WO1992012213A1 - Laminating adhesive - Google Patents
Laminating adhesive Download PDFInfo
- Publication number
- WO1992012213A1 WO1992012213A1 PCT/US1991/008618 US9108618W WO9212213A1 WO 1992012213 A1 WO1992012213 A1 WO 1992012213A1 US 9108618 W US9108618 W US 9108618W WO 9212213 A1 WO9212213 A1 WO 9212213A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition
- monomer
- acrylate
- ester
- polymer
- Prior art date
Links
- 239000012939 laminating adhesive Substances 0.000 title claims description 17
- 239000000203 mixture Substances 0.000 claims abstract description 122
- 239000000178 monomer Substances 0.000 claims abstract description 104
- 239000004816 latex Substances 0.000 claims abstract description 46
- 229920000126 latex Polymers 0.000 claims abstract description 46
- 230000001070 adhesive effect Effects 0.000 claims abstract description 29
- 239000000853 adhesive Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- -1 aliphatic ester Chemical class 0.000 claims description 32
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 20
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 17
- 150000002148 esters Chemical class 0.000 claims description 17
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 14
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 12
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 9
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 9
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 239000011888 foil Substances 0.000 claims description 7
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 claims description 7
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 229920000298 Cellophane Polymers 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 3
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 3
- OQYUFQVPURDFKC-UHFFFAOYSA-N 2-methylbut-1-enylbenzene Chemical compound CCC(C)=CC1=CC=CC=C1 OQYUFQVPURDFKC-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims 7
- JLPJLDMWVRIIBH-UHFFFAOYSA-M [Na+].C(C=C)(=O)OC(C)S(=O)(=O)[O-] Chemical compound [Na+].C(C=C)(=O)OC(C)S(=O)(=O)[O-] JLPJLDMWVRIIBH-UHFFFAOYSA-M 0.000 claims 6
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 claims 6
- VIHLMVXPYHFZNP-UHFFFAOYSA-M sodium;1-(2-methylprop-2-enoyloxy)ethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(C)OC(=O)C(C)=C VIHLMVXPYHFZNP-UHFFFAOYSA-M 0.000 claims 5
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims 4
- 239000010410 layer Substances 0.000 claims 4
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims 3
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 claims 3
- 231100000252 nontoxic Toxicity 0.000 claims 2
- 230000003000 nontoxic effect Effects 0.000 claims 2
- 239000012790 adhesive layer Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000010030 laminating Methods 0.000 abstract description 7
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 239000000839 emulsion Substances 0.000 description 23
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- 239000010408 film Substances 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000004094 surface-active agent Substances 0.000 description 13
- 238000007792 addition Methods 0.000 description 12
- 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 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 7
- 125000000129 anionic group Chemical group 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 230000000845 anti-microbial effect Effects 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 239000013530 defoamer Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- BTJYKXPSPBJJDQ-UHFFFAOYSA-M sodium;1,4-bis(4-methylpentan-2-yloxy)-1,4-dioxobutane-2-sulfonate Chemical compound [Na+].CC(C)CC(C)OC(=O)CC(S([O-])(=O)=O)C(=O)OC(C)CC(C)C BTJYKXPSPBJJDQ-UHFFFAOYSA-M 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000443 aerosol Substances 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- ZRKMQKLGEQPLNS-UHFFFAOYSA-N 1-Pentanethiol Chemical compound CCCCCS ZRKMQKLGEQPLNS-UHFFFAOYSA-N 0.000 description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical class C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 2
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 229920002113 octoxynol Polymers 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Chemical class 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000006460 Cyana Species 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920003182 Surlyn® Polymers 0.000 description 1
- 229920001646 UPILEX Polymers 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
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- 229920005601 base polymer Polymers 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
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- 239000003085 diluting agent Substances 0.000 description 1
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical class [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
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- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
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- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 229920009441 perflouroethylene propylene Polymers 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical class CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 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
- 238000005086 pumping Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
Definitions
- the aqueous lattices of the invention can be used as laminating adhesives in joining film layers.
- the latex adhesives of the invention combine a blend of ethylenically unsaturated monomers, resulting in superior properties that the latex imparts to the laminated product.
- aqueous lattices comprising polymers made from ethylenically unsaturated monomers that can be used in a variety of applications.
- the aqueous lattices of the invention exhibit improved properties in the emulsion form and in the laminate form when compared to solvent based polymer adhesives due to the lack of toxicity and flammability in the aqueous diluent.
- aqueous materials have certain processing advantages over hot melt materials as well related to viscosity and machinability properties.
- Aqueous lattices are prepared by the polymerization of ethylenically unsaturated monomers typically in a water dispersion using thermal or redox catalysts.
- a variety of monomer types, polymerization conditions, and catalysts have been investigated in the preparation of aqueous lattices.
- the search for a water-resistant self-emulsifiable, high solids, colloidally stable adhesive continues.
- the preferred latex adhesives of the invention should have a solids content of greater than 50 wt-% and an aqueous viscosity of less than about 5,000 preferably less than 1,000 cP.
- the adhesive should also be moisture-resistant, mechanically stable, resistant to surfactant migration, exhibit wet and dry properties, able to be readily processed, and able to be manufactured at low cost.
- an aqueous laminating latex adhesive composition that is self- emulsifiable, contains an appropriate anionic hydrophobic balance so as to obtain a good colloidal stability and high adhesion, wets typical film surfaces, is generally non- migrating, and has adequate adhesion properties so as to maintain the laminate structure.
- the polymer latex of the invention is made by polymerizing a monomer mixture consisting of: "soft" monomers that upon polymerization result in a low T g ; hard monomers such as vinyl acetate, methyl methacrylate, methyl acrylate, styrene, etc.; and a blend of anionic monomers that provide the desired lamination and stable dispersion properties.
- the resulting polymers are polydisperse and have an effective low molecular weight fraction such that the tendency of the polymer latex to wet common film surfaces is increased.
- the polymerization system has an appropriate anionic hydrophobic balance that aids colloidal stability but prevents surfactant migration.
- the resulting polymer due to the blend hard monomers, vinyl acetate, methyl methacrylate, methyl acrylate, styrene, and the "soft" monomers, has a T g that ranges from about -65 °C to 15 °C with adequate flexibility and adhesive properties at room temperature.
- the solids content is greater than 50 wt-%, the viscosity is less than 1,000 and can be less than 500 cP, and the peel strength and T-shear peel strength show adequate utility for laminating applications.
- the monomers useful in the preparation of the laminating latex of the invention comprise: (a) about 40 to 95 wt-% of at least one C 2 _ 10 aliphatic ester of acrylic or methacrylic acid; (b) about 0.1 to 5 wt-% of an alpha, beta olefinically unsaturated monomer; (c) about 0.1 to 5 wt-% of a monomer of the formula:
- R is hydrogen or a C 5 alkyl
- n is 1 to 12
- X is a proton, an alkali metal or an alkaline earth metal ion.
- the polymer formulation set forth above can also contain other monomers that can aid to optimize laminating properties.
- the latex can contain additional ingredients that can act to further enhance or stabilize the latex.
- the invention also relates to a laminate comprising two film layers bonded by the laminating latex of the inventio .
- the latex of the invention contains a C 2 _ 10 aliphatic alcohol ester of acrylic or methacrylic acid, methyl acrylate or methyl methacrylate, an olefinically unsaturated monomer containing a pendant carboxylic acid group, an ester of an alkanoic acid, and the sulfonic acid or sulfonate-containing monomer set forth above.
- the alcohol ester of acrylic or methacrylic acid can comprise ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl methacrylate, n- butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, isooctyl, amylacrylate, isoamylacrylate, etc.
- the ester of an alkanoic acrylate acid can comprise vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, etc.
- the carboxylic acid-containing monomer useful in the manufacture of the latex polymers of the invention include monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, a vinyl benzoic acid, and dicarboxylic acid half esters.
- the monomer blend useful for manufacturing the latex of the invention can also contain a variety of other ethylenically unsaturated monomers including styrene, ethylmethylstyrene, acrylonitrile, methacrylonitrile, vinyl toluene, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl butyrate, and other well known vinyl monomers.
