EP0109463B1 - Polymeric compositions useful as binders in coating colors and coating colors prepared therefrom - Google Patents
Polymeric compositions useful as binders in coating colors and coating colors prepared therefrom Download PDFInfo
- Publication number
- EP0109463B1 EP0109463B1 EP82201490A EP82201490A EP0109463B1 EP 0109463 B1 EP0109463 B1 EP 0109463B1 EP 82201490 A EP82201490 A EP 82201490A EP 82201490 A EP82201490 A EP 82201490A EP 0109463 B1 EP0109463 B1 EP 0109463B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- copolymer
- weight percent
- binder
- polymeric composition
- 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.)
- Expired
Links
- 239000011230 binding agent Substances 0.000 title claims abstract description 70
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 238000000576 coating method Methods 0.000 title claims description 48
- 239000011248 coating agent Substances 0.000 title claims description 43
- 239000003086 colorant Substances 0.000 title description 18
- 229920001577 copolymer Polymers 0.000 claims abstract description 99
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 31
- 150000002148 esters Chemical class 0.000 claims abstract description 30
- 238000004132 cross linking Methods 0.000 claims abstract description 17
- 150000002825 nitriles Chemical class 0.000 claims abstract description 13
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims description 65
- 238000000518 rheometry Methods 0.000 claims description 28
- 150000001993 dienes Chemical class 0.000 claims description 23
- 229920002554 vinyl polymer Polymers 0.000 claims description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 22
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 21
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 13
- 229920001567 vinyl ester resin Polymers 0.000 claims description 8
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 7
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 7
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 7
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 229920001519 homopolymer Polymers 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 5
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 claims description 4
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 claims description 4
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 238000002360 preparation method Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- 239000002253 acid Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 10
- 150000007513 acids Chemical class 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 239000003945 anionic surfactant Substances 0.000 description 5
- 239000008199 coating composition Substances 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 229920001059 synthetic polymer Polymers 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- -1 butenyl acrylates Chemical class 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000005395 methacrylic acid group Chemical class 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 239000002491 polymer binding agent Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- QISOBCMNUJQOJU-UHFFFAOYSA-N 4-bromo-1h-pyrazole-5-carboxylic acid Chemical compound OC(=O)C=1NN=CC=1Br QISOBCMNUJQOJU-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-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
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical class NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- ZWKNLRXFUTWSOY-QPJJXVBHSA-N (e)-3-phenylprop-2-enenitrile Chemical compound N#C\C=C\C1=CC=CC=C1 ZWKNLRXFUTWSOY-QPJJXVBHSA-N 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- ZJQIXGGEADDPQB-UHFFFAOYSA-N 1,2-bis(ethenyl)-3,4-dimethylbenzene Chemical group CC1=CC=C(C=C)C(C=C)=C1C ZJQIXGGEADDPQB-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- VTPNYMSKBPZSTF-UHFFFAOYSA-N 1-ethenyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C=C VTPNYMSKBPZSTF-UHFFFAOYSA-N 0.000 description 1
- OMNYXCUDBQKCMU-UHFFFAOYSA-N 2,4-dichloro-1-ethenylbenzene Chemical group ClC1=CC=C(C=C)C(Cl)=C1 OMNYXCUDBQKCMU-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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- SZSWKGVWJBZNIH-UHFFFAOYSA-N 2-chloro-1-ethenyl-4-methylbenzene Chemical compound CC1=CC=C(C=C)C(Cl)=C1 SZSWKGVWJBZNIH-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical group ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- ICBJBNAUJWZPBY-UHFFFAOYSA-N 2-hydroxyethyl 3-methylbut-2-enoate Chemical compound CC(=CC(=O)OCCO)C ICBJBNAUJWZPBY-UHFFFAOYSA-N 0.000 description 1
- ANCPBLUIOKGULL-UHFFFAOYSA-N 2-methylidene-3-oxopent-4-enamide Chemical group NC(=O)C(=C)C(=O)C=C ANCPBLUIOKGULL-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-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
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229950005228 bromoform 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- USCHNMKOGGUZHC-UHFFFAOYSA-N cyclohexene;dodecane-1-thiol Chemical compound C1CCC=CC1.CCCCCCCCCCCCS USCHNMKOGGUZHC-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001522 polyglycol ester Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920006216 polyvinyl aromatic Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- LQAZPMXASFNKCD-UHFFFAOYSA-M potassium;dodecane-1-sulfonate Chemical compound [K+].CCCCCCCCCCCCS([O-])(=O)=O LQAZPMXASFNKCD-UHFFFAOYSA-M 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 235000019983 sodium metaphosphate 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
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/46—Non-macromolecular organic compounds
- D21H19/48—Diolefins, e.g. butadiene; Aromatic vinyl monomers, e.g. styrene; Polymerisable unsaturated acids or derivatives thereof, e.g. acrylic acid
Definitions
- the present invention relates to a synthetic polymer composition useful as the binder component in coating colors and to coating colors containing these polymeric compositions.
- the paper surface is often coated with a composition (commonly referred to as a coating color) which imparts desirable properties such as printability to the paper.
- a coating color consists primarily of suspension of a pigment and/or filler such as clay in an aqueous medium containing a binder.
- the coating is continuously transferred as a liquid film from an applicator roll to the paper surface, with any applied excess removed using suitable means such as blade or air-knife ' techniques.
- suitable means such as blade or air-knife ' techniques.
- the paper is often coated sequential with a coating color of one composition and thereafter with a coating color of a second composition.
- the two coating colors contain the same or similar binders but different filler materials.
- the coating colors advantageously exhibit desirable physical properties, e.g., stability and rheological properties. These properties are particularly important in the preparation of quality paper grades such as those printed by gravure techniques.
- a natural, high molecular weight material such as starch or protein has been used as the binder component of the coating color.
- these natural materials are susceptible to attack by microorganisms and when employed alone give brittle coatings.
- using a starch binder the coated paper often does not possess the required print quality due to insufficient coat hold-out, i.e., excessive penetration of the coating into the paper.
- the first latex is a film-forming polymer (copolymer A) that is insoluble and not swellable to any substantial extent in aqueous alkali and is a copolymer of styrene and/or methyl methacrylate, an ethylenically unsaturated carboxylic acid and butadiene.
- the second polymer (copolymer B) is substantially swellable and insoluble in aqueous alkali and is a cross-linked copolymer of butadiene, styrene and/or methyl methacrylate and an ethylenically unsaturated acid.
- the paper coated with these compositions does not possess the desired balance of properties.
- USP 3 297 615 discloses a pigment coating composition
- a pigment coating composition comprising an adhesive derived from 75 to 95 percent ethylacrylate, 4 to 24 percent acrylonitrile and 1 to 3 percent methacrylic acid.
- the coating composition can further contain a supplemental adhesive such as starch or polyvinyl alcohol or a preservative such as a melamine-formaldehyde resin.
- German Patent 1,546,315 discloses a synthetic polymer binder comprising 60 to 95 percent of a first copolymer of butadiene, styrene and/or acrylonitrile and 5 to 40 percent of a second copolymer of acrylic or methacrylic acid, a monomer which forms a water-insoluble homopolymer (at least a portion of which is an ester of acrylic or methacrylic acid) and, optionally, acryl- or methacrylamide.
- coating colors prepared from this binder are generally deficient, particularly using gravure printing techniques, due again to insufficient coat hold-out.
- using coating colors prepared from the described polymeric binders difficulties are experienced in the preparation of a double coated paper. Specifically, an undesirable number of paper breaks and discontinuities on the coated paper are experienced using the coating colors prepared from these copolymer binders.
- EP 57 857 describes the use of an aqueous dispersion of a copolymer derived from a C,-C8 alkyl acrylate and an acrylic or methacrylic acid as the sole binder and thickener in a paper coating.
- a wide variety of optionally employed comonomers are also stated to be useful in the preparation of the binder/thickener copolymer.
- a number of conventional additives, including polymeric additives can be employed in combination with the sole binder/thickener copolymer, there is no suggestion nor any reason to employ a binder copolymer with the specified copolymer.
