos Calendar +120°C.
８０ ｋｇ／ ｃ＋ｎ、 １ ｐａｓｓ原 紙二市販
厚板（２２０ｇ／イ）
得られた塗被板紙は、その特性を次の方法により測定し
た。80 kg/c+n, 1 pass base paper 2 commercially available thick board (220 g/l) The properties of the obtained coated paperboard were measured by the following method.
■Ｒ１ドライビック：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段階で評価した。点数の高いものほど良好で
ある。１１Ｉｌ定回数６回の平均値で表示した。(2) R1 Dry Vic: Indicator of adhesive strength The degree of picking when printed with the R1 printing machine was visually judged and evaluated on a five-point scale. The higher the score, the better. It is expressed as the average value of 6 constant times of 11Il.
■Ｒ１ウェットピック：耐水性の指標
Ｒ１印刷機でモルトンロールを用い湿し水を与えたとき
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。測定回数６回の平
均値で表示した。(2) R1 Wet Pick: Indicator of Water Resistance The degree of picking when dampening water was applied using a Morton roll using an R1 printing machine was visually judged and evaluated using a five-point scale. The higher the score, the better. The average value of 6 measurements was displayed.
■印刷光沢 村上式光沢度計を使用して測定したく７５゜７５”）。■Print gloss Measured using a Murakami gloss meter (75°75").
■印刷光沢
Ｒ１印刷機を使用してウェブオフセット用インキをベタ
刷りし、村上式光沢度計を使用して測定した（７５’
−７５’ ）。■Printing Gloss R1 printing machine was used to print the web offset ink, and Murakami type gloss meter was used to measure it (75'
-75').
０着肉性
Ｒ１印刷機でモルトンロールを用い湿し水を与えたとき
のインク転移の程度を測定して判定する。0 Ink receptivity R1 Judgment is made by measuring the degree of ink transfer when dampening water is applied using a Molton roll on a printing machine.
濃度の高いものほど良好である。測定回数６回の平均値
で表示した。The higher the concentration, the better. The average value of 6 measurements was displayed.
■ブリスターパック適性
白紙および印刷を施した塗被紙にブリスターパック用接
着剤＃１１とＬジューサー（いずれも荒用塗料工業社製
）の１：１混合液をコーティングロッドで均一の厚さに
塗布し乾燥させ、この面に一定面積のブリスターパック
用硬質塩化ビニルシート片を重ね、裏面よりヒートシー
ラにより１５０℃で５秒間圧着する。■ Suitability for blister packs Apply a 1:1 mixture of blister pack adhesive #11 and L juicer (both manufactured by Arayo Toyo Kogyo Co., Ltd.) to a uniform thickness on white paper and printed coated paper using a coating rod. After drying, a fixed area of a hard vinyl chloride sheet for blister packs was placed on this side, and the back side was pressed with a heat sealer at 150°C for 5 seconds.
白紙面６枚、印刷面６枚、計１２枚の試験片より塩化ビ
ニルシートをはぎ取り、肉眼で各試験片の塗被面と塩化
ビニルシート片の接着強さを５点法で判定し、１２枚の
試験片の評点の平均値でブリスターパック適性を表示し
た。印刷面はＲ１印刷機でオフセット用型インクを用い
てベタ刷りした面である。The vinyl chloride sheets were peeled off from a total of 12 test pieces, 6 on the blank side and 6 on the printed side, and the adhesive strength between the coated side of each test piece and the vinyl chloride sheet piece was judged with the naked eye using a 5-point method. The blister pack suitability was expressed as the average score of the test pieces. The printed surface is a solid surface printed using an offset type ink using an R1 printing machine.
■糊付性
塗被紙表面にライフボンドＡＶ−６５０（日栄化工社製
）を幅５ｍｍ、長さ８０龍、厚さ０．２ｍｍとなるよう
にスペーサーを用いて塗布し、この塗布面に同紙の非塗
被面が対面するように重ね、２ ｋｇの荷重を１分間か
けて圧着、除圧後２０℃、湿度６０％の恒温恒湿下に２
４時間放置する。その後、塗被紙を剥ぎ取り、接着強さ
を圧着面付近の破壊状態により肉眼で５点法で判定し、
６点測定をしたものの平均点で糊付性として表示した。■Stictability Apply Lifebond AV-650 (manufactured by Nichiei Kako Co., Ltd.) to the surface of the coated paper using a spacer so that the width is 5 mm, the length is 80 mm, and the thickness is 0.2 mm. Stack them so that the non-coated surfaces face each other, press them together under a load of 2 kg for 1 minute, remove the pressure, and then heat them at a constant temperature and humidity of 20°C and 60% humidity.
