KR102675803B1 - Adhesive composition, adhesive sheet and display using the same - Google Patents
Adhesive composition, adhesive sheet and display using the same Download PDFInfo
- Publication number
- KR102675803B1 KR102675803B1 KR1020230026131A KR20230026131A KR102675803B1 KR 102675803 B1 KR102675803 B1 KR 102675803B1 KR 1020230026131 A KR1020230026131 A KR 1020230026131A KR 20230026131 A KR20230026131 A KR 20230026131A KR 102675803 B1 KR102675803 B1 KR 102675803B1
- Authority
- KR
- South Korea
- Prior art keywords
- adhesive
- random copolymer
- adhesive sheet
- weight
- adhesive composition
- Prior art date
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- 239000000853 adhesive Substances 0.000 title claims abstract description 100
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 100
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229920005604 random copolymer Polymers 0.000 claims abstract description 41
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 230000009477 glass transition Effects 0.000 claims abstract description 14
- 238000003860 storage Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- FFBZKUHRIXKOSY-UHFFFAOYSA-N aziridine-1-carboxamide Chemical compound NC(=O)N1CC1 FFBZKUHRIXKOSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000007983 Tris buffer Substances 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- FYAMXEPQQLNQDM-UHFFFAOYSA-N Tris(1-aziridinyl)phosphine oxide Chemical compound C1CN1P(N1CC1)(=O)N1CC1 FYAMXEPQQLNQDM-UHFFFAOYSA-N 0.000 claims description 2
- OEOQTSUNXODXQL-UHFFFAOYSA-N [2-[3-(2-methylaziridin-1-yl)propanoyloxy]-2-[3-(2-methylaziridin-1-yl)propanoyloxymethyl]butyl] 3-(2-methylaziridin-1-yl)propanoate Chemical compound C1C(C)N1CCC(=O)OCC(OC(=O)CCN1C(C1)C)(CC)COC(=O)CCN1CC1C OEOQTSUNXODXQL-UHFFFAOYSA-N 0.000 claims description 2
- IUCJMVBFZDHPDX-UHFFFAOYSA-N tretamine Chemical compound C1CN1C1=NC(N2CC2)=NC(N2CC2)=N1 IUCJMVBFZDHPDX-UHFFFAOYSA-N 0.000 claims description 2
- 229950001353 tretamine Drugs 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 description 37
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 239000012790 adhesive layer Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- -1 2-hydroxypropyl Chemical group 0.000 description 11
- 229920001296 polysiloxane Polymers 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 7
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 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 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 239000002313 adhesive film Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- OADIZUFHUPTFAG-UHFFFAOYSA-N 2-[2-(2-ethylhexoxy)ethoxy]ethanol Chemical compound CCCCC(CC)COCCOCCO OADIZUFHUPTFAG-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- LFULEKSKNZEWOE-UHFFFAOYSA-N propanil Chemical compound CCC(=O)NC1=CC=C(Cl)C(Cl)=C1 LFULEKSKNZEWOE-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- LMAUULKNZLEMGN-UHFFFAOYSA-N 1-ethyl-3,5-dimethylbenzene Chemical compound CCC1=CC(C)=CC(C)=C1 LMAUULKNZLEMGN-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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- CBECDWUDYQOTSW-UHFFFAOYSA-N 2-ethylbut-3-enal Chemical compound CCC(C=C)C=O CBECDWUDYQOTSW-UHFFFAOYSA-N 0.000 description 1
- JGRXEBOFWPLEAV-UHFFFAOYSA-N 2-ethylbutyl prop-2-enoate Chemical compound CCC(CC)COC(=O)C=C JGRXEBOFWPLEAV-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- RKNUGRGVOVDCAX-UHFFFAOYSA-N 2-methylaziridine-1-carboxamide Chemical compound CC1CN1C(N)=O RKNUGRGVOVDCAX-UHFFFAOYSA-N 0.000 description 1
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 1
- YAHLUTXNMRWKSM-UHFFFAOYSA-N 2-prop-2-enoyloxybutanoic acid Chemical compound CCC(C(O)=O)OC(=O)C=C YAHLUTXNMRWKSM-UHFFFAOYSA-N 0.000 description 1
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 1
- JCQAEBFXPWPFOG-UHFFFAOYSA-N 3-(2-methylaziridin-1-yl)propanoic acid Chemical compound CC1CN1CCC(O)=O JCQAEBFXPWPFOG-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 1
- RWMLHXXJCLCEMR-UHFFFAOYSA-N 9h-carbazole;prop-2-enoic acid Chemical compound OC(=O)C=C.C1=CC=C2C3=CC=CC=C3NC2=C1 RWMLHXXJCLCEMR-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 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
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003006 anti-agglomeration agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229920005994 diacetyl cellulose Polymers 0.000 description 1
- ISRJTGUYHVPAOR-UHFFFAOYSA-N dihydrodicyclopentadienyl acrylate Chemical compound C1CC2C3C(OC(=O)C=C)C=CC3C1C2 ISRJTGUYHVPAOR-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- VIBDJEWPNNCFQO-UHFFFAOYSA-N ethane-1,1,2-triol Chemical compound OCC(O)O VIBDJEWPNNCFQO-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- JTHNLKXLWOXOQK-UHFFFAOYSA-N n-propyl vinyl ketone Natural products CCCC(=O)C=C JTHNLKXLWOXOQK-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
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- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
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- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
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- 239000004417 polycarbonate Substances 0.000 description 1
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- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 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
- 238000010926 purge Methods 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- XZHNPVKXBNDGJD-UHFFFAOYSA-N tetradecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C=C XZHNPVKXBNDGJD-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
- G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
본 발명은 아크릴계 랜덤 공중합체 및 아지리딘계 화합물을 포함하며, 상기 아크릴계 랜덤 공중합체는 유리전이온도가 0℃ 이상이고, 상기 아지리딘계 화합물은 상기 아크릴계 랜덤 공중합체 100 중량부에 대하여 2 중량부 이상 포함하는 것인, 점착제 조성물과, 이를 포함하는 점착시트 및 디스플레이에 관한 것으로, 탄성력을 향상시키면서도 점착성 및 점착력 유지율이 우수하여 폴더블 디스플레이에 적합한 점착제 조성물, 점착시트 및 디스플레이를 제공할 수 있다.The present invention includes an acrylic random copolymer and an aziridine-based compound, wherein the acrylic random copolymer has a glass transition temperature of 0° C. or higher, and the aziridine-based compound contains at least 2 parts by weight based on 100 parts by weight of the acrylic random copolymer. The present invention relates to an adhesive composition, an adhesive sheet, and a display containing the same, and provides an adhesive composition, adhesive sheet, and display suitable for a foldable display as it improves elasticity and has excellent adhesion and adhesion retention rate.
Description
본 발명은 점착제 조성물, 이를 포함하는 점착 시트 및 디스플레이에 관한 것이다.The present invention relates to an adhesive composition, an adhesive sheet containing the same, and a display.
최근 디스플레이 산업에서는 터치패널 또는 터치스크린을 탑재하거나, 고휘도 및 고투과성을 얻기 위해 광학적으로 투명한 점착제를 다수 이용하고 있다.Recently, the display industry has been using many optically transparent adhesives to mount touch panels or touch screens or to achieve high brightness and high transparency.
