WO2010033381A1 - Acrylic pressure sensitive adhesive formulation and articles comprising same - Google Patents
Acrylic pressure sensitive adhesive formulation and articles comprising same Download PDFInfo
- Publication number
- WO2010033381A1 WO2010033381A1 PCT/US2009/055735 US2009055735W WO2010033381A1 WO 2010033381 A1 WO2010033381 A1 WO 2010033381A1 US 2009055735 W US2009055735 W US 2009055735W WO 2010033381 A1 WO2010033381 A1 WO 2010033381A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- article
- sensitive adhesive
- pressure sensitive
- poly
- macromer
- Prior art date
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 43
- 239000000203 mixture Substances 0.000 title claims abstract description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims description 32
- 238000009472 formulation Methods 0.000 title abstract description 6
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims description 46
- -1 poly(ethylene-butylene) Polymers 0.000 claims description 44
- 239000000853 adhesive Substances 0.000 claims description 36
- 230000001070 adhesive effect Effects 0.000 claims description 36
- 239000000758 substrate Substances 0.000 claims description 26
- 239000011521 glass Substances 0.000 claims description 19
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 9
- 229920001451 polypropylene glycol Polymers 0.000 claims description 8
- 230000009477 glass transition Effects 0.000 claims description 7
- 239000002985 plastic film Substances 0.000 claims description 7
- 229920006255 plastic film Polymers 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 229920001519 homopolymer Polymers 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000002650 laminated plastic Substances 0.000 claims description 3
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 2
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N dodecahydrosqualene Natural products CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 claims 1
- 239000005340 laminated glass Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 26
- 238000000034 method Methods 0.000 description 18
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 14
- 238000010992 reflux Methods 0.000 description 12
- 235000019439 ethyl acetate Nutrition 0.000 description 11
- 239000002998 adhesive polymer Substances 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000005060 rubber Substances 0.000 description 10
- 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 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000003431 cross linking reagent Substances 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- 230000032798 delamination Effects 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000007792 addition Methods 0.000 description 6
- 229920000578 graft copolymer Polymers 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000005250 alkyl acrylate group Chemical group 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 3
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- DUDCYUDPBRJVLG-UHFFFAOYSA-N ethoxyethane methyl 2-methylprop-2-enoate Chemical compound CCOCC.COC(=O)C(C)=C DUDCYUDPBRJVLG-UHFFFAOYSA-N 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000013032 Hydrocarbon resin Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229920002633 Kraton (polymer) Polymers 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 229920006270 hydrocarbon resin Polymers 0.000 description 2
- 239000002651 laminated plastic film Substances 0.000 description 2
- 229920001427 mPEG Polymers 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- IAXXETNIOYFMLW-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) 2-methylprop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C(=C)C)CC1C2(C)C IAXXETNIOYFMLW-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-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
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- AEPWOCLBLLCOGZ-UHFFFAOYSA-N 2-cyanoethyl prop-2-enoate Chemical class C=CC(=O)OCCC#N AEPWOCLBLLCOGZ-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- 229940095095 2-hydroxyethyl acrylate Drugs 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- KGQLBLGDIQNGSB-UHFFFAOYSA-N benzene-1,4-diol;methoxymethane Chemical compound COC.OC1=CC=C(O)C=C1 KGQLBLGDIQNGSB-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- TVFJAZCVMOXQRK-UHFFFAOYSA-N ethenyl 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC(=O)OC=C TVFJAZCVMOXQRK-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000012939 laminating adhesive Substances 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical class CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- YRDNVESFWXDNSI-UHFFFAOYSA-N n-(2,4,4-trimethylpentan-2-yl)prop-2-enamide Chemical compound CC(C)(C)CC(C)(C)NC(=O)C=C YRDNVESFWXDNSI-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical compound [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003190 viscoelastic substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- 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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
- Y10T428/2891—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31645—Next to addition polymer from unsaturated monomers
- Y10T428/31649—Ester, halide or nitrile of addition polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
Definitions
- the present invention relates to pressure sensitive adhesive formulations.
- the invention relates to pressure sensitive adhesive formulations comprising an acrylic polymer grafted with rubber macromer and/or a poly(alkylene oxide) macromer.
- the adhesives are particularly useful in the manufacture of impact resistant articles.
- Typical acrylic pressure sensitive adhesive formulations are copolymers of alkyl ester monomers, a functional monomer such as acrylic acid, and may be crosslinked using, for example, aluminum or titanium chelates. These adhesives may be further tackified to improve adhesion on different types of substrates, although usually with limitations in resistance to degradation and aging for most graphics and industrial tape applications in which acrylic solutions are conventionally used.
- U.S. Pat. Appl. No. 2005/0142357 discloses a high strength pressure sensitive adhesive comprising a blend of a cross-linked liquid polymer, at least one tackifying resin which is compatible with the liquid polymer, and at least one resin which is incompatible or at least partially incompatible with the liquid polymer.
- the formulated products described in this disclosure provide very high performance at ambient temperature, their high temperature performance will be limited by the Tg of the incompatible phase.
- U.S. Pat. No. 5,625,005, No. 6,642,298 and No. 6,670,417 disclose hybrid rubber-acrylic pressure sensitive adhesives described as having good UV resistance and aging characteristics along with high adhesion to non-polar surfaces.
- Pressure sensitive adhesives that will pass the UL-972 Testing for Burglary Resistant Glazing Materials standard would provide for the manufacture of glass/plastic laminates exhibiting a minimum amount of delamination of a glass substrate from a polyester facestock following impact. This requirement translates into a strong bonding of the pressure sensitive adhesive under a very high speed delamination process, i.e., about 1000Ox fold higher than regular peeling test speed of 127min. Current pressure sensitive adhesive products used for this application do not give satisfactory results when tested by the UL-972 standard.
- the invention provides the art with high impact resistance articles manufactured using a pressure sensitive adhesive comprising a polymer having an acrylic backbone and side chains of macromer.
- the high impact resistant article is prepared using a pressure-sensitive adhesive comprising an acrylic polymer backbone grafted with rubber macromers including, but not limited to, ethylene-butylene macromers, ethylene-propylene macromers and ethylene-butylene-propylene macromers.
- the high impact resistant article is prepared using a pressure-sensitive adhesive comprising an acrylic polymer backbone grafted with macromers having a polyether backbone.
- Nonlimiting examples include poly(ethylene glycol) macromers (PEG), polypropylene glycol) macromers (PPG) and poly(tetramethylene gylcol) macromers (PTMG).
- Monomers used to prepare the acrylic polymers used in the practice of the invention will generally comprise at least one low glass transition temperature (Tg) alkyl acrylate monomer (i.e., monomers, homopolymers of which have a Tg less than O 0 C) and may also comprise at least one monomer having a high glass transition temperature (i.e., monomers, homopolymers of which have a Tg greater than O 0 C).
- Tg low glass transition temperature
- Monomers used to prepare the acrylic polymer may also desirably include acid containing monomers and/or hydroxy containing monomers.
- a crosslinking agent such as an aluminum or a titanium crosslinking agent, is used.
- Useful acrylic polymers include, for example, acrylic polymers prepared from 2-ethyl hexyl acrylate monomers, acrylic acid monomers, and vinyl acetate or methyl acrylate monomers.
- the acrylic polymer comprises 2-ethyl hexyl acrylate, methyl acrylate and acrylic acid.
- the adhesives may also comprise a tackifier.
- the article comprises a glass substrate bonded to a plastic film.
- the plastic film is a plastic laminate.
- the impact resistant glass laminates are used in windows, doors, partitions, picture glass, show case panels and storefronts and such articles are encompassed by the invention.
- Another embodiment of the invention is directed to methods of preparing glass laminates having high impact resistance and to high impact resistant articles or products prepared using the high impact resistant glass laminates.
- the method comprising applying a pressure sensitive adhesive to at least a first substrate, the pressure sensitive adhesive comprising the reaction product of an acrylic polymer and a macromer, and bringing at least a second substrate in contact with the adhesive applied to the first substrate.
- the substrates may be the same or different. In one embodiment, both the first and the second substrates are transparent and clear.
- High impact resistant articles/products include impact resistant laminates, in particular laminates made by bonding a brittle or breakable surface to a flexible facestock.
- Nonlimiting examples of high impact resistant articles prepared using the method of the invention include windows for homes, storefronts such as convenience stores, automobiles, and sliding glass doors, LCD displays, display cabinets, and the like.
- High impact products comprise a glass substrate bonded to a plastic substrate such as a polyester film.
- the plastic films used may desirably be plastic film laminates bonded together, preferably, with the adhesive of the invention.
- the laminate comprises two glass substrates and one or more interlays of a plastic film. Such may be used in the manufacture of windows, doors, partitions, show case panels, storefronts and the like.
- Yet another embodiment of the invention is directed toward pressure sensitive adhesives comprising an acrylic polymer backbone grafted with poly(alkylene glycol) macromers and to pressure sensitive adhesive articles comprising such an adhesive.
- adhesive articles include industrial tapes, transfer films, and the like.
- pressure-sensitive adhesive refers to a viscoelastic material which adheres instantaneously to most substrates with the application of slight pressure and remains permanently tacky.
- a polymer is a pressure-sensitive adhesive within the meaning of the term as used herein if it has the properties of a pressure-sensitive adhesive per se or functions as a pressure-sensitive adhesive by admixture with tackifiers, plasticizers or other additives.
- impact resistant articles may be prepared by using a pressures sensitive adhesive comprising an acrylic polymer backbone grafted with rubber macromers.
