WO2014193112A1 - Adhesive composite - Google Patents
Adhesive composite Download PDFInfo
- Publication number
- WO2014193112A1 WO2014193112A1 PCT/KR2014/004534 KR2014004534W WO2014193112A1 WO 2014193112 A1 WO2014193112 A1 WO 2014193112A1 KR 2014004534 W KR2014004534 W KR 2014004534W WO 2014193112 A1 WO2014193112 A1 WO 2014193112A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- weight
- formula
- carbon atoms
- acrylic copolymer
- Prior art date
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- 239000000853 adhesive Substances 0.000 title claims abstract description 34
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title abstract 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 30
- 125000003277 amino group Chemical group 0.000 claims abstract description 28
- 229920006243 acrylic copolymer Polymers 0.000 claims description 68
- 239000000178 monomer Substances 0.000 claims description 52
- 125000004432 carbon atom Chemical group C* 0.000 claims description 47
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 39
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 239000003431 cross linking reagent Substances 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000005270 trialkylamine group Chemical group 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract 2
- 230000003247 decreasing effect Effects 0.000 abstract 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 44
- 238000002360 preparation method Methods 0.000 description 40
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 23
- -1 isocyanate compound Chemical class 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 206010040844 Skin exfoliation Diseases 0.000 description 9
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 8
- 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 8
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 8
- 239000002216 antistatic agent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 210000002858 crystal cell Anatomy 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-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 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 0 CC(COCN(*)*)=C Chemical compound CC(COCN(*)*)=C 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- VAWQANAQMBEQFM-UHFFFAOYSA-N 10-ethenoxydecan-1-ol Chemical compound OCCCCCCCCCCOC=C VAWQANAQMBEQFM-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- FVCHRIQAIOHAIC-UHFFFAOYSA-N 2-[1-[1-[1-(oxiran-2-ylmethoxy)propan-2-yloxy]propan-2-yloxy]propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COC(C)COC(C)COCC1CO1 FVCHRIQAIOHAIC-UHFFFAOYSA-N 0.000 description 1
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- AGXAFZNONAXBOS-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethyl)phenyl]methyl]oxirane Chemical compound C=1C=CC(CC2OC2)=CC=1CC1CO1 AGXAFZNONAXBOS-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- BCTDCDYHRUIHSF-UHFFFAOYSA-N 5-ethenoxypentan-1-ol Chemical compound OCCCCCOC=C BCTDCDYHRUIHSF-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- ASPUDHDPXIBNAP-UHFFFAOYSA-N 6-ethenoxyhexan-1-ol Chemical compound OCCCCCCOC=C ASPUDHDPXIBNAP-UHFFFAOYSA-N 0.000 description 1
- BRZKTGZFBAGKBB-UHFFFAOYSA-N 7-ethenoxyheptan-1-ol Chemical compound OCCCCCCCOC=C BRZKTGZFBAGKBB-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- RDJHNDDZKQCDPL-UHFFFAOYSA-N 8-ethenoxyoctan-1-ol Chemical compound OCCCCCCCCOC=C RDJHNDDZKQCDPL-UHFFFAOYSA-N 0.000 description 1
- ZQKPLAFCERPWCI-UHFFFAOYSA-N 9-ethenoxynonane-1,1-diol Chemical compound C(=C)OCCCCCCCCC(O)O ZQKPLAFCERPWCI-UHFFFAOYSA-N 0.000 description 1
- FIQBJLHOPOSODG-UHFFFAOYSA-N CC(C(OCCOC(c1ccccc1C(O)=O)=O)=O)=C Chemical compound CC(C(OCCOC(c1ccccc1C(O)=O)=O)=O)=C FIQBJLHOPOSODG-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical group N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
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- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
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- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- KBWLNCUTNDKMPN-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) hexanedioate Chemical compound C1OC1COC(=O)CCCCC(=O)OCC1CO1 KBWLNCUTNDKMPN-UHFFFAOYSA-N 0.000 description 1
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- VIBDJEWPNNCFQO-UHFFFAOYSA-N ethane-1,1,2-triol Chemical compound OCC(O)O VIBDJEWPNNCFQO-UHFFFAOYSA-N 0.000 description 1
- NBEMQPLNBYYUAZ-UHFFFAOYSA-N ethyl acetate;propan-2-one Chemical compound CC(C)=O.CCOC(C)=O NBEMQPLNBYYUAZ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SJPFBRJHYRBAGV-UHFFFAOYSA-N n-[[3-[[bis(oxiran-2-ylmethyl)amino]methyl]phenyl]methyl]-1-(oxiran-2-yl)-n-(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC=1C=C(CN(CC2OC2)CC2OC2)C=CC=1)CC1CO1 SJPFBRJHYRBAGV-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Chemical group 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UOMUPDCRXJLVGR-UHFFFAOYSA-N propane-1,2,2-triol Chemical compound CC(O)(O)CO UOMUPDCRXJLVGR-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
Definitions
- the present invention relates to an adhesive composition with improved cohesion.
- a strong adhesive material which improves the adhesive performance by increasing the molecular weight of the components constituting the adhesive or increasing the crosslinking density is generally used.
- Japanese Patent Application Laid-Open No. 2002-169017 proposes an adhesive crosslinking an acrylic polymer and a multifunctional metal chelate comprising a monomer unit of an alkyl (meth) acrylate as a main skeleton and containing a monomer unit having a carboxyl group.
- the pressure-sensitive adhesive improves the adhesive performance, but under high temperature and high humidity conditions, it is impossible to keep up with the shape change caused by shrinkage or swelling of the sheet including the organic material of the pressure-sensitive adhesive, which causes various problems.
- the polarizing plate may be peeled off to reuse an expensive liquid crystal cell after a predetermined time has elapsed after the attachment. Therefore, there is a need for an adhesive that can be peeled relatively easily from the liquid crystal cell even after a certain time has elapsed after being attached to the liquid crystal cell through the adhesive applied to the polarizing plate.
- Korean Patent Publication No. 2007-76469 discloses an adhesive containing two acrylic copolymers and an active energy ray-curable compound, wherein the active energy ray-curable compound is used as a crosslinking agent to improve cohesion.
- Korean Patent Publication Nos. 2014-0013916 and 2014-0013917 include (meth) acrylic acid ester monomers having C4 to C10 carbon atoms of alkyl groups, copolymerizable monomers containing hydroxyl groups, and copolymerizable monomers containing carboxyl groups.
- the adhesive composition which consists of an acryl-type polymer which is a copolymer to further contain an antistatic agent which is an ionic compound whose melting
- an antistatic agent which is an ionic compound whose melting
- An object of the present invention is to provide a pressure-sensitive adhesive composition having increased cohesion force by an ionic bond reaction between an acrylic copolymer and a covalent bond between an acrylic copolymer and a crosslinking agent.
- an object of the present invention is to provide a pressure-sensitive adhesive composition which is excellent in durability by improving the cohesive force and at the same time capable of re-peeling after a lapse of time.
- the present invention comprises an acrylic copolymer and a crosslinking agent, the acrylic copolymer provides an adhesive composition containing an acrylic copolymer having an amino group and an acrylic copolymer having a carboxyl group.
- the acrylic copolymer may contain 10 to 90% by weight of the acrylic copolymer having an amino group and 10 to 90% by weight of the acrylic copolymer having a carboxyl group.
- the monomer for preparing the acryl-based copolymer having an amino group may contain a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and at least one monomer selected from the group consisting of the following Chemical Formulas 1 to 5.
- R 1 is hydrogen or a methyl group
- R 2 and R 3 are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or a trialkylamine group having 1 to 6 carbon atoms
- R 1 is hydrogen or a methyl group
- R 2 and R 3 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms
- R 4 is a hydroxy group or an alkoxy group having 1 to 3 carbon atoms
- l and n are 1 An integer from 12 to m
- m is an integer of 0 or 1)
- R 1 is hydrogen or methyl group, X is O or N substituted with an alkyl group having 1 to 3 carbon atoms
- R 1 is hydrogen or a methyl group
- R 2 and R 3 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms
- R 1 is hydrogen or a methyl group
- R 4 is a hydroxy group or an alkoxy group having 1 to 3 carbon atoms
- R 5 is hydrogen, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, a halogen, an alkoxy group having 1 to 4 carbon atoms, or An alkylamino group having 1 to 4 carbon atoms
- n is an integer of 1 to 12
- m is 0 or an integer of 1)
- the at least one monomer selected from the group consisting of Formulas 1 to 5 may contain 1 to 20 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms.
- the monomer for preparing the acryl-based copolymer having a carboxyl group may contain a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and at least one monomer selected from the group consisting of the following Chemical Formulas 6 to 14.
- the at least one monomer selected from the group consisting of Chemical Formulas 6 to 14 may contain 0.1 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms.
- the cohesive force of the pressure-sensitive adhesive composition is improved by the ionic bond reaction between the acrylic copolymer and the covalent bond between the aglylic copolymer and the crosslinking agent.
- the improved cohesive force may exhibit excellent reworkability equivalent to that of the related art while having excellent durability to maintain adhesive force even when exposed to a high temperature or high temperature and high humidity environment.
- the present invention relates to an adhesive composition with improved cohesion.
- the pressure-sensitive adhesive composition of the present invention includes an acrylic copolymer and a crosslinking agent, and the acrylic copolymer contains an acrylic copolymer having an amino group and an acrylic copolymer having a carboxyl group.
- the pressure-sensitive adhesive composition of the present invention may exhibit excellent durability by covalent bonding between the crosslinking agent and the acrylic copolymer, and simultaneously performing ionic bonding between the acrylic copolymer to improve the cohesive force of the pressure-sensitive adhesive composition.
- the acrylic copolymer may contain 10 to 90% by weight of the acrylic copolymer having an amino group and 10 to 90% by weight of the acrylic copolymer having a carboxyl group.
- the effect of improving cohesion may be insufficient and it may not be easy to achieve a sufficient adhesive durability (heat resistance and heat and moisture resistance) improvement effect.
- the monomer for preparing the acrylic copolymer having an amino group of the present invention may contain at least one monomer selected from the group consisting of a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and the following formulas (1) to (5).
- (meth) acrylate means acrylate and methacrylate, and the content of each component is based on solid content.