- the blend of monomers used in the latex preparation can be adjusted using well known polymerization techniques to obtain the desired T g .
- the polymer latex of the invention also contains a sulfonic acid or sulfonate-containing monomer having the formula:
- R is a hydrogen or a C x _ 5 alkyl
- n is 1-12
- X is a proton, an amine salt, an alkali metal or an alkaline earth metal ion.
- Such monomer in combination with the carboxylic acid pendant monomer, provides anionic functionality which copolymerizes with the hard and soft monomer components to form the preferred adhesive latex systems of the invention.
- Such a blend of monomers produces the molecular weight distribution, hydrophobic anionic balance, and adhesive properties necessary to achieve a level of success required for commercial adhesive latex material.
- Suitable monomers include a sulfonic acid-substituted ethyl acrylate, sodium sulfonate- substituted n-butyl methacrylate, sodium sulfonated- substituted ethyl methacrylate, 1-propane sulfonic acid, 2- hydroxy-3-(2-propenyloxy)-sodium vinyl sulfonate, etc.
- This functional monomer contains a vinyl group to allow for incorporation into the base polymer, and a sulfonic acid or sulfonate end group to provide emulsion stability without significantly affecting water sensitivity of the dried adhesive laminate.
- a particularly preferred monomer of this type is a 2-sulfoethyl methacrylate known as Sipomer 2-SEM, which is available from W. R. Grace.
- Certain compositions of the invention can include surfactants, chain transfer agents, and polymerization initiators.
- a low level of a free surfactant enhances the emulsion stability under shear forces of pumping or coating operations without adversely affecting the water sensitivity of the adhesive laminate.
- Any of the known surfactants can be used, as for example. Aerosol MA-80, which is a dihexyl ester of sodium sulfosuccinate and is available from American Cyana ide.
- surfactants include monophenol ethoxylates, sodium dodecyl benzene sulfonates, sodium dioctyl sulfosuccinate, octyl phenol ethoxylates, octyl phenol ethoxylate sulfonates, the ammonium salt and mixtures thereof, and the like.
- the amount of surfactant in the composition is within the range of about 0.1 to 1 wt-%, preferably about 0.3 wt-%, based upon the total weight of the composition.
- Surfactants can be added prior to polymerization or after polymerization is complete.
- a chain transfer agent is used in certain preferred compositions to modify the molecular weight of the polymer.
- a particularly preferred such agent is lauryl mercaptan, e.g., n-dodecyl or t-dodecyl mercaptan.
- Other useable chain transfer agents include butyl mercaptan, amyl mercaptan, octyl mercaptan, etc.
- the chain transfer agent is generally included in the compositions at a relatively low level, i.e., within a range of about 0.01 to 2 wt-% based on the total weight of the emulsion.
- a polymerization initiator that is thermally activated is used to advantage in certain preferred emulsions of the invention as a source of free radical species.
- the initiator is typically present in an amount of about 0.01 to 4 wt-%, based on the total weight of the emulsion.
- Sodium persulfate is a particularly useful initiator.
- Others include potassium persulfate, ammonium persulfate, hydrogen peroxide, and t-butyl hydroperoxide and Vazo type irritations such as WACO 50.
- the aqueous medium is typically maintained at an acid pH of less than about 6, preferably less than about 3.
- the pH can be adjusted with commonly available bases.
- a preferred base is ammonium hydroxide.
- the polymerization is typically conducted under conventional polymerization conditions using adequate agitation, typical reactor and reaction temperature control, and maintaining the temperature between about 45 °C to 100 °C.
- the aqueous polymerization system contains greater than about 40 wt-%, preferably greater than about 50 wt-%, solids based on the total emulsion.
- conventional free radical initiators of the thermal and redox type can be used.
- chain transfer agents can be employed conventionally, to control molecular weight and distribution.
- the major thrust of the latex system of the invention is the blend of hard monomers, soft monomers, carboxylic functional monomers, and sulfonic acid substituted monomers which copolymerize to form the useful adhesive of the invention.
- minimal amounts of additional emulsifiers can be used in the preparation of the emulsion.
- Resin can be recovered if desired, preferably by spray drying, coagulation, dewatering or drying to yield a hard particulate resin.
- the material is sold in aqueous concentrate form.
- Films that can be used for forming the laminates of the invention are commonly organic film-forming compositions that can be formed from a variety of common polymeric films including printed papers, metallized papers, metal foils, or various chemical or energy surface treated films.
- Thermoplastic resins are also useful in the laminate films of the invention.
- Useful addition polymers include poly alpha-olefins, polyethylene, polypropylene, poly 4- methyl-pentene-1, ethylene/vinyl copolymers ethylene vinyl acetate copolymers, ethylene acrylic acid copolymers, ethylene methacrylate copolymers, ethyl-methylacrylate copolymers, etc.; thermoplastic propylene polymers such as polypropylene, ethylene-propylene copolymers, etc.; vinyl chloride polymers and copolymers; vinylidene chloride polymers and copolymers; polyvinyl alcohols, acrylic polymers made from acrylic acid, methacrylic acid, methylacrylate, methacrylate, acrylamide and others.
- Fluorocarbon resins such as polytetrafluoroethylene, polyvinylidiene fluoride, and fluorinated ethylene- propylene resins.
- Styrene resins such as a polystyrene, alpha-methylstyrene, high impact polystyrene acrylonitrile- butadiene-styrene polymers and others.
- Preferred material for use in the laminate of the invention are polyester film materials such as poly- ethylene-teraphthlate, polybutylene teraphthlate and polyimide materials. These film materials are sold by duPont, Allied-Apical, Tiejin, Kanega-fuchi, as Mylar , Kapton ® , Apical , Upilex , etc., films.
- the polymerization process of the invention includes a first step of introducing the monomers singly, or in the mixture, into the aqueous solution contained within a conventional polymerization reactor.
- the water contains a small amount of a free surfactant.
- the monomer feed and polymerization reaction is generally carried out at a temperature of from about 25 °C to about 100 °C, preferably at a temperature within the range of about 60 °C to 90 °C. More preferably, the reactor charge is heated to about 70 °C to 80 °C. A small amount of the monomer mix is then added (about 2%).
- the monomer mix typically contains all monomers and the chain transfer agent, but not the sulfonate-containing component if it is not soluble in the particular mix of monomers.
- the time of reaction is not critical but depends on many variables such as particular monomer blends, concentration of initiator, heat removal capacity, reactor size, batch size, etc.
- the initiator is then added in an amount within the range of about 0.1 to 4 wt-%, preferably at about 2 wt-% of the total weight of the emulsion.
- the reactor charge is then further heated to about 78 °C to 82 °C.
- the remainder of the monomer mix, the catalyst, and the sulfonate-containing component are then added separately and slowly to the reactor charge. After a hold period of about 30 minutes to one hour, the reactor contents are cooled to ambient and the emulsion is filtered.
- the latex prepared by the process of the invention can contain up to 70 wt-% of the polymer based on the total weight of the latex, and preferably from about 45 to 65 wt- %.
- the latex adhesive produced provides great flexibility in producing quick tack, peel strength, shear strength, viscosity, emulsion stability, etc.
- the lattices prepared using the process of the invention have relatively high surface tension due to the absence of free surfactant in the latex. Depending on the polymer film and other variables in the lamination process, the surface tension may be modified by adding small amounts of surfactants.
- the latex produced by the process of the invention may also contain other additives well known to those skilled in the art including pH control agents, foam control agents, salts and organic solvents, dyes, perfumes, etc.
- the latex adhesive compositions of the invention may be used to produce laminates from a wide variety of sheet-like flexible webs.
- the preferred laminates are made from polyethylene, polypropylene, polyesters such as polyethylene teraphthlate, cellophane, polyimide polyvinyl chloride, polyvinylidiene dichloride, nylon, paper, woven and nonwoven fabrics made from fibers comprising cotton, polyester polyolefin, polyamide, polyimide, and the like can be used. Additionally, metallic sheet-like materials such as aluminum foil, metallized film, paper and paperboard, foam materials, etc., can be used.