Leave it for 4 hours. After that, the coated paper was peeled off, and the adhesive strength was judged with the naked eye using a 5-point method based on the state of destruction near the crimped surface.
The average score of 6 measurements was expressed as adhesiveness.
評価結果を第２表に示す。第２表より次のことがわかる
。The evaluation results are shown in Table 2. The following can be seen from Table 2.
適用例１〜６は、本発明の共重合体ラテックスを用いた
例であり、本発明の目的とする効果のものが得られてい
る。Application Examples 1 to 6 are examples in which the copolymer latex of the present invention was used, and the desired effects of the present invention were obtained.
比較適用例１，２．３は、本発明の範囲外の重合連鎖移
動剤を用いて重合して得られた共重合体ラテックスを用
いた例であり、ラテックス中の微細凝固物が多く、かつ
ドライビック、ウェットビック、白紙光沢１着肉性が劣
る。Comparative Application Examples 1 and 2.3 are examples in which a copolymer latex obtained by polymerization using a polymerization chain transfer agent outside the scope of the present invention is used, and there are many fine coagulates in the latex, and Dry Vic, Wet Vic, White paper gloss 1 Poor ink receptivity.
比較適用例４は、本発明の成分（ｃ）の単量体を使用し
ない共重合体ラテックスを用いた例であり、塗工紙物性
が全般に劣り、特にブリスターパック適性および糊付性
が劣る。Comparative Application Example 4 is an example using a copolymer latex that does not use the monomer of component (c) of the present invention, and the coated paper properties are generally poor, and in particular, the blister pack suitability and pasting properties are poor. .
（ゲートロール塗工用紙塗被組成物の調製）共重合体ラ
テックス（（Ａ）〜（ｃ）と（ａ）。(Preparation of coating composition for gate roll coating paper) Copolymer latex ((A) to (c) and (a)).
（ｂ）および（ｄ）を用いて、下記の処方により、ゲー
トロール塗工用紙塗被組成物を調製した。A gate roll coated paper coating composition was prepared using (b) and (d) according to the following formulation.
配 合；
クレー ８０部炭酸カルシウム
２０部共重合体ラテックス（固形分
） １２部スターチ １０部
水は固形分濃度が６０％となるように添加した。Blend: Clay 80 parts Calcium carbonate 20 parts Copolymer latex (solid content) 12 parts Starch 10 parts Water was added so that the solid content concentration was 60%.
なお、原紙として中質原紙（６４ｇ／ｒｒｒ）を用いた
。Note that medium-quality base paper (64 g/rrr) was used as the base paper.
得られた塗工紙の特性を板紙用塗被組成物の場合と同様
の方法によって測定した。また、共重合体ラテックスの
安定度は既述の方法で測定した。The properties of the resulting coated paper were measured in the same manner as in the case of the coating composition for paperboard. Further, the stability of the copolymer latex was measured by the method described above.
なお、粘着性は次の方法によってｎ１定した。In addition, the adhesion was determined as n1 by the following method.
粘着性ニドラム乾燥におけるドラム汚染の指標ポリエス
テルフィルム上に共重合体ラテックスを塗布、乾燥して
フィルムを形成した。このフィルムに洋紙を圧着した後
、引き剥して洋紙の残存度合を目視で判定する。Indicator of drum contamination in sticky Ni drum drying A copolymer latex was coated on a polyester film and dried to form a film. After press-bonding Western paper to this film, it is peeled off and the degree of residual Western paper is visually determined.
Ｏ：残存なく良好
△：少し残存する
×：大部分残存する
評価結果を第３表に示す。第３表から次のことがわかる
。O: Good with no residue △: Slightly remaining ×: Most remaining The evaluation results are shown in Table 3. The following can be seen from Table 3.