- R 1 is hydrogen or a methyl group
- R 2 and R 3 are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or a trialkylamine group having 1 to 6 carbon atoms
- R 1 is hydrogen or a methyl group
- R 2 and R 3 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms
- R 4 is a hydroxy group or an alkoxy group having 1 to 3 carbon atoms
- l and n are 1 An integer from 12 to m
- m is an integer of 0 or 1)
- R 1 is hydrogen or methyl group, X is O or N substituted with an alkyl group having 1 to 3 carbon atoms
- R 1 is hydrogen or a methyl group
- R 2 and R 3 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms
- R 1 is hydrogen or a methyl group
- R 4 is a hydroxy group or an alkoxy group having 1 to 3 carbon atoms
- R 5 is hydrogen, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, a halogen, an alkoxy group having 1 to 4 carbon atoms, or An alkylamino group having 1 to 4 carbon atoms
- n is an integer of 1 to 12
- m is 0 or an integer of 1)
- Examples of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms include n-butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl (meth).
- the at least one monomer selected from the group consisting of Formulas 1 to 5 preferably contains 1 to 20 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms, more preferably 2 It is good that it is 10 weight part. If the content is less than 1 part by weight, the effect of improving cohesion may be insignificant, and if it exceeds 20 parts by weight, the hydrophilicity may be excessively increased to reduce moisture resistance, the peeling force of the release film may be excessively increased, or the liquid stability may deteriorate. Etc. Other physical properties of the adhesive may be deteriorated.
- the monomer for preparing an acrylic copolymer having an amino group of the present invention may be a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and a monomer having a hydroxy group in addition to at least one monomer selected from the group consisting of Formulas 1 to 5 above. It may contain.
- the monomer having a hydroxy group serves to enhance the cohesion or adhesive strength of the pressure-sensitive adhesive composition by chemical bonding to impart durability and cutability.
- the monomer having a hydroxy group is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acryl 2-hydroxyhexyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate, 2-hydroxypropylene glycol (meth) acrylate, and hydroxyalkylene having 2 to 4 carbon atoms of an alkylene group.
- Glycol (meth) acrylate 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 7-hydroxyheptyl vinyl ether, 8-hydroxyoctyl vinyl ether, 9-hydroxy Hydroxynonyl vinyl ether, 10-hydroxydecyl vinyl ether, etc. are mentioned, Among these, 4-hydroxy butyl vinyl ether is preferable.
- the monomer which has such a hydroxyl group is contained in 0.05-10 weight part with respect to 100 weight part of (meth) acrylate monomers which have a C1-C12 alkyl group, More preferably, it is 0.1-8 weight part. If the content is less than 0.05 parts by weight, the cohesive force of the pressure-sensitive adhesive may be reduced, the durability may be lowered. If the content is more than 10 parts by weight, the adhesive strength is lowered by a high gel fraction may cause problems in durability.
- the acrylic copolymer having an amino group of the present invention may further contain other polymerizable monomers other than the above monomers in a range of not lowering the adhesive strength, for example, 10 parts by weight or less based on the total amount.
- the manufacturing method of the acryl-type copolymer which has an amino group is not specifically limited, It can manufacture using methods, such as block polymerization, solution polymerization, emulsion polymerization, or suspension polymerization conventionally used in the field, and solution polymerization is preferable.
- a solvent, a polymerization initiator, a chain transfer agent for molecular weight control, and the like, which are usually used in the polymerization may be used.
- the acrylic copolymer having an amino group preferably has a weight average molecular weight (polystyrene equivalent, Mw) measured by gel permeation chromatography (GPC) of 50,000 to 2 million, more preferably 400,000 to 200 It is good to be. If the weight average molecular weight is less than 50,000, there is a lack of cohesion between the copolymers may cause problems in adhesion durability, if the weight average molecular weight is more than 2 million may require a large amount of dilution solvent to ensure fairness during coating.
- Mw polystyrene equivalent
- the monomer for preparing an acrylic copolymer having a carboxyl group of the present invention preferably contains a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and at least one monomer selected from the group consisting of the following Chemical Formulas 6 to 14. .
- the at least one monomer selected from the group consisting of Chemical Formulas 6 to 14 preferably contains 0.1 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms, more preferably 2 It is good to be 6 weight part. If the content is less than 0.1 part by weight, the effect of improving cohesion may be insignificant. If the content is more than 10 parts by weight, the hydrophilicity is excessively increased, and there is a fear that the damp-heat resistance is lowered.
- the acrylic copolymer having a carboxyl group of the present invention may contain a monomer having a hydroxy group in addition to at least one monomer selected from the group consisting of Chemical Formulas 6 to 14.
- the type of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms, the type and content of the monomer having a hydroxy group, the production method of the copolymer, the weight average molecular weight of the copolymer, and the like are determined in the acrylic copolymer having the amino group. Same as the description.
- the present invention has a low content of the low molecular weight copolymer which is not crosslinked by the crosslinking reaction (ion bonding) between the acrylic copolymers, thereby improving the durability degradation due to the bleed-out of the low molecular weight copolymer, Dense crosslinking improves cohesion and ensures durability.
- the crosslinking agent is used to improve the cohesion and to improve durability, and in particular, to satisfy both heat resistance and heat and moisture resistance.
- the crosslinking agent may react with a hydroxy group or a carboxy group, and isocyanate or epoxy may be used alone or in combination of two or more.
- isocyanate-based crosslinking agent examples include tolylene diisocyanate, xylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate, Diisocyanate compounds such as naphthalene diisocyanate; Diisocyanate obtained from 2 moles of an adduct obtained by reacting 3 moles of a diisocyanate compound with 1 mole of a polyhydric alcohol compound such as trimethylolpropane, an isocyanurate obtained by self-condensing 3 moles of the diisocyanate compound, and 3 moles of the diisocyanate compound And polyfunctional isocyanate compounds containing three functional groups such as biuret, triphenylmethanetriisocyanate, and methylenebistriisocyanate
- epoxy-based crosslinking agents examples include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene.
- Glycol diglycidyl ether neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether , Diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, resorcin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythrate Lithol polyglycidyl ether, sorbitol polyglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, tris (glycidyl) iso Anurate, tris (glycidoxyethyl) isocyan
- Such a crosslinking agent may be contained in an amount of 0.1 to 5 parts by weight, preferably 0.2 to 1.0 part by weight based on 100 parts by weight of the total amount of the acrylic copolymer having an amino group and the acrylic copolymer having a carboxyl group.
- the content of the crosslinking agent is less than 0.1 part by weight, the effect of improving cohesion may be insufficient.
- the content of the crosslinking agent is more than 5 parts by weight, the cohesion may be reduced due to excessive increase in cohesion.
- the pressure-sensitive adhesive composition according to the present invention may further contain an antistatic agent, and an ionic antistatic agent may be preferably used.
- the ionic antistatic agent is not particularly limited as long as the ionic antistatic agent is capable of imparting ionic conductivity to the pressure-sensitive adhesive with ionic salts composed of anions and cations.
- a cation selected from the group consisting of alkali metal salts, ammonium salts, sulfonium salts and phosphonium salts; It may be an ionic salt consisting of an anion selected from the group consisting of fluorine-containing inorganic salts, fluorine-containing organic salts and iodine ions.
- Such an ionic antistatic agent may contain 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the acrylic copolymer. If the content is less than 0.1 parts by weight may be insufficient antistatic properties and if it exceeds 5 parts by weight it may be difficult to secure durability.
- the pressure-sensitive adhesive composition according to the present invention in order to adjust the adhesion, cohesion, viscosity, elastic modulus, glass transition temperature, etc. required according to the use, tackifying resin, antioxidant, leveling agent, surface lubricant, dye, Additives, such as a pigment, an antifoamer, a filler, and a light stabilizer, can be further contained.
- the double silane coupling agent plays a role of improving adhesion between the pressure-sensitive adhesive and the base material, it is preferable to contain it, and an alkoxysilane containing functional groups such as amino group, epoxy group, acetoacetyl group, polyalkylene glycol group, acryl group and alkyl group Can be used.
- Such additives may be appropriately adjusted in a range not impairing the effects of the present invention, for example, the silane coupling agent in consideration of the adhesion and durability, etc., the total amount of the acrylic copolymer having the amino group and the acrylic copolymer having a carboxyl group 0.01 to 2 parts by weight, preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight. If the content is less than 0.01 parts by weight, the adhesion may be lowered, and if it exceeds 2 parts by weight, peeling may occur under heat-resistant conditions.
- the pressure-sensitive adhesive composition of the present invention can be used as a pressure-sensitive adhesive for polarizing plates and a surface protective film for bonding to liquid crystal cells.
- it can be used as a general commercial adhesive sheet product as well as a protective film, a reflective sheet, a structural adhesive sheet, a photographic adhesive sheet, a lane marking adhesive sheet, an optical adhesive product, an adhesive for electronic parts, and the like.
- n-butyl acrylate BA
- MA methyl acrylate
- dimethylaminoethyl acrylate 100 parts by weight of ethyl acetate (acetone) was added as a solvent. Then, after purging nitrogen gas for 1 hour to remove oxygen, it was maintained at 62 ° C.
- AIBN azobis isobutyronitrile
- AIBN azobisisobutyronitrile
- the pressure-sensitive adhesive composition prepared above was applied on a release film coated with a silicone release agent to have a thickness of 25 ⁇ m, and dried at 100 ° C. for 1 minute to form an adhesive layer.
- a pressure-sensitive adhesive polarizing plate was prepared by laminating the pressure-sensitive adhesive layer prepared above on an iodine-based polarizing plate having a thickness of 185 ⁇ m.
- the pressure-sensitive adhesive polarizing plate was cut out to a size of 25 mm in width and 100 mm in length, and the release film was peeled off.
- Treatment to prepare an evaluation sample After putting in a 50 °C oven was taken out after 5 hours and left at room temperature for 120 hours, it was peeled off at a rate of 1.3 cm / s. In addition, after being put into an oven at 60 ° C. and 90 RH% of humidity conditions, it was taken out after 4 hours and left at room temperature for 120 hours, followed by peeling at a speed of 1.3 cm / s.
- the adhesive remains on the panel under more than one condition or the polarizer is torn during the peeling process: ⁇
- the pressure-sensitive adhesive composition of Examples 1 to 23 containing an acrylic copolymer having an amino group and an acrylic copolymer having a carboxyl group according to the present invention as an acrylic copolymer as shown in Table 2 is at least equivalent to the rework It was confirmed that the heat resistance and the heat-and-moisture resistance were excellent while maintaining the properties.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
The present invention relates to an adhesive composite and, more specifically, to an adhesive composite having a decreased non-cross-linked copolymer content and an improved cohesive force of the adhesive composite by containing an acrylic-based copolymer having an amino group and an acrylic-based copolymer having a carboxyl group, and thus can maintain an adhesive force and have excellent reworkability even if the adhesive composite is exposed to a high-temperature environment or a high-temperature and high-humidity environment.