- Laminates can be formed using the adhesive of the invention using conventional techniques employed to apply aqueous based adhesive emulsions to a continuous web.
- the adhesive may be applied to film web by any standard mechanical coating process such as road coating, 3 roll coating gravure processing, etc. Most commonly, the adhesive is coated on the primary web and is heated to remove residual water. The adhesive is then laminated with an additional film web or substrate.
- the product of the present invention exhibits excellent mechanical stability, good wetting to a variety of film substrates, and minimal foaming.
- the laminating adhesive latex composition of the present invention may exhibit varying leveling qualities during application. An addition of about 2 wt-% or less of n-propyl alcohol or isopropyl alcohol to the composition can improve the leveling qualities.
- higher machine speeds as surfactants such as acetylnic glycol or sodium dioctyl sulfosuccinate can produce better leveling.
- a smoothing bar may be used to enhance leveling.
- Example 1 The laminating adhesive surfactant-free latex composition made according to Example 1 was coated at 1.5 to 2.0 lbs/3000 ft 2 dry on 2.0 mil thick polyester and laminated to one of the following substrates: LDPE, aluminum foil, polyprolylene, surlyn, PVDC cellophane. This was also done for a solvent-based system and for a surfactant-stabilized system. These laminations were aged for three days under ambient conditions prior to exposure to humidity or further testing. The data listed below under the "Dry Peel” results were for samples that were aged for 21 days at ambient temperature and humidity. The data listed below under the "Wet Peel” results were for samples that were aged for 21 days at room temperature and 100% relative humidity.
- the material has a theoretical Tg of -41 °C and contains 52% solids.
- Example 2 A preferred laminating adhesive surfactant-free latex composition was prepared in the following manner. At room temperature, deionized water (32.65 parts by weight). Aerosol M-80 (0.07 parts by weight), and aqueous ammonia (26° Braume, 0.14 parts by weight) were charged to a reactor equipped with a nitrogen purge. With mixing, the reactor charge was heated to 75.5°C. A monomer mix was prepared from 29.47 parts by weight 2-ethyl-hexyl-acrylate, 9.97 parts by weight methyl methacrylate, 7.25 parts by weight vinyl acetate, 1.00 parts by weight glacial acrylic acid, and 0.14 parts by weight lauryl mercaptan. About 2% of the monomer mix wa then added to the reactor.
- Sodium persulfate (0.27 parts by weight) in deionized water (1.39 parts by weight) was then added to the reactor and the contents were immediately heated to 82.5°C. with steam and held at that temperature (plus or minus about 1.5°C.)_ for about 15 minutes.
- the remainder of the monomer mix, sodium persulfate (0.14 parts by weight) in deionized water (4.18 parts by weight), and 2-SEM (0.42 parts by weight) in deionized water (4.18 parts by weight) with Aerosol MA-80 (0.33 parts by weight) were then added separately and slowly to the reactor charge.
- the remaining monomer mix was added over a period of 3 hours, the catalyst (sodium persulfate) was added over a period of 3.5 hours, and the 2-SEM mixture was added over a period of 3 hours.
- the temperature was maintained with the range of 81.5°C. to 83.5°C. during the period of addition and after all additions were made for an additional hour.
- the reactor contents were cooled to room temperature (about 25°C).
- Defoamer (0.50 parts by weight, available from Colloids) and antimicrobial (0.05 parts by weight, available from ICI), were then added and the emulsion mixed for 10 minutes. The emulsion was then filtered through a 75 micron filter.
- Example 3 A preferred laminating adhesive surfactant-free latex composition was prepared in the following manner. At room temperature, deionized water (32.65 parts by weight) and aqueous ammonia (26° Baume, 0.14 parts by weight) were charged to a reactor equipped with a nitrogen purge. With mixing, the reactor charge was heated to 75.5°C. A monomer mix was prepared from 41.82 parts by eight n-butyl acrylate, 9.97 parts by weight methyl methacrylate, 3.20 parts by weight vinyl acetate, 1.00 parts by weight glacial acrylic acid, and 0.14 parts by weight tert-dodeyl mercaptan. About 2% of the monomer mix was then added to the reactor.
- Sodium persulfate (0.27 parts by weight) in deionized water (1.39 parts by weight) was then added to the reactor and the contents were immediately heated to 82.5°C. with steam and held at that temperature (plus or minus about 1.5°C.) for about 15 minutes.
- the remainder of the monomer mix, sodium persulfate (0.14 parts by weight) in deionized water (4.18 parts by weight), and 2-SEM (0.42 parts by weight) in deionized water (4.18 parts by weight) with Aerosol MA-80 (0.33 parts by weight) were then added separately and slowly to the reactor charge.
- the remaining monomer mix was added over a period of 3 hours, the catalyst (sodium persulfate) was added over a period of 3.5 hours, and the 2-SEM mixture was added over a period of 3 hours.
- the temperature was maintained within the range of 81.5°C. to 83.5°C. during the period of addition and after all additions were made for an additional hour.
- the reactor contents were cooled to room temperature (about 25°C).
- Defoamer 0.05 parts by weight, available from Colloids
- antimicrobial 0.05 parts by weight, available from ICI
- Example 4 A preferred laminating adhesive surfactant-free latex composition was prepared in the following manner. At room temperature, deionized water (32.65 parts by weight), and Aerosol OT-75 (0.07 parts by weight), 0.14 parts by weight) were charged to a reactor equipped with a nitrogen purge. With mixing, the reactor charge was heated to 75.5°C. A monomer mix was prepared from 36.24 parts by weight n-butyl acrylate, 6.97 parts by weight 2-ethyl hexyl acrylate, 9.97 parts by weight methyl methacrylate, 1.81 parts by weight vinyl acetate, 1.00 parts by weight glacial acrylic acid, and 0.14 parts by weight lauryl mercaptan. About 2% of the monomer mix was then added to the reactor.
- Potassium persulfate (0.27 parts by weight) in deionized water (1.39 parts by weight) was then added to the reactor and the contents were immediately heated to 82.5°C. with steam and held at that temperature (plus or minus about 1.5°C.) for about 15 minutes.
- the remainder of the monomer mix, potassium persulfate (0.14 parts by weight) in deionized water (4.18 parts by weight), and 2-SEM (0.42 parts by weight) in deionized water (4.18 parts by weight) with Aerosol OT-75 (0.33 parts by weight) were then added separately and slowly to the reactor charge.
- Example 5 A preferred laminating adhesive surfactant-free latex composition was prepared in the following manner.
- deionized water 32.65 parts by weight
- Aerosol M-80 (0.07 parts by weight)
- aqueous ammonia 26 degrees Baume, 0.14 parts by weight
- a monomer mix was prepared from 43.21 parts by weight n-butyl acrylate, 9.97 parts by weight methyl methacrylate, 1.81 parts by weight vinyl acetate, 1.00 parts by weight glacial acrylic acid, and 0.14 parts by weight lauryl mercaptan. About 2% of the monomer mix was then added to the reactor.
- Sodium persulfate (0.27 parts by weight) in deionized water (1.39 parts by weight) was then added to the reactor and the contents were immediately heated to 82 °C with steam and held at that temperature (plus or minus about 1 °C) for about 15 minutes.
- the remainder of the monomer mix, sodium persulfate (0.14 parts by weight) in deionized water (4.18 parts by weight), and 2-SEM (0.42 parts by weight) in deionized water (4.18 parts by weight) with Aerosol MA-80 (0.33 parts by weight) were then added separately and slowly to the reactor charge.
- the remaining monomer mix was added over a period of 3 hours, the catalyst (sodium persulfate) was added over a period of 3.5 hours, and the 2-SEM mixture was added over a period of 3 hours.
- the temperature was maintained within the range of 81 °C to 83 °C during the period of addition and after all additions were made for an additional hour.
- the reactor contents were cooled to room temperature (about 25 °C) .