- Rubber macromers include, but are not limited to, ethylene-butylene macromers, ethylene- propylene macromers and ethylene-butylene-propylene macromers.
- impact resistant articles may be prepared using a pressure- sensitive adhesive comprising an acrylic polymer backbone grafted with macromers having a polyether backbone, which may alternatively be referred to herein as an acrylic polymer backbone grafted with polyether macromers.
- Nonlimiting examples include poly(ethylene glycol) macromers (PEG), poly(propylene glycol) macromers (PPG) and poly(tetramethylene gylcol) macromers (PTMG).
- Polymers having an acrylic backbone and side chains of macromer whether rubber macromers or polyether macromers will generically and interchangeably be referred to herein as grafted polymers or as hybrid polymers.
- the acrylic polymer backbone contemplated for use in the practice of the invention is formed of acrylate monomers of one or more low Tg alkyl acrylates.
- Low transition temperature monomers are those having a Tg of less than about O 0 C.
- Preferred alkyl acrylates which may be used to practice the invention have up to about 18 carbon atoms in the alkyl group, preferably from about 4 to about 10 carbon atoms in the alkyl group.
- Alkyl acrylates for use in the invention include butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, decyl acrylate, dodecyl acrylates, isomers thereof, and combinations thereof.
- One preferred alkyl acrylate for use in the practice of the invention is 2-ethyl hexyl acrylate.
- the monomer system used to make the acrylic backbone polymer could be solely based on low Tg alkyl acrylate ester monomers, but is preferably modified by inclusion of high Tg monomers and/or functional comonomers, in particular carboxy-containing functional monomers and/or hydroxy-containing functional monomers.
- High Tg monomer components which may be present, and in some embodiments are preferably present, include methyl acrylate, ethyl acrylate, isobutyl methacrylate, and/or vinyl acetate.
- the high Tg monomers may be present in a total amount of up to about 50% by weight, preferably from about 5 to about 50% by weight, even more preferably from about 10 to about 40% by weight, based on total weight of the hybrid polymer.
- the acrylic backbone polymer may also comprise one or more functional monomers.
- Carboxy functional monomers will typically be present in the hybrid polymer in an amount of up to about 7% by weight, more typically from about 1 to about 5% by weight, based on the total weight of the monomers.
- Useful carboxylic acids preferably contain from about 3 to about 5 carbon atoms and include, among others, acrylic acid, methacrylic acid, itaconic acid, and the like. Acrylic acid, methacrylic acid and mixtures thereof are preferred.
- the acrylic backbone comprises hydroxy functional monomers such as hydroxyalkyl (meth)acrylate esters, and acrylic polymers used to form the backbone of the invention are preferably acrylic ester/hydroxy (meth)alkyl ester copolymers.
- hydroxy functional monomers include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate. Hydroxy functional monomers are generally used in an amount of from about 1 to about 10%, preferably from about 3 to about 7%.
- comonomers can be used to modify the Tg of the acrylic polymer, to further enhance adhesion to various surfaces and/or to further enhance high temperature shear properties.
- Such comonomers include N-vinyl pyrrolidone, N-vinyl caprolactam, N-alkyl (meth)acrylamides such as t-octyl acrylamide, vinyl esters such as vinyl neodecanoate, cyanoethylacrylates, diacetoneacrylamide, N-vinyl acetamide, N-vinyl formamide, glycidyl methacrylate and allyl glycidyl ether.
- the monomer proportions of the acrylic polymer are adjusted in such a way that the backbone polymer has a glass transition temperature of less than about -10 0 C, preferably from about -2O 0 C to about -60°C.
- the macromers which may be used to prepare the graft copolymers will typically have a glass transition temperature of about -30°C or less, preferably about -50°C to about -7O 0 C, as determined by differential scanning calorimetry (DSC), and are preferably present in an amount of from about 5 to about 50 percent by weight of the grafted polymer. Tg by DSC is taken as the inflection point of the baseline shift at a scan rate of 20 °C/min.
- the molecular weight of the macromer can range from about 2,000 to about 30,000
- macromers for use in practicing the invention will preferably have a molecular weight range of from about 2,000 to about 10,000, as determined by gel permeation chromatography (GPC).
- saturated rubber macromers may be prepared by a number of well-known methods.
- One method involves an anionic polymerization to produce a hydroxyl terminated conjugated diene polymer formed from, for example, 1 ,3-butadiene and/or isoprene monomer, as described in U.S. Pat. No. 5,625,005, the disclosure of which is incorporated herein by reference.
- Reduction of at least 90%, preferably at least 95%, of the unsaturation in the low molecular weight monool can be achieved through catalytic hydrogenation as taught in U.S. Pat. Nos. Re. 27,145 and 4,970,254, the disclosures of which are incorporated by reference herein.
- Suitable saturated rubber monools were obtained from Kraton Polymers Company.
- Kraton ® L 1203 is a preferred grade.
- the hydroxyl termination is reacted to form an acrylate or methacrylate group by any of a number of well known methods. These include esterification or transesterification using a strong acid or metal-containing catalyst (e.g., compounds of Ti, Sn and the like), by reaction with an acid chloride, or via a urethane reaction employing a metal catalyst, as described in U.S. Pat. No. 5,625,005.
- a strong acid or metal-containing catalyst e.g., compounds of Ti, Sn and the like
- Polyether macromers having a polyether backbone such as PEG are commercially available from, for example, Aldrich.
- the grafted polymer used in the practice of the invention may be prepared by conventional polymerization methods familiar to those of skill in the art. These methods include, without limitation, solution polymerization, suspension polymerization and bulk polymerization. In solution, the graft copolymers are synthesized by conventional free radical techniques using a solvent mixture. The solvent blend, preferably ethyl acetate, hexane and/or heptane, and toluene, imparts the solubility that is necessary for good coating behavior at low and high coat weights. In the practice of the invention, it may also be advantageous to reduce the residual monomer content following polymerization using methods which are known and conventional in the art.
- the method of preparing the grafted polymers is not limiting to the practice of the invention.
- the polymers may be prepared by any method that produces a comb-type copolymer having an acrylic backbone and side chains of low Tg macromer.
- the polymers may be prepared, for example, by copolymerizing alkyl acrylate ester monomers in the presence of a macromers containing a reactive acrylic, methacrylic or vinyl end group.
- the macromers may be post grafted to the acrylic polymer.
- the monomer is grafted by copolymerization with the acrylic monomers through an olefin end group.
- the adhesive compositions are preferably crosslinked using a chemical crosslinking agent such as aluminum and titanium crosslinking agents. Specific examples are Aluminum Acetylacetonate and Tyzor GBA as shown in Table 2 and Table 4.
- the crosslinker is typically added in an amount of from about 0.3% to about 2% by weight of the hybrid polymer.
- the adhesive compositions of this invention may optionally be tackified.
- the acrylic and rubber components of the hybrid polymer are believed to form a microphase separated structure in the solid state. Support for this comes from the appearance of two distinct Tg's in the temperature spectrum of viscoelastic properties corresponding to each component. Tackifying resins useful in these compositions are compatible with the rubber macromer phase.
- Tackifiers compatible with the acrylic phase can, of course, be used with any acrylic polymer and the hybrid polymer of this invention is no exception.
- tackifiers are typically derived from natural rosin and are associated with poor aging characteristics. It is an objective of this invention to overcome these problems.
- the preferred tackifiers are synthetic hydrocarbon resins derived from petroleum.
- rubber phase associating resins include aliphatic olefin derived resins such as those available from Goodyear under the Wingtack ® tradename and the Escorez ® 1300 series from Exxon.
- a common C 5 tackifying resin in this class is a diene-olefin copolymer of piperylene and 2-methyl-2-butene having a softening point of about 95°C.
- This resin is available commercially under the tradename Wingtack 95.
- the resins normally have ring and ball softening points as determined by ASTM method E28 between about 2O 0 C and 15O 0 C.
- C 9 aromatic/aliphatic olefin-derived resins available from Exxon in the Escorez 2000 series. Hydrogenated hydrocarbon resins are especially useful when the long term resistance to oxidation and ultraviolet light exposure is required.
- These hydrogenated resins include such resins as the Escorez 5000 series of hydrogenated cycloaliphatic resins from Exxon, hydrogenated C 9 and/or C 5 resins such as Arkon ® P series of resins by Arakawa Chemical, hydrogenated aromatic hydrocarbon resins such as Regalrez ® 1018, 1085 and the Regalite ® R series of resins from Hercules Specialty Chemicals.
- Other useful resins include hydrogenated polyterpenes such as Clearon ® P-105, P-
- the tackifying resin will be present at a level of from 0 to 50% by weight of the adhesive composition.
- the formulated adhesive may also include, diluents, emollients, plasticizers, excipients, antioxidants, UV stabilizers, anti-irritants, opacifiers, fillers, such as clay and silica, pigments and mixtures thereof, preservatives, as well as other components or additives.
- the invention also relates to novel adhesive polymers comprising an acrylic backbone and grafted with macromers having a polyether backbones such as, for example, PEG, PPG and PTMG, and to pressure sensitive adhesive articles.
- Pressure sensitive adhesives comprising an acrylic backbone grafted with PEG, PPG and/or PTMG macromers may advantageously be used in the manufacture of adhesive articles including, but not limited to, industrial tapes and transfer films.
- the adhesive articles are useful over a wide temperature range and adhere to a wide variety of substrates, including low energy surfaces, such as polyolefins, e.g., polyethylene and polypropylene, polyvinyl fluoride, ethylene vinyl acetate, acetal, polystyrene, powder-coated paints, and the like.