Description
본 발명은 응집력이 향상된 점착제 조성물에 관한 것이다.The present invention relates to an adhesive composition with improved cohesion.
유기 재료를 포함하는 시트가 점착제를 개입시켜 유리, 세라믹 및 금속과 같은 피착체에 부착되는 경우, 시간이 경과함에 따라 시트 단부(end part)가 벗겨져 나가거나 들리는 바람직하지 않은 상황이 빈번하게 발생되어 왔다.When sheets containing organic materials are attached to adherends such as glass, ceramics and metals via an adhesive, an undesirable situation frequently arises in which the sheet end parts are peeled off or heard over time. come.
이를 해결하기 위하여, 상기 점착제를 구성하는 성분의 분자량을 높이거나 가교 밀도를 높임으로써 점착성능을 개선시킨 강력 점착성 재료가 일반적으로 이용된다. In order to solve this problem, a strong adhesive material which improves the adhesive performance by increasing the molecular weight of the components constituting the adhesive or increasing the crosslinking density is generally used.
구체적으로 일본공개특허 제2002-169017호는 알킬(메타)아크릴레이트의 모노머 유닛을 주골격으로 하고, 카르복실기를 갖는 모노머 유닛을 함유하여 이루어진 아크릴계 폴리머와 다작용성 금속 킬레이트를 가교한 점착제가 제시되었다. 상기 점착제는 점착성능은 향상되나, 고온 및 고습 조건 하에서 점착제의 유기 재료를 포함하는 시트의 수축이나 팽윤에 의해 초래되는 형태 변화를 따라갈 수 없게 되어 다양한 문제점이 발생하는 요인이 된다.Specifically, Japanese Patent Application Laid-Open No. 2002-169017 proposes an adhesive crosslinking an acrylic polymer and a multifunctional metal chelate comprising a monomer unit of an alkyl (meth) acrylate as a main skeleton and containing a monomer unit having a carboxyl group. The pressure-sensitive adhesive improves the adhesive performance, but under high temperature and high humidity conditions, it is impossible to keep up with the shape change caused by shrinkage or swelling of the sheet including the organic material of the pressure-sensitive adhesive, which causes various problems.
또한, 액정 표시장치 등의 제조 공정에 있어서, 편광판을 액정셀과 같은 광학 부품에 부착하는 경우, 상기 편광판은 부착 후 일정 시간이 경과한 후에 고가의 액정셀을 재이용하기 위해 박리될 수 있다. 따라서, 편광판에 도포되어 있는 점착제를 개입시켜 액정 셀에 부착된 후 일정 시간이 경과한 후에도 상기 액정 셀로부터 비교적 용이하게 박리될 수 있는 점착제가 요구되고 있다. In addition, in a manufacturing process such as a liquid crystal display device, when attaching a polarizing plate to an optical component such as a liquid crystal cell, the polarizing plate may be peeled off to reuse an expensive liquid crystal cell after a predetermined time has elapsed after the attachment. Therefore, there is a need for an adhesive that can be peeled relatively easily from the liquid crystal cell even after a certain time has elapsed after being attached to the liquid crystal cell through the adhesive applied to the polarizing plate.
이에, 한국공개특허 제2007-76469호에서는 2종의 아크릴계 공중합체와 활성 에너지선-경화형 화합물을 함유하여, 상기 활성 에너지선-경화형 화합물이 가교제로 사용되어 응집력을 향상시키는 점착제가 제시되었다. 또한 한국공개특허 제2014-0013916호 및 제2014-0013917호에는 알킬기의 탄소수가 C4∼C10인 (메타)아크릴산에스테르 모노머와, 수산기를 함유하는 공중합 가능한 모노머와, 카르복실기를 함유하는 공중합 가능한 모노머를 포함하는 공중합체인 아크릴계 폴리머로 이루어지고, 융점이 30∼80℃인 이온성 화합물인 대전 방지제를 추가로 함유하거나 3관능 이상의 이소시아네이트 화합물을 추가로 함유하는 점착제 조성물을 개시하고 있다. 그러나 상기 기술들은 응집력이 향상되어 점착 내구성이 우수하고, 일정 시간 경과 후에도 재 박리가 가능(리워크성)하다고 하나, 최근 편광판이 대형화됨에 따른 충분한 내구성의 확보가 어려운 단점이 있다.Accordingly, Korean Patent Publication No. 2007-76469 discloses an adhesive containing two acrylic copolymers and an active energy ray-curable compound, wherein the active energy ray-curable compound is used as a crosslinking agent to improve cohesion. In addition, Korean Patent Publication Nos. 2014-0013916 and 2014-0013917 include (meth) acrylic acid ester monomers having C4 to C10 carbon atoms of alkyl groups, copolymerizable monomers containing hydroxyl groups, and copolymerizable monomers containing carboxyl groups. The adhesive composition which consists of an acryl-type polymer which is a copolymer to further contain an antistatic agent which is an ionic compound whose melting | fusing point is 30-80 degreeC, or contains a trifunctional or more than trifunctional isocyanate compound further is disclosed. However, the above techniques have improved cohesive strength and excellent adhesion durability, and can be re-peeled even after a certain time (reworkability), but it is difficult to secure sufficient durability as the polarizer is recently enlarged.
본 발명은 아크릴계 공중합체와 가교제와의 공유결합과 함께 아크릴계 공중합체간의 이온결합 반응으로 응집력을 증가시킨 점착제 조성물을 제공하는 데 그 목적이 있다.An object of the present invention is to provide a pressure-sensitive adhesive composition having increased cohesion force by an ionic bond reaction between an acrylic copolymer and a covalent bond between an acrylic copolymer and a crosslinking agent.
또한, 본 발명은 상기 응집력 향상으로 내구성이 우수하면서 동시에 일정 시간 경과 후에도 재 박리가 가능한 점착제 조성물을 제공하는 데 그 목적이 있다.In addition, an object of the present invention is to provide a pressure-sensitive adhesive composition which is excellent in durability by improving the cohesive force and at the same time capable of re-peeling after a lapse of time.
상기 목적을 달성하기 위하여, 본 발명은 아크릴계 공중합체와 가교제를 포함하며, 상기 아크릴계 공중합체는 아미노기를 갖는 아크릴계 공중합체 및 카르복시기를 갖는 아크릴계 공중합체를 함유하는 점착제 조성물을 제공한다.In order to achieve the above object, the present invention comprises an acrylic copolymer and a crosslinking agent, the acrylic copolymer provides an adhesive composition containing an acrylic copolymer having an amino group and an acrylic copolymer having a carboxyl group.
상기 아크릴계 공중합체는 아미노기를 갖는 아크릴계 공중합체 10 내지 90중량% 및 카르복시기를 갖는 아크릴계 공중합체 10 내지 90중량%를 함유할 수 있다.The acrylic copolymer may contain 10 to 90% by weight of the acrylic copolymer having an amino group and 10 to 90% by weight of the acrylic copolymer having a carboxyl group.
상기 아미노기를 갖는 아크릴계 공중합체를 제조하기 위한 단량체는 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 및 하기 화학식 1 내지 5로 이루어진 군에서 선택된 1종 이상의 단량체를 함유할 수 있다.The monomer for preparing the acryl-based copolymer having an amino group may contain a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and at least one monomer selected from the group consisting of the following Chemical Formulas 1 to 5.
[화학식 1][Formula 1]
(식 중, R1은 수소 또는 메틸기이고, R2 및 R3는 각각 독립적으로 수소, 탄소수 1 내지 4의 알킬기, 또는 탄소수 1 내지 6의 트리알킬아민기임)(Wherein R 1 is hydrogen or a methyl group, R 2 and R 3 are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or a trialkylamine group having 1 to 6 carbon atoms)
[화학식 2][Formula 2]
(식 중, R1은 수소 또는 메틸기이고, R2 및 R3는 각각 독립적으로 수소 또는 탄소수 1 내지 4의 알킬기이고, R4는 히드록시기 또는 탄소수 1 내지 3의 알콕시기이고, l 및 n은 1 내지 12의 정수이며, m은 0 또는 1의 정수임)Wherein R 1 is hydrogen or a methyl group, R 2 and R 3 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, R 4 is a hydroxy group or an alkoxy group having 1 to 3 carbon atoms, and l and n are 1 An integer from 12 to m, and m is an integer of 0 or 1)
[화학식 3][Formula 3]
(식 중, R1은 수소 또는 메틸기이고, X는 O 또는 탄소수 1 내지 3의 알킬기가 치환된 N임)(Wherein R 1 is hydrogen or methyl group, X is O or N substituted with an alkyl group having 1 to 3 carbon atoms)
[화학식 4][Formula 4]
(식 중, R1은 수소 또는 메틸기이고, R2 및 R3는 각각 독립적으로 수소 또는 탄소수 1 내지 4의 알킬기임)(Wherein R 1 is hydrogen or a methyl group, R 2 and R 3 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms)
[화학식 5][Formula 5]
(식 중, R1은 수소 또는 메틸기이고, R4는 히드록시기 또는 탄소수 1 내지 3의 알콕시기이고, R5는 수소, 탄소수 1 내지 4의 지방족 탄화수소기, 할로겐, 탄소수 1 내지 4의 알콕시기 또는 탄소수 1 내지 4의 알킬아미노기이고, n은 1 내지 12의 정수이며, m은 0 또는 1의 정수임)Wherein R 1 is hydrogen or a methyl group, R 4 is a hydroxy group or an alkoxy group having 1 to 3 carbon atoms, R 5 is hydrogen, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, a halogen, an alkoxy group having 1 to 4 carbon atoms, or An alkylamino group having 1 to 4 carbon atoms, n is an integer of 1 to 12, and m is 0 or an integer of 1)
상기 화학식 1 내지 5로 이루어진 군에서 선택된 1종 이상의 단량체는 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 100중량부에 대하여 1 내지 20중량부를 함유할 수 있다.The at least one monomer selected from the group consisting of Formulas 1 to 5 may contain 1 to 20 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms.
상기 카르복시기를 갖는 아크릴계 공중합체를 제조하기 위한 단량체는 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 및 하기 화학식 6 내지 14로 이루어진 군에서 선택된 1종 이상의 단량체를 함유할 수 있다.The monomer for preparing the acryl-based copolymer having a carboxyl group may contain a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and at least one monomer selected from the group consisting of the following Chemical Formulas 6 to 14.