- Defoamer 0.05 parts by weight, available from Colloids
- antimicrobial 0.05 parts by weight, available from ICI
- Example 6 A preferred laminating adhesive surfactant-free latex composition was prepared in the following manner. At room temperature, deionized water (32.65 parts by weight), Aerosol M-80 (0.07 parts by weight), and aqueous ammonia (26° Baume, 0.14 parts by weight) were charged to a reactor equipped with a nitrogen purge. With mixing, the reactor charge was heated to 75.5°C. A monomer mix was prepared from 44.55 parts by weight n-butyl acrylate, 3.48 parts by weight methyl methacrylate, 6.96 parts by weight styrene, 1.00 parts by weight glacial acrylic acid, and 0.14 parts by weight tert-dodecyl mercaptan.
- the remaining monomer mix was added over a period of 3 hours, the catalyst (potassium persulfate) was added over a period of 3.5 hours, and the 2-SEM mixture was added over a period of 3 hours.
- the temperature was maintained within the range of 81.5°C. to 83.5°C. during the period of addition and after all additions were made for an additional our.
- the reactor contents were cooled to room temperature (about 25°C).
- Defoamer 0.05 parts by weight, available from Colloids
- antimicrobial 0.05 parts by weight, available from ICI
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Laminating latex adhesive materials have been prepared by polymerizing a blend of ethylenically unsaturated monomers in combination with a particular class of a copolymerizable surfactant-functional monomer.
Description
LAMINATING ADHESIVE
Field of the Invention
The aqueous lattices of the invention can be used as laminating adhesives in joining film layers. The latex adhesives of the invention combine a blend of ethylenically unsaturated monomers, resulting in superior properties that the latex imparts to the laminated product.
Background of the Invention A great deal of attention has been directed in recent years to the preparation of aqueous lattices comprising polymers made from ethylenically unsaturated monomers that can be used in a variety of applications. The aqueous lattices of the invention exhibit improved properties in the emulsion form and in the laminate form when compared to solvent based polymer adhesives due to the lack of toxicity and flammability in the aqueous diluent. Further, aqueous materials have certain processing advantages over hot melt materials as well related to viscosity and machinability properties.
Aqueous lattices are prepared by the polymerization of ethylenically unsaturated monomers typically in a water dispersion using thermal or redox catalysts. A variety of monomer types, polymerization conditions, and catalysts have been investigated in the preparation of aqueous lattices. In the manufacture of aqueous latex adhesives for film lamination purposes, however, the search for a water-resistant self-emulsifiable, high solids, colloidally stable adhesive continues.
We have found that there is no adequate aqueous latex laminating adhesive available to date that has a blend of properties that adequately serves the needs of laminate manufacturers in the food and non-food flexible packaging
marketplace. To meet these needs, the preferred latex adhesives of the invention should have a solids content of greater than 50 wt-% and an aqueous viscosity of less than about 5,000 preferably less than 1,000 cP. The adhesive should also be moisture-resistant, mechanically stable, resistant to surfactant migration, exhibit wet and dry properties, able to be readily processed, and able to be manufactured at low cost.
Accordingly, a substantial need exists for an aqueous laminating latex adhesive composition that is self- emulsifiable, contains an appropriate anionic hydrophobic balance so as to obtain a good colloidal stability and high adhesion, wets typical film surfaces, is generally non- migrating, and has adequate adhesion properties so as to maintain the laminate structure.
Summary of the Invention We have found a novel laminating latex that is manufactured by polymerization of anionic and hydrophobic monomers, produces a polymer having a range of molecular weights and T. that is colloidally stable, and wets common film surfaces. The polymer latex of the invention is made by polymerizing a monomer mixture consisting of: "soft" monomers that upon polymerization result in a low Tg; hard monomers such as vinyl acetate, methyl methacrylate, methyl acrylate, styrene, etc.; and a blend of anionic monomers that provide the desired lamination and stable dispersion properties. We have found that the resulting polymers are polydisperse and have an effective low molecular weight fraction such that the tendency of the polymer latex to wet common film surfaces is increased. We have found that the polymerization system has an appropriate anionic hydrophobic balance that aids colloidal stability but prevents surfactant migration. The resulting polymer, due to the blend hard monomers, vinyl acetate, methyl
methacrylate, methyl acrylate, styrene, and the "soft" monomers, has a Tg that ranges from about -65 °C to 15 °C with adequate flexibility and adhesive properties at room temperature. The solids content is greater than 50 wt-%, the viscosity is less than 1,000 and can be less than 500 cP, and the peel strength and T-shear peel strength show adequate utility for laminating applications.
The monomers useful in the preparation of the laminating latex of the invention comprise: (a) about 40 to 95 wt-% of at least one C2_10 aliphatic ester of acrylic or methacrylic acid; (b) about 0.1 to 5 wt-% of an alpha, beta olefinically unsaturated monomer; (c) about 0.1 to 5 wt-% of a monomer of the formula:
wherein R is hydrogen or a C 5 alkyl, n is 1 to 12 and X is a proton, an alkali metal or an alkaline earth metal ion. The polymer formulation set forth above can also contain other monomers that can aid to optimize laminating properties. Further, the latex can contain additional ingredients that can act to further enhance or stabilize the latex. The invention also relates to a laminate comprising two
film layers bonded by the laminating latex of the inventio .
Detailed Description of the Invention As set forth above, the latex of the invention contains a C2_10 aliphatic alcohol ester of acrylic or methacrylic acid, methyl acrylate or methyl methacrylate, an olefinically unsaturated monomer containing a pendant carboxylic acid group, an ester of an alkanoic acid, and the sulfonic acid or sulfonate-containing monomer set forth above.
The alcohol ester of acrylic or methacrylic acid can comprise ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl methacrylate, n- butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, isooctyl, amylacrylate, isoamylacrylate, etc. The ester of an alkanoic acrylate acid can comprise vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, etc. The carboxylic acid-containing monomer useful in the manufacture of the latex polymers of the invention include monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, a vinyl benzoic acid, and dicarboxylic acid half esters. The monomer blend useful for manufacturing the latex of the invention can also contain a variety of other ethylenically unsaturated monomers including styrene, ethylmethylstyrene, acrylonitrile, methacrylonitrile, vinyl toluene, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl butyrate, and other well known vinyl monomers. The blend of monomers used in the latex preparation can be adjusted using well known polymerization techniques to obtain the desired Tg.
The polymer latex of the invention also contains a sulfonic acid or sulfonate-containing monomer having the formula:
wherein R is a hydrogen or a Cx_5 alkyl, n is 1-12 and X is a proton, an amine salt, an alkali metal or an alkaline earth metal ion. Such monomer, in combination with the carboxylic acid pendant monomer, provides anionic functionality which copolymerizes with the hard and soft monomer components to form the preferred adhesive latex systems of the invention. Such a blend of monomers produces the molecular weight distribution, hydrophobic anionic balance, and adhesive properties necessary to achieve a level of success required for commercial adhesive latex material. Examples of suitable monomers include a sulfonic acid-substituted ethyl acrylate, sodium sulfonate- substituted n-butyl methacrylate, sodium sulfonated- substituted ethyl methacrylate, 1-propane sulfonic acid, 2- hydroxy-3-(2-propenyloxy)-sodium vinyl sulfonate, etc. This functional monomer contains a vinyl group to allow for incorporation into the base polymer, and a sulfonic acid or sulfonate end group to provide emulsion stability without
significantly affecting water sensitivity of the dried adhesive laminate. A particularly preferred monomer of this type is a 2-sulfoethyl methacrylate known as Sipomer 2-SEM, which is available from W. R. Grace. Certain compositions of the invention can include surfactants, chain transfer agents, and polymerization initiators. A low level of a free surfactant enhances the emulsion stability under shear forces of pumping or coating operations without adversely affecting the water sensitivity of the adhesive laminate. Any of the known surfactants can be used, as for example. Aerosol MA-80, which is a dihexyl ester of sodium sulfosuccinate and is available from American Cyana ide. Other surfactants include monophenol ethoxylates, sodium dodecyl benzene sulfonates, sodium dioctyl sulfosuccinate, octyl phenol ethoxylates, octyl phenol ethoxylate sulfonates, the ammonium salt and mixtures thereof, and the like. The amount of surfactant in the composition is within the range of about 0.1 to 1 wt-%, preferably about 0.3 wt-%, based upon the total weight of the composition. Surfactants can be added prior to polymerization or after polymerization is complete.