기술의 발전으로 인해 디스플레이산업에서 사용되는 터치스크린 또는 터치패널은 점점 폴더블 형태로 전환되고 있으며, 이러한 터치 스크린 또는 터치패널에 투명 필름 또는 UTG(ultra thin glass)를 부착하기 위해 사용되는 점착제는 각종 기재에 대한 점착성과 동시에 고탄성의 성능을 필요로 한다.Due to technological advancements, touch screens or touch panels used in the display industry are increasingly being converted to foldable forms, and the adhesives used to attach transparent films or UTG (ultra thin glass) to these touch screens or touch panels are of various types. It requires adhesion to the substrate and high elasticity at the same time.
대한민국 공개특허 제10-2016-0073329호에는 유리전이온도가 -10℃ 이하인 블록 공중합체를 약 90중량% 포함하는 점착제 조성물이 개시되어 있는데, 0℃ 미만의 유리전이온도를 나타내는 상기 블록 공중합체를 적용한 점착제 조성물은 고탄성 특성을 발휘하기 어려우며, 따라서 폴딩 형태로 구동되는 폴더블 디스플레이에 사용하는 경우 탄성력의 부족으로 점착 시트가 파단되거나 들뜨게되어 주름이 형성되는 문제가 발생할 수 있다. Republic of Korea Patent Publication No. 10-2016-0073329 discloses an adhesive composition containing about 90% by weight of a block copolymer having a glass transition temperature of -10°C or lower. The block copolymer having a glass transition temperature of less than 0°C is disclosed. It is difficult for the applied adhesive composition to exhibit high elastic properties, and therefore, when used in a foldable display driven in a folded form, the adhesive sheet may be broken or lifted due to lack of elasticity, resulting in the formation of wrinkles.
한편 탄성력이 높아지면 점착제 조성물의 택(Tack)성이 부족해지게 되며, 일반적으로 초기 점착력과 감압 후 점착력 사이에 차이가 발생되므로, 궁극적으로 점착력이 유지되지 못하는 문제가 발생될 수 있다. On the other hand, as the elasticity increases, the tack of the adhesive composition becomes insufficient, and generally a difference occurs between the initial adhesive force and the adhesive force after decompression, which may ultimately lead to a problem in which the adhesive strength is not maintained.
따라서, 폴딩 형태로 구동되는 폴더블 디스플레이에 적용되어도 점착 시트의 파단 또는 들뜸 현상이 발생되지 않도록 탄성력이 우수하면서도 점착력에 영향을 미치지 않으며, 감압 후 점착력 역시 우수한 점착제 조성물의 개발이 요구되고 있다.Therefore, there is a need to develop an adhesive composition that has excellent elasticity so that the adhesive sheet does not break or lift when applied to a foldable display that is driven in a folded form, but does not affect the adhesive strength and also has excellent adhesive strength after decompression.
본 발명은, 폴더블 디스플레이에 적합하도록, 탄성력을 향상시키면서도 점착성 및 점착력 유지율이 우수한 점착제 조성물을 제공하고자 한다. The present invention seeks to provide an adhesive composition that improves elasticity and has excellent adhesion and adhesion retention rate so that it is suitable for foldable displays.
또한, 본 발명은, 탄성력 및 점착성이 우수한 점착시트 및 이를 포함하는 디스플레이를 제공하고자 한다.In addition, the present invention seeks to provide an adhesive sheet with excellent elasticity and adhesiveness and a display including the same.
그러나, 본원이 해결하고자 하는 과제는 이상에서 언급한 과제로 제한되지 않으며, 언급되지 않은 또 다른 과제들은 아래의 기재로부터 통상의 기술자에게 명확하게 이해될 수 있을 것이다.However, the problem to be solved by the present application is not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.
상기 목적을 달성하기 위해, 본 발명은 아크릴계 랜덤 공중합체 및 아지리딘계 화합물을 포함하며, 상기 아크릴계 랜덤 공중합체는 유리전이온도가 0℃ 이상이고, 상기 아지리딘계 화합물은 상기 아크릴계 랜덤 공중합체 100 중량부에 대하여 2 중량부 이상 포함하는 것인, 점착제 조성물을 제공한다.In order to achieve the above object, the present invention includes an acrylic random copolymer and an aziridine-based compound, wherein the acrylic random copolymer has a glass transition temperature of 0° C. or higher, and the aziridine-based compound is 100 parts by weight of the acrylic random copolymer. It provides an adhesive composition comprising 2 parts by weight or more.
또한, 본 발명은 상술한 점착제 조성물을 포함하는 점착 시트 및 디스플레이를 제공한다.Additionally, the present invention provides an adhesive sheet and a display including the above-described adhesive composition.
본 발명에 따른 점착제 조성물은, 탄성력이 향상되면서도 점착성 및 점착력 유지율이 우수하여 폴더블 디스플레이에 적합한 점착제 조성물을 제공할 수 있다.The adhesive composition according to the present invention has improved elasticity and excellent adhesion and adhesive strength retention, thereby providing an adhesive composition suitable for a foldable display.
또한 본 발명은, 탄성력과 점착성이 우수한 점착 시트 및 이를 포함하는 디스플레이를 제공할 수 있다.Additionally, the present invention can provide an adhesive sheet with excellent elasticity and adhesiveness and a display including the same.
본 발명은, 아크릴계 랜덤 공중합체 및 아지리딘계 화합물을 포함하며, 상기 아크릴계 랜덤 공중합체는 유리전이온도가 0℃ 이상이고, 상기 아지리딘계 화합물은 상기 아크릴계 랜덤 공중합체 100 중량부에 대하여 2 중량부 이상 포함하는 것으로, 탄성력이 우수하면서도 점착성 및 점착력 유지율이 우수한 점착제 조성물, 점착시트 및 디스플레이에 관한 것이다.The present invention includes an acrylic random copolymer and an aziridine-based compound, wherein the acrylic random copolymer has a glass transition temperature of 0° C. or higher, and the aziridine-based compound is present in an amount of at least 2 parts by weight based on 100 parts by weight of the acrylic random copolymer. It relates to an adhesive composition, adhesive sheet, and display having excellent elasticity and excellent adhesion and adhesion retention rate.
이하, 본 발명에 대하여 보다 구체적으로 설명하도록 한다. 다만, 본 명세서에서 사용되는 용어는 실시 형태를 설명하기 위한 것이며, 본 발명을 제한하고자 하는 것은 아니다. 본 명세서에서, 점착 시트는 점착층 및 점착 필름을 포함하는 의미일 수 있다.Hereinafter, the present invention will be described in more detail. However, the terms used in this specification are for describing embodiments and are not intended to limit the present invention. In this specification, an adhesive sheet may mean including an adhesive layer and an adhesive film.
< 점착제 조성물 >< Adhesive composition >
본 발명에 따른 점착제 조성물은 아크릴계 랜덤 공중합체 및 아지리딘계 화합물을 포함한다.The adhesive composition according to the present invention includes an acrylic random copolymer and an aziridine-based compound.
아크릴계 랜덤 공중합체Acrylic random copolymer
본 발명의 점착제 조성물에 포함되는, 상기 아크릴계 랜덤 공중합체는 고탄성 특성의 확보를 위하여 유리전이온도가 0℃ 이상인 것이 바람직하며, 더욱 바람직하게는 0 내지 25℃인 것일 수 있다.The acrylic random copolymer included in the adhesive composition of the present invention preferably has a glass transition temperature of 0°C or higher to ensure high elastic properties, and more preferably 0 to 25°C.