- Single and double face tapes, as well as supported and unsupported free films are encompassed by the invention.
- labels, decals, name plates, decorative and reflective materials, reclosable fasteners, theft prevention and anti-counterfeit devices are included, without limitation, without limitation, and are labels, decals, name plates, decorative and reflective materials, reclosable fasteners, theft prevention and anti-counterfeit devices.
- the adhesive article comprises an adhesive coated on at least one major surface of a backing having a first and second major surface.
- useful backing substrates include, but are not limited to foam, metal, fabric, and various polymer films such as polypropylene, polyamide and polyester.
- the adhesive may be present on one or both surfaces of the backing. When the adhesive is coated on both surfaces of the backing, the adhesive on each surface can be the same or different.
- Both the adhesives prepared using rubber macromers and the adhesives prepared using poly(alkylene glycol) methacrylate macromers have been discovered to be particularly useful when used in the manufacture of high impact resistance articles.
- Articles requiring impact resistance may advantageously be manufactured using the described pressure sensitive adhesive as a laminating adhesive to bond breakable or otherwise brittle substrates such as glass to flexible substrates made of, e.g., polymer films such as polyvinyl butyl ral (PVB), polypropylene, polyamide and polyester. Included are LCD displays, plate glass for use in windows, doors, partitions and the like for commercial and residential uses.
- the adhesive is advantageously used in end use applications where the manufactured article is subjected to vibration, stress or is vulnerable or prone to impact.
- the invention provides laminated glass panels and panes that are able to pass the Underwriters Laboratory test standard UL 972.
- This test considers the ability of a laminated glass to resist burglary or forced entry (e.g., "smash and grab" type burglaries).
- the test consists of dropping a 3.25 inch, 5 Ib (2.25kg) steel ball through a designated vertical distance onto a sample measuring 24 in by 24 in (61cm x 61 cm). Resistance is determined by whether the steel ball, after 5 impacts per sample, is able to penetrate the laminate. It will be appreciated that when impacted or otherwise attacked, the glass unit will crack. The structural integrity once the glass is cracked becomes dependent on the plastic layer of the laminate.
- the polymer film used will be a plastic film laminate of 2 or more film layers, more preferable 3 or more film layers bonded together using the adhesive of the invention.
- Individual films within the film laminate may be of the same, or may be of different thicknesses.
- Individual films used to prepare the film laminate will generally range from about 2 to about 10 mils.
- the adhesive will typically be applied in the 0.5 mil to 3 mils range.
- the adhesive solutions were cast on a silicone coated release liner, air dried for 15 minutes, and then dried for 3 minutes at 250 0 F in a forced air oven. The films were then laminated to a backing film and conditioned overnight at 22 0 C and 50% relative humidity. Unless otherwise indicated the dried adhesive film thickness was 1 mil (25 microns) and the backing film was 2 mil PET (polyethylene terephthate) film. Peel Adhesion:
- Peel adhesion at 180° between the backing and the adherend test panel was measured according to Test Method number 1 of the Pressure Sensitive Tape Council (PSTC), Northbrook, III., adapted as follows. The peel strength was measured after wetting out a stainless steel (SS) test panel for 20 minutes or as otherwise indicated. The testing was also carried out on high density polyethylene (HDPE) test panels. Unless otherwise indicated, all testing was performed at 22°C and 50% relative humidity. Shear Holding Power:
- PSTC Pressure Sensitive Tape Council
- Shear holding power was measured according to PSTC Test Method number 7, adapted as follows. The holding power was measured under a shear load of 1 kg on a 0.5 inch wide by 1 inch long area, applied after wetting out the test panel for 15 minutes. Unless otherwise indicated, all testing was performed at 22°C and 50% relative humidity. Hot Shear: [0052] Shear Holding was also measured at elevated temperature conditions. 5 Ib weight with
- the industrial standard, UL 972 for Burglary Resisting Glazing material consists of multiple impact tests wherein a 5 Ib steel ball is dropped onto 2' x 2' laminated glass substrate over different distances (8 - 40 feet) and under different temperatures (-10 to 49 0 C).
- PSA pressure sensitive adhesive
- PET film delaminated from glass plate was measured after the collision, less of which indicates a better impact resistance of the product. Broken glass pieces that remained laminated to PET film, with minimum amount of delamination taking place had better impact resistance.
- VAc vinyl acetate
- HEMA hydroxyethyl methacrylate
- IBMA isobutyl methacrylate
- PEG macromer poly(ethylene glycol) methyl ether methacrylate with Mn 1100, inhibited with 100 ppm monomethyl ether hydroquinone and 300 ppm butylated hydroxytoluene; available from Aldrich.
- Al(acac)3 aluminum acetylacetonate from Aldrich
- Tyzor GBA 75% solution in alcohols of bis (2,4'-pentanedionate-O, O 1 ) bis (2- propanolato)-titanium; available from Du Pont Co., Wilmington, Del.
- Acrylic polymer sample A served as control polymer.
- the composition of acrylic polymer sample A is shown both in Tables 1 and 3, and was prepared as follows. [0070] An initial charge mixture containing 9.4 g 2-ethylhexyl acrylate (2-EHA), 20.1 g Vinyl Acetate (VAc), 0.6 g of Acrylic Acid (AA) 1 10.12 g ethyl acetate (EtOAc), 13.71 g heptanes (a standard mixed isomer grade), and 0.05 g azobis(isobutyronitrile) (AIBN) was prepared and charged to a 3 liter 4-neck round bottomed flask equipped with stainless steel stirrer, thermometer, condenser, water bath, and slow addition funnels.
- the initial charge was heated to reflux while stirring. After 10 minutes at reflux a monomer mix containing 65.5 g 2-EHA, 4.39 g Acrylic Acid and an initiator mix containing 6.23 g EtOAc, 8 g heptanes, 0.25 g AIBN were simultaneously, separately, and uniformly added over a period of 2 hours and 3 hours, respectively. At the end of the additions the flask contents were held at reflux for a further 2 hours. Next the residual monomers were scavenged using a short half-life initiator added over a one hour period and the solution was held under reflux for a further hour.
- the polymer solution had a solids content of 53.21% and a Brookfield viscosity of 9380 cps.
- This example describes the preparation of an adhesive polymer solution sample B using a methacrylate terminated ethylene-butylene macromer.
- Adhesive polymer sample B has the composition shown in Table 1 and was prepared as follows.
- the polymer solution had a solids content of 42.7% and a Brookfield viscosity of 2500 cps.
- Adhesive polymer samples C, D and E, having the compositions shown in Table 1 were similarly prepared.
- Adhesive polymers A-E were formulated using an amount of the crosslinking agent shown in Table 2.
- Polymer B was formulated with Tyzor GBA and aluminum acetylacetonate as crosslinking agent, respectively.
- the formulated polymer was tested and performance results are also shown in Table 2. In comparison to control A, it can be seen that glass delamination after collision was greatly reduced when using a hybrid acrylic polymer. Use of a rubber acrylic hybrid adhesive significantly improves impact resistance.
- This example describes the preparation of an adhesive polymer sample BB using a poly(ethylene oxide) methyl ether methacrylate as macromer.
- Adhesive polymer sample BB has the composition shown in Table 3 and was prepared as follows.
- An initial charge mixture containing 9.4 g 2-ethylhexyl acrylate (2-EHA), 10 g of Vinyl Acetate (VAc), 0.6 g of Acrylic Acid (AA), 10.12 g ethyl acetate (EtOAc) 1 13.71 g heptanes (a standard mixed isomer grade), and 0.05 g azobis(isobutyronitrile) (AIBN) was prepared and charged to a 3 liter 4-neck round bottomed flask equipped with stainless steel stirrer, thermometer, condenser, water bath, and slow addition funnels. The initial charge was heated to reflux while stirring.
- diluent consisting of 13.13 g Xylene, 8.78 g Heptanes and 15 g lsopropanol was slowly added to the reactor contents while cooling the contents to room temperature.
- the polymer solution maintained a fluid viscosity throughout the reaction and showed no tendency to climb the reactor stirring shaft.
- the polymer solution had a solids content of 48.5% and a Brookfield viscosity of 2230 cps.
- Adhesive polymer samples CC, DD and EE, having the compositions shown in Table 3 were similarly was prepared.
- Adhesive polymers A, BB, CC, DD and EE were formulated using an amount of the crosslinking agent shown in Table 4.
- Polymer BB was formulated with Tyzor GBA and aluminum acetylacetonate as crosslinking agent, respectively.
- the formulated polymer was tested and performance results are also shown in Table 4. In comparison to control A, it can be seen that glass delamination after collision was greatly reduced when using an adhesive polymer comprising the reaction product of an acrylic polymer and a poly(alkylene oxide) macromer. Use of the type of adhesive significantly improves impact resistance.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Pressure sensitive adhesive formulations of an acrylic polymer grafted with a macromer are particularly well suited for use in the manufacture of impact resistant articles such as impact resistant Glass laminates and Products comprising such laminates.
Description
ACRYLIC PRESSURE SENSITIVE ADHESIVE FORMULATION AND ARTICLES
COMPRISING SAME
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to United States Patent Application Serial No. 12/211481 filed September 16, 2008, the contents of which are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to pressure sensitive adhesive formulations. In a particular embodiment, the invention relates to pressure sensitive adhesive formulations comprising an acrylic polymer grafted with rubber macromer and/or a poly(alkylene oxide) macromer. The adhesives are particularly useful in the manufacture of impact resistant articles.