- the present invention is such an improved polymeric composition useful as the binder component in a coating color.
- the polymeric composition is composed of two polymeric components, the improvement in said composition comprising the inclusion, as one of the two polymeric components, of a lightly cross-linked copolymer comprising, in polymerized form, an ⁇ , ⁇ -ethylenically, unsaturated carboxylic acid, an ester of an ⁇ , ⁇ -ethyIenicaIIy unsaturated carboxylic acid and an unsaturated nitrile.
- the lightly cross-linked copolymer (hereinafter referred to as the "rheology control copolymer") is cross-linked sufficiently to improve the rheological and/or other properties of the polymeric composition and/or coating colors prepared therefrom, which is achieved by using a small amount of from 0.01 to 10 weight percent of a cross-linking monomer.
- the other copolymer (hereinafter referred to as the binder copolymer”) is generally a copolymer of a vinyl aromatic monomer, a conjugated diene and, optionally, other copolymerizable monomers or a copolymer of an ester of an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid, a comonomer which forms a water-insoluble homopolymer and, optionally, one or more copolymerizable monomers.
- the binder copolymer is generally a copolymer of a vinyl aromatic monomer, a conjugated diene and, optionally, other copolymerizable monomers or a copolymer of an ester of an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid, a comonomer which forms a water-insoluble homopolymer and, optionally, one or more copolymerizable monomers.
- the polymeric composition comprises from 60 to 90 weight parts of the binder copolymer and from 10 to 40 weight parts of the rheology control copolymer.
- the binder copolymer comprises, based on 100 weight parts, at least 60 weight parts in polymerized form, of a vinyl aromatic monomer and a conjugated diene, these monomers being employed in an amount such that the binder copolymer comprises from 10 to 90 weight percent of the vinyl aromatic copolymer and from 10 to 90 weight percent of a conjugated diene, said weight percents being based on the total weight of the vinyl aromatic monomer and the conjugated diene.
- the binder copolymer can optionally comprise, in polymerized form, up to 20 weight parts of an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid and up to 20 weight parts of other copolymerized monomers.
- the rheology control polymer comprises, based on 100 weight parts, in polymerized form, from 40 to 90 weight parts of an ester of an ⁇ , ⁇ -ethyIenicaIIy unsaturated carboxylic acid; from 1 to 30 parts of an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid; from 0.5 to 30 weight parts of an ethylenically unsaturated nitrile and from 0.01 to 10 weight parts of a cross-linking monomer.
- the coating colors containing a sufficiently cross-linked polymeric component possess rheological and/or other properties which cannot be obtained without the cross-linking.
- the flexibility imparted by the cross-linked structure allows ready adaptability of the polymeric binder composition to various formulations in the preparation of coating colors. Paper coated with the coating colors exhibit unexpectedly high binding strengths and excellent printability.
- the polymeric compositions of the present invention are useful as the binder component in various compositions, particularly coating colors. They are particularly useful as the binder component in coating colors employed in the two step coating processes for preparing the highest quality paper used in rotogravure printing.
- the polymeric composition of the present invention comprises two polymeric components, herein referred to as a binder copolymer and a rheological control polymer.
- the binder copolymer which primarily imparts the binding strengths and other properties to the coated paper is preferably derived from a vinyl aromatic monomer, a conjugated diene and, optionally, other monomers copolymerizable therewith.
- vinyl aromatic monomers include styrene; a-alkyl styrenes such as a-methyl styrene and a-ethyl styrene; nuclear substituted, alkyl substituted styrenes such as vinyl toluene, o-ethyl styrene, 2,4-dimethyl styrene, nuclear substituted halo-styrene such as chlorostyrene and 2,4-dichlorostyrene; styrene substituted with both a halo and an alkyl group such as 2,2-chloro-4-methyl styrene and combinations thereof.
- styrene or a combination of styrene with small amounts (i.e., less than 10 weight percent of the monovinylidene aromatic employed) of one or more other vinyl aromatic monomers, particularly an a-alkylstyrene, are preferred. Most preferably, styrene is employed as the vinyl aromatic monomer.
- the conjugated diene is an alkadiene, preferably a 1,3-conjugated diene such as butadiene, isoprene, properylene, chloropene and the like.
- the preferred conjugated diene is 1,3-butadiene.
- the binder copolymer comprises one or more additional copolymerizable monomers.
- additional copolymerizable monomers Such comonomers are employed to vary the properties of the resulting polymer and the specific comonomers and their amounts selected to obtain a copolymer having desirable properties.
- an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid such as acrylic, methacrylic, itaconic, fumaric or maleic acid in the preparation of the binder copolymer.
- Preferred of such acids are itaconic or acrylic acid or a combination thereof.
- the relative proportions of the vinyl aromatic monomer, conjugated diene and other comonomers, if employed in the preparation of the preferred binder copolymer are dependent on a variety of factors including the specific vinyl aromatic monomer and conjugated diene employed and the desired properties of the binder copolymer.
- the binder copolymer advantageously exhibits a second-order transition temperature, as defined by P. J. Flory in "Principles of Polymer Chemistry” published in 1953 by Cornell University Press, Ithaca, N.Y., p. 56 between -60° and +40°C and the monomers and their amounts selected accordingly.
- the binder copolymer comprises at least 60, preferably at least 80, more preferably at least 90, weight percent of the vinyl aromatic monomer and conjugated diene, said weight percents being based on the total weight of the first copolymer.
- the vinyl aromatic monomer is employed in amounts from 10 to 90, preferably from 50 to 70, weight percent and the conjugated diene is employed in amounts from 10 to 90, preferably from 30 to 50, weight percent, said weight percents being based on the total amount of vinyl aromatic monomer and conjugated diene employed in the preparation of the binder copolymer.
- the ⁇ , ⁇ -ethyIenicaIIy unsaturated carboxylic acids are employed in amounts from 0 to 20 weight percent, preferably from 1 to 5 weight percent, and the other copolymerizable monomers are employed in amounts from 0 to 20, more generally from 0 to 5, weight percent, said weight percents being based on the total weight of the binder copolymer.
- the binder copolymer of the present invention is preferably derived from 50 to 70 weight percent of a vinyl aromatic monomer, particularly styrene, from 30 to 50 weight percent of a conjugated diene, particularly 1,3-butadiene, and from 1 to 5 weight percent of an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid, particularly itaconic acid, acrylic acid or a combination thereof.
- the binder copolymer is derived from an ester of an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid and a comonomer which forms a water-insoluble homopolymer.
- Representative esters are the esters of acrylic and/or methacrylic acids with alcohols having from 1 to 8 carbon atoms including ethyl acrylate, n-butylacrylate, i-butylacrylate, 2-ethylhexylacrylate and the like. Esters of acrylic acid with alcohols having from 4 to 8 carbon atoms are preferred.
- Representative comonomers which form a water-insoluble homopolymer include generally the vinyl aromatic monomers, particularly styrene; the unsaturated nitriles, particularly acrylonitrile; the vinyl esters of a monocarboxylic acid, particularly vinyl acetate or vinyl propionate; the halo-olefins such as vinyl chloride or vinylidene chloride; or a combination thereof.
- the preferred of such comonomers are the vinyl esters, particularly vinyl acetate and vinyl propionate.
- the binder copolymer will comprise from 10 to 90, preferably from 35 to 60, weight percent of the ester of an unsaturated carboxylic acid and from 10 to 90, preferably from 35 to 60, weight percent of the vinyl acetate, and optionally, up to 10 weight percent of a further comonomer, said weight percents being based on the total weight of the binder copolymer.
- Such further comonomer can be a comonomer which forms a water-insoluble homopolymer, it is more advantageously an a,(3-ethylenically unsaturated carboxylic acid, preferably an acid having from 3 to 5 carbon atoms, including acrylic, methacrylic, crotonic, maleic, fumaric or itaconic acid and their amides, monoalkylamides, dialkylamides, N-methylolamides and esters of the N-methylolamides, including the half amides and half esters of the di-carboxylic acids; or a more strongly acidic comonomer such as vinyl sulfonic acid and p-toluene sulfonic acid.