상기 아크릴계 랜덤 공중합체의 유리전이온도가 0℃ 미만의 경우 탄성력이 부족하여 폴딩 형태로 구동되는 폴더블 디스플레이에 적용시 점착 시트의 파단 또는 들뜸 현상이 발생되는 문제가 있다.If the glass transition temperature of the acrylic random copolymer is less than 0°C, there is a problem in that the adhesive sheet may be broken or lifted when applied to a foldable display driven in a folded form due to insufficient elasticity.
나아가 상기 아크릴계 랜덤 공중합체의 유리전이온도가 25℃ 이하인 경우, 이를 포함하는 점착제 조성물을 기재에 도포할 때 발림성이 우수하여, 본 발명의 점착제 조성물을 포함하여 점착 시트의 제조시 공정에 유리할 수 있으며, 탄성력 및 점착성 모두 더욱 우수한 효과를 나타낼 수 있는 이점이 있으므로 바람직하다.Furthermore, when the glass transition temperature of the acrylic random copolymer is 25°C or lower, the adhesive composition containing it has excellent spreadability when applied to a substrate, which can be advantageous in the process of manufacturing an adhesive sheet including the adhesive composition of the present invention. , it is preferable because it has the advantage of showing better effects in both elasticity and adhesiveness.
한편, 본 발명의 아크릴계 랜덤 공중합체는 산가가 0.1 이하인 것일 수 있다. 상기 아크릴계 랜덤 공중합체의 산가가 0.1을 초과하는 경우, 후술하는 아지리딘계 첨가제가 점착 부여제가 아닌 가교제로 작용하게 됨으로써 공중합체의 가교도를 높이게 되어, 이를 포함하는 점착제 조성물의 점착력이 저하될 수 있다.Meanwhile, the acrylic random copolymer of the present invention may have an acid value of 0.1 or less. When the acid value of the acrylic random copolymer exceeds 0.1, the aziridine-based additive described later acts as a cross-linking agent rather than a tackifier, thereby increasing the degree of cross-linking of the copolymer, and the adhesive strength of the pressure-sensitive adhesive composition containing it may decrease.
본 발명의 아크릴계 랜덤 공중합체를 형성하는 단량체는, 상기와 같은 특성을 만족할 수 있는 아크릴계 랜덤 공중합체로 중합될 수 있는 것이면 특별히 제한되지 않으며, 예를 들면, n-부틸 아크릴레이트, t-부틸 아크릴레이트, sec-부틸 아크릴레이트, 펜틸 아크릴레이트, 2-에틸부틸 아크릴레이트, 2-에틸헥실 아크릴레이트, 2-에틸헥실디글리콜아크릴레이트, n-옥틸 아크릴레이트, 이소옥틸 아크릴레이트, 이소노닐 아크릴레이트, 라우릴 아크릴레이트, 테트라데실 아크릴레이트, (메트)아크릴로일모르폴린, N-비닐피롤리돈, 이소보르닐(메타)아크릴레이트, 메타아크릴레이트, 카바졸아크릴레이트, 디히드로디사이클로펜타다이엔닐 아크릴레이트, 포타슘 아크릴레이트, 수산기를 갖는 (메트)아크릴계 단량체, 카르복시산기를 갖는 (메트)아크릴계 단량체로 이루어진 군에서 선택되는 1종 이상을 포함하는 것일 수 있다.The monomer forming the acrylic random copolymer of the present invention is not particularly limited as long as it can be polymerized into an acrylic random copolymer that can satisfy the above characteristics, for example, n-butyl acrylate, t-butyl acrylate. Latex, sec-butyl acrylate, pentyl acrylate, 2-ethylbutyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyldiglycol acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate , lauryl acrylate, tetradecyl acrylate, (meth)acryloylmorpholine, N-vinylpyrrolidone, isobornyl (meth)acrylate, methacrylate, carbazole acrylate, dihydrodicyclopenta It may include one or more types selected from the group consisting of dienyl acrylate, potassium acrylate, (meth)acrylic monomers having a hydroxyl group, and (meth)acrylic monomers having a carboxylic acid group.
상기 수산기를 갖는 (메트)아크릴계 단량체는 특별히 제한되지 않지만, 예들 들면, 2-하이드록시에틸 (메트)아크릴레이트, 2-하이드록시프로필 (메트)아크릴레이트, 4-하이드록시부틸(메트)아크릴레이트, 6-하이드록시헥실(메트)아크릴레이트, 8-하이드록시옥틸(메트)아크릴레이트, 2-하이드록시에틸렌글리콜(메트)아크릴레이트, 또는 2-하이드록시프로필렌글리콜(메트)아크릴레이트 등을 들 수 있다.The (meth)acrylic monomer having the hydroxyl group is not particularly limited, but examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. , 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 2-hydroxyethylene glycol (meth)acrylate, or 2-hydroxypropylene glycol (meth)acrylate, etc. You can.
상기 카르복시산기를 갖는 (메트)아크릴계 단량체는 특별히 제한되지 않지만, 예들 들면, (메트)아크릴산, 2-(메트)아크릴로일옥시아세트산, 3-(메트)아크릴로일옥시프로필산, 4-(메트)아크릴로일옥시부틸산, 아크릴산 이중체, 이타콘산, 말레산, 또는 말레산 무수물 등을 들 수 있다.The (meth)acrylic monomer having the carboxylic acid group is not particularly limited, but examples include (meth)acrylic acid, 2-(meth)acryloyloxyacetic acid, 3-(meth)acryloyloxypropylic acid, and 4-(meth)acrylic acid. ) Acryloyloxybutyric acid, acrylic acid doublet, itaconic acid, maleic acid, or maleic anhydride can be mentioned.
상기 아크릴계 랜덤 공중합체는, 상기 단량체들 이외에도 탄성력 및 점착력을 저하시키지 않는 범위 내에서, 본 발명이 속한 기술분야에서 통상적으로 사용되는 다른 단량체를 더 포함하는 것일 수 있다.In addition to the above monomers, the acrylic random copolymer may further include other monomers commonly used in the technical field to which the present invention pertains, within a range that does not reduce elasticity and adhesion.
상기 아크릴계 랜덤 공중합체는, 겔투과크로마토그래피(Gel Permeation Chromatography; GPC)에 의해 측정된 중량평균분자량(폴리스티렌 환산; Mw)이 30만 내지 200만일 수 있으며, 더욱 바람직하게는 50만 내지 120만일 수 있다. 아크릴계 랜덤 공중합체의 중량평균분자량이 30만 미만일 경우, 자외선 중합 및 경화 후 점착 시트의 구조 내에 사슬 구조가 단순하고, 길이가 짧아지기 때문에 기포가 발생하는 등 신뢰성의 측면에서 불리하고, 변색 등에 따른 내구성 저하가 발생할 수 있고, 200만을 초과할 경우, 점착필름 제조 시 점착수지 조성물의 점도가 너무 높아서 제조에 필요한 적정 점도를 맞추기 위해 다량의 단량체의 희석이 필요하며, 이에 따라 자외선 중합 및 경화 시 높은 에너지를 필요로 하거나 반응하지 않은 단량체가 잔류할 수 있다.The acrylic random copolymer may have a weight average molecular weight (polystyrene conversion; Mw) measured by gel permeation chromatography (GPC) of 300,000 to 2 million, more preferably 500,000 to 1.2 million. there is. If the weight average molecular weight of the acrylic random copolymer is less than 300,000, the chain structure within the structure of the adhesive sheet after ultraviolet polymerization and curing is simple and the length is short, which is disadvantageous in terms of reliability, such as the generation of bubbles, and causes discoloration, etc. Deterioration in durability may occur, and if it exceeds 2 million, the viscosity of the adhesive resin composition when manufacturing the adhesive film is too high, so dilution of a large amount of monomer is necessary to achieve the appropriate viscosity required for manufacturing, and as a result, high Monomers that require energy or that have not reacted may remain.