A chain transfer agent is used in certain preferred compositions to modify the molecular weight of the polymer. A particularly preferred such agent is lauryl mercaptan, e.g., n-dodecyl or t-dodecyl mercaptan. Other useable chain transfer agents include butyl mercaptan, amyl mercaptan, octyl mercaptan, etc. The chain transfer agent is generally included in the compositions at a relatively low level, i.e., within a range of about 0.01 to 2 wt-% based on the total weight of the emulsion.
A polymerization initiator that is thermally activated is used to advantage in certain preferred emulsions of the invention as a source of free radical species. The initiator is typically present in an amount of about 0.01
to 4 wt-%, based on the total weight of the emulsion. Sodium persulfate is a particularly useful initiator. Others include potassium persulfate, ammonium persulfate, hydrogen peroxide, and t-butyl hydroperoxide and Vazo type irritations such as WACO 50.
In the preparation of the aqueous latex of the invention, the aqueous medium is typically maintained at an acid pH of less than about 6, preferably less than about 3. The pH can be adjusted with commonly available bases. A preferred base is ammonium hydroxide. The polymerization is typically conducted under conventional polymerization conditions using adequate agitation, typical reactor and reaction temperature control, and maintaining the temperature between about 45 °C to 100 °C. Generally, the aqueous polymerization system contains greater than about 40 wt-%, preferably greater than about 50 wt-%, solids based on the total emulsion. As stated above, conventional free radical initiators of the thermal and redox type can be used. Also, chain transfer agents can be employed conventionally, to control molecular weight and distribution.
The major thrust of the latex system of the invention is the blend of hard monomers, soft monomers, carboxylic functional monomers, and sulfonic acid substituted monomers which copolymerize to form the useful adhesive of the invention. To enhance the properties of the latex of this invention, minimal amounts of additional emulsifiers can be used in the preparation of the emulsion. Resin can be recovered if desired, preferably by spray drying, coagulation, dewatering or drying to yield a hard particulate resin. Preferably, however, the material is sold in aqueous concentrate form.
Film Substrate Materials Films that can be used for forming the laminates of the invention are commonly organic film-forming compositions that can be formed from a variety of common polymeric films including printed papers, metallized papers, metal foils, or various chemical or energy surface treated films.
Thermoplastic resins are also useful in the laminate films of the invention. Useful addition polymers include poly alpha-olefins, polyethylene, polypropylene, poly 4- methyl-pentene-1, ethylene/vinyl copolymers ethylene vinyl acetate copolymers, ethylene acrylic acid copolymers, ethylene methacrylate copolymers, ethyl-methylacrylate copolymers, etc.; thermoplastic propylene polymers such as polypropylene, ethylene-propylene copolymers, etc.; vinyl chloride polymers and copolymers; vinylidene chloride polymers and copolymers; polyvinyl alcohols, acrylic polymers made from acrylic acid, methacrylic acid, methylacrylate, methacrylate, acrylamide and others. Fluorocarbon resins such as polytetrafluoroethylene, polyvinylidiene fluoride, and fluorinated ethylene- propylene resins. Styrene resins such as a polystyrene, alpha-methylstyrene, high impact polystyrene acrylonitrile- butadiene-styrene polymers and others. Preferred material for use in the laminate of the invention are polyester film materials such as poly- ethylene-teraphthlate, polybutylene teraphthlate and polyimide materials. These film materials are sold by duPont, Allied-Apical, Tiejin, Kanega-fuchi, as Mylar , Kapton®, Apical , Upilex , etc., films.
In somewhat greater detail, the polymerization process of the invention includes a first step of introducing the monomers singly, or in the mixture, into the aqueous solution contained within a conventional polymerization reactor. Typically, the water contains a small amount of a
free surfactant. The monomer feed and polymerization reaction is generally carried out at a temperature of from about 25 °C to about 100 °C, preferably at a temperature within the range of about 60 °C to 90 °C. More preferably, the reactor charge is heated to about 70 °C to 80 °C. A small amount of the monomer mix is then added (about 2%). The monomer mix typically contains all monomers and the chain transfer agent, but not the sulfonate-containing component if it is not soluble in the particular mix of monomers. The time of reaction is not critical but depends on many variables such as particular monomer blends, concentration of initiator, heat removal capacity, reactor size, batch size, etc. After a small amount of the monomer mix has been added, the initiator is then added in an amount within the range of about 0.1 to 4 wt-%, preferably at about 2 wt-% of the total weight of the emulsion. The reactor charge is then further heated to about 78 °C to 82 °C. The remainder of the monomer mix, the catalyst, and the sulfonate-containing component are then added separately and slowly to the reactor charge. After a hold period of about 30 minutes to one hour, the reactor contents are cooled to ambient and the emulsion is filtered.
The latex prepared by the process of the invention and can contain up to 70 wt-% of the polymer based on the total weight of the latex, and preferably from about 45 to 65 wt- %. The latex adhesive produced provides great flexibility in producing quick tack, peel strength, shear strength, viscosity, emulsion stability, etc. Generally, the lattices prepared using the process of the invention have relatively high surface tension due to the absence of free surfactant in the latex. Depending on the polymer film and other variables in the lamination process, the surface tension may be modified by adding small amounts of surfactants.
The latex produced by the process of the invention may also contain other additives well known to those skilled in the art including pH control agents, foam control agents, salts and organic solvents, dyes, perfumes, etc. The latex adhesive compositions of the invention may be used to produce laminates from a wide variety of sheet-like flexible webs.
The preferred laminates are made from polyethylene, polypropylene, polyesters such as polyethylene teraphthlate, cellophane, polyimide polyvinyl chloride, polyvinylidiene dichloride, nylon, paper, woven and nonwoven fabrics made from fibers comprising cotton, polyester polyolefin, polyamide, polyimide, and the like can be used. Additionally, metallic sheet-like materials such as aluminum foil, metallized film, paper and paperboard, foam materials, etc., can be used.
Laminates can be formed using the adhesive of the invention using conventional techniques employed to apply aqueous based adhesive emulsions to a continuous web. Thus, the adhesive may be applied to film web by any standard mechanical coating process such as road coating, 3 roll coating gravure processing, etc. Most commonly, the adhesive is coated on the primary web and is heated to remove residual water. The adhesive is then laminated with an additional film web or substrate.
The product of the present invention exhibits excellent mechanical stability, good wetting to a variety of film substrates, and minimal foaming. As with many water-based products, the laminating adhesive latex composition of the present invention may exhibit varying leveling qualities during application. An addition of about 2 wt-% or less of n-propyl alcohol or isopropyl alcohol to the composition can improve the leveling qualities. In addition, higher machine speeds as surfactants such as acetylnic glycol or sodium dioctyl sulfosuccinate can produce better leveling.
In some cases a smoothing bar may be used to enhance leveling.
The following examples and test data illustrate the preparation of the emulsion adhesives of the invention and their use in the preparation of film laminates.
Example 1 The laminating adhesive surfactant-free latex composition made according to Example 1 was coated at 1.5 to 2.0 lbs/3000 ft2 dry on 2.0 mil thick polyester and laminated to one of the following substrates: LDPE, aluminum foil, polyprolylene, surlyn, PVDC cellophane. This was also done for a solvent-based system and for a surfactant-stabilized system. These laminations were aged for three days under ambient conditions prior to exposure to humidity or further testing. The data listed below under the "Dry Peel" results were for samples that were aged for 21 days at ambient temperature and humidity. The data listed below under the "Wet Peel" results were for samples that were aged for 21 days at room temperature and 100% relative humidity.