適用例７〜９は、本発明の共重合体ラテックスを用いた
例であり、本発明の目的とする効果のものが得られてい
る。Application Examples 7 to 9 are examples in which the copolymer latex of the present invention was used, and the desired effects of the present invention were obtained.
比較適用例５．６は、本発明の範囲外の重合連鎖移動剤
を使用した共重合体ラテックスを用いた例であり、共重
合体ラテックスの微細凝固物が多く、機械的安定性が悪
く操業性に劣る。Comparative application example 5.6 is an example using a copolymer latex using a polymerization chain transfer agent outside the scope of the present invention, and there are many fine coagulates of the copolymer latex, resulting in poor mechanical stability and difficulty in operation. inferior to sex.
比較適用例７は、本発明の成分（ｃ）の単量体を使用し
ない共重合体ラテックスを用いた例であり、共重合体ラ
テックスの微細凝固物が多くてカラー粘度が高く、さら
に機械的安定性が悪く、操業性が劣る。Comparative Application Example 7 is an example using a copolymer latex that does not use the monomer of component (c) of the present invention, and has a high color viscosity due to a large amount of fine coagulation of the copolymer latex. Poor stability and poor operability.
［発明の効果］
本発明によれば、重合中の微細凝固物の発生が極めて少
なく、接着性および機械的安定性に優れた共重合体ラテ
ックスを高い生産性で製造することができる。[Effects of the Invention] According to the present invention, a copolymer latex with extremely low generation of fine coagulates during polymerization and excellent adhesiveness and mechanical stability can be produced with high productivity.
本発明により得られた共重合体ラテックスは、コート紙
、特に板紙あるいはゲートロール用の紙塗被組成物とし
て有用であり、優れた接着強度。The copolymer latex obtained according to the present invention is useful as a paper coating composition for coated paper, especially paperboard or gate rolls, and has excellent adhesive strength.
白紙光沢、印刷光沢１着肉性、糊付性、ブリスターバッ
ク適性等の塗工紙物性を有し、かつ高固形分化を達成し
ながら高い操業性を発揮することができる。It has coated paper physical properties such as white paper gloss, printing gloss 1 ink receptivity, sizing property, and blister-back suitability, and can exhibit high workability while achieving high solids content.
その他力−ペットのバッキングや接着剤などにも使用で
きる。Other forces: Can also be used for pet backing, adhesives, etc.
Claims (2)
アクリートから選ばれる少なくとも１種０．１〜１０重
量％、 （ｄ）エチレン系不飽和カルボン酸０．５〜１０重量％
、 （ｅ）他の共重合可能な単量体０〜４０重量％、を含む
単量体を、α−メチルスチレンダイマーの存在下、乳化
重合することを特徴とする共重合体ラテックスの製造方
法。(1) (a) Conjugated diene compound 10 to 60% by weight, (b) Aromatic vinyl compound 10 to 65% by weight, (c) Amide vinyl compound and hydroxy (meth)
0.1 to 10% by weight of at least one selected from acrylates; (d) 0.5 to 10% by weight of ethylenically unsaturated carboxylic acid;
(e) A method for producing a copolymer latex, which comprises emulsion polymerizing a monomer containing 0 to 40% by weight of another copolymerizable monomer in the presence of an α-methylstyrene dimer. .
アクリートから選ばれる少なくとも１種０．１〜１０重
量％、 （ｄ）エチレン系不飽和カルボン酸０．５〜１０重量％
、 （ｅ）他の共重合可能な単量体０〜４０重量％、を含む
単量体を、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
化合物の存在下、乳化重合することを特徴とする共重合
体ラテックスの製造方法。(2) (a) Conjugated diene compound 10 to 60% by weight, (b) Aromatic vinyl compound 10 to 65% by weight, (c) Amide vinyl compound and hydroxy (meth)
0.1 to 10% by weight of at least one selected from acrylates; (d) 0.5 to 10% by weight of ethylenically unsaturated carboxylic acid;
(e) Emulsifying a monomer containing 0 to 40% by weight of other copolymerizable monomers in the presence of at least one compound selected from terpinelene, α-terpinene, γ-terpinene, and dipentene. A method for producing a copolymer latex characterized by polymerization.