상기 아크릴계 랜덤 공중합체의 제조방법은 특별히 한정되지 않는다. 예를 들어, 본 발명이 속한 기술분야에서 통상적으로 사용되는, 괴상중합, 용액중합, 유화중합, 현탁중합, UV 중합 등의 방법이 사용될 수 있으며, 바람직하게는, 용액중합 또는 UV 중합이 사용될 수 있다.The method for producing the acrylic random copolymer is not particularly limited. For example, methods commonly used in the technical field to which the present invention pertains, such as bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, and UV polymerization, may be used. Preferably, solution polymerization or UV polymerization may be used. there is.
아지리딘계 화합물Aziridine-based compounds
본 발명의 점착제 조성물에 포함되는, 상기 아지리딘계 화합물은 점착 부여제로서 포함될 수 있으며, 상기 아크릴계 랜덤 공중합체와 함께 포함되어 점착력을 향상시키는 역할을 할 수 있다. The aziridine-based compound included in the adhesive composition of the present invention may be included as a tackifier and may be included together with the acrylic random copolymer to improve adhesive strength.
본 발명의 아지리딘계 화합물은, 펜타에리스톨-트리스-(베타-(N-아지리디닐)프로피오네이트, 트리메틸올프로판-트리스(베타-N-아지리디닐)프로피오네이트, 트리메틸올프로판 트리스(2-메틸-1-아지리딘프로피오네이트), N,N'-톨루엔-2,4-비스(1-아지리딘카르복사미드), N,N'-디페닐메탄-4,4'-비스(1-아지리딘카르복사미드), 트리에틸렌 멜라민, 비스이소프로탈로일-1-(2-메틸아지리딘) 및 트리-1-아지리디닐포스핀옥시드로 이루어진 군에서 선택되는 1종 이상을 포함하는 것일 수 있다.Aziridine-based compounds of the present invention include pentaerythol-tris-(beta-(N-aziridinyl)propionate, trimethylolpropane-tris(beta-N-aziridinyl)propionate, and trimethylolpropane tris. (2-methyl-1-aziridinepropionate), N,N'-toluene-2,4-bis(1-aziridinecarboxamide), N,N'-diphenylmethane-4,4'- At least one selected from the group consisting of bis(1-aziridinecarboxamide), triethylene melamine, bisisoprotaloyl-1-(2-methylaziridine), and tri-1-aziridinylphosphine oxide. It may include.
본 발명의 아지리딘계 화합물은 산가가 0.1 이하인 아크릴계 랜덤 공중합체와 함께 포함됨으로써, 점착 부여제로 역할을 수행할 수 있는 것으로, 상기 아크릴계 랜덤 공중합체 100 중량부에 대하여 2 중량부 이상 포함될 수 있으며, 바람직하게는 2 내지 20 중량부 포함되어 본 발명의 점착제 조성물의 점착력을 더욱 향상시킬 수 있다. The aziridine-based compound of the present invention can function as a tackifier by being included with an acrylic random copolymer having an acid value of 0.1 or less, and may be included at least 2 parts by weight based on 100 parts by weight of the acrylic random copolymer, and is preferably included. It can be included in an amount of 2 to 20 parts by weight to further improve the adhesive strength of the adhesive composition of the present invention.
본 발명의 아지리딘계 화합물이 상기 아크릴계 랜덤 공중합체 100 중량부에 대하여 2 중량부 미만 포함되는 경우 기재에 대한 밀착성 및 점착성이 저하될 수 있으며, 20 중량부를 초과하면 잔류하는 화합물로 인하여 탄성력이 저하될 수 있다.If the aziridine-based compound of the present invention is contained less than 2 parts by weight based on 100 parts by weight of the acrylic random copolymer, the adhesion and adhesion to the substrate may be reduced, and if it exceeds 20 parts by weight, the elasticity may be reduced due to the remaining compound. You can.
첨가제additive
본 발명의 점착제 조성물은 전술한 성분들 외에 본 발명의 목적을 해치지 않는 범위에서 통상의 기술자의 필요에 따라 코팅성, 밀착성 등을 증진시키기 위해서 첨가제를 더 포함할 수 있다. In addition to the above-described components, the adhesive composition of the present invention may further include additives to improve coating properties, adhesion, etc., according to the needs of those skilled in the art, within a range that does not impair the purpose of the present invention.
이를 위해 당해 기술분야에서 일반적으로 사용되는 성분들 예를 들어, 계면 활성제, 실란 커플링제, 산화 방지제, 자외선 흡수제 및/또는 응집 방지제 등을 더 포함할 수 있으며, 이 외에도 본 발명이 속하는 기술 분야에서 통상적으로 사용되는 첨가제를 추가로 포함할 수 있다. 이는 1종을 단독으로 사용해도 되고, 2종 이상을 임의의 조합 및 비율로 병용해도 된다.To this end, components commonly used in the technical field, such as surfactants, silane coupling agents, antioxidants, ultraviolet absorbers and/or aggregation inhibitors, may be further included, and in addition to these, components commonly used in the technical field to which the present invention pertains may be included. Commonly used additives may be additionally included. One type may be used individually, or two or more types may be used together in any combination and ratio.
상기 계면활성제는 코팅성 및 밀착성을 증진시키기 위하여 실란 커플링제 또는 레벨링제 용을 목적으로 포함할 수 있다. 예를 들어 실리콘계, 불소계, 에스테르계, 양이온계, 음이온계, 비이온계, 양성 등의 계면 활성제 등을 들 수 있고, 이들은 각각 단독으로도 2 종 이상을 조합하여 사용할 수 있으며, 실리콘계 및/또는 불소계 계면활성제를 사용하는 것이 더욱 바람직하나, 이에 한정되는 것은 아니다.The surfactant may be included as a silane coupling agent or leveling agent to improve coating properties and adhesion. Examples include silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants. These can be used alone or in combination of two or more, and silicone-based and/or It is more preferable to use a fluorine-based surfactant, but it is not limited thereto.
상기 실리콘계 계면활성제는 예를 들면 시판품으로서 다우코닝 도레이 실리콘사의 DC3PA, DC7PA, SH11PA, SH21PA, SH-8400 등이 있고 GE 도시바 실리콘사의 TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 등이 있다. 상기 불소계 계면활성제는 예를 들면 시판품으로서 다이닛본 잉크 가가꾸 고교사의 메가피스 F-470, F-471, F-475, F-482, F-489, F-554 등이 있다. 상기 예시된 계면활성제는 각각 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.The silicone-based surfactants are, for example, commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA, SH-8400 from Dow Corning Toray Silicone, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, and TSF from GE Toshiba Silicone. -4460, TSF-4452, etc. Examples of the fluorine-based surfactant include commercially available products such as Megapeace F-470, F-471, F-475, F-482, F-489, and F-554 manufactured by Dainippon Ink Chemicals. The surfactants exemplified above can be used individually or in combination of two or more types.