- carboxylic acid preferably an acid having from 3 to 5 carbon atoms, including acrylic, methacrylic, crotonic, maleic, fumaric or itaconic acid and their amides, monoalkylamides, dialkylamides,
- Preferred of such comonomers are the ⁇ , ⁇ -ethylenically unsaturated acids, particularly those acids having from 3 to 5 carbon atoms. These acids are preferably employed in amounts from 0.1 to 5 weight percent based on the total weight of the binding copolymer.
- the rheology control polymeric component comprises a lightly cross-linked copolymer of an ⁇ , ⁇ -ethylenically unsaturated acid, an ester of an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid and an unsaturated nitrile.
- esters of the ⁇ , ⁇ -ethylenically unsaturated acids advantageously employed in the present invention are those esters of a carboxylic acid having from 3 to 5 carbon atoms such as acrylic, methacrylic, maleic, fumaric or itaconic acids (preferably acrylic or methacrylic acids) with alcohols having from 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms.
- Examplary examples of such esters are ethyl acrylate, propyl acrylate, butyl acrylate, propyl methacrylate and the like.
- the unsaturated carboxylic acids advantageously employed herein are those carboxylic acids which contain from 3 to 10 carbon atoms. Representative of such acids are acrylic, methacrylic, crotonic, itaconic, fumaric and ethacrylic acids.
- ethylenically unsaturated nitriles include acrylonitrile, methacrylonitrile, maleic nitrile and cinnamonitrile.
- a cross-linking monomer i.e., a copolymerizable monomer which when included in the polymerization recipe introduces cross- linkages into the resulting polymer, is employed to lightly cross-link the rheology control copolymer.
- Representative cross-linking monomers include the ethylenically unsaturated monomers which contain two or more non-conjugated terminal ethylenic groups.
- Such monomers are the polyvinyl aromatics such as divinylbenzene, divinyl toluene, divinyl xylene .and trivinylbenzene; the allyl or butenyl acrylates and/or methacrylates such as allyl methacrylate, ethylene glycol dimethylacrylate and the like.
- Preferred cross-linking monomers contain from 4 to 15 carbon atoms, with allyl acrylate and allyl methacrylate being most preferred.
- the specific monomer components and the relative proportions of each, including the cross-linking monomer and its amounts, most advantageously employed in preparing the rheology control polymer are dependent on a variety of factors including the composition of the binder copolymer employed and the desired properties of the coating color prepared therefrom.
- the binder copolymer is a copolymer of an ester of an unsaturated acid and a vinyl ester of an unsaturated carboxylic acid
- the desired polymeric properties of the copolymers can often be obtained using a lightly cross-linked polymer derived from the ester of an unsaturated carboxylic acid, preferably from 40 to 90 weight percent of an ester of acrylic acid with an alcohol having from 1 to 8 carbon atoms; the unsaturated carboxylic acid, preferably from 5 to 40 weight percent of acrylic and/or methacrylic acid; and an unsaturated nitrile, preferably from 0.5 to 25 weight percent of acrylonitrile, said weight percents being based on the total weight of the rheology control polymer.
- the cross-linking monomer is advantageously incorporated using from 0.05 to 5 weight percent of a cross-linking monomer, preferably from 0.05 to 2 weight percent of allyl acrylate or methacrylate.
- small amounts (i.e., less than 10 weight percent) of a vinyl ester of a monocarboxylic acid can optionally be employed.
- the lightly cross-linked rheology control copolymer is advantageously derived from 40 to 90 weight percent of the ester of an unsaturated carboxylic acid, preferably from 45 to 75 weight percent of ethyl acrylate and/or ethyl methacrylate; from 1 to 30 weight percent of an unsaturated carboxylic acid, preferably from 5 to 25 weight percent acrylic and/or methacrylic acid; from 0.5 to 30 weight percent of an unsaturated nitrile, preferably from 5 to 25 weight percent of acrylonitrile or mixtures of acrylonitrile with maleic nitrile or methacrylonitrile; and 0.01 to 10 weight percent of a cross-linking monomer, preferably from 0.05 to 5 weight percent of allyl acrylate and/or allyl methacrylate, wherein said weight percents are
- the rheology control copolymer comprises, in polymerized form, from 50 to 70 weight percent ethyl acrylate, from 10 to 20 weight percent methacrylic acid, from 10 to 20 weight percent acrylonitrile and from 0.05 to 2 weight percent of a cross-linking monomer, particularly allyl methacrylate.
- the binder copolymer and rheology control copolymer are prepared separately using continuous, semi-continuous or batch emulsion polymerization techniques. Such techniques are well-known in the art and reference is made thereto for the purposes of this invention.
- the polymeric components are prepared by dispersing the desired monomers in an aqueous polymerization medium which typically contains an emulsifying agent and other conventionally employed polymerization aids, e.g., chain transfer agent and chelating agent.
- Free radical initiation means which are advantageously employed include UV light and conventional chemical initiators such as per- oxygens, e.g., hydrogen peroxide and cumene hydroperoxide; persulfates, e.g., potassium persulfate, sodium persulfate and ammonium persulfate; organic azo compounds such as azobisisobutyronitrile; redox initiators such as peroxide in combination with a sulfite or thiosulfate reducing agent; and the like.
- conventional chemical initiators such as per- oxygens, e.g., hydrogen peroxide and cumene hydroperoxide; persulfates, e.g., potassium persulfate, sodium persulfate and ammonium persulfate; organic azo compounds such as azobisisobutyronitrile; redox initiators such as peroxide in combination with a sulfite or thiosulfate reducing agent; and the like.
- surfactants advantageously employed are anionic and nonionic surfactants conventionally employed heretofore in emulsion polymerizations.
- anionic surfactants useful herein include the alkyl aryl sulfonates such as sodium dodecyl benzene sulfonate, alkyl phenoxy polyethylene sulfonates and phosphates, sodium lauryl sulfate, potassium lauryl sulfonate and the like.
- nonionic surfactants useful herein include the reaction product of an alkylene oxide with alkylated phenols or long chain e.g., from 6 to 20 carbon atoms, fatty alcohols, fatty acids, alkyl mercaptans and primary amines; mono esters, e.g., the reaction product of polyethylene glycol with a long chain carboxylic acid with polyglycol esters of a polyhydric alcohol.
- the surfactants are employed in an amount which effectively stabilizes the dispersion during polymerization. In general, such amount will vary from 0.1 to 5 weight percent based on the total weight of the monomers employed. to assist in controlling the molecular weight of the monomers employed.
- a chain transfer agent is often, but optionally included in the aqueous polymerization medium.
- chain transfer agents which have conventionally been employed heretofore in emulsion polymerization processes can be employed in the practice of the present invention.
- Representative of such chain transfer agents include the mercaptans such as n-dodecyl mercaptan cyclohexene, bromoform, carbon tetrabromide, carbon tetrachloride and the like.
- the chain transfer agents are generally advantageously employed in amounts from 0.05 to 5 weight percent based on the total weight of the monomers.
- Polymerization is advantageously conducted at as low a temperature sufficient to polymerize the monomers at a practical rate.
- the polymerization is conducted at temperatures from 40-100°C, preferably from 60 ⁇ 90°C, for periods sufficient to convert desired amounts of monomer to the desired polymer (generally the conversion of at least 90 percent of the monomer to polymer) which conventionally takes from 1-6 hours.
- the polymer dispersions may be prepared over a wide range of concentrations, with the resulting aqueous dispersions advantageously ranging from 20 to 60 weight percent solids.
- the polymeric composition of the present invention is prepared by admixing the desired amounts of the binder copolymer with the rheology control copolymer.
- the relative concentrations of the binder copolymer and the rheology control copolymer are selected on the basis of the desired properties of the polymeric composition and the coating color prepared therefrom.
- the binder copolymer is employed in amounts from 50 to 97, preferably 60 to 90, more preferably 70 to 90, weight percent and the rheology control copolymer is used in amounts from 3 to 50, preferably 10 to 40, more preferably 10 to 30, weight percent, said weight percents being based on the total weight of the two copolymers.
- the method by which the two polymers are admixed is not particularly critical to the practice of the present invention.