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 |
|---|---|
| JPH03109450A true JPH03109450A (en) | 1991-05-09 |
| JP2792165B2 JP2792165B2 (en) | 1998-08-27 |
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 |
| JP32347989A Expired - Lifetime JPH0776324B2 (en) | 1989-06-30 | 1989-12-13 | Composition for coating |
| JP1323482A Expired - Lifetime JP2792165B2 (en) | 1989-06-30 | 1989-12-13 | Method for producing copolymer latex |
| JP1327973A Expired - Lifetime JP2792166B2 (en) | 1989-06-30 | 1989-12-18 | Method for producing copolymer latex |
Family Applications Before (3)
| 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 |
| JP32347989A Expired - Lifetime JPH0776324B2 (en) | 1989-06-30 | 1989-12-13 | Composition for coating |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2676609C1 (en) * | 2017-12-12 | 2019-01-09 | Публичное акционерное общество "СИБУР Холдинг" | Method of obtaining latex |
Families Citing this family (16)
| 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 |
| JPH07166496A (en) * | 1993-12-14 | 1995-06-27 | Sumitomo Dow Ltd | Double coated paper |
| JP4763916B2 (en) * | 2001-05-28 | 2011-08-31 | 三菱レイヨン株式会社 | Methacrylic resin composition and method for producing methacrylic resin molded product |
| 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 |
| CA2729409C (en) | 2008-07-04 | 2014-02-04 | Asahi Kasei Chemicals Corporation | Copolymer latex and method for producing the same |
| JP4606517B1 (en) * | 2010-09-03 | 2011-01-05 | 香代子 吉田 | Shelf lifting device |
| 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 |
| KR20230022162A (en) * | 2020-06-05 | 2023-02-14 | 니폰 제온 가부시키가이샤 | Acrylic rubber veil with excellent roll processability and banbury processability |
| KR20230020397A (en) * | 2020-06-05 | 2023-02-10 | 니폰 제온 가부시키가이샤 | Acrylic rubber veil with excellent 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 |
| WO2021261216A1 (en) * | 2020-06-23 | 2021-12-30 | 日本ゼオン株式会社 | Acrylic rubber bale having excellent banbury processability and injection moldability |
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| JPS57108104A (en) * | 1980-12-26 | 1982-07-06 | Olympus Optical Co Ltd | Production of transparent plastic with increased conversion in prepolymerization |
| JPS6084315A (en) * | 1983-10-14 | 1985-05-13 | Mitsubishi Monsanto Chem Co | Production of weather- and impact-resistant resin |
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- 1989-12-11 JP JP1320952A patent/JP2541324B2/en not_active Expired - Lifetime
- 1989-12-13 JP JP32347989A patent/JPH0776324B2/en not_active Expired - Lifetime
- 1989-12-13 JP JP1323482A patent/JP2792165B2/en not_active Expired - Lifetime
- 1989-12-18 JP JP1327973A patent/JP2792166B2/en not_active Expired - Lifetime
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| JPS53118489A (en) * | 1977-03-24 | 1978-10-16 | Nippon Synthetic Chem Ind Co Ltd:The | Production of vinyl ester polymer |
| JPS53121891A (en) * | 1977-04-01 | 1978-10-24 | Mitsubishi Chem Ind Ltd | Preparation of methyl methacrylate polymer |
| JPS57108104A (en) * | 1980-12-26 | 1982-07-06 | Olympus Optical Co Ltd | Production of transparent plastic with increased conversion in prepolymerization |
| JPS6084315A (en) * | 1983-10-14 | 1985-05-13 | Mitsubishi Monsanto Chem Co | Production of weather- and impact-resistant resin |
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|---|---|---|---|---|
| RU2676609C1 (en) * | 2017-12-12 | 2019-01-09 | Публичное акционерное общество "СИБУР Холдинг" | Method of obtaining latex |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03113097A (en) | 1991-05-14 |
| JP2555294B2 (en) | 1996-11-20 |
| JPH0776324B2 (en) | 1995-08-16 |
| JP2541324B2 (en) | 1996-10-09 |
| JP2792165B2 (en) | 1998-08-27 |
| JP2792166B2 (en) | 1998-08-27 |
| JPH03109451A (en) | 1991-05-09 |
| JPH03113096A (en) | 1991-05-14 |
| JPH03109470A (en) | 1991-05-09 |
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