상기 실란 커플링제의 구체적인 예로서는 비닐트리메톡시실란, 비닐트리에톡시실란, 비닐트리스(2-메톡시에톡시)실란, N-(2-아미노에틸)-3-아미노프로필메틸디메톡시실란, N-(2-아미노에틸)-3-아미노프로필트리메톡시실란, 3-아미노프로필트리에톡시실란, 3-글리시독시프로필트리메톡시실란, 3-글리시독시프로필메틸디메톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란, 3-클로로프로필메틸디메톡시실란, 3-클로로프로필트리메톡시실란, 3-메타크릴옥시프로필트리메톡시실란, 3-머캅토프로필트리메톡시실란, 3-이소시아네이트프로필트리메톡시실란, 3-이소시아네이트프로필트리에톡시실란 등을 들 수 있다. 상기에서 예시한 밀착 촉진제는 각각 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N -(2-Aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri Methoxysilane, 3-isocyanate propyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, etc. are mentioned. The adhesion promoters exemplified above can be used individually or in combination of two or more.
상기 산화 방지제의 구체적인 예로는 2,2'-티오비스(4-메틸-6-t-부틸페놀), 2,6-디-t-부틸-4-메틸페놀 등을 들 수 있다.Specific examples of the antioxidant include 2,2'-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and the like.
상기 자외선 흡수제의 구체적인 예로는 2-(3-tert-부틸-2-히드록시-5-메틸페닐)- 5-클로로벤조티리아졸, 알콕시벤조페논 등을 들 수 있다.Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzothiriazole, alkoxybenzophenone, etc.
상기 응집 방지제의 구체적인 예로는 폴리아크릴산 나트륨 등을 들 수 있다.Specific examples of the anti-agglomeration agent include sodium polyacrylate.
상기 첨가제는 본 발명의 효과를 저해하지 않는 범위에서 당업자가 적절히 추가하여 사용이 가능하다. 예컨대 상기 첨가제는 상기 아크릴계 랜덤 공중합체 100중량부에 대하여 0.01 내지 10 중량부, 바람직하게는 0.05 내지 5 중량부로 사용할 수 있으나, 이에 한정되는 것은 아니다.The above additives can be appropriately added and used by those skilled in the art as long as they do not impair the effect of the present invention. For example, the additive may be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the acrylic random copolymer, but is not limited thereto.
< 점착 시트 ><Adhesive sheet>
본 발명의 일 실시 형태는, 상술한 점착제 조성물을 포함하는 점착 시트에 관한 것이다. One embodiment of the present invention relates to an adhesive sheet containing the above-described adhesive composition.
본 발명의 점착 시트는, 앞서 정의한 바와 같이 점착층 및 점착 필름을 포함하는 의미일 수 있다.The adhesive sheet of the present invention may include an adhesive layer and an adhesive film as previously defined.
본 발명의 점착 시트는 상술한 점착제 조성물을 포함함으로써, 25℃ 및 1Hz에서의 저장탄성률이 10MPa 이상인 것일 수 있으며, 두께 5㎛에서의 점착력이 600gf/25mm 이상인 것일 수 있다.By containing the above-described adhesive composition, the adhesive sheet of the present invention may have a storage modulus of 10 MPa or more at 25°C and 1 Hz, and may have an adhesive force of 600 gf/25 mm or more at a thickness of 5 μm.
상기 점착 시트의 25℃ 및 1Hz에서의 저장탄성률이 10MPa 미만인 경우, 폴더블 디스플레이에 적용시 점착 시트가 손상되거나 들뜨게 되어 주름이 형성되는 문제가 발생할 수 있다.If the storage modulus of the adhesive sheet at 25°C and 1Hz is less than 10 MPa, the adhesive sheet may be damaged or lifted when applied to a foldable display, causing wrinkles to form.
또한 상기 점착 시트의 두께 5㎛에서의 점착력이 600gf/25mm 미만인 경우, 점착 시트의 점착력이 확보되지 않아 디스플레이에 적용시 점착 시트의 점착력이 유지되지 않는 문제가 발생할 수 있다.Additionally, if the adhesive strength of the adhesive sheet at a thickness of 5㎛ is less than 600gf/25mm, the adhesive strength of the adhesive sheet may not be secured and a problem may occur in which the adhesive strength of the adhesive sheet is not maintained when applied to a display.
따라서 본 발명의 점착제 조성물을 포함하는 점착 시트는, 높은 탄성력을 가짐과 동시에 우수한 점착력을 확보할 수 있어, 내구성이 우수한 디스플레이를 제공할 수 있다. Therefore, the adhesive sheet containing the adhesive composition of the present invention has high elasticity and can secure excellent adhesive strength at the same time, thereby providing a display with excellent durability.
본 발명의 점착 시트는, 상술한 점착제 조성물을 포함하는 것을 제외하고, 동 분야의 점착 시트를 제조하기 위해 사용되는 구성 및 제조 방법을 사용할 수 있다.The pressure-sensitive adhesive sheet of the present invention can use the composition and manufacturing method used for manufacturing pressure-sensitive adhesive sheets in the same field, except that it contains the pressure-sensitive adhesive composition described above.
예를 들어, 상기 점착 시트는, 기재 필름 및 상기 기재 필름의 적어도 일면 상에 적층된 점착제층을 포함할 수 있는 것으로, 기재 필름 상에 본 발명에 따른 점착제 조성물로부터 점착제층이 형성된 것이거나, 2 매의 기재 필름 사이에 본 발명에 따른 점착제 조성물로부터 형성된 점착제층이 개재된 것일 수 있다.For example, the adhesive sheet may include a base film and an adhesive layer laminated on at least one side of the base film, where the adhesive layer is formed from the adhesive composition according to the present invention on the base film, or 2 An adhesive layer formed from the adhesive composition according to the present invention may be interposed between each base film.
상기 기재 필름은, 당 업계에서 사용되는 기재라면 특별한 제한 없이 사용될 수 있으며, 투명성, 기계적 강도, 열안정성, 수분차폐성, 등방성 등이 우수한 필름이 바람직하다. 일 또는 복수의 실시 형태에 있어서, 상기 기재 필름은, 폴리에틸렌테레프탈레이트, 폴리에틸렌이소프탈레이트, 폴리에틸렌나프탈레이트, 폴리부틸렌테레프탈레이트 등의 폴리에스테르계 수지; 디아세틸셀룰로오스, 트리아세틸셀룰로오스 등의 셀룰로오스계 수지; 폴리카보네이트계 수지; 폴리메틸(메타)아크릴레이트, 폴리에틸(메타)아크릴레이트 등의 아크릴계 수지; 폴리스티렌, 아크릴로니트릴-스티렌 공중합체 등의 스티렌계 수지; 폴리에틸렌, 폴리프로필렌, 시클로계 또는 노보넨 구조를 갖는 폴리올레핀, 에틸렌-프로필렌 공중합체 등의 폴리올레핀계 수지; 염화비닐계 수지; 나일론, 방향족 폴리아미드 등의 아미드계 수지; 이미드계 수지; 술폰계 수지; 폴리에테르술폰계 수지; 폴리에테르에테르케톤계 수지; 황화 폴리페닐렌계 수지; 비닐알콜계 수지; 염화비닐리덴계 수지; 비닐부티랄계 수지; 알릴레이트계 수지; 폴리옥시메틸렌계 수지; 에폭시계 수지 등과 같은 열가소성 수지로 구성된 필름을 들 수 있으며, 상기 열가소성 수지의 블렌드물로 구성된 필름도 사용할 수 있다. 또한, (메타)아크릴계, 우레탄계, 아크릴우레탄계, 에폭시계, 실리콘계 등의 열경화성 수지 또는 자외선 경화형 수지로 된 필름을 이용할 수도 있으며, 본 발명의 실시형태에 따르면, 반복적인 굽힘에 대한 내구성이 우수하여 플렉서블한 디스플레이에 적용이 보다 용이하도록 폴리이미드계 수지를 사용할 수 있다.The base film can be used without particular limitations as long as it is a base material used in the industry, and a film having excellent transparency, mechanical strength, thermal stability, moisture shielding, isotropy, etc. is preferred. In one or more embodiments, the base film includes polyester resins such as polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, and polybutylene terephthalate; Cellulose-based resins such as diacetylcellulose and triacetylcellulose; polycarbonate-based resin; Acrylic resins such as polymethyl (meth)acrylate and polyethyl (meth)acrylate; Styrene-based resins such as polystyrene and acrylonitrile-styrene copolymer; Polyolefin resins such as polyethylene, polypropylene, polyolefins with cyclo- or norbornene structures, and ethylene-propylene copolymers; Vinyl chloride-based resin; Amide resins such as nylon and aromatic polyamide; imide-based resin; Sulfone-based resin; polyethersulfone-based resin; polyetheretherketone-based resin; Sulfated polyphenylene-based resin; Vinyl alcohol-based resin; Vinylidene chloride-based resin; Vinyl butyral resin; Allylate resin; polyoxymethylene-based resin; A film composed of a thermoplastic resin such as an epoxy resin may be used, and a film composed of a blend of the thermoplastic resin may also be used. In addition, films made of thermosetting resins such as (meth)acrylic, urethane, acrylic urethane, epoxy, and silicone or ultraviolet curable resins may be used. According to an embodiment of the present invention, the film has excellent durability against repeated bending, making it flexible. Polyimide-based resin can be used to make it easier to apply to one display.