BACKGROUND OF THE INVENTION
[0003] Typical acrylic pressure sensitive adhesive formulations are copolymers of alkyl ester monomers, a functional monomer such as acrylic acid, and may be crosslinked using, for example, aluminum or titanium chelates. These adhesives may be further tackified to improve adhesion on different types of substrates, although usually with limitations in resistance to degradation and aging for most graphics and industrial tape applications in which acrylic solutions are conventionally used.
[0004] U.S. Pat. Appl. No. 2005/0142357 discloses a high strength pressure sensitive adhesive comprising a blend of a cross-linked liquid polymer, at least one tackifying resin which is compatible with the liquid polymer, and at least one resin which is incompatible or at least partially incompatible with the liquid polymer. Although the formulated products described in this disclosure provide very high performance at ambient temperature, their high temperature performance will be limited by the Tg of the incompatible phase.
[0005] U.S. Pat. No. 5,625,005, No. 6,642,298 and No. 6,670,417 disclose hybrid rubber-acrylic pressure sensitive adhesives described as having good UV resistance and aging characteristics along with high adhesion to non-polar surfaces.
[0006] Despite these advancements in the art, there continues to be a need for high performance pressure sensitive adhesives having high adhesion and heat resistance properties that are able to meet higher requirements in applications such as industrial tapes and transfer films. There is also a need for a pressure sensitive product with extremely good performances in other areas, such as impact resistance.
[0007] Pressure sensitive adhesives that will pass the UL-972 Testing for Burglary Resistant Glazing Materials standard would provide for the manufacture of glass/plastic laminates exhibiting a minimum amount of delamination of a glass substrate from a polyester facestock following impact. This requirement translates into a strong bonding of the pressure sensitive adhesive under a very high speed delamination process, i.e., about 1000Ox fold higher than regular peeling test speed of 127min. Current pressure sensitive adhesive products used for this application do not give satisfactory results when tested by the UL-972 standard.
[0008] There is thus a need in the art for pressure sensitive adhesives that will pass the UL-972 standard when used to bond glass to plastic. The present invention addresses this need.
SUMMARY OF THE INVENTION
[0009] The invention provides the art with high impact resistance articles manufactured using a pressure sensitive adhesive comprising a polymer having an acrylic backbone and side chains of macromer.
[0010] In one aspect of this embodiment the high impact resistant article is prepared using a pressure-sensitive adhesive comprising an acrylic polymer backbone grafted with rubber macromers including, but not limited to, ethylene-butylene macromers, ethylene-propylene macromers and ethylene-butylene-propylene macromers.
[0011] In another aspect of this embodiment the high impact resistant article is prepared using a pressure-sensitive adhesive comprising an acrylic polymer backbone grafted with macromers having a polyether backbone. Nonlimiting examples include poly(ethylene glycol) macromers (PEG), polypropylene glycol) macromers (PPG) and poly(tetramethylene gylcol) macromers (PTMG).
[0012] Monomers used to prepare the acrylic polymers used in the practice of the invention will generally comprise at least one low glass transition temperature (Tg) alkyl acrylate monomer (i.e., monomers, homopolymers of which have a Tg less than O0C) and may also comprise at least one monomer having a high glass transition temperature (i.e., monomers, homopolymers of which have a Tg greater than O0C). Monomers used to prepare the acrylic polymer may also desirably include acid containing monomers and/or hydroxy containing monomers. Preferably, a crosslinking agent such as an aluminum or a titanium crosslinking agent, is used. [0013] Useful acrylic polymers include, for example, acrylic polymers prepared from 2-ethyl hexyl acrylate monomers, acrylic acid monomers, and vinyl acetate or methyl acrylate monomers. In one preferred embodiment, the acrylic polymer comprises 2-ethyl hexyl acrylate, methyl acrylate and acrylic acid. The adhesives may also comprise a tackifier. [0014] In one aspect of this embodiment, the article comprises a glass substrate bonded to a plastic film. In one preferred aspect, the plastic film is a plastic laminate. The impact resistant glass laminates are used in windows, doors, partitions, picture glass, show case panels and storefronts and such articles are encompassed by the invention.
[0015] Another embodiment of the invention is directed to methods of preparing glass laminates having high impact resistance and to high impact resistant articles or products prepared using the high impact resistant glass laminates. The method comprising applying a pressure sensitive adhesive to at least a first substrate, the pressure sensitive adhesive comprising the reaction product of an acrylic polymer and a macromer, and bringing at least a second substrate in
contact with the adhesive applied to the first substrate. The substrates may be the same or different. In one embodiment, both the first and the second substrates are transparent and clear.
[0016] High impact resistant articles/products include impact resistant laminates, in particular laminates made by bonding a brittle or breakable surface to a flexible facestock. Nonlimiting examples of high impact resistant articles prepared using the method of the invention include windows for homes, storefronts such as convenience stores, automobiles, and sliding glass doors, LCD displays, display cabinets, and the like.
[0017] Preparation of high impact resistant products prepared using the method of the invention provides the art with a method of preparing burglary resistant products, such as high impact resistant windows, doors and show cases, that will pass the UL-972 testing standard. High impact products comprise a glass substrate bonded to a plastic substrate such as a polyester film. The plastic films used may desirably be plastic film laminates bonded together, preferably, with the adhesive of the invention. In one embodiment the laminate comprises two glass substrates and one or more interlays of a plastic film. Such may be used in the manufacture of windows, doors, partitions, show case panels, storefronts and the like. [0018] Yet another embodiment of the invention is directed toward pressure sensitive adhesives comprising an acrylic polymer backbone grafted with poly(alkylene glycol) macromers and to pressure sensitive adhesive articles comprising such an adhesive. Non-limiting examples of adhesive articles include industrial tapes, transfer films, and the like.
DETAILED DESCRIPTION OF THE INVENTION
[0019] As used herein, the term "pressure-sensitive adhesive" refers to a viscoelastic material which adheres instantaneously to most substrates with the application of slight pressure and remains permanently tacky. A polymer is a pressure-sensitive adhesive within the meaning of the term as used herein if it has the properties of a pressure-sensitive adhesive per se or
functions as a pressure-sensitive adhesive by admixture with tackifiers, plasticizers or other additives.
[0020] The invention provides the art with impact resistance articles manufactured using an adhesive comprising polymers having an acrylic backbone and side chains of macromer [0021] In one embodiment, impact resistant articles may be prepared by using a pressures sensitive adhesive comprising an acrylic polymer backbone grafted with rubber macromers. Rubber macromers include, but are not limited to, ethylene-butylene macromers, ethylene- propylene macromers and ethylene-butylene-propylene macromers. [0022] In another embodiment, impact resistant articles may be prepared using a pressure- sensitive adhesive comprising an acrylic polymer backbone grafted with macromers having a polyether backbone, which may alternatively be referred to herein as an acrylic polymer backbone grafted with polyether macromers. Nonlimiting examples include poly(ethylene glycol) macromers (PEG), poly(propylene glycol) macromers (PPG) and poly(tetramethylene gylcol) macromers (PTMG).
[0023] Polymers having an acrylic backbone and side chains of macromer, whether rubber macromers or polyether macromers will generically and interchangeably be referred to herein as grafted polymers or as hybrid polymers.
[0024] The acrylic polymer backbone contemplated for use in the practice of the invention is formed of acrylate monomers of one or more low Tg alkyl acrylates. Low transition temperature monomers are those having a Tg of less than about O0C. Preferred alkyl acrylates which may be used to practice the invention have up to about 18 carbon atoms in the alkyl group, preferably from about 4 to about 10 carbon atoms in the alkyl group. Alkyl acrylates for use in the invention include butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, decyl acrylate, dodecyl acrylates, isomers thereof, and combinations thereof. One preferred alkyl acrylate for use in the practice of the invention is 2-ethyl hexyl acrylate.
[0025] The monomer system used to make the acrylic backbone polymer could be solely based on low Tg alkyl acrylate ester monomers, but is preferably modified by inclusion of high Tg monomers and/or functional comonomers, in particular carboxy-containing functional monomers and/or hydroxy-containing functional monomers.
[0026] High Tg monomer components which may be present, and in some embodiments are preferably present, include methyl acrylate, ethyl acrylate, isobutyl methacrylate, and/or vinyl acetate. The high Tg monomers may be present in a total amount of up to about 50% by weight, preferably from about 5 to about 50% by weight, even more preferably from about 10 to about 40% by weight, based on total weight of the hybrid polymer.
[0027] The acrylic backbone polymer may also comprise one or more functional monomers.
Preferred are carboxy and/or hydroxy functional monomers.
[0028] Carboxy functional monomers will typically be present in the hybrid polymer in an amount of up to about 7% by weight, more typically from about 1 to about 5% by weight, based on the total weight of the monomers. Useful carboxylic acids preferably contain from about 3 to about 5 carbon atoms and include, among others, acrylic acid, methacrylic acid, itaconic acid, and the like. Acrylic acid, methacrylic acid and mixtures thereof are preferred.
[0029] In a particularly preferred embodiment, the acrylic backbone comprises hydroxy functional monomers such as hydroxyalkyl (meth)acrylate esters, and acrylic polymers used to form the backbone of the invention are preferably acrylic ester/hydroxy (meth)alkyl ester copolymers. Specific examples of hydroxy functional monomers include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate. Hydroxy functional monomers are generally used in an amount of from about 1 to about 10%, preferably from about 3 to about 7%.