[화학식 6][Formula 6]
[화학식 7][Formula 7]
[화학식 8][Formula 8]
[화학식 9][Formula 9]
[화학식 10][Formula 10]
[화학식 11][Formula 11]
[화학식 12][Formula 12]
[화학식 13][Formula 13]
[화학식 14][Formula 14]
상기 화학식 6 내지 14로 이루어진 군에서 선택된 1종 이상의 단량체는 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 100중량부에 대하여 0.1 내지 10중량부 함유할 수 있다.The at least one monomer selected from the group consisting of Chemical Formulas 6 to 14 may contain 0.1 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms.
본 발명의 점착제 조성물은 아그릴계 공중합체와 가교제와의 공유결합과 함께 아크릴계 공중합체간의 이온결합 반응으로 점착제 조성물의 응집력이 향상된다. 상기 향상된 응집력에 의해 고온 또는 고온 다습한 환경에 노출된 경우에도 점착력을 유지할 수 있는 우수한 내구성을 가지면서, 종래와 동등 이상의 리워크성을 나타낼 수 있다.In the pressure-sensitive adhesive composition of the present invention, the cohesive force of the pressure-sensitive adhesive composition is improved by the ionic bond reaction between the acrylic copolymer and the covalent bond between the aglylic copolymer and the crosslinking agent. The improved cohesive force may exhibit excellent reworkability equivalent to that of the related art while having excellent durability to maintain adhesive force even when exposed to a high temperature or high temperature and high humidity environment.
본 발명은 응집력이 향상된 점착제 조성물에 관한 것이다.The present invention relates to an adhesive composition with improved cohesion.
이하 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명의 점착제 조성물은 아크릴계 공중합체와 가교제를 포함하며, 상기 아크릴계 공중합체는 아미노기를 갖는 아크릴계 공중합체 및 카르복시기를 갖는 아크릴계 공중합체를 함유한다.The pressure-sensitive adhesive composition of the present invention includes an acrylic copolymer and a crosslinking agent, and the acrylic copolymer contains an acrylic copolymer having an amino group and an acrylic copolymer having a carboxyl group.
이러한 본 발명의 점착제 조성물은 가교제와 아크릴계 공중합체간의 공유결합과 함께, 아크릴계 공중합체간의 이온결합이 동시에 수행되어 점착제 조성물의 응집력을 향상시킴으로써 우수한 내구성을 나타낼 수 있다.The pressure-sensitive adhesive composition of the present invention may exhibit excellent durability by covalent bonding between the crosslinking agent and the acrylic copolymer, and simultaneously performing ionic bonding between the acrylic copolymer to improve the cohesive force of the pressure-sensitive adhesive composition.
이때, 상기 아크릴계 공중합체는 아미노기를 갖는 아크릴계 공중합체 10 내지 90중량% 및 카르복시기를 갖는 아크릴계 공중합체 10 내지 90중량%를 함유할 수 있다. In this case, the acrylic copolymer may contain 10 to 90% by weight of the acrylic copolymer having an amino group and 10 to 90% by weight of the acrylic copolymer having a carboxyl group.
상기 아미노기를 갖는 아크릴계 공중합체의 함량이 10중량% 미만이거나 90중량%를 초과하는 경우에는 응집력 향상 효과가 미비하여 충분한 점착 내구성(내열성 및 내습열성) 개선 효과 달성이 용이하지 않을 수 있다.When the content of the acrylic copolymer having an amino group is less than 10% by weight or more than 90% by weight, the effect of improving cohesion may be insufficient and it may not be easy to achieve a sufficient adhesive durability (heat resistance and heat and moisture resistance) improvement effect.
본 발명의 아미노기를 갖는 아크릴계 공중합체를 제조하기 위한 단량체는 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 및 하기 화학식 1 내지 5로 이루어진 군에서 선택된 1종 이상의 단량체를 함유할 수 있다. 본 발명에 있어서, (메타)아크릴레이트는 아크릴레이트 및 메타크릴레이트를 의미하고, 각 성분의 함량은 고형분을 기준으로 한 것이다.The monomer for preparing the acrylic copolymer having an amino group of the present invention may contain at least one monomer selected from the group consisting of a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and the following formulas (1) to (5). In the present invention, (meth) acrylate means acrylate and methacrylate, and the content of each component is based on solid content.
[화학식1][Formula 1]
(식 중, R1은 수소 또는 메틸기이고, R2 및 R3는 각각 독립적으로 수소, 탄소수 1 내지 4의 알킬기, 또는 탄소수 1 내지 6의 트리알킬아민기임)(Wherein R 1 is hydrogen or a methyl group, R 2 and R 3 are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or a trialkylamine group having 1 to 6 carbon atoms)
[화학식 2][Formula 2]
(식 중, R1은 수소 또는 메틸기이고, R2 및 R3는 각각 독립적으로 수소 또는 탄소수 1 내지 4의 알킬기이고, R4는 히드록시기 또는 탄소수 1 내지 3의 알콕시기이고, l 및 n은 1 내지 12의 정수이며, m은 0 또는 1의 정수임)Wherein R 1 is hydrogen or a methyl group, R 2 and R 3 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, R 4 is a hydroxy group or an alkoxy group having 1 to 3 carbon atoms, and l and n are 1 An integer from 12 to m, and m is an integer of 0 or 1)
[화학식 3][Formula 3]
(식 중, R1은 수소 또는 메틸기이고, X는 O 또는 탄소수 1 내지 3의 알킬기가 치환된 N임)(Wherein R 1 is hydrogen or methyl group, X is O or N substituted with an alkyl group having 1 to 3 carbon atoms)
[화학식 4][Formula 4]
(식 중, R1은 수소 또는 메틸기이고, R2 및 R3는 각각 독립적으로 수소 또는 탄소수 1 내지 4의 알킬기임)(Wherein R 1 is hydrogen or a methyl group, R 2 and R 3 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms)
[화학식5][Formula 5]
(식 중, R1은 수소 또는 메틸기이고, R4는 히드록시기 또는 탄소수 1 내지 3의 알콕시기이고, R5는 수소, 탄소수 1 내지 4의 지방족 탄화수소기, 할로겐, 탄소수 1 내지 4의 알콕시기 또는 탄소수 1 내지 4의 알킬아미노기이고, n은 1 내지 12의 정수이며, m은 0 또는 1의 정수임)Wherein R 1 is hydrogen or a methyl group, R 4 is a hydroxy group or an alkoxy group having 1 to 3 carbon atoms, R 5 is hydrogen, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, a halogen, an alkoxy group having 1 to 4 carbon atoms, or An alkylamino group having 1 to 4 carbon atoms, n is an integer of 1 to 12, and m is 0 or an integer of 1)
상기 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체로는 n-부틸(메타)아크릴레이트, 2-부틸(메타)아크릴레이트, t-부틸(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, 에틸(메타)아크릴레이트, 메틸(메타)아크릴레이트, n-프로필(메타)아크릴레이트, 이소프로필(메타)아크릴레이트, 펜틸(메타)아크릴레이트, n-옥틸(메타)아크릴레이트, 이소옥틸(메타)아크릴레이트, 노닐(메타)아크릴레이트, 데실(메타)아크릴레이트, 라우릴(메타)아크릴레이트 등을 들 수 있으며, 이들 중에서 n-부틸아크릴레이트, 2-에틸헥실아크릴레이트 또는 이들의 혼합물이 바람직하다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Examples of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms include n-butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl (meth). ) Acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, pentyl (meth) acrylate, n-octyl (meth) acrylate Isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, and the like, among which n-butyl acrylate and 2-ethylhexyl acrylate Or mixtures thereof. These can be used individually or in mixture of 2 or more types.
상기 화학식 1 내지 5로 이루어진 군에서 선택된 1종 이상의 단량체는 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 100중량부에 대하여 1 내지 20중량부를 함유하는 것이 바람직하고, 보다 바람직하기로는 2 내지 10중량부인 것이 좋다. 그 함량이 1중량부 미만이면 응집력 향상 효과가 미비할 수 있고, 20중량부를 초과하는 경우에는 친수성이 지나치게 증가하여 내습성이 저하되거나, 이형필름의 박리력이 지나치게 상승되거나, 조액안정성이 악화 되는 등 점착제의 기타 물성이 악화될 수 있다.The at least one monomer selected from the group consisting of Formulas 1 to 5 preferably contains 1 to 20 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms, more preferably 2 It is good that it is 10 weight part. If the content is less than 1 part by weight, the effect of improving cohesion may be insignificant, and if it exceeds 20 parts by weight, the hydrophilicity may be excessively increased to reduce moisture resistance, the peeling force of the release film may be excessively increased, or the liquid stability may deteriorate. Etc. Other physical properties of the adhesive may be deteriorated.
본 발명의 아미노기를 갖는 아크릴계 공중합체를 제조하기 위한 단량체는 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 및 상기 화학식 1 내지 5로 이루어진 군에서 선택된 1종 이상의 단량체 이외에 히드록시기를 갖는 단량체를 함유할 수 있다.The monomer for preparing an acrylic copolymer having an amino group of the present invention may be a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and a monomer having a hydroxy group in addition to at least one monomer selected from the group consisting of Formulas 1 to 5 above. It may contain.
상기 히드록시기를 갖는 단량체는 화학 결합에 의해 점착제 조성물의 응집력 또는 점착 강도를 보강하여 내구성과 절단성을 부여하는 역할을 한다.The monomer having a hydroxy group serves to enhance the cohesion or adhesive strength of the pressure-sensitive adhesive composition by chemical bonding to impart durability and cutability.
구체적으로 상기 히드록시기를 갖는 단량체는 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 2-히드록시부틸(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 6-히드록시헥실(메타)아크릴레이트, 2-히드록시에틸렌글리콜(메타)아크릴레이트, 2-히드록시프로필렌글리콜(메타)아크릴레이트, 알킬렌기의 탄소수가 2-4인 히드록시알킬렌글리콜(메타)아크릴레이트, 4-히드록시부틸비닐에테르, 5-히드록시펜틸비닐에테르, 6-히드록시헥실비닐에테르, 7-히드록시헵틸비닐에테르, 8-히드록시옥틸비닐에테르, 9-히드록시노닐비닐에테르, 및 10-히드록시데실비닐에테르 등을 들 수 있으며, 이들 중에서 4-히드록시부틸비닐에테르가 바람직하다. Specifically, the monomer having a hydroxy group is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acryl 2-hydroxyhexyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate, 2-hydroxypropylene glycol (meth) acrylate, and hydroxyalkylene having 2 to 4 carbon atoms of an alkylene group. Glycol (meth) acrylate, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 7-hydroxyheptyl vinyl ether, 8-hydroxyoctyl vinyl ether, 9-hydroxy Hydroxynonyl vinyl ether, 10-hydroxydecyl vinyl ether, etc. are mentioned, Among these, 4-hydroxy butyl vinyl ether is preferable.