- the two polymer dispersions will be compatible with one another, especially if any carboxyl groups contained in either or both copolymer are not neutralized or only partially neutralized prior to admixture.
- the admixture of the two polymer dispersions is readily achieved by mixing the dispersion of the first binder copolymer, as prepared, with the dispersion of the rheology control copolymer, as prepared, using mild agitation.
- the polymeric composition of the present invention is commonly admixed with other optionally employed adjuncts, such as fillers and/or pigments including clay and, optionally chalk, or calcium carbonate, and, if desired, other adjuncts such as dispersing agents, lubricants or the like.
- adjuncts can be mixed with either copolymer prior to their subsequent admixture in general, an aqueous dispersion of the pigment and/or filler is prepared and the two copolymers are added thereto, with agitation shortly before use.
- the carboxylic groups Prior to the application of a coating color containing the polymeric composition of the present invention to a paper surface, the carboxylic groups are advantageously neutralized by adding a basic material such as sodium or potassium hydroxide or ammonia, preferably sodium hydroxide.
- a basic material such as sodium or potassium hydroxide or ammonia, preferably sodium hydroxide.
- the alkali is added in an amount sufficient to give the aqueous dispersion containing the polymer a pH from 8 to 9.5.
- the resulting coating color can be applied to raw papers using any of the known methods.
- a suitably sized polymerization flask equipped with agitation means, heating and cooling means, thermometer, and addition funnel is added 60 parts water, 0.1 parts of an anionic surfactant, 0.8 parts of a free-radical initiator and 3 parts of a chain transfer agent.
- the vessel is purged with nitrogen and heated to 90°C. Over a 4 hour period, 57 parts of styrene, 39 parts of butadiene, 1 part of itaconic and 3 parts of acrylic acid are added cocurrently with an aqueous stream comprising additional surfactant and free-radical initiator.
- the vessel is maintained at 90°C during this addition and for an additional 2 hours. At this time, the polymerization is stopped.
- the resulting emulsion contains 50 percent solids and the particle size of the resulting styrene/buta- diene/itaconic acid/acrylic acid copolymer is found to be approximately 180 nm.
- Preparation of the rheology control polymer To a suitably sized polymerization vessel similar to that used in the preparation of the first copolymer is added 188 parts of water, 0.02 parts of a chelating agent and 0.5 parts of an anionic surfactant. The vessel is then heated to 80°C. A first monomer feed stream comprising 60 parts ethylacrylate, 15 parts acrylonitrile, 25 parts methacrylic acid and 0.05 parts of allylmethacrylate are added to the mildly stirred aqueous polymerization mixture for a period of about 4 hours.
- a polymeric blend is prepared by admixing, with mild agitation, 84 parts, on a dry basis, of the emulsion containing the binder copolymer with 16 parts, on a dry basis, of the emulsion containing the rheology control copolymer to form a blend of 46 weight percent solids.
- a pre-coat, paper coating composition is prepared by adding 5 parts of this blend to 100 parts of calcium carbonate dispersed in an aqueous solution of 0.1 parts sodium polyacrylate and 0.2 parts sodium metaphosphate using vigorous agitation. The pH of the resulting admixture is then adjusted to 8.5 by the addition of caustic soda. The resulting pre-coat has 62 percent solids with a viscosity of 900 Mpas measured using a Brookfield@ viscometer, type No. RVT, using Spindle No. 5 at 100 rpm and 25°C.
- top-coat paper coating composition is prepared except that 100 parts of Dinkie@ A clay is used in place of the calcium carbonate.
- the resulting top-coat has 58 percent solids with a viscosity of 1600 mPa. s measured using a Brookfield viscometer, type No. RVT, using Spindle No. 5 at 100 rpm and 15°C.
- a base paper of 36 grams per square meter (g/m 2 ) is coated with the pre-coat composition at a speed of 600 m/min and at 10 g/m 2 coat weight with 6 percent moisture using a conventional blade coating technique.
- the pre-coated paper is then dried and subsequently coated with the top-coat composition at a speed of 600 m/min and at 10 g/m 2 coat weight with 6 percent moisture using a conventional blade coating technique.
- Excellent runability characteristics were observed.
- the binding strength of the coated paper is found to be 48 cm/sec when measured using conventional IGT test equipment with a pendulum drive, with the result being reported in centimeters per second to the first pick of the coated paper using a low viscosity oil at a printing pressure of 350 newtons per square centimeter.
- the printability of the coated paper is found to be above 45 mm when measured using a testing device, for measuring printability of paper printed using rotagravure printing techniques, which has been adapted to a pendulum drive IGI tester, Type 2A, with the results being reported in millimeters (mm) to twenty missing dots using a printing pressure of 250 newtons/cm 2 .
- a double coated paper is prepared using the same coating techniques by coating the base paper with identical pre-coat and top-coat compositions except prepared with a polymeric binder composition of a first polymer of an acrylate and vinyl acetate and a second copolymer of an acrylate, carboxylic acid and an amide.
- the double coated paper exhibits a binding strength of only 24 cm/sec and approximately the same printability as the double coated paper using the pre-coat and top-coat composition prepared using the polymeric binder of the present invention.
- the polymeric compositions of the present invention are exceptional binders for paper coatings. Specifically, the paper coatings prepared using the polymeric compositions of the present invention impart unexpectedly high binding strengths in combination with excellent printability characteristics.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
Abstract
Description
- The present invention relates to a synthetic polymer composition useful as the binder component in coating colors and to coating colors containing these polymeric compositions.
- In the production of paper, the paper surface is often coated with a composition (commonly referred to as a coating color) which imparts desirable properties such as printability to the paper. Conventionally, the coating color consists primarily of suspension of a pigment and/or filler such as clay in an aqueous medium containing a binder.
- In one conventional method for applying the coating color, the coating is continuously transferred as a liquid film from an applicator roll to the paper surface, with any applied excess removed using suitable means such as blade or air-knife ' techniques. In the preparation of the highest quality paper, the paper is often coated sequential with a coating color of one composition and thereafter with a coating color of a second composition. In general, in the preparation of the double coated paper, the two coating colors contain the same or similar binders but different filler materials.
- For various reasons, paper producers have continuously strived to reduce the finished weight of the coated paper. One method by which this can be achieved is by reducing the amount of the coating color applied to the paper. Unfortunately, a reduction in the coat weight generally results in a drop of the finished paper properties, particularly in the print quality. To effectively coat the paper, at the desirable coat weight, the coating colors advantageously exhibit desirable physical properties, e.g., stability and rheological properties. These properties are particularly important in the preparation of quality paper grades such as those printed by gravure techniques.
- Heretofore, a natural, high molecular weight material such as starch or protein has been used as the binder component of the coating color. Unfortunately, these natural materials are susceptible to attack by microorganisms and when employed alone give brittle coatings. Moreover, using a starch binder, the coated paper often does not possess the required print quality due to insufficient coat hold-out, i.e., excessive penetration of the coating into the paper.
- It has heretofore been suggested to employ synthetic polymers as the binder in paper coatings. Many such synthetic polymer binders consist of two polymeric components with one copolymer being employed primarily to impart the desired binding strength and other properties to the coated paper and the second copolymer component being employed primarily to affect the rheological properties of the coating colors prepared therefrom. For example, U.S. Patent 3 694 394 discloses an aqueous coating composition comprising a blend of two latexes. The first latex is a film-forming polymer (copolymer A) that is insoluble and not swellable to any substantial extent in aqueous alkali and is a copolymer of styrene and/or methyl methacrylate, an ethylenically unsaturated carboxylic acid and butadiene. The second polymer (copolymer B) is substantially swellable and insoluble in aqueous alkali and is a cross-linked copolymer of butadiene, styrene and/or methyl methacrylate and an ethylenically unsaturated acid. However, the paper coated with these compositions does not possess the desired balance of properties. USP 3 297 615 discloses a pigment coating composition comprising an adhesive derived from 75 to 95 percent ethylacrylate, 4 to 24 percent acrylonitrile and 1 to 3 percent methacrylic acid. The coating composition can further contain a supplemental adhesive such as starch or polyvinyl alcohol or a preservative such as a melamine-formaldehyde resin. German Patent 1,546,315 discloses a synthetic polymer binder comprising 60 to 95 percent of a first copolymer of butadiene, styrene and/or acrylonitrile and 5 to 40 percent of a second copolymer of acrylic or methacrylic acid, a monomer which forms a water-insoluble homopolymer (at least a portion of which is an ester of acrylic or methacrylic acid) and, optionally, acryl- or methacrylamide. Unfortunately, coating colors prepared from this binder are generally deficient, particularly using gravure printing techniques, due again to insufficient coat hold-out. In addition, using coating colors prepared from the described polymeric binders, difficulties are experienced in the preparation of a double coated paper. Specifically, an undesirable number of paper breaks and discontinuities on the coated paper are experienced using the coating colors prepared from these copolymer binders.