[0030] Other comonomers can be used to modify the Tg of the acrylic polymer, to further enhance adhesion to various surfaces and/or to further enhance high temperature shear
properties. Such comonomers include N-vinyl pyrrolidone, N-vinyl caprolactam, N-alkyl (meth)acrylamides such as t-octyl acrylamide, vinyl esters such as vinyl neodecanoate, cyanoethylacrylates, diacetoneacrylamide, N-vinyl acetamide, N-vinyl formamide, glycidyl methacrylate and allyl glycidyl ether.
[0031] The monomer proportions of the acrylic polymer are adjusted in such a way that the backbone polymer has a glass transition temperature of less than about -100C, preferably from about -2O0C to about -60°C.
[0032] The macromers which may be used to prepare the graft copolymers will typically have a glass transition temperature of about -30°C or less, preferably about -50°C to about -7O0C, as determined by differential scanning calorimetry (DSC), and are preferably present in an amount of from about 5 to about 50 percent by weight of the grafted polymer. Tg by DSC is taken as the inflection point of the baseline shift at a scan rate of 20 °C/min. [0033] While the molecular weight of the macromer can range from about 2,000 to about 30,000, macromers for use in practicing the invention will preferably have a molecular weight range of from about 2,000 to about 10,000, as determined by gel permeation chromatography (GPC).
[0034] Conventionally, saturated rubber macromers may be prepared by a number of well- known methods. One method involves an anionic polymerization to produce a hydroxyl terminated conjugated diene polymer formed from, for example, 1 ,3-butadiene and/or isoprene monomer, as described in U.S. Pat. No. 5,625,005, the disclosure of which is incorporated herein by reference. Reduction of at least 90%, preferably at least 95%, of the unsaturation in the low molecular weight monool can be achieved through catalytic hydrogenation as taught in U.S. Pat. Nos. Re. 27,145 and 4,970,254, the disclosures of which are incorporated by reference herein. Suitable saturated rubber monools were obtained from Kraton Polymers Company. Kraton® L 1203 is a preferred grade. In the final step, the hydroxyl termination is
reacted to form an acrylate or methacrylate group by any of a number of well known methods. These include esterification or transesterification using a strong acid or metal-containing catalyst (e.g., compounds of Ti, Sn and the like), by reaction with an acid chloride, or via a urethane reaction employing a metal catalyst, as described in U.S. Pat. No. 5,625,005. [0035] Polyether macromers having a polyether backbone, such as PEG are commercially available from, for example, Aldrich.
[0036] The grafted polymer used in the practice of the invention may be prepared by conventional polymerization methods familiar to those of skill in the art. These methods include, without limitation, solution polymerization, suspension polymerization and bulk polymerization. In solution, the graft copolymers are synthesized by conventional free radical techniques using a solvent mixture. The solvent blend, preferably ethyl acetate, hexane and/or heptane, and toluene, imparts the solubility that is necessary for good coating behavior at low and high coat weights. In the practice of the invention, it may also be advantageous to reduce the residual monomer content following polymerization using methods which are known and conventional in the art.
[0037] It is to be understood that the method of preparing the grafted polymers is not limiting to the practice of the invention. The polymers may be prepared by any method that produces a comb-type copolymer having an acrylic backbone and side chains of low Tg macromer. The polymers may be prepared, for example, by copolymerizing alkyl acrylate ester monomers in the presence of a macromers containing a reactive acrylic, methacrylic or vinyl end group. Alternatively, the macromers may be post grafted to the acrylic polymer. In one preferred embodiment, the monomer is grafted by copolymerization with the acrylic monomers through an olefin end group.
[0038] The adhesive compositions are preferably crosslinked using a chemical crosslinking agent such as aluminum and titanium crosslinking agents. Specific examples are Aluminum
Acetylacetonate and Tyzor GBA as shown in Table 2 and Table 4. The crosslinker is typically added in an amount of from about 0.3% to about 2% by weight of the hybrid polymer. [0039] The adhesive compositions of this invention may optionally be tackified. The acrylic and rubber components of the hybrid polymer are believed to form a microphase separated structure in the solid state. Support for this comes from the appearance of two distinct Tg's in the temperature spectrum of viscoelastic properties corresponding to each component. Tackifying resins useful in these compositions are compatible with the rubber macromer phase. Tackifiers compatible with the acrylic phase can, of course, be used with any acrylic polymer and the hybrid polymer of this invention is no exception. However, such tackifiers are typically derived from natural rosin and are associated with poor aging characteristics. It is an objective of this invention to overcome these problems. Thus the preferred tackifiers are synthetic hydrocarbon resins derived from petroleum. Non-limiting examples of rubber phase associating resins include aliphatic olefin derived resins such as those available from Goodyear under the Wingtack® tradename and the Escorez® 1300 series from Exxon. A common C5 tackifying resin in this class is a diene-olefin copolymer of piperylene and 2-methyl-2-butene having a softening point of about 95°C. This resin is available commercially under the tradename Wingtack 95. The resins normally have ring and ball softening points as determined by ASTM method E28 between about 2O0C and 15O0C. Also useful are C9 aromatic/aliphatic olefin-derived resins available from Exxon in the Escorez 2000 series. Hydrogenated hydrocarbon resins are especially useful when the long term resistance to oxidation and ultraviolet light exposure is required. These hydrogenated resins include such resins as the Escorez 5000 series of hydrogenated cycloaliphatic resins from Exxon, hydrogenated C9 and/or C5 resins such as Arkon® P series of resins by Arakawa Chemical, hydrogenated aromatic hydrocarbon resins such as Regalrez® 1018, 1085 and the Regalite® R series of resins from Hercules Specialty
Chemicals. Other useful resins include hydrogenated polyterpenes such as Clearon® P-105, P-
115 and P-125 from the Yasuhara Yushi Kogyo Company of Japan.
[0040] The tackifying resin will be present at a level of from 0 to 50% by weight of the adhesive composition.
[0041] The formulated adhesive may also include, diluents, emollients, plasticizers, excipients, antioxidants, UV stabilizers, anti-irritants, opacifiers, fillers, such as clay and silica, pigments and mixtures thereof, preservatives, as well as other components or additives.
[0042] In addition to the use of adhesives comprising acrylic hybrid polymers to prepare high impact resistant glass laminates and products comprising such glass laminates, the invention also relates to novel adhesive polymers comprising an acrylic backbone and grafted with macromers having a polyether backbones such as, for example, PEG, PPG and PTMG, and to pressure sensitive adhesive articles.
[0043] Pressure sensitive adhesives comprising an acrylic backbone grafted with PEG, PPG and/or PTMG macromers may advantageously be used in the manufacture of adhesive articles including, but not limited to, industrial tapes and transfer films. The adhesive articles are useful over a wide temperature range and adhere to a wide variety of substrates, including low energy surfaces, such as polyolefins, e.g., polyethylene and polypropylene, polyvinyl fluoride, ethylene vinyl acetate, acetal, polystyrene, powder-coated paints, and the like. Single and double face tapes, as well as supported and unsupported free films are encompassed by the invention. Also included, without limitation, are labels, decals, name plates, decorative and reflective materials, reclosable fasteners, theft prevention and anti-counterfeit devices.
[0044] In one embodiment, the adhesive article comprises an adhesive coated on at least one major surface of a backing having a first and second major surface. Useful backing substrates include, but are not limited to foam, metal, fabric, and various polymer films such as polypropylene, polyamide and polyester. The adhesive may be present on one or both surfaces
of the backing. When the adhesive is coated on both surfaces of the backing, the adhesive on each surface can be the same or different.
[0045] Both the adhesives prepared using rubber macromers and the adhesives prepared using poly(alkylene glycol) methacrylate macromers have been discovered to be particularly useful when used in the manufacture of high impact resistance articles. Articles requiring impact resistance may advantageously be manufactured using the described pressure sensitive adhesive as a laminating adhesive to bond breakable or otherwise brittle substrates such as glass to flexible substrates made of, e.g., polymer films such as polyvinyl butyl ral (PVB), polypropylene, polyamide and polyester. Included are LCD displays, plate glass for use in windows, doors, partitions and the like for commercial and residential uses. The adhesive is advantageously used in end use applications where the manufactured article is subjected to vibration, stress or is vulnerable or prone to impact.
[0046] The invention provides laminated glass panels and panes that are able to pass the Underwriters Laboratory test standard UL 972. This test considers the ability of a laminated glass to resist burglary or forced entry (e.g., "smash and grab" type burglaries). The test consists of dropping a 3.25 inch, 5 Ib (2.25kg) steel ball through a designated vertical distance onto a sample measuring 24 in by 24 in (61cm x 61 cm). Resistance is determined by whether the steel ball, after 5 impacts per sample, is able to penetrate the laminate. It will be appreciated that when impacted or otherwise attacked, the glass unit will crack. The structural integrity once the glass is cracked becomes dependent on the plastic layer of the laminate. In one preferred embodiment, the polymer film used will be a plastic film laminate of 2 or more film layers, more preferable 3 or more film layers bonded together using the adhesive of the invention. Individual films within the film laminate may be of the same, or may be of different thicknesses. Individual films used to prepare the film laminate will generally range from about 2 to about 10 mils. The adhesive will typically be applied in the 0.5 mil to 3 mils range.
[0047] While glass laminates are tested and rated in the industry by Underwriters Laboratory according to standards set forth in UL-972, in the following test examples impact resistance was measured by a Pendulum Impact Tester using the procedure described below.