이러한 히드록시기를 갖는 단량체는 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 100중량부에 대하여 0.05 내지 10중량부로 포함되는 것이 바람직하고, 보다 바람직하게는 0.1 내지 8중량부인 것이 좋다. 함량이 0.05중량부 미만인 경우 점착제의 응집력이 작아지게 되어 내구성이 저하될 수 있으며, 10중량부 초과인 경우 높은 겔분율에 의해 점착력이 떨어지고 내구성에 문제를 야기할 수 있다. It is preferable that the monomer which has such a hydroxyl group is contained in 0.05-10 weight part with respect to 100 weight part of (meth) acrylate monomers which have a C1-C12 alkyl group, More preferably, it is 0.1-8 weight part. If the content is less than 0.05 parts by weight, the cohesive force of the pressure-sensitive adhesive may be reduced, the durability may be lowered. If the content is more than 10 parts by weight, the adhesive strength is lowered by a high gel fraction may cause problems in durability.
또한, 본 발명의 아미노기를 갖는 아크릴계 공중합체는 상기 단량체들 이외에 다른 중합성 단량체를 점착력을 저하시키지 않는 범위, 예컨대 총량에 대하여 10중량부 이하로 더 함유할 수 있다. In addition, the acrylic copolymer having an amino group of the present invention may further contain other polymerizable monomers other than the above monomers in a range of not lowering the adhesive strength, for example, 10 parts by weight or less based on the total amount.
아미노기를 갖는 아크릴계 공중합체의 제조방법은 특별히 한정되지 않으며, 당 분야에서 통상적으로 사용되는 괴상중합, 용액중합, 유화중합 또는 현탁중합 등의 방법을 이용하여 제조할 수 있으며, 용액중합이 바람직하다. 또한, 중합 시 통상 사용되는 용매, 중합개시제, 분자량 제어를 위한 연쇄이동제 등을 사용할 수 있다. The manufacturing method of the acryl-type copolymer which has an amino group is not specifically limited, It can manufacture using methods, such as block polymerization, solution polymerization, emulsion polymerization, or suspension polymerization conventionally used in the field, and solution polymerization is preferable. In addition, a solvent, a polymerization initiator, a chain transfer agent for molecular weight control, and the like, which are usually used in the polymerization, may be used.
상기 아미노기를 갖는 아크릴계 공중합체는 겔투과크로마토그래피(Gel permeation chromatography, GPC)에 의해 측정된 중량평균분자량(폴리스티렌 환산, Mw)이 5만 내지 200만인 것이 바람직하며, 보다 바람직하기로는 40만 내지 200만인 것이 좋다. 중량평균분자량이 5만 미만인 경우 공중합체 간의 응집력이 부족하여 점착 내구성에 문제를 야기할 수 있고, 200만 초과인 경우 도공 시 공정성을 확보하기 위하여 다량의 희석 용매를 필요로 할 수 있다. The acrylic copolymer having an amino group preferably has a weight average molecular weight (polystyrene equivalent, Mw) measured by gel permeation chromatography (GPC) of 50,000 to 2 million, more preferably 400,000 to 200 It is good to be. If the weight average molecular weight is less than 50,000, there is a lack of cohesion between the copolymers may cause problems in adhesion durability, if the weight average molecular weight is more than 2 million may require a large amount of dilution solvent to ensure fairness during coating.
본 발명의 카르복시기를 갖는 아크릴계 공중합체를 제조하기 위한 단량체는 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 및 하기 화학식 6 내지 14로 이루어진 군에서 선택된 1종 이상의 단량체를 함유하는 것이 바람직하다.The monomer for preparing an acrylic copolymer having a carboxyl group of the present invention preferably contains a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and at least one monomer selected from the group consisting of the following Chemical Formulas 6 to 14. .
[화학식 6][Formula 6]
[화학식 7][Formula 7]
[화학식 8][Formula 8]
[화학식 9][Formula 9]
[화학식 10][Formula 10]
[화학식 11][Formula 11]
[화학식 12][Formula 12]
[화학식 13][Formula 13]
[화학식 14][Formula 14]
상기 화학식 6 내지 14로 이루어진 군에서 선택된 1종 이상의 단량체는 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 100중량부에 대하여 0.1 내지 10중량부 함유하는 것이 바람직하고, 보다 바람직하기로는 2 내지 6중량부인 것이 좋다. 함량이 0.1중량부 미만이면 응집력 향상 효과가 미비할 수 있고, 10 중량부를 초과하는 경우에는 친수성이 지나치게 증가하여 내습열성의 저하가 우려된다. The at least one monomer selected from the group consisting of Chemical Formulas 6 to 14 preferably contains 0.1 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms, more preferably 2 It is good to be 6 weight part. If the content is less than 0.1 part by weight, the effect of improving cohesion may be insignificant. If the content is more than 10 parts by weight, the hydrophilicity is excessively increased, and there is a fear that the damp-heat resistance is lowered.
본 발명의 카르복시기를 갖는 아크릴계 공중합체는 상기 화학식 6 내지 14로 이루어진 군에서 선택된 1종 이상의 단량체 이외에 히드록시기를 갖는 단량체를 함유할 수 있다.The acrylic copolymer having a carboxyl group of the present invention may contain a monomer having a hydroxy group in addition to at least one monomer selected from the group consisting of Chemical Formulas 6 to 14.
상기 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체의 종류, 히드록시기를 갖는 단량체의 종류 및 함량, 공중합체의 제조방법, 공중합체의 중량평균분자량 등은 상기 아미노기를 갖는 아크릴계 공중합체에서의 설명과 동일하다.The type of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms, the type and content of the monomer having a hydroxy group, the production method of the copolymer, the weight average molecular weight of the copolymer, and the like are determined in the acrylic copolymer having the amino group. Same as the description.
본 발명은 아크릴계 공중합체간의 가교반응(이온결합)으로 미가교 된 저분자량 공중합체의 함량이 적어, 저분자량 공중합체의 블리드 아웃(bleed-out)에 의한 내구성 저하를 개선할 수 있고, 공중합체간의 조밀한 가교결합으로 응집력이 향상되어 내구성 확보가 가능하다.The present invention has a low content of the low molecular weight copolymer which is not crosslinked by the crosslinking reaction (ion bonding) between the acrylic copolymers, thereby improving the durability degradation due to the bleed-out of the low molecular weight copolymer, Dense crosslinking improves cohesion and ensures durability.
상기 가교제는 응집력을 향상시켜 내구성을 개선하는 역할을 하기 위하여 사용되고, 특히 내열성과 내습열성을 동시에 만족시키기 위해서 사용된다.The crosslinking agent is used to improve the cohesion and to improve durability, and in particular, to satisfy both heat resistance and heat and moisture resistance.
내습열 조건에서는 수분이 흡수되어 고분자간의 수소결합이나 이온결합이 끊어질 수 있으므로 이를 방지하기 위하여 가교제가 사용된다. In the heat and humidity conditions, water is absorbed and the hydrogen bonds and ionic bonds between the polymers may be interrupted, so a crosslinking agent is used to prevent this.
상기 가교제는 히드록시기 또는 카르복시기와 반응할 수 있는 것으로, 이소시아네이트계 또는 에폭시계 등이 각각 단독 또는 2종 이상 혼합 사용될 수 있다.The crosslinking agent may react with a hydroxy group or a carboxy group, and isocyanate or epoxy may be used alone or in combination of two or more.
상기 이소시아네이트계 가교제로는 톨릴렌디이소시아네이트, 자일렌디이소시아네이트, 2,4-디페닐메탄디이소시아네이트, 4,4-디페닐메탄디이소시아네이트, 헥사메틸렌디이소시아네이트, 이소포론디이소시아네이트, 테트라메틸자일렌디이소시아네이트, 나프탈렌디이소시아네이트 등의 디이소시아네이트화합물; 트리메틸올프로판 등의 다가 알콜계 화합물 1몰에 디이소시아네이트 화합물 3몰을 반응시킨 부가체, 디이소시아네이트 화합물 3몰을 자기 축합시킨 이소시아누레이트체, 디이소시아네이트 화합물 3몰 중 2몰로부터 얻어지는 디이소시아네이트 우레아에 나머지 1몰의 디이소시아네이트가 축합된 뷰렛체, 트리페닐메탄트리이소시아네이트, 메틸렌비스트리이소시아네이트 등의 3개의 관능기를 함유하는 다관능 이소시아네이트 화합물 등을 들 수 있다.Examples of the isocyanate-based crosslinking agent include tolylene diisocyanate, xylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate, Diisocyanate compounds such as naphthalene diisocyanate; Diisocyanate obtained from 2 moles of an adduct obtained by reacting 3 moles of a diisocyanate compound with 1 mole of a polyhydric alcohol compound such as trimethylolpropane, an isocyanurate obtained by self-condensing 3 moles of the diisocyanate compound, and 3 moles of the diisocyanate compound And polyfunctional isocyanate compounds containing three functional groups such as biuret, triphenylmethanetriisocyanate, and methylenebistriisocyanate, in which the remaining 1 mole of diisocyanate is condensed to urea.
상기 에폭시계 가교제로는 에틸렌글리콜디글리시딜에테르, 디에틸렌글리콜디글리시딜에테르, 폴리에틸렌글리콜디글리시딜에테르, 프로필렌글리콜디글리시딜에테르, 트리프로필렌글리콜디글리시딜에테르, 폴리프로필렌글리콜디글리시딜에테르, 네오펜틸글리콜디글리시딜에테르, 1,6-헥산디올디글리시딜에테르, 폴리테트라메틸렌글리콜디글리시딜에테르, 글리세롤디글리시딜에테르, 글리세롤트리글리시딜에테르, 디글리세롤폴리글리시딜에테르, 폴리글리세롤폴리글리시딜에테르, 레졸신디글리시딜에테르, 2,2-디브로모네오펜틸글리콜디글리시딜에테르, 트리메틸올프로판트리글리시딜에테르, 펜타에리트리톨폴리글리시딜에테르, 소르비톨폴리글리시딜에테르, 아디핀산디글리시딜에스테르, 프탈산디글리시딜에스테르, 트리스(글리시딜)이소시아누레이트, 트리스(글리시독시에틸)이소시아누레이트, 1,3-비스(N,N-글리시딜아미노메틸)시클로헥산, N,N,N',N'-테트라글리시딜-m-자일릴렌디아민 등을 들 수 있다.Examples of the epoxy-based crosslinking agents include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene. Glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether , Diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, resorcin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythrate Lithol polyglycidyl ether, sorbitol polyglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, tris (glycidyl) iso Anurate, tris (glycidoxyethyl) isocyanurate, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-m -Xylylenediamine, etc. are mentioned.