The surfactant-based system contains 30.84% 2-ethyl hexyl acrylate, 16.84% vinyl acetate, 0.7% 2-hydroxy ethyl acrylate, 0.36 lauryl mercaptan, 47.26% deionized water, 1.04% sodium lauryl sulfate, 1.08% nonylphenoxypoly(ethyleneoxy)ethanol (HLB = 13.0), 1.14 hydroxyehtylcellulose, 0.28 ammonium persulfate initiator, 0.39 sodium bicarbonate buffer, 0.07% preservative. The material has a theoretical Tg of -41 °C and contains 52% solids.
Example 2 A preferred laminating adhesive surfactant-free latex composition was prepared in the following manner. At room temperature, deionized water (32.65 parts by weight).
Aerosol M-80 (0.07 parts by weight), and aqueous ammonia (26° Braume, 0.14 parts by weight) were charged to a reactor equipped with a nitrogen purge. With mixing, the reactor charge was heated to 75.5°C. A monomer mix was prepared from 29.47 parts by weight 2-ethyl-hexyl-acrylate, 9.97 parts by weight methyl methacrylate, 7.25 parts by weight vinyl acetate, 1.00 parts by weight glacial acrylic acid, and 0.14 parts by weight lauryl mercaptan. About 2% of the monomer mix wa then added to the reactor. Sodium persulfate (0.27 parts by weight) in deionized water (1.39 parts by weight) was then added to the reactor and the contents were immediately heated to 82.5°C. with steam and held at that temperature (plus or minus about 1.5°C.)_ for about 15 minutes. The remainder of the monomer mix, sodium persulfate (0.14 parts by weight) in deionized water (4.18 parts by weight), and 2-SEM (0.42 parts by weight) in deionized water (4.18 parts by weight) with Aerosol MA-80 (0.33 parts by weight) were then added separately and slowly to the reactor charge. The remaining monomer mix was added over a period of 3 hours, the catalyst (sodium persulfate) was added over a period of 3.5 hours, and the 2-SEM mixture was added over a period of 3 hours. The temperature was maintained with the range of 81.5°C. to 83.5°C. during the period of addition and after all additions were made for an additional hour. The reactor contents were cooled to room temperature (about 25°C). Defoamer (0.50 parts by weight, available from Colloids) and antimicrobial (0.05 parts by weight, available from ICI), were then added and the emulsion mixed for 10 minutes. The emulsion was then filtered through a 75 micron filter.
Example 3 A preferred laminating adhesive surfactant-free latex composition was prepared in the following manner. At room
temperature, deionized water (32.65 parts by weight) and aqueous ammonia (26° Baume, 0.14 parts by weight) were charged to a reactor equipped with a nitrogen purge. With mixing, the reactor charge was heated to 75.5°C. A monomer mix was prepared from 41.82 parts by eight n-butyl acrylate, 9.97 parts by weight methyl methacrylate, 3.20 parts by weight vinyl acetate, 1.00 parts by weight glacial acrylic acid, and 0.14 parts by weight tert-dodeyl mercaptan. About 2% of the monomer mix was then added to the reactor. Sodium persulfate (0.27 parts by weight) in deionized water (1.39 parts by weight) was then added to the reactor and the contents were immediately heated to 82.5°C. with steam and held at that temperature (plus or minus about 1.5°C.) for about 15 minutes. The remainder of the monomer mix, sodium persulfate (0.14 parts by weight) in deionized water (4.18 parts by weight), and 2-SEM (0.42 parts by weight) in deionized water (4.18 parts by weight) with Aerosol MA-80 (0.33 parts by weight) were then added separately and slowly to the reactor charge. The remaining monomer mix was added over a period of 3 hours, the catalyst (sodium persulfate) was added over a period of 3.5 hours, and the 2-SEM mixture was added over a period of 3 hours. The temperature was maintained within the range of 81.5°C. to 83.5°C. during the period of addition and after all additions were made for an additional hour. The reactor contents were cooled to room temperature (about 25°C). Defoamer (0.05 parts by weight, available from Colloids) and antimicrobial (0.05 parts by weight, available from ICI) were then added and the emulsion mixed for 10 minutes. The emulsion was then filtered through a 75 micron filter.
Example 4 A preferred laminating adhesive surfactant-free latex composition was prepared in the following manner. At room
temperature, deionized water (32.65 parts by weight), and Aerosol OT-75 (0.07 parts by weight), 0.14 parts by weight) were charged to a reactor equipped with a nitrogen purge. With mixing, the reactor charge was heated to 75.5°C. A monomer mix was prepared from 36.24 parts by weight n-butyl acrylate, 6.97 parts by weight 2-ethyl hexyl acrylate, 9.97 parts by weight methyl methacrylate, 1.81 parts by weight vinyl acetate, 1.00 parts by weight glacial acrylic acid, and 0.14 parts by weight lauryl mercaptan. About 2% of the monomer mix was then added to the reactor. Potassium persulfate (0.27 parts by weight) in deionized water (1.39 parts by weight) was then added to the reactor and the contents were immediately heated to 82.5°C. with steam and held at that temperature (plus or minus about 1.5°C.) for about 15 minutes. The remainder of the monomer mix, potassium persulfate (0.14 parts by weight) in deionized water (4.18 parts by weight), and 2-SEM (0.42 parts by weight) in deionized water (4.18 parts by weight) with Aerosol OT-75 (0.33 parts by weight) were then added separately and slowly to the reactor charge. The remaining monomer mix was added over a period of 3 hours, the catalyst (potassium persulfate) was added over a period of 3.5 hours, and the 2-SEM mixture was added over a period of 3 hours. The temperature was maintained within the range of 81.5°C. to 83.5°C. during the period of addition and after all additions were made for an additional hour. The reactor contents were cooled to room temperature (about 25°C). Defoamer (0.05 parts by weight, available from Colloids) and antimicrobial (0.05 parts by weight, available from ICI) were then added and the emulsion mixed for 10 minutes. The emulsion was then filtered through a 75 micron filter.
Example 5 A preferred laminating adhesive surfactant-free latex composition was prepared in the following manner. At room temperature, deionized water (32.65 parts by weight), Aerosol M-80 (0.07 parts by weight), and aqueous ammonia (26 degrees Baume, 0.14 parts by weight) were charged to a reactor equipped with a nitrogen purge. With mixing, the reactor charge was heated to 75 °C. A monomer mix was prepared from 43.21 parts by weight n-butyl acrylate, 9.97 parts by weight methyl methacrylate, 1.81 parts by weight vinyl acetate, 1.00 parts by weight glacial acrylic acid, and 0.14 parts by weight lauryl mercaptan. About 2% of the monomer mix was then added to the reactor. Sodium persulfate (0.27 parts by weight) in deionized water (1.39 parts by weight) was then added to the reactor and the contents were immediately heated to 82 °C with steam and held at that temperature (plus or minus about 1 °C) for about 15 minutes. The remainder of the monomer mix, sodium persulfate (0.14 parts by weight) in deionized water (4.18 parts by weight), and 2-SEM (0.42 parts by weight) in deionized water (4.18 parts by weight) with Aerosol MA-80 (0.33 parts by weight) were then added separately and slowly to the reactor charge. The remaining monomer mix was added over a period of 3 hours, the catalyst (sodium persulfate) was added over a period of 3.5 hours, and the 2-SEM mixture was added over a period of 3 hours. The temperature was maintained within the range of 81 °C to 83 °C during the period of addition and after all additions were made for an additional hour. The reactor contents were cooled to room temperature (about 25 °C) . Defoamer (0.05 parts by weight, available from Colloids) and antimicrobial (0.05 parts by weight, available from ICI) were then added and the emulsion mixed for 10 minutes. The emulsion was then filtered through a 75 micron filter.