EXAMPLES
[0048] In the following examples, the following adhesive test methods were used. Preparation of Coatings:
[0049] The adhesive solutions were cast on a silicone coated release liner, air dried for 15 minutes, and then dried for 3 minutes at 2500F in a forced air oven. The films were then laminated to a backing film and conditioned overnight at 220C and 50% relative humidity. Unless otherwise indicated the dried adhesive film thickness was 1 mil (25 microns) and the backing film was 2 mil PET (polyethylene terephthate) film. Peel Adhesion:
[0050] Peel adhesion at 180° between the backing and the adherend test panel was measured according to Test Method number 1 of the Pressure Sensitive Tape Council (PSTC), Northbrook, III., adapted as follows. The peel strength was measured after wetting out a stainless steel (SS) test panel for 20 minutes or as otherwise indicated. The testing was also carried out on high density polyethylene (HDPE) test panels. Unless otherwise indicated, all testing was performed at 22°C and 50% relative humidity. Shear Holding Power:
[0051] Shear holding power was measured according to PSTC Test Method number 7, adapted as follows. The holding power was measured under a shear load of 1 kg on a 0.5 inch wide by 1 inch long area, applied after wetting out the test panel for 15 minutes. Unless otherwise indicated, all testing was performed at 22°C and 50% relative humidity. Hot Shear:
[0052] Shear Holding was also measured at elevated temperature conditions. 5 Ib weight with
1" x 1" overlap area. Samples conditioned at 1500F for 15 minutes before applying weight.
Impact resistance:
[0053] As noted above, the industrial standard, UL 972 for Burglary Resisting Glazing material, consists of multiple impact tests wherein a 5 Ib steel ball is dropped onto 2' x 2' laminated glass substrate over different distances (8 - 40 feet) and under different temperatures (-10 to 490C).
[0054] The ideal pressure sensitive adhesive (PSA) adhesive used in this laminate will lead to minimum amount of delamination of glass from plastic facestock. This requirement translates into a strong bonding of PSA under very high speed delamination process, about 1000Ox fold higher than regular peeling test speed of 127min.
[0055] To screen the impact resistance of PSA, a Pendulum Impact tester, with a 2.5 Ib metal ball dropping in pendulum motion over 2 feet in perpendicular distance. The laminated glass test panel consisted of 0.25 inch thick glass bonded with the adhesive sample to a PET laminate consisting of three films bonded together with the same adhesive sample. The percentage of
PET film delaminated from glass plate was measured after the collision, less of which indicates a better impact resistance of the product. Broken glass pieces that remained laminated to PET film, with minimum amount of delamination taking place had better impact resistance.
[0056] The following abbreviations are in the Examples and Tables.
[005η 2-EHA: 2-ethylhexyl acrylate
[0058] HEA: 2-hydroxyethyl acetate
[0059] MA: methyl acrylate
[0060] VAc: vinyl acetate
[0061] AA: acrylic acid
[0062] HEMA: hydroxyethyl methacrylate
[0063] IBMA: isobutyl methacrylate
[0064] PEG macromer: poly(ethylene glycol) methyl ether methacrylate with Mn 1100, inhibited with 100 ppm monomethyl ether hydroquinone and 300 ppm butylated hydroxytoluene; available from Aldrich.
[0065] Al(acac)3: aluminum acetylacetonate from Aldrich
[0066] Tyzor GBA: 75% solution in alcohols of bis (2,4'-pentanedionate-O, O1) bis (2- propanolato)-titanium; available from Du Pont Co., Wilmington, Del.
[0067] AF: adhesive failure to substrate
[0068] CF: cohesive failure
Example 1
[0069] Acrylic polymer sample A served as control polymer. The composition of acrylic polymer sample A is shown both in Tables 1 and 3, and was prepared as follows. [0070] An initial charge mixture containing 9.4 g 2-ethylhexyl acrylate (2-EHA), 20.1 g Vinyl Acetate (VAc), 0.6 g of Acrylic Acid (AA)1 10.12 g ethyl acetate (EtOAc), 13.71 g heptanes (a standard mixed isomer grade), and 0.05 g azobis(isobutyronitrile) (AIBN) was prepared and charged to a 3 liter 4-neck round bottomed flask equipped with stainless steel stirrer, thermometer, condenser, water bath, and slow addition funnels. The initial charge was heated to reflux while stirring. After 10 minutes at reflux a monomer mix containing 65.5 g 2-EHA, 4.39 g Acrylic Acid and an initiator mix containing 6.23 g EtOAc, 8 g heptanes, 0.25 g AIBN were simultaneously, separately, and uniformly added over a period of 2 hours and 3 hours, respectively. At the end of the additions the flask contents were held at reflux for a further 2 hours. Next the residual monomers were scavenged using a short half-life initiator added over a one hour period and the solution was held under reflux for a further hour. Then diluent consisting of 8.12 g Heptanes, 22.57 g of lsopropanol (IPOH) and 5.39 g of Xylene was slowly added to the reactor contents while cooling the contents to room temperature. The polymer
solution maintained a fluid viscosity throughout the reaction and showed no tendency to climb the reactor stirring shaft.
[0071] The polymer solution had a solids content of 53.21% and a Brookfield viscosity of 9380 cps.
Example 2
[0072] This example describes the preparation of an adhesive polymer solution sample B using a methacrylate terminated ethylene-butylene macromer. The molecular weight averages of the macromer were determined by GPC, relative to polystyrene standards, to be Mn = 6600, Mw = 7200 Daltons.
[0073] Adhesive polymer sample B has the composition shown in Table 1 and was prepared as follows.
[0074] An initial charge mixture containing 10.86 g 2-ethylhexyl acrylate (2-EHA), 4.13 g ethylene-butylene macromer, 3.1 g methyl acrylate (MA), 1.03 g 2-hydroxyethylacrylate (2- HEA), 10 g ethyl acetate (EtOAc), 11.67 g hexanes (a standard mixed isomer grade), and 0.05 g azobis(isobutyronitrile) (AIBN) was prepared and charged to a 3 liter 4-neck round bottomed flask equipped with stainless steel stirrer, thermometer, condenser, water bath, and slow addition funnels. The initial charge was heated to reflux while stirring. After 10 minutes at reflux a monomer mix containing 41.64 g 2-EHA, 23.38 g ethylene-butylene macromer, 11.9 g MA, 3.97 g HEA, and 5 g hexanes, and an initiator mix containing 40 g EtOAc, 10 g hexanes and 0.25 g AIBN were simultaneously, separately, and uniformly added over a period of 2 hours and 3 hours, respectively. At the end of the additions the flask contents were held at reflux for a further 2 hours. Next the residual monomers were scavenged using a short half-life initiator added over a one hour period and the solution was held under reflux for a further hour. Then diluent consisting of 33.3 g toluene was slowly added to the reactor contents while cooling the
contents to room temperature. The polymer solution maintained a fluid viscosity throughout the reaction and showed no tendency to climb the reactor stirring shaft.
[0075] The polymer solution had a solids content of 42.7% and a Brookfield viscosity of 2500 cps. The molecular weight averages, determined by gel permeation chromatography, were Mw
= 560,000 and Mn = 34,000.
[0076] Adhesive polymer samples C, D and E, having the compositions shown in Table 1 were similarly prepared.
[0077] Adhesive polymers A-E were formulated using an amount of the crosslinking agent shown in Table 2. Polymer B was formulated with Tyzor GBA and aluminum acetylacetonate as crosslinking agent, respectively. The formulated polymer was tested and performance results are also shown in Table 2. In comparison to control A, it can be seen that glass delamination after collision was greatly reduced when using a hybrid acrylic polymer. Use of a rubber acrylic hybrid adhesive significantly improves impact resistance.
Table 1
Example 3
[0078] This example describes the preparation of an adhesive polymer sample BB using a poly(ethylene oxide) methyl ether methacrylate as macromer.
[0079] Adhesive polymer sample BB has the composition shown in Table 3 and was prepared as follows.
[0080] An initial charge mixture containing 9.4 g 2-ethylhexyl acrylate (2-EHA), 10 g of Vinyl Acetate (VAc), 0.6 g of Acrylic Acid (AA), 10.12 g ethyl acetate (EtOAc)1 13.71 g heptanes (a standard mixed isomer grade), and 0.05 g azobis(isobutyronitrile) (AIBN) was prepared and charged to a 3 liter 4-neck round bottomed flask equipped with stainless steel stirrer, thermometer, condenser, water bath, and slow addition funnels. The initial charge was heated to reflux while stirring. After 10 minutes at reflux a monomer mix containing 65.5 g 2-EHA, 10.1 g poly(ethylene glycol) methyl ether methacrylate macromer, 4.39 g AA, and 15 g EtOAc, and an initiator mix containing 6.23 g EtOAc, 8 g heptanes, and 0.25 g AIBN were simultaneously, separately, and uniformly added over a period of 2 hours and 3 hours, respectively. At the end of the additions the flask contents were held at reflux for a further 2 hours. Next the residual monomers were scavenged using a short half-life initiator added over a one hour period and the solution was held under reflux for a further hour. Then diluent consisting of 13.13 g Xylene, 8.78 g Heptanes and 15 g lsopropanol was slowly added to the reactor contents while cooling
the contents to room temperature. The polymer solution maintained a fluid viscosity throughout the reaction and showed no tendency to climb the reactor stirring shaft.
[0081] The polymer solution had a solids content of 48.5% and a Brookfield viscosity of 2230 cps.
[0082] Adhesive polymer samples CC, DD and EE, having the compositions shown in Table 3 were similarly was prepared.
[0083] Adhesive polymers A, BB, CC, DD and EE were formulated using an amount of the crosslinking agent shown in Table 4. Polymer BB was formulated with Tyzor GBA and aluminum acetylacetonate as crosslinking agent, respectively. The formulated polymer was tested and performance results are also shown in Table 4. In comparison to control A, it can be seen that glass delamination after collision was greatly reduced when using an adhesive polymer comprising the reaction product of an acrylic polymer and a poly(alkylene oxide) macromer. Use of the type of adhesive significantly improves impact resistance.