- A similar synthetic polymeric binder except that the first copolymer is derived from an ester of acrylic or methacrylic acid, a vinyl ester or propionic acid, and optionally other copolymerizable monomers, is described by U.S. Patent No. 3,365,410. While coating colors prepared using these polymeric binders improve the print quality of paper prepared therefrom, a further improvement in the balance of the paper properties is required.
- EP 57 857 describes the use of an aqueous dispersion of a copolymer derived from a C,-C8 alkyl acrylate and an acrylic or methacrylic acid as the sole binder and thickener in a paper coating. A wide variety of optionally employed comonomers are also stated to be useful in the preparation of the binder/thickener copolymer. Although a number of conventional additives, including polymeric additives, can be employed in combination with the sole binder/thickener copolymer, there is no suggestion nor any reason to employ a binder copolymer with the specified copolymer.
- In view of the aforementioned deficiencies of the synthetic polymer binders employed heretofore, it remains highly desirable to provide a polymeric composition which can effectively be employed as the binder in a paper coating color to impart an improved balance of properties in the paper coated herewith.
- Accordingly, the present invention is such an improved polymeric composition useful as the binder component in a coating color. The polymeric composition is composed of two polymeric components, the improvement in said composition comprising the inclusion, as one of the two polymeric components, of a lightly cross-linked copolymer comprising, in polymerized form, an α,β-ethylenically, unsaturated carboxylic acid, an ester of an α,β-ethyIenicaIIy unsaturated carboxylic acid and an unsaturated nitrile. The lightly cross-linked copolymer (hereinafter referred to as the "rheology control copolymer") is cross-linked sufficiently to improve the rheological and/or other properties of the polymeric composition and/or coating colors prepared therefrom, which is achieved by using a small amount of from 0.01 to 10 weight percent of a cross-linking monomer. The other copolymer (hereinafter referred to as the binder copolymer") is generally a copolymer of a vinyl aromatic monomer, a conjugated diene and, optionally, other copolymerizable monomers or a copolymer of an ester of an α,β-ethylenically unsaturated carboxylic acid, a comonomer which forms a water-insoluble homopolymer and, optionally, one or more copolymerizable monomers.
- In a preferred embodiment, the polymeric composition comprises from 60 to 90 weight parts of the binder copolymer and from 10 to 40 weight parts of the rheology control copolymer. The binder copolymer comprises, based on 100 weight parts, at least 60 weight parts in polymerized form, of a vinyl aromatic monomer and a conjugated diene, these monomers being employed in an amount such that the binder copolymer comprises from 10 to 90 weight percent of the vinyl aromatic copolymer and from 10 to 90 weight percent of a conjugated diene, said weight percents being based on the total weight of the vinyl aromatic monomer and the conjugated diene. The binder copolymer can optionally comprise, in polymerized form, up to 20 weight parts of an α,β-ethylenically unsaturated carboxylic acid and up to 20 weight parts of other copolymerized monomers. The rheology control polymer comprises, based on 100 weight parts, in polymerized form, from 40 to 90 weight parts of an ester of an α,β-ethyIenicaIIy unsaturated carboxylic acid; from 1 to 30 parts of an α,β-ethylenically unsaturated carboxylic acid; from 0.5 to 30 weight parts of an ethylenically unsaturated nitrile and from 0.01 to 10 weight parts of a cross-linking monomer.
- The coating colors containing a sufficiently cross-linked polymeric component possess rheological and/or other properties which cannot be obtained without the cross-linking. In addition, the flexibility imparted by the cross-linked structure allows ready adaptability of the polymeric binder composition to various formulations in the preparation of coating colors. Paper coated with the coating colors exhibit unexpectedly high binding strengths and excellent printability.
- The polymeric compositions of the present invention are useful as the binder component in various compositions, particularly coating colors. They are particularly useful as the binder component in coating colors employed in the two step coating processes for preparing the highest quality paper used in rotogravure printing.
- The polymeric composition of the present invention comprises two polymeric components, herein referred to as a binder copolymer and a rheological control polymer. The binder copolymer which primarily imparts the binding strengths and other properties to the coated paper is preferably derived from a vinyl aromatic monomer, a conjugated diene and, optionally, other monomers copolymerizable therewith. Representative vinyl aromatic monomers include styrene; a-alkyl styrenes such as a-methyl styrene and a-ethyl styrene; nuclear substituted, alkyl substituted styrenes such as vinyl toluene, o-ethyl styrene, 2,4-dimethyl styrene, nuclear substituted halo-styrene such as chlorostyrene and 2,4-dichlorostyrene; styrene substituted with both a halo and an alkyl group such as 2,2-chloro-4-methyl styrene and combinations thereof. In general, styrene, or a combination of styrene with small amounts (i.e., less than 10 weight percent of the monovinylidene aromatic employed) of one or more other vinyl aromatic monomers, particularly an a-alkylstyrene, are preferred. Most preferably, styrene is employed as the vinyl aromatic monomer. The conjugated diene is an alkadiene, preferably a 1,3-conjugated diene such as butadiene, isoprene, properylene, chloropene and the like. The preferred conjugated diene is 1,3-butadiene.
- Often, but optionally, the binder copolymer comprises one or more additional copolymerizable monomers. Such comonomers are employed to vary the properties of the resulting polymer and the specific comonomers and their amounts selected to obtain a copolymer having desirable properties. For example, to increase the binding strength of a coated paper, it is often desirable to employ an α,β-ethylenically unsaturated carboxylic acid such as acrylic, methacrylic, itaconic, fumaric or maleic acid in the preparation of the binder copolymer. Preferred of such acids are itaconic or acrylic acid or a combination thereof. Other comonomers which are often advantageously employed in the presence of such copolymer binder include unsaturated nitriles such as acrylonitrile and methyl- acrylonitrile, the halo-substituted olefins such as vinylidene chloride, esters of α,β-ethylenically unsaturated carboxylic acids, ethylenically unsaturated amides such as acrylamide and methylacrylamide, and the ethylenically unsaturated alcohols.
- The relative proportions of the vinyl aromatic monomer, conjugated diene and other comonomers, if employed in the preparation of the preferred binder copolymer, are dependent on a variety of factors including the specific vinyl aromatic monomer and conjugated diene employed and the desired properties of the binder copolymer. For example, the binder copolymer advantageously exhibits a second-order transition temperature, as defined by P. J. Flory in "Principles of Polymer Chemistry" published in 1953 by Cornell University Press, Ithaca, N.Y., p. 56 between -60° and +40°C and the monomers and their amounts selected accordingly. In general, the binder copolymer comprises at least 60, preferably at least 80, more preferably at least 90, weight percent of the vinyl aromatic monomer and conjugated diene, said weight percents being based on the total weight of the first copolymer. In general, the vinyl aromatic monomer is employed in amounts from 10 to 90, preferably from 50 to 70, weight percent and the conjugated diene is employed in amounts from 10 to 90, preferably from 30 to 50, weight percent, said weight percents being based on the total amount of vinyl aromatic monomer and conjugated diene employed in the preparation of the binder copolymer. The α,β-ethyIenicaIIy unsaturated carboxylic acids are employed in amounts from 0 to 20 weight percent, preferably from 1 to 5 weight percent, and the other copolymerizable monomers are employed in amounts from 0 to 20, more generally from 0 to 5, weight percent, said weight percents being based on the total weight of the binder copolymer. In general, the binder copolymer of the present invention is preferably derived from 50 to 70 weight percent of a vinyl aromatic monomer, particularly styrene, from 30 to 50 weight percent of a conjugated diene, particularly 1,3-butadiene, and from 1 to 5 weight percent of an α,β-ethylenically unsaturated carboxylic acid, particularly itaconic acid, acrylic acid or a combination thereof.