일부 실시 형태에 있어서, 상기 점착 시트는, 기재 필름의 일면에 점착제층이 적층되고, 상기 점착제층이 적층되지 않은 기재 필름의 타면에 하드코팅층이 형성될 수 있다. 필요에 따라, 상기 점착제층의 일면에는 세퍼레이터가 형성될 수 있다.In some embodiments, the adhesive sheet may have an adhesive layer laminated on one side of a base film, and a hard coating layer may be formed on the other side of the base film on which the adhesive layer is not laminated. If necessary, a separator may be formed on one side of the adhesive layer.
상기 점착 시트의 제조 방법은, 특별히 한정되는 것은 아니나, 예를 들면, 상술한 점착제 조성물을 기재 필름의 한쪽 면 또는 양면에 도포해서 점착제층을 형성하고, 상기 점착제층을 경화시켜 제조할 수 있다. 일 실시 형태에 있어서, 상기 점착제 조성물을 실리콘이나 불소 등으로 표면이형 처리를 실시한 기재 필름의 표면에 도포하고 가열 건조해서 점착제층을 형성할 수도 있다. The method of manufacturing the adhesive sheet is not particularly limited, but for example, it can be manufactured by applying the above-described adhesive composition to one or both sides of a base film to form an adhesive layer, and then curing the adhesive layer. In one embodiment, the adhesive composition may be applied to the surface of a base film that has been subjected to surface release treatment with silicone, fluorine, etc., and then heated and dried to form an adhesive layer.
필요에 따라, 점착제층에 대한 밀착성을 향상시키기 위해, 상기 기재 필름의 표면에 코로나 방전 처리, 플라즈마 처리, 블라스트 처리, 케미컬 에칭 처리, 프라이머 처리 등을 실시할 수도 있다. If necessary, in order to improve adhesion to the adhesive layer, the surface of the base film may be subjected to corona discharge treatment, plasma treatment, blast treatment, chemical etching treatment, primer treatment, etc.
상기 도포는 일반적으로 나이프 코터, 롤 코터, 캘린더 코터, 콤마 코터 등에 의해 수행할 수 있다. 또한, 도포 두께나 상기 점착제 조성물의 점도에 따라서는 그라비어 코터, 로드 코터 등에 의해 수행할 수도 있다. 상기 점착제층의 두께는 예를 들어, 5 내지 80㎛로 형성할 수 있다. 상기 점착제층의 두께가 상기 범위이면 점착력이 우수하고, 광투과성, 신뢰성 및 단차 흡수성 등의 측면에서 이점이 있다.The application can generally be performed by a knife coater, roll coater, calendar coater, comma coater, etc. Additionally, depending on the application thickness or viscosity of the adhesive composition, it may be performed using a gravure coater, rod coater, etc. The thickness of the adhesive layer may be, for example, 5 to 80 μm. If the thickness of the adhesive layer is within the above range, adhesive strength is excellent and there are advantages in terms of light transparency, reliability, and step absorption.
< 디스플레이 ><Display>
본 발명의 일 실시 형태는, 상술한 점착 시트를 포함하는 디스플레이에 관한 것이다. 상기 디스플레이는 전술한 점착 시트를 포함하는 것이라면 이에 한정되지 않으며, 특히 폴더블 디스플레이 또는 플렉서블 디스플레이에 적용될 수 있다.One embodiment of the present invention relates to a display including the above-described adhesive sheet. The display is not limited to this as long as it includes the adhesive sheet described above, and may be particularly applied to a foldable display or flexible display.
상기 디스플레이는, 상술한 점착 시트를 포함하는 것을 제외하고는, 당해 기술 분야에서 통상적으로 알려진 구성을 포함하는 것일 수 있다.The display may include a configuration commonly known in the art, except that it includes the adhesive sheet described above.
이하, 본 발명을 실시 예에 기초하여 더욱 상세하게 설명하지만, 하기에 개시되는 본 발명의 실시 형태는 어디까지 예시로써, 본 발명의 범위는 이들의 실시 형태에 한정되지 않는다. 본 발명의 범위는 특허청구범위에 표시되었고, 더욱이 특허 청구범위 기록과 균등한 의미 및 범위 내에서의 모든 변경을 함유하고 있다. 또한, 이하의 실시 예, 비교 예에서 함유량을 나타내는 "%" 및 "부"는 특별히 언급하지 않는 한 질량 기준이다.Hereinafter, the present invention will be described in more detail based on examples, but the embodiments of the present invention disclosed below are merely examples and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and further includes all changes within the scope and meaning equivalent to the record of the claims. In addition, in the following examples and comparative examples, “%” and “part” indicating content are based on mass unless otherwise specified.
<제조예: 아크릴계 랜덤 공중합체 제조><Manufacture example: Preparation of acrylic random copolymer>
제조예 1Manufacturing Example 1
1L의 반응기에 2-에틸헥실아크릴레이트(2-EHA) 20중량%, 이소보로닐아크릴레이트(IBOA) 60중량%, 및 2-하이드록시에틸아크릴레이트(2-HEA) 20중량%를 포함하는 단량체 블렌드를 투입한 후, 용제로 에틸아세테이트(EAc) 100중량부를 투입하였다. A 1L reactor contains 20% by weight of 2-ethylhexyl acrylate (2-EHA), 60% by weight of isoboronylacrylate (IBOA), and 20% by weight of 2-hydroxyethyl acrylate (2-HEA). After adding the monomer blend, 100 parts by weight of ethyl acetate (EAc) was added as a solvent.
질소가스를 1시간 동안 퍼징하여 산소를 제거하고, 80℃로 유지하였다. 상기 단량체 혼합물을 균일하게 혼합한 후, 반응개시제로 아조비스이소부티로니트릴(AIBN) 0.07중량부를 투입하고, 8시간 동안 반응시켜 아크릴계 랜덤 공중합체를 제조하였다(중량평균분자량: 65만, PDI 4.5).Oxygen was removed by purging nitrogen gas for 1 hour, and the temperature was maintained at 80°C. After mixing the monomer mixture uniformly, 0.07 parts by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator and reacted for 8 hours to prepare an acrylic random copolymer (weight average molecular weight: 650,000, PDI 4.5) ).