[0084] From the results it can be seen that by reacting an acrylic polymer with a poly(alkylene oxide) macromer produces novel pressure sensitive adhesives having improved impact resistance.
Table 3
Table 4
[0085] Many modifications and variations of this invention can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. The specific embodiments described herein are offered by way of example only, and the invention is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled.
Claims
1. A high impact resistant article comprising a breakable substrate bonded to a flexible substrate, wherein the breakable substrate is bonded to the flexible substrate using a pressure sensitive adhesive comprising the reaction product of an acrylic polymer and a macromer, wherein the macromer has a glass transition temperature of about -3O0C or less.
2. The article of claim 1 wherein the macromer used to prepare the pressure sensitive adhesive has an aliphatic hydrocarbon backbone.
3. The article of claim 2 wherein the aliphatic hydrocarbon backbone is selected from the group consisting of poly(ethylene-butylene), poly(ethylene-propylene), poly(ethylene-butylene- propylene) and mixtures thereof.
4. The article of claim 1 wherein the macromer used to prepare the pressure sensitive adhesive has an alkylene oxide backbone.
5. The article of claim 4 wherein the alkylene oxide backbone is selected from the group consisting of poly(ethylene glycol), polypropylene glycol), poly(tetramethylene glycol) and mixtures thereof.
6. The article of any of claims 1-5 wherein the breakable substrate is a glass substrate.
7. The article of claim 6 comprising a glass substrate bonded to a plastic film.
8. The article of claim 7 where the plastic film is a plastic laminate.
9. The article of claim 7 wherein the plastic film is sandwiched between two glass substrates.
10. The article of claim 8 which is an impact resistant window, door or display case.
11. The article of claim 1 wherein the pressure sensitive adhesive comprises the reaction product of an acrylic polymer and a polyethylene-butylene macromer.
12. The article of claim 1 wherein the pressure sensitive adhesive comprises the reaction product of an acrylic polymer and a poly(ethylene glycol) macromer.
13. The article of claim 1 wherein the pressure sensitive adhesive comprises an acrylic polymer prepared from monomers selected from the group consisting of acrylate monomers, homopolymers of which have a glass transition temperature less than 00C1 monomers, homopolymers of which have a glass transition temperature greater than 00C, acid functional monomers, hydroxy functional monomers and mixtures thereof.
14. The article of claim 13 wherein the pressure sensitive adhesive comprises an acrylic polymer prepared from 2-ethyl hexyl acrylate, acrylic acid, and vinyl acetate or methacrylate.
15. A pressure-sensitive adhesive comprising the reaction product of an acrylic polymer and a macromer having an alkylene oxide backbone.
16. The adhesive of claim 15 wherein the alkylene oxide backbone is selected from the group consisting of poly(ethylene glycol), polypropylene glycol), poly(tetramethylene glycol) and mixtures thereof.
17. The adhesive of claim 16 wherein the alkylene oxide backbone is poly(ethylene glycol).
18. A pressure sensitive adhesive article comprising the pressure sensitive adhesive of claim 15.
19. The article of claim 1 δ which is a tape, film or label.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP09792172.0A EP2326693B1 (en) | 2008-09-16 | 2009-09-02 | Acrylic pressure sensitive adhesive formulation and articles comprising same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/211,481 | 2008-09-16 | ||
US12/211,481 US8440304B2 (en) | 2008-09-16 | 2008-09-16 | Acrylic pressure sensitive adhesive formulation and articles comprising same |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010033381A1 true WO2010033381A1 (en) | 2010-03-25 |
Family
ID=41136700
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2009/055735 WO2010033381A1 (en) | 2008-09-16 | 2009-09-02 | Acrylic pressure sensitive adhesive formulation and articles comprising same |
Country Status (3)
Country | Link |
---|---|
US (1) | US8440304B2 (en) |
EP (1) | EP2326693B1 (en) |
WO (1) | WO2010033381A1 (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102010026879A1 (en) | 2010-02-11 | 2011-08-11 | AMW GmbH, 83627 | Transdermal system, useful for indicating and preventing multiple sclerosis, immunomodulator including quinolines or isoxazoles, metabolite forming groups, skin protective layer, a reservoir and a carrier impermeable to active substance |
DE102010026883A1 (en) | 2010-03-11 | 2011-12-15 | Amw Gmbh | Transdermal system useful e.g. for indication of breast cancer with progesterone-receptor positive status, comprises e.g. aromatase inhibitor, active substance puller protection layer, active substance reservoir |
DE102011100619A1 (en) | 2010-05-05 | 2012-01-05 | Amw Gmbh | Therapeutic system, useful to treat chronic pain, comprises active agent impermeable carrier, active agent reservoir containing e.g. opioid receptor agonist, optionally active agent-permeable membrane and active agent impermeable layer |
US9029452B2 (en) | 2010-05-27 | 2015-05-12 | E I Du Pont De Nemours And Company | Fluoropolymer additive for coatings |
US9290596B2 (en) | 2010-05-27 | 2016-03-22 | The Chemours Company Fc, Llc | Solvent-based fluoropolymer additives and their use in coating compositions |
DE102010026903A1 (en) | 2010-07-12 | 2012-01-12 | Amw Gmbh | Transdermal therapeutic system with avocado oil or palm oil as adjuvant |
TWI621681B (en) * | 2012-05-21 | 2018-04-21 | Lg化學股份有限公司 | Optical member, pressure-sensitive adhesive composition, and liquid crystal display |
WO2014152454A1 (en) * | 2013-03-15 | 2014-09-25 | Nal Pharmaceuticals, Ltd. | Transdermal drug delivery system containing rivastigmine |
KR102199986B1 (en) * | 2014-02-17 | 2021-01-08 | 엘지이노텍 주식회사 | Light emitting apparatus |
BR112016024108B1 (en) | 2014-04-21 | 2021-10-26 | Henkel IP & Holding GmbH | CURABLE COMPOSITION WITHOUT SOLVENT, ARTICLE AND FORMATION PROCESS OF A HYBRID COPOLYMER |
WO2015164095A2 (en) * | 2014-04-21 | 2015-10-29 | Henkel IP & Holding GmbH | Curable adhesive compositions and use thereof |
BR112017024470A2 (en) * | 2015-05-18 | 2018-07-24 | Basf Se | pressure sensitive adhesive polymer, process for preparing a polymer, use of a polymer, and hair styling and restyling composition. |
EP3983458A1 (en) * | 2019-06-14 | 2022-04-20 | 3M Innovative Properties Company | Polymers derived from a (meth)acrylate macromer, adhesive compositions, and articles |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5006582A (en) * | 1988-08-01 | 1991-04-09 | E. I. Du Pont De Nemours And Company | Acrylic hot melt pressure sensitive adhesive compositions |
US5116910A (en) * | 1988-08-31 | 1992-05-26 | Mitsubishi Rayon Co., Ltd. | Preparation method of comb copolymer, acrylic comb copolymer, and impact resistant resin composition |
US5502108A (en) * | 1990-04-20 | 1996-03-26 | Minnesota Mining And Manufacturing Company | Pressure-sensitive adhesive comprising solid tacky microspheres and macromonomer-containing binder copolymer |
US5625005A (en) * | 1993-07-08 | 1997-04-29 | Avery Dennison Corporation | Acrylic saturated rubber hybrid pressure-sensitive adhesives |
WO2001027162A2 (en) * | 1999-10-08 | 2001-04-19 | Adhesives Research, Inc. | Non-corrosive, low volatiles containing strippable graft copolymer pressure sensitive adhesive |
US6239228B1 (en) * | 1997-02-21 | 2001-05-29 | Adhesives Research, Inc. | Pressure sensitive adhesive containing macromer having repeat hydrophilic moieties |
US6642298B2 (en) * | 2001-03-16 | 2003-11-04 | National Starch And Chemical Investment Holding Corporation | Rubber-acrylic adhesive formulation |
US6670417B2 (en) * | 2001-03-16 | 2003-12-30 | National Starch And Chemical Investment Holding Corporation | Rubber-acrylic adhesive formulation |
Family Cites Families (51)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USRE27145E (en) * | 1969-05-20 | 1971-06-22 | Side-chain | |
US4150170A (en) * | 1978-03-02 | 1979-04-17 | Celanese Corporation | Ultraviolet initiator systems for pressure-sensitive adhesives |
JPS5974149A (en) | 1982-10-20 | 1984-04-26 | Kanegafuchi Chem Ind Co Ltd | Curable composition |
JPS60235747A (en) | 1984-05-07 | 1985-11-22 | Nippon Telegr & Teleph Corp <Ntt> | Reinforcement of connecting part of optical fiber |