Example 6 A preferred laminating adhesive surfactant-free latex composition was prepared in the following manner. At room temperature, deionized water (32.65 parts by weight), Aerosol M-80 (0.07 parts by weight), and aqueous ammonia (26° Baume, 0.14 parts by weight) were charged to a reactor equipped with a nitrogen purge. With mixing, the reactor charge was heated to 75.5°C. A monomer mix was prepared from 44.55 parts by weight n-butyl acrylate, 3.48 parts by weight methyl methacrylate, 6.96 parts by weight styrene, 1.00 parts by weight glacial acrylic acid, and 0.14 parts by weight tert-dodecyl mercaptan. About 2% of the monomer mix was then added to the reactor. Potassium persulfate (0.27 parts by weight) in deionized water (1.39 parts by weight) was then added to the reactor and the contents were immediately heated to 82.5°C. with steam and held at that temperature (plus or minus about 1.5°C.) for 15 minutes. The remainder of the monomer mix, potassium persulfate (0.14 parts by weight) in deionized water (4.18 parts by weight), and 2-SEM (0.42 parts by weight) in deionized water (4.18 parts by weight) with Aerosol MA-80 (0.33 parts by weight) were then added separately and slowly to the reactor charge. The remaining monomer mix was added over a period of 3 hours, the catalyst (potassium persulfate) was added over a period of 3.5 hours, and the 2-SEM mixture was added over a period of 3 hours. The temperature was maintained within the range of 81.5°C. to 83.5°C. during the period of addition and after all additions were made for an additional our. The reactor contents were cooled to room temperature (about 25°C). Defoamer (0.05 parts by weight, available from Colloids) and antimicrobial (0.05 parts by weight, available from ICI) were then added and the emulsion mixed for 10 minutes. The emulsion was then filtered through a 75 micron filter.
The above specification, examples, comparative examples and data provide detailed explanation and discussion of the current embodiment of the claimed invention. However, many embodiments to the invention can be made without departing from the spirit and scope of the invention. Accordingly, the invention resides on the claims hereinafter appended.
Claims
1. A laminating adhesive latex composition comprising a major proportion of water and dispersed therein a polymer composition comprising: (a) about 40 to 95 wt-% of at least one C2_10 aliphatic ester of acrylic or methacrylic acid;
(b) about 0.1 to 5 wt-% of an alpha,beta olefinically unsaturated carboxylic acid monomer; and
(c) about 0.1 to 5 wt-% of a monomer of the formula:
2. The composition of claim 1 wherein the ester comprises n-butyl acrylate, n-butyl methacrylate, isopropyl acrylate, tertiary butyl methacrylate, 2-ethylhexyl acrylate, isooctyl acrylate, cycloxhexylacrylate, amylacrylate, or mixtures thereof.
3. The composition of claim 1 wherein the ester monomer comprises n-butyl-acrylate.
4. The composition of claim 3 wherein polymer additionally comprises a methyl methacrylate monomer which is present in the polymer at a concentration of about 2 to 30 wt-%.
5. The composition of claim 3 wherein the carboxylic acid monomer comprises acrylic acid which is present at a concentration of about 1 to 10 wt-%.
6. The composition of claim 3 wherein the sulfonic acid functional monomer comprises methacryloxyethane-1-
sulfonic acid sodium salt, acryloxyethane-1-sulfonic acid sodium salt, or mixtures thereof.
7. A laminating adhesive latex composition comprising a major proportion of water and dispersed therein a polymer composition comprising:
(a) about 40 to 95 wt-% of at least one C2_10 aliphatic alcohol ester of acrylic or methacrylic acid;
(b) about 5 to 20 wt-% of methyl acrylate or methyl methacrylate; (c) about 0.1 to 5 wt-% of an alpha, beta olefinically unsaturated carboxylic acid monomer; and
(d) about 0.1 to 5 wt-% of a monomer of the . formula:
wherein R is H or a C^ alkyl, N is 1-12 and X is a proton, an amine salt, an alkali metal ion, or an alkaline earth metal ion.
8. The composition of claim 7 wherein the ester comprises n-butyl acrylate, n-butyl methacrylate, isopropyl acrylate, tertiary butyl methacrylate, 2-ethylhexyl acrylate, isooctyl acrylate, cycloxhexylacrylate, amylacrylate, or mixtures thereof.
9. The composition of claim 7 wherein the ester monomer comprises n-butyl-acrylate.
10. The composition of claim 7 wherein the methyl methacrylate monomer is present in the polymer at a concentration of about 2 to 30 wt-%.
11. The composition of claim 7 wherein the carboxylic
acid containing monomer comprises acrylic acid which is present at a concentration of about 1 to 10 wt-%.
12. The composition of claim 7 wherein the sulfonic acid functional monomer comprises methacryloxyethane-1- sulfonic acid sodium salt, acryloxyethane-1-sulfonic acid sodium salt, or mixtures thereof.
13. A laminating adhesive latex composition comprising a major proportion of water and dispersed therein a polymer composition comprising: (a) about 40 to 95 wt-% of at least one C2.10 aliphatic alcohol ester of acrylic or methacrylic acid;
(b) about 5 to 20 wt-% of methyl acrylate or methyl methacrylate;
(c) about 0.1 to 5 wt-% of an vinyl acetate; (d) about 0.1 to 5 wt-% of an olefinically unsaturated monomer having a pendant carboxylic acid group; and
(e) about 0.1 to 5 wt-% of a monomer of the formula:
CH2-CH(R)-C-0-CH2-CH2-S03~_<
wherein R is H or a C^5 alkyl, n is 1-12 and X is a proton, an alkali metal ion, or an alkaline earth metal ion.
14. A laminate comprising at least two layers of a sheet-like material bonded by a laminating adhesive latex composition comprising a major proportion of water and dispersed therein a polymer composition comprising:
(a) about 40 to 95 wt-% of at least one C2.10 aliphatic alcohol ester of acrylic or methacrylic acid;
(b) about 0.1 to 5 wt-% of an alpha,beta olefinically unsaturated carboxylic acid monomer; and
(c) about 0.1 to 5 wt-% of a monomer of the formula:
CH2-CH(R)-C-0-CH2-CH2-S03 )T
wherein R is H or a C^ alkyl, N is 1-12 and X is a proton, an alkali metal ion, or an alkaline earth metal ion.
15. The laminate of claim 14 wherein each layer is independently selected from the group of films consisting of aluminum foil, polypropylene, polyvinylidene chloride and cellophane.
16. The composition of claim 15 wherein the ester comprises n-butyl acrylate, n-butyl methacrylate, isopropyl acrylate, tertiary butyl methacrylate, cycloxhexylacrylate, amylacrylate, or mixtures thereof.
17. The composition of claim 15 wherein the ester monomer comprises n-butyl-acrylate.
18. The composition of claim 15 wherein polymer additionally comprises a methyl methacrylate monomer which is present in the polymer at a concentration of about 2 to 30 wt-%.
19. The composition of claim 15 wherein the carboxylic acid monomer comprises acrylic acid which is present at a concentration of about 1 to 10 wt-%.
20. The composition of claim 15 wherein the sulfonic acid functional monomer comprises methacryloxyethane-1-
sulfonic acid sodium salt, acryloxyethane-1-sulfonic acid sodium salt, or mixtures thereof.
AMENDED CLAIMS
[received by the International Bureau on 13 May 1992 (13.05.92) ; original claims 8-13 cancel led; original claims 1 ,3-7, 14 and -20 amended ; new claims 21 -36 added ; other claims unchanged (6 pages)]
1. A laminating adhesive latex composition comprising a major proportion of water and dispersed therein a polymer composition comprising: ( a) about 40 to 95 wt-% of at least one C2_I0 aliphatic ester of acrylic or methacrylic acid;
(b) about 0.1 to 5 wt-% of an alpha,beta olefinically unsaturated carboxylic acid monomer; and
(c) about 0.1 to 5 wt-% of a monomer of the formula:
0
II
CH2=C(R)-C-O-(CH2)a-S03 "X+
wherein R is H or a C^ alkyl, n is 1-12 and X is a proton, an amine salt, an alkali metal ion, or an alkaline earth metal ion; wherein the composition, in combination with one or more flexible substrates, dries to form a non-toxic, flexible laminate.
2. The composition of claim 1 wherein the ester comprises n-butyl acrylate, n-butyl methacrylate, isopropyl acrylate, tertiary butyl methacrylate, 2-ethylhexyl acrylate, isooctyl acrylate, cyclohexylacrylate, amylacrylate, or mixtures thereof.