이러한 가교제는 상기 아미노기를 갖는 아크릴계 공중합체 및 카르복시기를 갖는 아크릴계 공중합체의 합계량 100중량부에 대하여 0.1 내지 5중량부, 바람직하기로는 0.2 내지 1.0중량부 함유될 수 있다. 상기 가교제의 함유량이 0.1중량부 미만이면 응집력 향상효과가 부족할 수 있으며, 5중량부를 초과할 경우에는 응집력의 지나친 증가에 의해 점착력이 저하될 수 있다.Such a crosslinking agent may be contained in an amount of 0.1 to 5 parts by weight, preferably 0.2 to 1.0 part by weight based on 100 parts by weight of the total amount of the acrylic copolymer having an amino group and the acrylic copolymer having a carboxyl group. When the content of the crosslinking agent is less than 0.1 part by weight, the effect of improving cohesion may be insufficient. When the content of the crosslinking agent is more than 5 parts by weight, the cohesion may be reduced due to excessive increase in cohesion.
또한, 본 발명에 따른 점착제 조성물은 대전방지제를 추가로 함유할 수 있으며, 이온성 대전방지제가 바람직하게 사용될 수 있다. 상기 이온성 대전방지제는 음이온과 양이온으로 구성된 이온성염류로 점착제에 이온 전도성을 부여할 수 있는 것이면 특별히 그 종류를 한정하지 않는다. In addition, the pressure-sensitive adhesive composition according to the present invention may further contain an antistatic agent, and an ionic antistatic agent may be preferably used. The ionic antistatic agent is not particularly limited as long as the ionic antistatic agent is capable of imparting ionic conductivity to the pressure-sensitive adhesive with ionic salts composed of anions and cations.
구체적으로 알칼리 금속염, 암모늄염, 설포늄염 및 포스포늄염으로 이루어진 군에서 선택된 양이온과; 불소함유 무기염, 불소함유 유기염 및 요오드이온로 이루어진 군에서 선택된 음이온으로 이루어진 이온성염류일 수 있다.Specifically, a cation selected from the group consisting of alkali metal salts, ammonium salts, sulfonium salts and phosphonium salts; It may be an ionic salt consisting of an anion selected from the group consisting of fluorine-containing inorganic salts, fluorine-containing organic salts and iodine ions.
이러한 이온성 대전방지제는 아크릴계 공중합체 100중량부에 대하여 0.1 내지 5중량부, 바람직하기로는 0.5 내지 3중량부 함유할 수 있다. 함량이 0.1 중량부 미만일 경우 대전방지성이 불충분할 수 있고 5중량부를 초과하는 경우에는 내구성 확보가 곤란할 수 있다.Such an ionic antistatic agent may contain 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the acrylic copolymer. If the content is less than 0.1 parts by weight may be insufficient antistatic properties and if it exceeds 5 parts by weight it may be difficult to secure durability.
상기와 같은 성분 이외에, 본 발명에 따른 점착제 조성물은 용도에 따라 요구되는 점착력, 응집력, 점성, 탄성률, 유리전이온도 등을 조절하기 위하여, 점착성 부여 수지, 산화방지제, 레벨링제, 표면윤활제, 염료, 안료, 소포제, 충전제, 광안정제 등의 첨가제를 더 함유할 수 있다. In addition to the components as described above, the pressure-sensitive adhesive composition according to the present invention, in order to adjust the adhesion, cohesion, viscosity, elastic modulus, glass transition temperature, etc. required according to the use, tackifying resin, antioxidant, leveling agent, surface lubricant, dye, Additives, such as a pigment, an antifoamer, a filler, and a light stabilizer, can be further contained.
이중 실란커플링제는 점착제와 기재와의 밀착력을 향상시키는 역할을하므로 이를 함유하는 것이 바람직하며, 아미노기, 에폭시기, 아세토아세틸기, 폴리알킬렌글리콜기, 아크릴기, 알킬기 등의 관능기를 함유하는 알콕시실란을 사용할 수 있다.Since the double silane coupling agent plays a role of improving adhesion between the pressure-sensitive adhesive and the base material, it is preferable to contain it, and an alkoxysilane containing functional groups such as amino group, epoxy group, acetoacetyl group, polyalkylene glycol group, acryl group and alkyl group Can be used.
이러한 첨가제는 본 발명의 효과를 저해하지 않는 범위내에서 적절히 함량을 조절할 수 있으며, 일례로 실란커플링제는 밀착력 및 내구성 등을 고려하여 상기 아미노기를 갖는 아크릴계 공중합체 및 카르복시기를 갖는 아크릴계 공중합체의 합계량 100중량부에 대하여 0.01 내지 2중량부, 바람직하기로는 0.1 내지 0.5중량부 함유할 수 있다. 그 함량이 0.01중량부 미만이면 밀착력이 저하될 수 있으며, 2중량부를 초과하는 경우에는 내열 조건에서 박리가 발생할 수 있다.Such additives may be appropriately adjusted in a range not impairing the effects of the present invention, for example, the silane coupling agent in consideration of the adhesion and durability, etc., the total amount of the acrylic copolymer having the amino group and the acrylic copolymer having a carboxyl group 0.01 to 2 parts by weight, preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight. If the content is less than 0.01 parts by weight, the adhesion may be lowered, and if it exceeds 2 parts by weight, peeling may occur under heat-resistant conditions.
본 발명의 점착제 조성물은 특히 액정셀과의 접합을 위한 편광판용 점착제, 표면보호필름용 점착제로 사용할 수 있다. 또한, 보호필름, 반사시트, 구조용 점착시트, 사진용 점착시트, 차선표시용 점착시트, 광학용 점착제품, 전자부품용 점착제뿐만 아니라 일반 상업용 점착시트제품으로도 사용 가능하다. In particular, the pressure-sensitive adhesive composition of the present invention can be used as a pressure-sensitive adhesive for polarizing plates and a surface protective film for bonding to liquid crystal cells. In addition, it can be used as a general commercial adhesive sheet product as well as a protective film, a reflective sheet, a structural adhesive sheet, a photographic adhesive sheet, a lane marking adhesive sheet, an optical adhesive product, an adhesive for electronic parts, and the like.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.
제조예 1 : 아미노기를 갖는 아크릴계 공중합체Preparation Example 1 Acrylic Copolymer Having an Amino Group
제조예 1-1Preparation Example 1-1
질소가스가 환류되고 온도조절이 용이하도록 냉각장치를 설치한 1L의 반응기에 n-부틸아크릴레이트(BA) 90중량부, 메틸아크릴레이트(MA) 7중량부, 디메틸아미노에틸아크릴레이트 3중량부로 이루어진 단량체 혼합물을 투입한 후, 용제로 에틸아세테이트(아세톤) 100중량부를 투입하였다. 그 다음 산소를 제거하기 위하여 질소가스를 1시간 동안 퍼징한 후, 62 ℃로 유지하였다. 상기 혼합물을 균일하게 한 후, 반응개시제로 아조비 스이소부티로니트릴(AIBN) 0.07중량부를 투입하고, 6시간 동안 반응시켜 중량평균분자량 약100만인 아미노기를 갖는 아크릴계 공중합체를 제조하였다.90 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA), and 3 parts by weight of dimethylaminoethyl acrylate in a 1 L reactor equipped with a refrigeration system to allow nitrogen gas to be refluxed and for easy temperature control. After the monomer mixture was added, 100 parts by weight of ethyl acetate (acetone) was added as a solvent. Then, after purging nitrogen gas for 1 hour to remove oxygen, it was maintained at 62 ° C. After the mixture was homogeneous, 0.07 parts by weight of azobis isobutyronitrile (AIBN) was added as a reaction initiator, and reacted for 6 hours to prepare an acrylic copolymer having an amino group having a weight average molecular weight of about 1 million.
제조예 1-2Preparation Example 1-2
상기 제조예 1-1과 동일하게 실시하되, 디메틸아미노에틸아크릴레이트 대신에 아크릴로일몰포린을 이용하여 아미노기를 갖는 아크릴계 공중합체를 제조하였다.An acrylic copolymer having an amino group was prepared in the same manner as in Preparation Example 1-1, using acryloylmorpholine instead of dimethylaminoethylacrylate.
제조예 1-3Preparation Example 1-3
상기 제조예 1-1과 동일하게 실시하되, n-부틸아크릴레이트(BA) 83중량부, 메틸아크릴레이트(MA) 7중량부, 디메틸아미노에틸아크릴레이트 대신에 
10중량부를 이용하여 아미노기를 갖는 아크릴계 공중합체를 제조하였다.In the same manner as in Preparation Example 1-1, 83 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA), instead of dimethylaminoethyl acrylate An acrylic copolymer having an amino group was prepared using 10 parts by weight.
제조예 1-4Preparation Example 1-4
상기 제조예 1-1과 동일하게 실시하되, n-부틸아크릴레이트(BA) 83중량부, 메틸아크릴레이트(MA) 7중량부, 디메틸아미노에틸아크릴레이트 대신에 
10중량부를 이용하여 아미노기를 갖는 아크릴계 공중합체를 제조하였다.In the same manner as in Preparation Example 1-1, 83 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA), instead of dimethylaminoethyl acrylate An acrylic copolymer having an amino group was prepared using 10 parts by weight.
제조예 1-5Preparation Example 1-5
상기 제조예 1-1과 동일하게 실시하되, n-부틸아크릴레이트(BA) 73중량부, 메틸아크릴레이트(MA) 7중량부, 디메틸아미노에틸아크릴레이트 대신에 
20중량부를 이용하여 아미노기를 갖는 아크릴계 공중합체를 제조하였다.In the same manner as in Preparation Example 1-1, 73 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA), instead of dimethylaminoethyl acrylate An acrylic copolymer having an amino group was prepared using 20 parts by weight.