US4722976A (en) * | 1985-11-22 | 1988-02-02 | Pony Industries, Inc. | Macromonomer-based polymer concrete compositions |
US4783504A (en) | 1986-02-28 | 1988-11-08 | Shell Oil Company | Hot melt adhesive containing a silane grafted hydrogenated block polymer |
GB8625528D0 (en) | 1986-10-24 | 1986-11-26 | Swift Adhesives Ltd | Adhesive compositions |
CA1312408C (en) | 1987-10-09 | 1993-01-05 | Peter W. Merz | Reactive, thixotropic hot-melt adhesive on silane basis |
JP2650696B2 (en) | 1987-12-18 | 1997-09-03 | 横浜ゴム株式会社 | Hot melt adhesive composition |
GB8811615D0 (en) | 1988-05-17 | 1988-06-22 | Swift Adhesives Ltd | Adhesive compositions |
GB8811616D0 (en) | 1988-05-17 | 1988-06-22 | Swift Adhesives Ltd | Compositions |
JP2649824B2 (en) | 1988-05-31 | 1997-09-03 | 三井・デュポンポリケミカル株式会社 | Crosslinkable resin composition |
US4970254A (en) | 1988-09-22 | 1990-11-13 | Shell Oil Company | Method for hydrogenating functionalized polymer and products thereof |
US5097053A (en) | 1988-10-13 | 1992-03-17 | Basf Corporation | Fast-cure polyurethane sealant composition containing silyl-substituted guanidine accelerators |
JPH02150488A (en) | 1988-12-02 | 1990-06-08 | Mitsui Toatsu Chem Inc | Primer composition and bonding operation |
GB8924619D0 (en) | 1989-11-01 | 1989-12-20 | Swift Adhesives Ltd | Crosslinkable polymers |
GB8927003D0 (en) | 1989-11-29 | 1990-01-17 | Swift Adhesives Ltd | Chemical compounds |
US5331049A (en) | 1990-06-22 | 1994-07-19 | Exxon Chemical Patents Inc. | Water-curable, hot melt adhesive composition |
US5210150A (en) | 1991-11-22 | 1993-05-11 | E. I. Du Pont De Nemours And Company | Moisture-curable melt-processible ethylene copolymer adhesives |
GB2292154A (en) | 1994-08-10 | 1996-02-14 | Minnesota Mining & Mfg | Abrasive elements comprising adhesives cross-linked via silyl groups |
US5669940A (en) | 1995-08-09 | 1997-09-23 | Minnesota Mining And Manufacturing Company | Abrasive article |
JP3681854B2 (en) | 1997-03-17 | 2005-08-10 | ダイセル化学工業株式会社 | Silane-modified thermoplastic elastomer and hot melt adhesive |
US6828403B2 (en) | 1998-04-27 | 2004-12-07 | Essex Specialty Products, Inc. | Method of bonding a window to a substrate using a silane functional adhesive composition |
WO1999055794A1 (en) | 1998-04-27 | 1999-11-04 | The Dow Chemical Company | Cure on demand adhesives and window module with cure on demand adhesive thereon |
US6121354A (en) | 1998-11-19 | 2000-09-19 | Bostik, Inc. | High performance single-component sealant |
JP3030020B1 (en) | 1998-12-10 | 2000-04-10 | コニシ株式会社 | Urethane resin and method for producing the same |
US6777485B1 (en) | 1999-01-05 | 2004-08-17 | Kaneka Corporation | Curable resin composition |
EP1036807B1 (en) | 1999-03-18 | 2007-12-12 | Kaneka Corporation | Curable composition |
CA2302934A1 (en) | 1999-03-25 | 2000-09-25 | Hiroshi Iwakiri | Curable composition |
CA2302653A1 (en) | 1999-03-29 | 2000-09-29 | Hideharu Jyono | Curable composition |
JP4414045B2 (en) | 1999-06-01 | 2010-02-10 | 株式会社カネカ | Curable resin composition |
DE10132678A1 (en) | 2000-07-26 | 2002-02-07 | Henkel Kgaa | Binding agent useful in surface coating agents, foams or adhesives contains at least graft polymer having at least two alkylsilyl groups, with graft branches |
US6433055B1 (en) | 2000-09-13 | 2002-08-13 | Dow Corning Corporation | Electrically conductive hot-melt silicone adhesive composition |
US6664323B2 (en) | 2001-02-02 | 2003-12-16 | General Electric Company | Moisture curable sealants |
EP1379577B1 (en) * | 2001-03-23 | 2004-08-25 | Solutia Inc. | Controlling solar radiation in safety glass laminates |
DE10129612A1 (en) * | 2001-06-20 | 2003-01-09 | Tesa Ag | PSA, especially for non-polar surfaces |
DE10139132A1 (en) | 2001-08-09 | 2003-02-27 | Consortium Elektrochem Ind | Alkoxy crosslinking one-component moisture-curing compositions |
DE60203973T2 (en) | 2001-08-14 | 2006-02-23 | Kaneka Corp. | Hardenable resin |
ATE348862T1 (en) | 2001-11-29 | 2007-01-15 | Kaneka Corp | CURDABLE COMPOSITION |
JP3621678B2 (en) | 2001-12-26 | 2005-02-16 | コニシ株式会社 | Urethane resin hot melt adhesive |
US6649016B2 (en) | 2002-03-04 | 2003-11-18 | Dow Global Technologies Inc. | Silane functional adhesive composition and method of bonding a window to a substrate without a primer |
DE10218570B4 (en) * | 2002-04-26 | 2007-10-18 | Lohmann Gmbh & Co Kg | Acrylate copolymers and PSAs obtainable therefrom for bonding low-energy surfaces and their use |
US6749943B1 (en) | 2002-07-02 | 2004-06-15 | 3M Innovative Properties Company | Silane based moisture curing hot-melt adhesives |
WO2004011568A2 (en) | 2002-07-29 | 2004-02-05 | Adhesives Research, Inc. | High strength pressure sensitive adhesive |
TW200407390A (en) | 2002-09-03 | 2004-05-16 | Rohm & Haas | Reactive hot-melt adhesive compositions with improved adhesion to difficult substrates |
JP2004176028A (en) | 2002-11-27 | 2004-06-24 | Hitachi Kasei Polymer Co Ltd | Reactive hot melt adhesive composition |
US6803412B2 (en) | 2003-03-13 | 2004-10-12 | H.B. Fuller Licensing & Financing Inc. | Moisture curable hot melt sealants for glass constructions |
DE10338344A1 (en) | 2003-08-21 | 2005-03-24 | Clariant Gmbh | Modified polyolefin waxes |
WO2006028927A1 (en) | 2004-09-02 | 2006-03-16 | Henkel Corporation | Silicone-containing hot-melt compositions |
DE102004055450A1 (en) | 2004-11-17 | 2006-05-18 | Degussa Ag | Moisture-curing binder |
DE102004062653A1 (en) | 2004-12-24 | 2006-07-06 | Bayer Materialscience Ag | Moisture-curing composition and hot melt adhesive |
-
2008
- 2008-09-16 US US12/211,481 patent/US8440304B2/en active Active
-
2009
- 2009-09-02 EP EP09792172.0A patent/EP2326693B1/en active Active
- 2009-09-02 WO PCT/US2009/055735 patent/WO2010033381A1/en active Application Filing
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5006582A (en) * | 1988-08-01 | 1991-04-09 | E. I. Du Pont De Nemours And Company | Acrylic hot melt pressure sensitive adhesive compositions |
US5116910A (en) * | 1988-08-31 | 1992-05-26 | Mitsubishi Rayon Co., Ltd. | Preparation method of comb copolymer, acrylic comb copolymer, and impact resistant resin composition |
US5502108A (en) * | 1990-04-20 | 1996-03-26 | Minnesota Mining And Manufacturing Company | Pressure-sensitive adhesive comprising solid tacky microspheres and macromonomer-containing binder copolymer |
US5625005A (en) * | 1993-07-08 | 1997-04-29 | Avery Dennison Corporation | Acrylic saturated rubber hybrid pressure-sensitive adhesives |
US6239228B1 (en) * | 1997-02-21 | 2001-05-29 | Adhesives Research, Inc. | Pressure sensitive adhesive containing macromer having repeat hydrophilic moieties |
WO2001027162A2 (en) * | 1999-10-08 | 2001-04-19 | Adhesives Research, Inc. | Non-corrosive, low volatiles containing strippable graft copolymer pressure sensitive adhesive |
US6642298B2 (en) * | 2001-03-16 | 2003-11-04 | National Starch And Chemical Investment Holding Corporation | Rubber-acrylic adhesive formulation |
US6670417B2 (en) * | 2001-03-16 | 2003-12-30 | National Starch And Chemical Investment Holding Corporation | Rubber-acrylic adhesive formulation |
Also Published As
Publication number | Publication date |
---|---|
EP2326693B1 (en) | 2021-04-21 |
US8440304B2 (en) | 2013-05-14 |
US20100068515A1 (en) | 2010-03-18 |
EP2326693A1 (en) | 2011-06-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8440304B2 (en) | Acrylic pressure sensitive adhesive formulation and articles comprising same | |
US6670417B2 (en) | Rubber-acrylic adhesive formulation | |
US6642298B2 (en) | Rubber-acrylic adhesive formulation | |
EP2513242B1 (en) | Pressure sensitive adhesives for low surface energy substrates | |
EP0707604B1 (en) | Acrylic-saturated rubber hybrid pressure-sensitive adhesives | |
KR101602515B1 (en) | Low surface energy adhesive | |
EP2479231B1 (en) | Adhesive compounds | |
US8101276B2 (en) | Pressure sensitive adhesive compositions and articles prepared using such compositions | |
KR100537089B1 (en) | Acrylic copolymer, acrylic pressure-sensitive adhesive composition, acrylic pressure-sensitive adhesive tape or sheet, and acrylic adhesive composition | |
EP2675837B1 (en) | Adhesive composition comprising grafted isobutylene copolymer composition | |
EP2652060B1 (en) | Pressure sensitive adhesives for low surface energy substrates | |
US20160304754A1 (en) | Multi-phase polymer composition | |
AU2002303289B2 (en) | Rubber-acrylic adhesive formulation |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09792172 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009792172 Country of ref document: EP |