- Alternatively, but less preferably, the binder copolymer is derived from an ester of an α,β-ethylenically unsaturated carboxylic acid and a comonomer which forms a water-insoluble homopolymer. Representative esters are the esters of acrylic and/or methacrylic acids with alcohols having from 1 to 8 carbon atoms including ethyl acrylate, n-butylacrylate, i-butylacrylate, 2-ethylhexylacrylate and the like. Esters of acrylic acid with alcohols having from 4 to 8 carbon atoms are preferred. Representative comonomers which form a water-insoluble homopolymer include generally the vinyl aromatic monomers, particularly styrene; the unsaturated nitriles, particularly acrylonitrile; the vinyl esters of a monocarboxylic acid, particularly vinyl acetate or vinyl propionate; the halo-olefins such as vinyl chloride or vinylidene chloride; or a combination thereof. The preferred of such comonomers are the vinyl esters, particularly vinyl acetate and vinyl propionate. In general, the binder copolymer will comprise from 10 to 90, preferably from 35 to 60, weight percent of the ester of an unsaturated carboxylic acid and from 10 to 90, preferably from 35 to 60, weight percent of the vinyl acetate, and optionally, up to 10 weight percent of a further comonomer, said weight percents being based on the total weight of the binder copolymer. Although such further comonomer can be a comonomer which forms a water-insoluble homopolymer, it is more advantageously an a,(3-ethylenically unsaturated carboxylic acid, preferably an acid having from 3 to 5 carbon atoms, including acrylic, methacrylic, crotonic, maleic, fumaric or itaconic acid and their amides, monoalkylamides, dialkylamides, N-methylolamides and esters of the N-methylolamides, including the half amides and half esters of the di-carboxylic acids; or a more strongly acidic comonomer such as vinyl sulfonic acid and p-toluene sulfonic acid. Preferred of such comonomers are the α,β-ethylenically unsaturated acids, particularly those acids having from 3 to 5 carbon atoms. These acids are preferably employed in amounts from 0.1 to 5 weight percent based on the total weight of the binding copolymer.
- The rheology control polymeric component comprises a lightly cross-linked copolymer of an α,β-ethylenically unsaturated acid, an ester of an α,β-ethylenically unsaturated carboxylic acid and an unsaturated nitrile.
- The esters of the α,β-ethylenically unsaturated acids advantageously employed in the present invention are those esters of a carboxylic acid having from 3 to 5 carbon atoms such as acrylic, methacrylic, maleic, fumaric or itaconic acids (preferably acrylic or methacrylic acids) with alcohols having from 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms. Examplary examples of such esters are ethyl acrylate, propyl acrylate, butyl acrylate, propyl methacrylate and the like.
- . The unsaturated carboxylic acids advantageously employed herein are those carboxylic acids which contain from 3 to 10 carbon atoms. Representative of such acids are acrylic, methacrylic, crotonic, itaconic, fumaric and ethacrylic acids.
- Representative of ethylenically unsaturated nitriles include acrylonitrile, methacrylonitrile, maleic nitrile and cinnamonitrile.
- In general, a cross-linking monomer, i.e., a copolymerizable monomer which when included in the polymerization recipe introduces cross- linkages into the resulting polymer, is employed to lightly cross-link the rheology control copolymer. Representative cross-linking monomers include the ethylenically unsaturated monomers which contain two or more non-conjugated terminal ethylenic groups. Examples of such monomers are the polyvinyl aromatics such as divinylbenzene, divinyl toluene, divinyl xylene .and trivinylbenzene; the allyl or butenyl acrylates and/or methacrylates such as allyl methacrylate, ethylene glycol dimethylacrylate and the like. Preferred cross-linking monomers contain from 4 to 15 carbon atoms, with allyl acrylate and allyl methacrylate being most preferred.
- The specific monomer components and the relative proportions of each, including the cross-linking monomer and its amounts, most advantageously employed in preparing the rheology control polymer are dependent on a variety of factors including the composition of the binder copolymer employed and the desired properties of the coating color prepared therefrom. For example, if the binder copolymer is a copolymer of an ester of an unsaturated acid and a vinyl ester of an unsaturated carboxylic acid, the desired polymeric properties of the copolymers can often be obtained using a lightly cross-linked polymer derived from the ester of an unsaturated carboxylic acid, preferably from 40 to 90 weight percent of an ester of acrylic acid with an alcohol having from 1 to 8 carbon atoms; the unsaturated carboxylic acid, preferably from 5 to 40 weight percent of acrylic and/or methacrylic acid; and an unsaturated nitrile, preferably from 0.5 to 25 weight percent of acrylonitrile, said weight percents being based on the total weight of the rheology control polymer. The cross-linking monomer is advantageously incorporated using from 0.05 to 5 weight percent of a cross-linking monomer, preferably from 0.05 to 2 weight percent of allyl acrylate or methacrylate. In addition, small amounts (i.e., less than 10 weight percent) of a vinyl ester of a monocarboxylic acid can optionally be employed.
- Alternatively, when the binder copolymer is a copolymer derived primarily from a vinyl aromatic monomer and a conjugated diene, to obtain the most desirable properties, the lightly cross-linked rheology control copolymer is advantageously derived from 40 to 90 weight percent of the ester of an unsaturated carboxylic acid, preferably from 45 to 75 weight percent of ethyl acrylate and/or ethyl methacrylate; from 1 to 30 weight percent of an unsaturated carboxylic acid, preferably from 5 to 25 weight percent acrylic and/or methacrylic acid; from 0.5 to 30 weight percent of an unsaturated nitrile, preferably from 5 to 25 weight percent of acrylonitrile or mixtures of acrylonitrile with maleic nitrile or methacrylonitrile; and 0.01 to 10 weight percent of a cross-linking monomer, preferably from 0.05 to 5 weight percent of allyl acrylate and/or allyl methacrylate, wherein said weight percents are based on the total weight of the rheology control copolymer.
- Most preferably, the rheology control copolymer comprises, in polymerized form, from 50 to 70 weight percent ethyl acrylate, from 10 to 20 weight percent methacrylic acid, from 10 to 20 weight percent acrylonitrile and from 0.05 to 2 weight percent of a cross-linking monomer, particularly allyl methacrylate.
- The binder copolymer and rheology control copolymer are prepared separately using continuous, semi-continuous or batch emulsion polymerization techniques. Such techniques are well-known in the art and reference is made thereto for the purposes of this invention. In general, the polymeric components are prepared by dispersing the desired monomers in an aqueous polymerization medium which typically contains an emulsifying agent and other conventionally employed polymerization aids, e.g., chain transfer agent and chelating agent.
- Free radical initiation means which are advantageously employed include UV light and conventional chemical initiators such as per- oxygens, e.g., hydrogen peroxide and cumene hydroperoxide; persulfates, e.g., potassium persulfate, sodium persulfate and ammonium persulfate; organic azo compounds such as azobisisobutyronitrile; redox initiators such as peroxide in combination with a sulfite or thiosulfate reducing agent; and the like. Typically, such initiators are employed in amounts which generally range from 0.01 to 5 weight percent based on the total weight of the monomers being polymerized.