제조예 1-6Preparation Example 1-6
상기 제조예 1-1과 동일하게 실시하되, n-부틸아크릴레이트(BA) 68중량부, 메틸아크릴레이트(MA) 7중량부, 디메틸아미노에틸아크릴레이트 25중량부를 이용하여 아미노기를 갖는 아크릴계 공중합체를 제조하였다.The same procedure as in Preparation Example 1-1, except that 68 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA), and 25 parts by weight of dimethylaminoethyl acrylate have an acrylic copolymer. Was prepared.
제조예 1-7Preparation Example 1-7
상기 제조예 1-1과 동일하게 실시하되, n-부틸아크릴레이트(BA) 83중량부, 메틸아크릴레이트(MA) 7중량부, 디메틸아미노에틸아크릴레이트 대신에 
10중량부를 이용하여 아미노기를 갖는 아크릴계 공중합체를 제조하였다.In the same manner as in Preparation Example 1-1, 83 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA), instead of dimethylaminoethyl acrylate An acrylic copolymer having an amino group was prepared using 10 parts by weight.
제조예 1-8Preparation Example 1-8
상기 제조예 1-1과 동일하게 실시하되, n-부틸아크릴레이트(BA) 83중량부, 메틸아크릴레이트(MA) 7중량부, 디메틸아미노에틸아크릴레이트 대신에 
10중량부를 이용하여 아미노기를 갖는 아크릴계 공중합체를 제조하였다.In the same manner as in Preparation Example 1-1, 83 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA), instead of dimethylaminoethyl acrylate An acrylic copolymer having an amino group was prepared using 10 parts by weight.
제조예 2: 카르복시기를 갖는 아크릴계 공중합체Preparation Example 2 Acrylic Copolymer Having a Carboxyl Group
제조예 2-1Preparation Example 2-1
질소가스가 환류되고 온도조절이 용이하도록 냉각장치를 설치한 1L의 반응기에 n-부틸아크릴레이트(BA) 89중량부, 메틸아크릴레이트(MA) 7.0중량부, 
(화학식 6) 3.0중량부, 4-히드록시부틸아크릴레이트 (4HBA) 1.0중량부로 이루어진 단량체 혼합물을 투입한 후, 용제로 아세톤 100중량부를 투입하였다. 그 다음 산소를 제거하기 위하여 질소가스를 1시간 동안 퍼징한 후, 62℃로 유지하였다. 상기 혼합물을 균일하게 한 후, 반응개시제로 아조비스이소부티로니트릴(AIBN) 0.07중량부를 투입하고, 6시간 동안 반응시켜 중량평균분자량이 약 100만인 카르복시기를 갖는 아크릴계 공중합체를 제조하였다.89 parts by weight of n-butyl acrylate (BA), 7.0 parts by weight of methyl acrylate (MA) in a 1 L reactor equipped with a refrigeration system to allow nitrogen gas to be refluxed and to facilitate temperature control. After the addition of a monomer mixture consisting of 3.0 parts by weight and 1.0 parts by weight of 4-hydroxybutyl acrylate (4HBA), 100 parts by weight of acetone was added as a solvent. Then, after purging nitrogen gas for 1 hour to remove oxygen, it was maintained at 62 ℃. After the mixture was uniform, 0.07 parts by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator, and reacted for 6 hours to prepare an acrylic copolymer having a carboxyl group having a weight average molecular weight of about 1 million.
제조예 2-2Preparation Example 2-2
상기 제조예 2-1과 동일하게 실시하되, 
(화학식 6) 대신에 
(화학식 7)을 사용하여 카르복시기를 갖는 아크릴계 공중합체를 제조하였다.In the same manner as in Preparation Example 2-1, Instead of (Formula 6) Using the general formula (7) to prepare an acrylic copolymer having a carboxyl group.
제조예 2-3Preparation Example 2-3
상기 제조예 2-1과 동일하게 실시하되, 
(화학식 6) 대신에 
(화학식 8)을 사용하여 카르복시기를 갖는 아크릴계 공중합체를 제조하였다.In the same manner as in Preparation Example 2-1, Instead of (Formula 6) (8) was used to prepare an acrylic copolymer having a carboxyl group.
제조예 2-4Preparation Example 2-4
상기 제조예 2-1과 동일하게 실시하되, 
(화학식 6) 대신에 
(화학식 9)을 사용하여 카르복시기를 갖는 아크릴계 공중합체를 제조하였다.In the same manner as in Preparation Example 2-1, Instead of (Formula 6) Using the formula (9) to prepare an acrylic copolymer having a carboxyl group.
제조예 2-5Preparation Example 2-5
상기 제조예 2-1과 동일하게 실시하되, 
(화학식 6) 대신에 
(화학식 10)을 사용하여 카르복시기를 갖는 아크릴계 공중합체를 제조하였다.In the same manner as in Preparation Example 2-1, Instead of (Formula 6) Using the formula (10) to prepare an acrylic copolymer having a carboxyl group.
제조예 2-6Preparation Example 2-6
상기 제조예 2-1과 동일하게 실시하되, 
(화학식 6) 대신에 
(화학식 11)을 사용하여 카르복시기를 갖는 아크릴계 공중합체를 제조하였다.In the same manner as in Preparation Example 2-1, Instead of (Formula 6) Using the general formula (11) to prepare an acrylic copolymer having a carboxyl group.
제조예 2-7Preparation Example 2-7
상기 제조예 2-1과 동일하게 실시하되, 
(화학식 6) 대신에 
(화학식 12)을 사용하여 카르복시기를 갖는 아크릴계 공중합체를 제조하였다.In the same manner as in Preparation Example 2-1, Instead of (Formula 6) Using the formula (12) to prepare an acrylic copolymer having a carboxyl group.
제조예 2-8Preparation Example 2-8
상기 제조예 2-1과 동일하게 실시하되, 
(화학식 6) 대신에 
(화학식 13)을 사용하여 카르복시기를 갖는 아크릴계 공중합체를 제조하였다.In the same manner as in Preparation Example 2-1, Instead of (Formula 6) Using the formula (13) to prepare an acrylic copolymer having a carboxyl group.
제조예 2-9Preparation Example 2-9
상기 제조예 2-1과 동일하게 실시하되, 
(화학식 6) 대신에 
(화학식 14)을 사용하여 카르복시기를 갖는 아크릴계 공중합체를 제조하였다.In the same manner as in Preparation Example 2-1, Instead of (Formula 6) (14) was used to prepare an acrylic copolymer having a carboxyl group.
제조예 2-10Preparation Example 2-10
상기 제조예 2-1과 동일하게 실시하되, n-부틸아크릴레이트(BA) 91중량부, 메틸아크릴레이트(MA) 7.0중량부, 
(화학식 6) 1.0중량부와 히드록시에틸아크릴레이트 1.0중량부를 사용하여 카르복시기를 갖는 아크릴계 공중합체를 제조하였다. In the same manner as in Preparation Example 2-1, n-butyl acrylate (BA) 91 parts by weight, methyl acrylate (MA) 7.0 parts by weight, An acrylic copolymer having a carboxyl group was prepared using 1.0 part by weight and 1.0 part by weight of hydroxyethyl acrylate.
제조예 2-11Preparation Example 2-11
상기 제조예 2-1과 동일하게 실시하되, n-부틸아크릴레이트(BA) 82 중량부, 메틸아크릴레이트(MA) 7.0중량부, 
(화학식 6) 10.0중량부와 히드록시에틸아크릴레이트 1.0중량부를 사용하여 카르복시기를 갖는 아크릴계 공중합체를 제조하였다.In the same manner as in Preparation Example 2-1, n-butyl acrylate (BA) 82 parts by weight, methyl acrylate (MA) 7.0 parts by weight, An acrylic copolymer having a carboxyl group was prepared using 10.0 parts by weight and 1.0 part by weight of hydroxyethyl acrylate.
제조예 2-12Preparation Example 2-12
상기 제조예 2-1과 동일하게 실시하되, n-부틸아크릴레이트(BA) 77 중량부, 메틸아크릴레이트(MA) 7.0중량부, 
(화학식 6) 15.0중량부와 히드록시에틸아크릴레이트 1.0중량부를 사용하여 카르복시기를 갖는 아크릴계 공중합체를 제조하였다.In the same manner as in Preparation Example 2-1, n-butyl acrylate (BA) 77 parts by weight, methyl acrylate (MA) 7.0 parts by weight, An acrylic copolymer having a carboxyl group was prepared using 15.0 parts by weight and 1.0 part by weight of hydroxyethyl acrylate.
실시예 1-23 및 비교예 1-2Example 1-23 and Comparative Example 1-2
하기 표 1의 조성으로 혼합한 후 에틸아세테이트에 희석하여 고형분 농도 15%의 점착제 조성물을 제조하였다. 상기에서 제조된 점착제 조성물을 실리콘 이형제가 코팅된 이형필름 상에 두께가 25㎛가 되도록 도포하고 100℃에서 1분 동안 건조시켜 점착층을 형성하였다. After mixing to the composition of Table 1 and diluted in ethyl acetate to prepare a pressure-sensitive adhesive composition of 15% solids concentration. The pressure-sensitive adhesive composition prepared above was applied on a release film coated with a silicone release agent to have a thickness of 25 μm, and dried at 100 ° C. for 1 minute to form an adhesive layer.
두께 185㎛의 요오드계 편광판에 상기 제조된 점착층을 점착 가공으로 적층하여 점착제 부착 편광판을 제조하였다.A pressure-sensitive adhesive polarizing plate was prepared by laminating the pressure-sensitive adhesive layer prepared above on an iodine-based polarizing plate having a thickness of 185 μm.
[표 1]TABLE 1
시험예Test Example
상기 실시예 및 비교예에서 제조된 점착제 부착 편광판의 물성을 하기의 방법으로 측정하고, 그 결과를 하기 표 2에 나타내었다. The physical properties of the pressure-sensitive adhesive polarizing plate prepared in Examples and Comparative Examples were measured by the following method, and the results are shown in Table 2 below.
1.내열성/내습열성1.Heat resistance / humidity heat resistance
점착제 부착 편광판의 이형필름을 제거하고, 점착제층 표면과 코닝글라스에 접합한 후, 80℃와 60℃/90RH%조건에서 각각 300시간 방치 후 외관을 확인하였다. After removing the release film of the polarizing plate with a pressure-sensitive adhesive, and bonded to the pressure-sensitive adhesive layer surface and Corning glass, after standing for 300 hours at 80 ℃ and 60 ℃ / 90 RH% conditions, the appearance was confirmed.