수득된 아크릴계 랜덤 공중합체의 중량평균분자량, 유리전이온도(DSC2500, TA Instruments Inc.) 및 산가는 하기 표 2에 나타내었다.The weight average molecular weight, glass transition temperature (DSC2500, TA Instruments Inc.), and acid value of the obtained acrylic random copolymer are shown in Table 2 below.
제조예 2 내지 7Preparation Examples 2 to 7
상기 제조예 1에서, 단량체를 하기 표 1의 조성으로 한 것을 제외하고 동일한 방법으로 아크릴계 랜덤 공중합체를 제조하였다. An acrylic random copolymer was prepared in the same manner as in Preparation Example 1, except that the monomer had the composition shown in Table 1 below.
2-EHA: 2-에틸헥실아크릴레이트 (시그마 알드리치사)2-EHA: 2-ethylhexyl acrylate (Sigma Aldrich)
삭제delete
EHDG-AT: 2-에틸헥실디글리콜아크릴레이트(2-Ethyl hexyl diglycol acrylate) (공영사)EHDG-AT: 2-Ethyl hexyl diglycol acrylate (Gongyoungsa)
IBOA: 이소보로닐아크릴레이트 (시그마 알드리치사)IBOA: Isoboronyl acrylate (Sigma Aldrich)
DCPA: 디히드로디사이클로펜타다이엔닐 아크릴레이트 (dihydrodicyclopentadienyl acrylate) (시그마 알드리치사) DCPA: dihydrodicyclopentadienyl acrylate (Sigma Aldrich)
2-HEA: 2-하이드록시에틸아크릴레이트 (시그마 알드리치사)2-HEA: 2-hydroxyethyl acrylate (Sigma Aldrich)
4-HBA: 4-하이드록시부틸아크릴레이트 (시그마 알드리치사)4-HBA: 4-hydroxybutylacrylate (Sigma Aldrich)
AA: 아크릴산 (시그마 알드리치사)AA: Acrylic acid (Sigma Aldrich)
(℃)glass transition temperature
(℃)
(mgKOH/g)Sanga
(mgKOH/g)
<실시예 및 비교예: 점착제 조성물 및 점착 시트 제조><Examples and Comparative Examples: Preparation of adhesive composition and adhesive sheet>
실시예 1~10 및 비교예 1~4Examples 1 to 10 and Comparative Examples 1 to 4
하기 표 3의 조성으로 조액하여 점착제 조성물을 제조하였으며, 실리콘 이형제가 코팅된 75㎛ 이형필름 상에 두께가 5㎛가 되도록 도포하고, 120℃에서 3분 동안 건조시킨 후 이형필름으로 적층하여 점착시트를 형성하였다. 그 위에 실리콘 이형제가 코팅된 이형필름을 라미네이션하여 점착시트를 제조하였다.An adhesive composition was prepared by mixing it with the composition shown in Table 3 below. It was applied to a thickness of 5㎛ on a 75㎛ release film coated with a silicone release agent, dried at 120°C for 3 minutes, and then laminated with the release film to form an adhesive sheet. was formed. An adhesive sheet was manufactured by laminating a release film coated with a silicone release agent thereon.
(중량부)Acrylic polymer
(part by weight)
(중량부)Aziridine-based compounds
(part by weight)
(중량부)Silane coupling agent
(part by weight)
A: 트리메틸올프로판 트리스(2-메틸-1-아지리딘프로피오네이트) (CL-467, 메다니오사)A: Trimethylolpropane tris(2-methyl-1-aziridine propionate) (CL-467, Medaniosa)
B: N,N`-(헥산-1,6-디일)비스(2-메틸아지리딘-1-카복시아마이드) (HDU-P25, 메다니오사)B: N,N`-(hexane-1,6-diyl)bis(2-methylaziridine-1-carboxamide) (HDU-P25, Medaniosa)
실란커플링제: 3-글리시독시프로필트리메톡시실란(KBM-403, 신에츠)Silane coupling agent: 3-glycidoxypropyltrimethoxysilane (KBM-403, Shin-Etsu)
<실험예><Experimental example>
상기 실시예 1~10 및 비교예 1~4에서 제조된 점착시트의 물성을 하기의 방법으로 평가하고, 그 결과를 하기 표 4에 나타내었다.The physical properties of the adhesive sheets prepared in Examples 1 to 10 and Comparative Examples 1 to 4 were evaluated by the following method, and the results are shown in Table 4 below.
(1) 탄성력 평가(1) Elasticity evaluation
상기 실시예 및 비교예에서 광학부재층이 적층되기 전의 각 점착 시트에 대하여 저장탄성률을 측정하였다. In the above examples and comparative examples, the storage modulus was measured for each adhesive sheet before the optical member layer was laminated.
각 점착 시트에 대해서, 25℃에서의 저장탄성률을 점탄성 측정 장치(MCR-301, Anton Paar사)를 사용해서 측정하였다. 보다 상세하게는, 점착 시트의 사이즈를 길이 30mm × 폭 30mm로 재단하고, 상기 재단한 점착 시트의 한 면에 부착된 이형필름을 제거한 뒤, 유리기판에 접합하였으며, 그 후 측정팁(tip)과 접착한 상태로, -20 내지 100℃의 온도 영역에서 주파수 1.0Hz, 변형 2％, 승온 속도 5℃/min의 조건 하에서 측정하고, 이 때, 25℃의 측정값을 판독하였으며, 측정 결과를 하기 표 4에 기재하였다.For each adhesive sheet, the storage modulus at 25°C was measured using a viscoelasticity measuring device (MCR-301, Anton Paar). More specifically, the size of the adhesive sheet was cut to 30 mm in length × 30 mm in width, the release film attached to one side of the cut adhesive sheet was removed, and then it was bonded to a glass substrate. In the bonded state, measurements were made in the temperature range of -20 to 100°C, under the conditions of a frequency of 1.0Hz, strain of 2%, and temperature increase rate of 5°C/min. At this time, the measured value at 25°C was read, and the measurement results are as follows. It is listed in Table 4.
<평가 기준><Evaluation criteria>
◎: 25℃에서의 저장탄성률 50MPa 이상◎: Storage modulus of 50 MPa or more at 25°C
○: 25℃에서의 저장탄성률 10MPa 이상 50MPa 미만○: Storage modulus at 25°C 10 MPa or more but less than 50 MPa
△: 25℃에서의 저장탄성률 8MPa 이상 10MPa 미만△: Storage modulus at 25°C: 8 MPa or more but less than 10 MPa
×: 25℃에서의 저장탄성률 8MPa 미만×: Storage modulus at 25°C less than 8 MPa
(2) 점착력 평가(2) Adhesion evaluation
제조된 점착시트를 25mm × 85mm의 크기로 절단하여 이형필름을 박리하고, 점착제 표면에 코로나 처리 또는 플라즈마 처리를 진행한 후 유리기판에 라미네이션하고 오토클레이브 처리하여 시편을 제작하였다. 상온 점착력은 제작된 시편을 23℃, 50%RH의 조건 하에서 24시간 방치한 후, 만능인장시험기(UTM, Instron)를 사용하여 박리속도 300mm/min, 박리각도 180°로 점착제층을 박리하여 측정하였다. The prepared adhesive sheet was cut to a size of 25 mm × 85 mm, the release film was peeled off, the surface of the adhesive was subjected to corona treatment or plasma treatment, and then laminated on a glass substrate and autoclaved to produce a specimen. Adhesion at room temperature was measured by leaving the manufactured specimen under conditions of 23°C and 50%RH for 24 hours and then peeling the adhesive layer at a peeling speed of 300mm/min and a peeling angle of 180° using a universal tensile tester (UTM, Instron). did.