3. The composition of any of claims 1-2 wherein the ester monomer comprises n-butyl-acrylate.
4. The composition of any of claims 1-3 wherein polymer additionally comprises a methyl methacrylate monomer or methyl acrylate monomer which are present in the polymer at a concentration of about 2 to 30 wt-%. 5. The composition of any of claims 1-4 wherein the carboxylic acid monomer comprises acrylic acid which is present at a concentration of about 1 to 10 wt-%.
6. The composition of any of claims 1-5 wherein the sulfonic acid functional monomer comprises methacryloxyethane-1-sulfonic acid sodium salt, acryloxyethane-1-sulfonic acid sodium salt, or mixtures thereof.
7. The composition of any of claims 1-7 wherein the polymer additionally comprises about 0.1 to 5 wt-% of a vinyl acetate.
14. A laminate comprising at least two layers of a sheet-like material bonded by a non-toxic and flexible laminating adhesive latex composition comprising a major proportion of water and dispersed therein a polymer composition comprising:
(a) about 40 to 95 wt-% of at least one C2.10 aliphatic alcohol ester of acrylic or methacrylic acid;
(b) about 0.1 to 5 wt-% of an alpha,beta olefinically unsaturated carboxylic acid monomer; and (c) about 0.1 to 5 wt-% of a monomer of the formula:
CH2=C ( R ) -C-0- ( CH2 ) _.-S03~X+
wherein R is H or a C^ alkyl, n is 1-12 and X is a proton, an a ine salt, an alkali metal ion, or an alkaline earth metal ion.
15. The laminate of claim 14 wherein each layer is independently selected from the group of films consisting of aluminum foil, polypropylene, polyvinylidene chloride and cellophane.
16. The laminate of any of claims 14-15 wherein the ester comprises n-butyl acrylate, n-butyl methacrylate, isopropyl acrylate, tertiary butyl methacrylate, cyclohexylacrylate, amylacrylate, or mixtures thereof.
17. The laminate of any of claims 14-16 wherein the ester monomer comprises n-butyl-acrylate.
18. The laminate of any of claims 14-17 wherein polymer additionally comprises a methyl methacrylate monomer which is present in the polymer at a concentration of about 2 to 30 wt-%.
19. The laminate of any of claims 14-18 wherein the carboxylic acid monomer comprises acrylic acid which is present at a concentration of about 1 to 10 wt-%. 20. The laminate of any of claims 14-19 wherein the sulfonic acid functional monomer comprises methacryloxyethane-1-sulfonic acid sodium salt.
acryloxyethane-1-sulfonic acid sodium salt, or mixtures thereof.
21. The composition of any of claims 1-7 which further comprises an ethylenically unsaturated monomer.
22. The composition of claim 21 wherein the ethylenically unsaturated monomer comprises styrene.
23. The composition of any of claims 14-20 which further comprises an ethylenically unsaturated monomer.
24. The composition of claim 23 wherein the ethylenically unsaturated monomer comprises styrene.
25. A method for preparing a flexible laminate comprising:
(a) applying to a first film substrate a latex adhesive composition comprising: (i) about 40 to 95 wt-% of at least one C2_10 aliphatic ester of acrylic or methacrylic acid;
(ii) about 0.1 to 5 wt-% of an A,A olefinically unsaturated carboxylic acid monomer; and (iϋ) about 0.1 to 5 wt-% of a monomer of the formula:
0
II
CH2=C(R)-C-0-(CH2)a-S03 "X+ wherein R is H or a C1_5 alkyl, n is 1-12, and X is a proton, an amine salt, an alkali metal ion, or an alkaline earth metal ion;
(b) drying the adhesive composition; and
(c) contacting a second film to the adhesive composition.
26. The composition of claim 25 wherein the ester comprises n-butyl acrylate, n-butyl methacrylate, isopropyl acrylate, tertiary butyl methacrylate, 2-ethylhexyl acrylate, isooctyl acrylate, cyclohexylacrylate, amylacrylate, or mixtures thereof.
27. The composition of any of claims 25-26 wherein the ester monomer comprises n-butyl-acrylate.
28. The composition of any of claims 25-27 wherein polymer additionally comprises a methyl methacrylate monomer which is present in the polymer at a concentration of about 2 to 30 wt-%.
29. The composition of any of claims 25-28 wherein the carboxylic acid monomer comprises acrylic acid which is present at a concentration of about 1 to 10 wt-%.
30. The composition of any of claims 25-29 wherein the sulfonic acid functional monomer comprises methacryloxyethane-a-sulfonic acid sodium salt, acryloxyethane-1-sulfonic acid sodium salt, or mixtures thereof.
31. The method of any of claims 25-30 which further comprises heating the adhesive composition to form a dry adhesive layer.
32. The method of any of claims 25-31 wherein the first film substrate is selected from the group consisting of polymeric films, printed papers, metallized papers, and metal foils.
33. The method of any of claims 25-32 wherein the second film substrate is selected from the group consisting of polymeric films, printed papers, metallized papers, and metal foils.
34. The method of any of claims 25-33 wherein the latex adhesive composition further comprises an ethylenically unsaturated monomer selected from the group consisting of styrene, ethylmethylstyrene, acrylonitrile, methacrylonitrile, vinyl toluene, vinyl chloride, vinylidene chloride and a mixture thereof.
35. The method of any of claims 25-34 wherein the latex adhesive composition further comprises about 0.1 to 5 wt-% of an ester of an alkanoic acrylic acid.
36. The method of claim 35 wherein the ester of an alkanoic acrylic acid is vinyl acetate.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US63378490A | 1990-12-26 | 1990-12-26 | |
US633,784 | 1990-12-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1992012213A1 true WO1992012213A1 (en) | 1992-07-23 |
Family
ID=24541111
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1991/008618 WO1992012213A1 (en) | 1990-12-26 | 1991-11-19 | Laminating adhesive |
Country Status (1)
Country | Link |
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WO (1) | WO1992012213A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4306822A1 (en) * | 1993-03-04 | 1994-09-08 | Wacker Chemie Gmbh | Use of aqueous polymer dispersions as gloss film laminating adhesives |
US6376094B1 (en) | 1996-11-29 | 2002-04-23 | Basf Aktiengesellschaft | Lamination adhesives |
US6727327B1 (en) | 1999-02-25 | 2004-04-27 | Basf Aktiengesellschaft | Aqueous n-butyl acrylate copolymer dispersions for use as laminating adhesives |
EP1696012A2 (en) * | 2005-02-24 | 2006-08-30 | LINTEC Corporation | Adhesive sheet |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4617343A (en) * | 1984-04-23 | 1986-10-14 | National Starch And Chemical Corporation | Laminating adhesives containing polymerized surfactant |
-
1991
- 1991-11-19 WO PCT/US1991/008618 patent/WO1992012213A1/en active Application Filing
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4617343A (en) * | 1984-04-23 | 1986-10-14 | National Starch And Chemical Corporation | Laminating adhesives containing polymerized surfactant |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4306822A1 (en) * | 1993-03-04 | 1994-09-08 | Wacker Chemie Gmbh | Use of aqueous polymer dispersions as gloss film laminating adhesives |
US5474638A (en) * | 1993-03-04 | 1995-12-12 | Wacker-Chemie Gmbh | Method of using aqueous polymer dispersions as lamination adhesives for glossy films |
US6376094B1 (en) | 1996-11-29 | 2002-04-23 | Basf Aktiengesellschaft | Lamination adhesives |
US6727327B1 (en) | 1999-02-25 | 2004-04-27 | Basf Aktiengesellschaft | Aqueous n-butyl acrylate copolymer dispersions for use as laminating adhesives |
EP1696012A2 (en) * | 2005-02-24 | 2006-08-30 | LINTEC Corporation | Adhesive sheet |
EP1696012A3 (en) * | 2005-02-24 | 2007-05-23 | LINTEC Corporation | Adhesive sheet |
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