<평가기준><Evaluation Criteria>
기포와 박리현상 3개이상 시인됨: ×Bubble and Peeling 3 or more admitted: ×
기포와 박리현상 2개 이하 시인됨: ○Less than 2 bubbles and peelings are admitted: ○
기포와 박리현상 미시인됨: ◎Bubbles and Peelings Unidentified: ◎
2. 리워크성 2. Reworkability
점착제 부착 편광판을 폭 25㎜, 길이 100㎜의 크기로 잘라내고, 이형필름을 박리한 후, 코닝사 #1737 유리에 0.25MPa의 압력으로 라미네이션하고 5기압, 50℃의 조건으로 20분 동안 오토클레이브를 처리하여 평가 샘플을 제조하였다. 50℃ 오븐에 넣은 후 5시간 뒤에 꺼내어 120시간 동안 상온에서 방치한 후 1.3㎝/s의 속도로 박리하였다. 또한, 내습조건인 60℃, 90RH% 오븐에 넣은 후 4시간 뒤에 꺼내어 120시간 동안 상온에서 방치한 후 1.3㎝/s의 속도로 박리하였다. The pressure-sensitive adhesive polarizing plate was cut out to a size of 25 mm in width and 100 mm in length, and the release film was peeled off. Laminated with Corning's # 1737 glass at a pressure of 0.25 MPa, and the autoclave was kept at 5 atmospheres and 50 ° C. for 20 minutes. Treatment to prepare an evaluation sample. After putting in a 50 ℃ oven was taken out after 5 hours and left at room temperature for 120 hours, it was peeled off at a rate of 1.3 cm / s. In addition, after being put into an oven at 60 ° C. and 90 RH% of humidity conditions, it was taken out after 4 hours and left at room temperature for 120 hours, followed by peeling at a speed of 1.3 cm / s.
<평가기준><Evaluation Criteria>
-양쪽 조건 모두에서 유리 기판에 점착제의 남음이 없고 편광판의 찢어짐 없이 깨끗이 박리: ○-In both conditions, there is no adhesive left on the glass substrate and peeling off without tearing of the polarizing plate: ○
-어느 한쪽 조건 이상에서 패널에 점착제가 남아있거나 박리과정에서 편광판이 찢어짐: ×The adhesive remains on the panel under more than one condition or the polarizer is torn during the peeling process: ×
[표 2]TABLE 2
상기 표 2와 같이 아크릴계 공중합체로 본 발명에 따라 아미노기를 갖는 아크릴계 공중합체 및 카르복시기를 갖는 아크릴계 공중합체를 함유한 실시예 1 내지 23의 점착제 조성물은 비교예 1 내지 2와 비교하여 동등 이상의 리워크성을 유지하면서, 내열성 및 내습열성은 우수하다는 것을 확인할 수 있었다.The pressure-sensitive adhesive composition of Examples 1 to 23 containing an acrylic copolymer having an amino group and an acrylic copolymer having a carboxyl group according to the present invention as an acrylic copolymer as shown in Table 2 is at least equivalent to the rework It was confirmed that the heat resistance and the heat-and-moisture resistance were excellent while maintaining the properties.
Claims (6)
- 아크릴계 공중합체와 가교제를 포함하며, It includes an acrylic copolymer and a crosslinking agent,상기 아크릴계 공중합체는 아미노기를 갖는 아크릴계 공중합체 및 카르복시기를 갖는 아크릴계 공중합체를 함유하는 점착제 조성물.The acrylic copolymer is an adhesive composition containing an acrylic copolymer having an amino group and an acrylic copolymer having a carboxyl group.
- 청구항 1에 있어서, 상기 아크릴계 공중합체는 아미노기를 갖는 아크릴계 공중합체 10 내지 90중량% 및 카르복시기를 갖는 아크릴계 공중합체 10 내지 90중량%를 함유하는 점착제 조성물.The pressure-sensitive adhesive composition of claim 1, wherein the acrylic copolymer contains 10 to 90% by weight of an acrylic copolymer having an amino group and 10 to 90% by weight of an acrylic copolymer having a carboxyl group.
- 청구항 1에 있어서, 상기 아미노기를 갖는 아크릴계 공중합체를 제조하기 위한 단량체는 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 및 하기 화학식 1 내지 5로 이루어진 군에서 선택된 1종 이상의 단량체를 함유하는 것인 점착제 조성물:The method of claim 1, wherein the monomer for producing an acrylic copolymer having an amino group contains a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and at least one monomer selected from the group consisting of Pressure-sensitive adhesive composition:[화학식 1][Formula 1]
(식 중, R1은 수소 또는 메틸기이고, R2 및 R3는 각각 독립적으로 수소, 탄소수 1 내지 4의 알킬기, 또는 탄소수 1 내지 6의 트리알킬아민기임)(Wherein R 1 is hydrogen or a methyl group, R 2 and R 3 are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or a trialkylamine group having 1 to 6 carbon atoms)[화학식 2][Formula 2]
(식 중, R1은 수소 또는 메틸기이고, R2 및 R3는 각각 독립적으로 수소 또는 탄소수 1 내지 4의 알킬기이고, R4는 히드록시기 또는 탄소수 1 내지 3의 알콕시기이고, l 및 n은 1 내지 12의 정수이며, m은 0 또는 1의 정수임)Wherein R 1 is hydrogen or a methyl group, R 2 and R 3 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, R 4 is a hydroxy group or an alkoxy group having 1 to 3 carbon atoms, and l and n are 1 An integer from 12 to m, and m is an integer of 0 or 1)[화학식 3][Formula 3]
(식 중, R1은 수소 또는 메틸기이고, X는 O 또는 탄소수 1 내지 3의 알킬기가 치환된 N임)(Wherein R 1 is hydrogen or methyl group, X is O or N substituted with an alkyl group having 1 to 3 carbon atoms)[화학식 4] [Formula 4]
(식 중, R1은 수소 또는 메틸기이고, R2 및 R3는 각각 독립적으로 수소 또는 탄소수 1 내지 4의 알킬기임)(Wherein R 1 is hydrogen or a methyl group, R 2 and R 3 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms)[화학식 5] [Formula 5]
(식 중, R1은 수소 또는 메틸기이고, R4는 히드록시기 또는 탄소수 1 내지 3의 알콕시기이고, R5는 수소, 탄소수 1 내지 4의 지방족 탄화수소기, 할로겐, 탄소수 1 내지 4의 알콕시기 또는 탄소수 1 내지 4의 알킬아미노기이고, n은 1 내지 12의 정수이며, m은 0 또는 1의 정수임).Wherein R 1 is hydrogen or a methyl group, R 4 is a hydroxy group or an alkoxy group having 1 to 3 carbon atoms, R 5 is hydrogen, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, a halogen, an alkoxy group having 1 to 4 carbon atoms, or An alkylamino group having 1 to 4 carbon atoms, n is an integer of 1 to 12, and m is 0 or an integer of 1). - 청구항 3에 있어서, 상기 화학식 1 내지 5로 이루어진 군에서 선택된 1종 이상의 단량체는 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 100중량부에 대하여 1 내지 20중량부를 함유하는 것인 점착제 조성물.The pressure-sensitive adhesive composition of claim 3, wherein the at least one monomer selected from the group consisting of Formulas 1 to 5 contains 1 to 20 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms. .
- 청구항 1에 있어서, 상기 카르복시기를 갖는 아크릴계 공중합체를 제조하기 위한 단량체는 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 및 하기 화학식 6 내지 14로 이루어진 군에서 선택된 1종 이상의 단량체를 함유하는 것인 점착제 조성물:The method of claim 1, wherein the monomer for preparing an acrylic copolymer having a carboxyl group contains a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and at least one monomer selected from the group consisting of the following formulas (6) to (14). Pressure-sensitive adhesive composition:[화학식 6][Formula 6]
[화학식 7][Formula 7]
[화학식 8][Formula 8]
[화학식 9][Formula 9]
[화학식 10][Formula 10]
[화학식 11][Formula 11]
[화학식 12][Formula 12]
[화학식 13][Formula 13]
[화학식 14][Formula 14]
- 청구항 5에 있어서, 상기 화학식 6 내지 14로 이루어진 군에서 선택된 1종 이상의 단량체는 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 100중량부에 대하여 0.1 내지 10중량부 함유하는 것인 점착제 조성물.The pressure-sensitive adhesive composition of claim 5, wherein the at least one monomer selected from the group consisting of Chemical Formulas 6 to 14 contains 0.1 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms. .
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| KR10-2013-0059503 | 2013-05-27 | ||
| KR20130059503 | 2013-05-27 | ||
| KR1020140031122A KR102145807B1 (en) | 2013-05-27 | 2014-03-17 | Adhesive composition |
| KR10-2014-0031122 | 2014-03-17 |
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| WO (1) | WO2014193112A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120073093A (en) * | 2010-12-24 | 2012-07-04 | 소켄 케미칼 앤드 엔지니어링 캄파니, 리미티드 | Adhesive composition for optical film and adhesive type optical film |
| KR20120078119A (en) * | 2010-12-31 | 2012-07-10 | 동우 화인켐 주식회사 | Adhesive composition, polarizing plate and liquid crystal display device comprising the same |
| KR20130038513A (en) * | 2011-10-10 | 2013-04-18 | 동우 화인켐 주식회사 | New (meth)acrylate compound and adhesive composition comprising the same |
| KR20130039242A (en) * | 2011-10-11 | 2013-04-19 | 제일모직주식회사 | Adhesive composition, adhesive film comprising the same, method for preparing the adhesive film and display member using the same |
| KR20130049776A (en) * | 2010-03-25 | 2013-05-14 | 닛토덴코 가부시키가이샤 | Acrylic adhesive composition and acrylic adhesive tape |
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2014
- 2014-05-21 WO PCT/KR2014/004534 patent/WO2014193112A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130049776A (en) * | 2010-03-25 | 2013-05-14 | 닛토덴코 가부시키가이샤 | Acrylic adhesive composition and acrylic adhesive tape |
| KR20120073093A (en) * | 2010-12-24 | 2012-07-04 | 소켄 케미칼 앤드 엔지니어링 캄파니, 리미티드 | Adhesive composition for optical film and adhesive type optical film |
| KR20120078119A (en) * | 2010-12-31 | 2012-07-10 | 동우 화인켐 주식회사 | Adhesive composition, polarizing plate and liquid crystal display device comprising the same |
| KR20130038513A (en) * | 2011-10-10 | 2013-04-18 | 동우 화인켐 주식회사 | New (meth)acrylate compound and adhesive composition comprising the same |
| KR20130039242A (en) * | 2011-10-11 | 2013-04-19 | 제일모직주식회사 | Adhesive composition, adhesive film comprising the same, method for preparing the adhesive film and display member using the same |
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