<평가 기준><Evaluation criteria>
◎: 1400gf/25mm이상◎: 1400gf/25mm or more
○: 1000gf/25mm이상 1400gf/25mm미만○: More than 1000gf/25mm but less than 1400gf/25mm
△: 600gf/25mm이상 1000gf/25mm미만△: 600gf/25mm or more but less than 1000gf/25mm
×: 600gf/25mm미만×: Less than 600gf/25mm
(3) 점착력 유지율(3) Adhesion retention rate
제조된 점착시트를 상온에서 7일간 보관 후, 25mm × 85mm의 크기로 절단하고 이형필름을 박리하고 점착제 표면에 코로나 처리 또는 플라즈마 처리를 진행한 후 유리기판에 라미네이션하고 오토클레이브 처리하여 시편을 제작하였다. 제작된 시편을 23℃, 50%RH의 조건 하에서 24시간 방치한 후, 만능인장시험기(UTM, Instron)를 사용하여 박리속도 300mm/min, 박리각도 180°로 점착제층을 박리하여 측정하였다. 이때, 측정은 23℃, 50%RH의 조건 하에서 실시하였다. 이때 측정된 값은 경시점착력이라 하였으며, 초기점착력에 대한 경시점착력의 유지율을 하기 식 1에 따라 계산하여 하기 표 4에 나타내었다. The prepared adhesive sheet was stored at room temperature for 7 days, cut into 25 mm . After the manufactured specimen was left for 24 hours under conditions of 23°C and 50%RH, the adhesive layer was peeled and measured using a universal tensile tester (UTM, Instron) at a peeling speed of 300 mm/min and a peeling angle of 180°. At this time, the measurement was conducted under conditions of 23°C and 50%RH. The value measured at this time was called adhesion over time, and the retention rate of adhesion over time relative to initial adhesion was calculated according to Equation 1 below and shown in Table 4 below.
[식 1][Equation 1]
점착력 유지율(%) = {1-[(초기점착력-경시점착력)/초기점착력]}*100Adhesion retention rate (%) = {1-[(initial adhesion - adhesion over time)/initial adhesion]}*100
[%]Adhesion retention rate
[%]
상기 물성 평가 결과, 본 발명의 유리전이온도가 0℃ 이상인 아크릴계 랜덤 공중합체를 포함하고, 아지리딘계 화합물을 아크릴계 랜덤 공중합체 100중량부에 대하여 2중량부 이상 포함하는 실시예 1 내지 10의 경우 탄성력, 점착력 및 점착력 유지율이 모두 우수한 것을 확인할 수 있다.As a result of the physical property evaluation, in Examples 1 to 10, which included an acrylic random copolymer having a glass transition temperature of 0° C. or higher, and an aziridine-based compound at least 2 parts by weight based on 100 parts by weight of the acrylic random copolymer, the elasticity , it can be seen that both adhesion and adhesion retention rate are excellent.
한편, 아지리딘계 화합물을 아크릴계 랜덤 공중합체 100중량부에 대하여 2중량부 미만 포함하는 비교예 1, 산가가 0.1을 초과하는 아크릴계 랜덤 공중합체를 포함하는 비교예 3, 4의 경우 점착력 및/또는 점착력 유지율이 불량한 것을 알 수 있으며, 유리전이온도가 0℃ 미만인 아크릴계 랜덤 공중합체를 포함하는 비교예 2는 탄성력이 매우 불량한 것을 확인할 수 있다.On the other hand, in the case of Comparative Example 1 containing less than 2 parts by weight of an aziridine-based compound based on 100 parts by weight of the acrylic random copolymer, and Comparative Examples 3 and 4 containing an acrylic random copolymer with an acid value exceeding 0.1, the adhesive strength and/or adhesion It can be seen that the retention rate is poor, and that Comparative Example 2, which includes an acrylic random copolymer with a glass transition temperature of less than 0°C, has very poor elasticity.
Claims (9)
상기 아크릴계 랜덤 공중합체는 유리전이온도가 0℃ 이상이고 산가가 0.1 이하이며,
상기 아지리딘계 화합물은 상기 아크릴계 랜덤 공중합체 100 중량부에 대하여 2 중량부 이상 포함하는 것인, 점착제 조성물.
Contains acrylic random copolymers and aziridine-based compounds,
The acrylic random copolymer has a glass transition temperature of 0°C or more and an acid value of 0.1 or less,
An adhesive composition comprising the aziridine-based compound in an amount of 2 parts by weight or more based on 100 parts by weight of the acrylic random copolymer.
상기 아크릴계 랜덤 공중합체는 유리전이온도가 0 내지 25℃인 것인, 점착제 조성물.
In claim 1,
The acrylic random copolymer has a glass transition temperature of 0 to 25°C.
상기 아지리딘계 화합물은 펜타에리스톨-트리스-(베타-(N-아지리디닐)프로피오네이트, 트리메틸올프로판-트리스(베타-N-아지리디닐)프로피오네이트, 트리메틸올프로판 트리스(2-메틸-1-아지리딘프로피오네이트), N,N'-톨루엔-2,4-비스(1-아지리딘카르복사미드), N,N'-디페닐메탄-4,4'-비스(1-아지리딘카르복사미드), 트리에틸렌 멜라민, 비스이소프로탈로일-1-(2-메틸아지리딘), 트리-1-아지리디닐포스핀옥시드 및 N,N`-(헥산-1,6-디일)비스(2-메틸아지리딘-1-카복시아마이드)로 이루어진 군에서 선택되는 1종 이상을 포함하는 것인, 점착제 조성물.
In claim 1,
The aziridine-based compounds include pentaerythol-tris-(beta-(N-aziridinyl)propionate, trimethylolpropane-tris(beta-N-aziridinyl)propionate, and trimethylolpropane tris(2- Methyl-1-aziridine propionate), N,N'-toluene-2,4-bis(1-aziridinecarboxamide), N,N'-diphenylmethane-4,4'-bis(1 -aziridinecarboxamide), triethylene melamine, bisisoprotaloyl-1-(2-methylaziridine), tri-1-aziridinylphosphine oxide and N,N`-(hexane-1,6) -diyl)bis(2-methylaziridine-1-carboxylamide), an adhesive composition comprising at least one member selected from the group consisting of.
상기 아지리딘계 화합물은 상기 아크릴계 랜덤 공중합체 100 중량부에 대하여 2 내지 20중량부 포함하는 것인, 점착제 조성물.
In claim 1,
An adhesive composition comprising 2 to 20 parts by weight of the aziridine-based compound based on 100 parts by weight of the acrylic random copolymer.
An adhesive sheet comprising the adhesive composition of any one of claims 1 to 2 and 4 to 5.
25℃ 및 1Hz에서의 저장탄성률이 10MPa 이상인, 점착 시트.
In claim 6,
An adhesive sheet with a storage modulus of 10 MPa or more at 25°C and 1 Hz.
두께 5㎛에서의 점착력이 600gf/25mm 이상인, 점착 시트.
In claim 6,
An adhesive sheet with an adhesive force of 600gf/25mm or more at a thickness of 5㎛.
A display comprising the adhesive sheet of claim 6.
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