- In preparing the copolymers, surfactants advantageously employed are anionic and nonionic surfactants conventionally employed heretofore in emulsion polymerizations. Representative anionic surfactants useful herein include the alkyl aryl sulfonates such as sodium dodecyl benzene sulfonate, alkyl phenoxy polyethylene sulfonates and phosphates, sodium lauryl sulfate, potassium lauryl sulfonate and the like. Representative nonionic surfactants useful herein include the reaction product of an alkylene oxide with alkylated phenols or long chain e.g., from 6 to 20 carbon atoms, fatty alcohols, fatty acids, alkyl mercaptans and primary amines; mono esters, e.g., the reaction product of polyethylene glycol with a long chain carboxylic acid with polyglycol esters of a polyhydric alcohol. The surfactants are employed in an amount which effectively stabilizes the dispersion during polymerization. In general, such amount will vary from 0.1 to 5 weight percent based on the total weight of the monomers employed. to assist in controlling the molecular weight of the monomers employed. To assist in controlling the molecular weight of the resulting polymers, a chain transfer agent is often, but optionally included in the aqueous polymerization medium. In general, chain transfer agents which have conventionally been employed heretofore in emulsion polymerization processes can be employed in the practice of the present invention. Representative of such chain transfer agents include the mercaptans such as n-dodecyl mercaptan cyclohexene, bromoform, carbon tetrabromide, carbon tetrachloride and the like. When employed, the chain transfer agents are generally advantageously employed in amounts from 0.05 to 5 weight percent based on the total weight of the monomers.
- Polymerization is advantageously conducted at as low a temperature sufficient to polymerize the monomers at a practical rate. In general, the polymerization is conducted at temperatures from 40-100°C, preferably from 60―90°C, for periods sufficient to convert desired amounts of monomer to the desired polymer (generally the conversion of at least 90 percent of the monomer to polymer) which conventionally takes from 1-6 hours. The polymer dispersions may be prepared over a wide range of concentrations, with the resulting aqueous dispersions advantageously ranging from 20 to 60 weight percent solids.
- The polymeric composition of the present invention is prepared by admixing the desired amounts of the binder copolymer with the rheology control copolymer. The relative concentrations of the binder copolymer and the rheology control copolymer are selected on the basis of the desired properties of the polymeric composition and the coating color prepared therefrom. In general, the binder copolymer is employed in amounts from 50 to 97, preferably 60 to 90, more preferably 70 to 90, weight percent and the rheology control copolymer is used in amounts from 3 to 50, preferably 10 to 40, more preferably 10 to 30, weight percent, said weight percents being based on the total weight of the two copolymers.
- The method by which the two polymers are admixed is not particularly critical to the practice of the present invention. In general, the two polymer dispersions will be compatible with one another, especially if any carboxyl groups contained in either or both copolymer are not neutralized or only partially neutralized prior to admixture. The admixture of the two polymer dispersions is readily achieved by mixing the dispersion of the first binder copolymer, as prepared, with the dispersion of the rheology control copolymer, as prepared, using mild agitation.
- In the preparation of coating colors using the polymeric compositions of this invention as the binder component, the polymeric composition of the present invention is commonly admixed with other optionally employed adjuncts, such as fillers and/or pigments including clay and, optionally chalk, or calcium carbonate, and, if desired, other adjuncts such as dispersing agents, lubricants or the like. Although such adjuncts can be mixed with either copolymer prior to their subsequent admixture in general, an aqueous dispersion of the pigment and/or filler is prepared and the two copolymers are added thereto, with agitation shortly before use. Prior to the application of a coating color containing the polymeric composition of the present invention to a paper surface, the carboxylic groups are advantageously neutralized by adding a basic material such as sodium or potassium hydroxide or ammonia, preferably sodium hydroxide. The alkali is added in an amount sufficient to give the aqueous dispersion containing the polymer a pH from 8 to 9.5. The resulting coating color can be applied to raw papers using any of the known methods.
- The following example is set forth to illustrate the invention and should not be construed to limit its scope. In the examples, all parts and percentages are by weight unless otherwise indicated.
- To a suitably sized polymerization flask equipped with agitation means, heating and cooling means, thermometer, and addition funnel, is added 60 parts water, 0.1 parts of an anionic surfactant, 0.8 parts of a free-radical initiator and 3 parts of a chain transfer agent. The vessel is purged with nitrogen and heated to 90°C. Over a 4 hour period, 57 parts of styrene, 39 parts of butadiene, 1 part of itaconic and 3 parts of acrylic acid are added cocurrently with an aqueous stream comprising additional surfactant and free-radical initiator. The vessel is maintained at 90°C during this addition and for an additional 2 hours. At this time, the polymerization is stopped. The resulting emulsion contains 50 percent solids and the particle size of the resulting styrene/buta- diene/itaconic acid/acrylic acid copolymer is found to be approximately 180 nm.
- Preparation of the rheology control polymer To a suitably sized polymerization vessel similar to that used in the preparation of the first copolymer is added 188 parts of water, 0.02 parts of a chelating agent and 0.5 parts of an anionic surfactant. The vessel is then heated to 80°C. A first monomer feed stream comprising 60 parts ethylacrylate, 15 parts acrylonitrile, 25 parts methacrylic acid and 0.05 parts of allylmethacrylate are added to the mildly stirred aqueous polymerization mixture for a period of about 4 hours. Coincident with the addition of the monomers, an additional 50 parts water, 2.0 parts of anionic surfactant, 0.2 parts of sodium hydroxide, and 0.7 parts of a free-radical initiator is added to the polymerization medium. The temperature of the vessel is maintained at 80°C during the addition of the monomer and polymerization aids and for an additional 2 hours. At the end of this period, the flask is then cooled to ambient temperatures and the subsequent emulsion subjected to steam distillation to remove the unconverted monomer. The resulting emulsion contains about 30 percent solids.
- A polymeric blend is prepared by admixing, with mild agitation, 84 parts, on a dry basis, of the emulsion containing the binder copolymer with 16 parts, on a dry basis, of the emulsion containing the rheology control copolymer to form a blend of 46 weight percent solids.
- A pre-coat, paper coating composition is prepared by adding 5 parts of this blend to 100 parts of calcium carbonate dispersed in an aqueous solution of 0.1 parts sodium polyacrylate and 0.2 parts sodium metaphosphate using vigorous agitation. The pH of the resulting admixture is then adjusted to 8.5 by the addition of caustic soda. The resulting pre-coat has 62 percent solids with a viscosity of 900 Mpas measured using a Brookfield@ viscometer, type No. RVT, using Spindle No. 5 at 100 rpm and 25°C.
- An identical top-coat paper coating composition is prepared except that 100 parts of Dinkie@ A clay is used in place of the calcium carbonate. The resulting top-coat has 58 percent solids with a viscosity of 1600 mPa. s measured using a Brookfield viscometer, type No. RVT, using Spindle No. 5 at 100 rpm and 15°C.
- A base paper of 36 grams per square meter (g/m2) is coated with the pre-coat composition at a speed of 600 m/min and at 10 g/m2 coat weight with 6 percent moisture using a conventional blade coating technique. The pre-coated paper is then dried and subsequently coated with the top-coat composition at a speed of 600 m/min and at 10 g/m2 coat weight with 6 percent moisture using a conventional blade coating technique. Excellent runability characteristics were observed. The binding strength of the coated paper is found to be 48 cm/sec when measured using conventional IGT test equipment with a pendulum drive, with the result being reported in centimeters per second to the first pick of the coated paper using a low viscosity oil at a printing pressure of 350 newtons per square centimeter. The printability of the coated paper is found to be above 45 mm when measured using a testing device, for measuring printability of paper printed using rotagravure printing techniques, which has been adapted to a pendulum drive IGI tester, Type 2A, with the results being reported in millimeters (mm) to twenty missing dots using a printing pressure of 250 newtons/cm2.
- A double coated paper is prepared using the same coating techniques by coating the base paper with identical pre-coat and top-coat compositions except prepared with a polymeric binder composition of a first polymer of an acrylate and vinyl acetate and a second copolymer of an acrylate, carboxylic acid and an amide. The double coated paper exhibits a binding strength of only 24 cm/sec and approximately the same printability as the double coated paper using the pre-coat and top-coat composition prepared using the polymeric binder of the present invention.
- As shown by this Example, the polymeric compositions of the present invention are exceptional binders for paper coatings. Specifically, the paper coatings prepared using the polymeric compositions of the present invention impart unexpectedly high binding strengths in combination with excellent printability characteristics.
Claims (13)
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT82201490T ATE22583T1 (en) | 1982-11-23 | 1982-11-23 | POLYMER COMPOSITIONS USED AS BINDERS IN COATING COMPOSITIONS AND COATING COMPOSITIONS PREPARED THEREFROM. |
DE8282201490T DE3273596D1 (en) | 1982-11-23 | 1982-11-23 | Polymeric compositions useful as binders in coating colors and coating colors prepared therefrom |
EP82201490A EP0109463B2 (en) | 1982-11-23 | 1982-11-23 | Polymeric compositions useful as binders in coating colors and coating colors prepared therefrom |
PCT/US1983/001842 WO1984002139A1 (en) | 1982-11-23 | 1983-11-22 | Polymeric compositions useful as binders in coating colors and coating colors prepared therefrom |
AU24123/84A AU565959B2 (en) | 1982-11-23 | 1983-11-22 | Polymeric compositions useful as binders in coating colors and coating colors prepared therefrom |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP82201490A EP0109463B2 (en) | 1982-11-23 | 1982-11-23 | Polymeric compositions useful as binders in coating colors and coating colors prepared therefrom |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0109463A1 EP0109463A1 (en) | 1984-05-30 |
EP0109463B1 true EP0109463B1 (en) | 1986-10-01 |
EP0109463B2 EP0109463B2 (en) | 1989-10-18 |
Family
ID=8189533
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP82201490A Expired EP0109463B2 (en) | 1982-11-23 | 1982-11-23 | Polymeric compositions useful as binders in coating colors and coating colors prepared therefrom |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0109463B2 (en) |
AT (1) | ATE22583T1 (en) |
AU (1) | AU565959B2 (en) |
DE (1) | DE3273596D1 (en) |
WO (1) | WO1984002139A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4833222A (en) * | 1987-10-22 | 1989-05-23 | The Dow Chemical Company | Crosslinker stabilizer for preparing absorbent polymers |
DE10008276A1 (en) * | 2000-02-23 | 2001-08-30 | Basf Ag | Paper coating slips based on slightly crosslinked binders |
CN114345175A (en) * | 2021-12-30 | 2022-04-15 | 金晨粉末涂料(江苏)有限公司 | Production equipment and production process of environment-friendly epoxy zinc-rich anticorrosive powder coating |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA813959A (en) * | 1969-05-27 | Addicks Guenther | Butadiene copolymer and acrylic copolymer paper coating binders | |
US3297615A (en) * | 1963-10-01 | 1967-01-10 | American Cyanamid Co | Pigment binder of acrylate-acrylonitrile-methacrylic acid for paper coatings |
NL131848C (en) * | 1963-11-20 | 1900-01-01 | ||
DE1258721B (en) * | 1964-03-03 | 1968-01-11 | Basf Ag | Binders for paper coating slips |
DE1546315B2 (en) * | 1965-01-27 | 1973-01-04 | Badische Anilin- & Soda-Fabrik Ag, 6700 Ludwigshafen | Binder mixture for paper coating slips |
GB1262460A (en) * | 1968-04-16 | 1972-02-02 | Doverstrand Ltd | Coating compositions |
US4336345A (en) * | 1971-04-23 | 1982-06-22 | Rohm And Haas Company | Composition comprising condensation cross-linkable novel methacrylate polymers |
DE2905765A1 (en) * | 1979-02-15 | 1980-09-04 | Basf Ag | PAPER COATING |
-
1982
- 1982-11-23 AT AT82201490T patent/ATE22583T1/en not_active IP Right Cessation
- 1982-11-23 DE DE8282201490T patent/DE3273596D1/en not_active Expired
- 1982-11-23 EP EP82201490A patent/EP0109463B2/en not_active Expired
-
1983
- 1983-11-22 WO PCT/US1983/001842 patent/WO1984002139A1/en unknown
- 1983-11-22 AU AU24123/84A patent/AU565959B2/en not_active Ceased
Also Published As
Publication number | Publication date |
---|---|
EP0109463A1 (en) | 1984-05-30 |
WO1984002139A1 (en) | 1984-06-07 |
DE3273596D1 (en) | 1986-11-06 |
AU565959B2 (en) | 1987-10-01 |
AU2412384A (en) | 1984-06-18 |
ATE22583T1 (en) | 1986-10-15 |
EP0109463B2 (en) | 1989-10-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA1167990A (en) | Use of an acrylate-based emulsion copolymer as the sole binder for a paper coating composition | |
US3081198A (en) | Mineral-coated paper products and methods for making them | |
EP0093206B1 (en) | Polymeric compositions useful as binders in coating colours and coating colours prepared therefrom | |
GB2101615A (en) | Hard shell soft core latex | |
EP0109463B1 (en) | Polymeric compositions useful as binders in coating colors and coating colors prepared therefrom | |
US4631312A (en) | Polymeric compositions useful as binders in coating colors and coating colors prepared therefrom | |
JP2811420B2 (en) | Method for producing resin latex | |
JP3242855B2 (en) | Diene copolymer latex | |
CA1211244A (en) | Polymeric compositions useful as binders in coating colors and coating colors prepared therefrom | |
JPH10298208A (en) | Production of copolymer latex and paper coating composition containing the copolymer latex | |
KR860001767B1 (en) | Polymeric compositions useful as binders in coating colors and coating colors prepared therefrom | |
JP3144874B2 (en) | Copolymer latex | |
KR900004686B1 (en) | Polymeric composition useful as binders in coating colors | |
JP2933985B2 (en) | Method for producing diene copolymer latex | |
JP3029298B2 (en) | Method for producing copolymer latex for paper coating | |
JP3693423B2 (en) | Copolymer latex | |
JP2011225631A (en) | Copolymer latex composition, paper-enameling composition, and enamel paper | |
JPH0441511A (en) | Production of diene copolymer latex | |
JPH0563502B2 (en) | ||
JP3089071B2 (en) | Pigment composition | |
JP3089080B2 (en) | Pigment composition | |
JPH0778320B2 (en) | Polymer compositions useful as binders for coating colorants and coating colorants made therefrom | |
JP4776341B2 (en) | Method for producing copolymer latex, copolymer latex and paper coating composition | |
JPH0441509A (en) | Production of new copolymer latex | |
JPH0819269B2 (en) | Diene copolymer latex |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19830616 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
RBV | Designated contracting states (corrected) |
Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: THE DOW CHEMICAL COMPANY |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
REF | Corresponds to: |
Ref document number: 22583 Country of ref document: AT Date of ref document: 19861015 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 3273596 Country of ref document: DE Date of ref document: 19861106 |
|
ITF | It: translation for a ep patent filed | ||
EN | Fr: translation not filed | ||
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
26 | Opposition filed |
Opponent name: ROEHM GMBH CHEMISCHE FABRIK Effective date: 19870625 |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: ROEHM GMBH CHEMISCHE FABRIK |
|
ET | Fr: translation filed | ||
REG | Reference to a national code |
Ref country code: FR Ref legal event code: BR |
|
PUAH | Patent maintained in amended form |
Free format text: ORIGINAL CODE: 0009272 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT MAINTAINED AS AMENDED |
|
27A | Patent maintained in amended form |
Effective date: 19891018 |
|
AK | Designated contracting states |
Kind code of ref document: B2 Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
ITF | It: translation for a ep patent filed | ||
ET3 | Fr: translation filed ** decision concerning opposition | ||
NLR2 | Nl: decision of opposition | ||
NLR3 | Nl: receipt of modified translations in the netherlands language after an opposition procedure | ||
ITTA | It: last paid annual fee | ||
EAL | Se: european patent in force in sweden |
Ref document number: 82201490.8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20010823 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20010827 Year of fee payment: 20 Ref country code: NL Payment date: 20010827 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20010828 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20010911 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20011022 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20011112 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20011116 Year of fee payment: 20 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20021122 Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20021122 Ref country code: CH Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20021122 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20021123 Ref country code: AT Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20021123 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 Effective date: 20021122 |
|
EUG | Se: european patent has lapsed | ||
NLV7 | Nl: ceased due to reaching the maximum lifetime of a patent |
Effective date: 20021123 |