KR20200114886A - Optically clear adhesive film and display device using the same - Google Patents
Optically clear adhesive film and display device using the same Download PDFInfo
- Publication number
- KR20200114886A KR20200114886A KR1020190037396A KR20190037396A KR20200114886A KR 20200114886 A KR20200114886 A KR 20200114886A KR 1020190037396 A KR1020190037396 A KR 1020190037396A KR 20190037396 A KR20190037396 A KR 20190037396A KR 20200114886 A KR20200114886 A KR 20200114886A
- Authority
- KR
- South Korea
- Prior art keywords
- acrylate
- meth
- optically transparent
- adhesive sheet
- transparent adhesive
- Prior art date
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- 239000002313 adhesive film Substances 0.000 title claims abstract description 26
- 230000001070 adhesive effect Effects 0.000 claims abstract description 83
- 239000000853 adhesive Substances 0.000 claims abstract description 79
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 104
- 239000000178 monomer Substances 0.000 claims description 54
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 38
- -1 2-ethylhexyl Chemical group 0.000 claims description 31
- 229920006243 acrylic copolymer Polymers 0.000 claims description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 24
- 239000003999 initiator Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 9
- 239000000516 sunscreening agent Substances 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 230000000475 sunscreen effect Effects 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 claims description 2
- VMRIVYANZGSGRV-UHFFFAOYSA-N 4-phenyl-2h-triazin-5-one Chemical compound OC1=CN=NN=C1C1=CC=CC=C1 VMRIVYANZGSGRV-UHFFFAOYSA-N 0.000 claims description 2
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 claims description 2
- 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 claims description 2
- 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 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 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 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 239000002981 blocking agent Substances 0.000 claims 1
- 229940052296 esters of benzoic acid for local anesthesia Drugs 0.000 claims 1
- 239000010408 film Substances 0.000 description 42
- 229920005989 resin Polymers 0.000 description 20
- 239000011347 resin Substances 0.000 description 20
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 239000011247 coating layer Substances 0.000 description 9
- 239000012788 optical film Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 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 7
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000008199 coating composition Substances 0.000 description 6
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 5
- 238000007142 ring opening reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 4
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000003302 UV-light treatment Methods 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000002354 daily effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000003851 corona treatment Methods 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 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 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000004904 shortening Methods 0.000 description 3
- 229940014800 succinic anhydride Drugs 0.000 description 3
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 description 2
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 2
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 2
- AHBNSOZREBSAMG-UHFFFAOYSA-N 1,5-diisocyanato-2-methylpentane Chemical compound O=C=NCC(C)CCCN=C=O AHBNSOZREBSAMG-UHFFFAOYSA-N 0.000 description 2
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 2
- QUPKOUOXSNGVLB-UHFFFAOYSA-N 1,8-diisocyanatooctane Chemical compound O=C=NCCCCCCCCN=C=O QUPKOUOXSNGVLB-UHFFFAOYSA-N 0.000 description 2
- KDLIYVDINLSKGR-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanatophenoxy)benzene Chemical compound C1=CC(N=C=O)=CC=C1OC1=CC=C(N=C=O)C=C1 KDLIYVDINLSKGR-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 2
- YQLRKXVEALTVCZ-UHFFFAOYSA-N 2-isocyanato-1,3-dimethylbenzene Chemical compound CC1=CC=CC(C)=C1N=C=O YQLRKXVEALTVCZ-UHFFFAOYSA-N 0.000 description 2
- CWNNYYIZGGDCHS-UHFFFAOYSA-N 2-methylideneglutaric acid Chemical compound OC(=O)CCC(=C)C(O)=O CWNNYYIZGGDCHS-UHFFFAOYSA-N 0.000 description 2
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- QSACPWSIIRFHHR-UHFFFAOYSA-N dimethylphenyl isocyanide Natural products CC1=CC=CC(C)=C1C#N QSACPWSIIRFHHR-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 150000002148 esters Chemical class 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
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- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 2
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- 150000003254 radicals Chemical class 0.000 description 2
- 150000003512 tertiary amines Chemical group 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
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- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
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- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- MRIKSZXJKCQQFT-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropyl) prop-2-enoate Chemical compound OCC(C)(C)COC(=O)C=C MRIKSZXJKCQQFT-UHFFFAOYSA-N 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
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- VAWQANAQMBEQFM-UHFFFAOYSA-N 10-ethenoxydecan-1-ol Chemical compound OCCCCCCCCCCOC=C VAWQANAQMBEQFM-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-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
- 229940095095 2-hydroxyethyl acrylate Drugs 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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Images
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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- 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
- 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
- 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
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
-
- 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)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
본 발명은 광학투명점착시트 및 이를 이용한 표시장치에 관한 것이다.The present invention relates to an optically transparent adhesive sheet and a display device using the same.
평판표시장치에는 액정 표시 장치(Liquid Crystal Display; LCD), 플라즈마 디스플레이 패널(Plasma Display Panel; PDP), 유기 발광 표시 장치(Organic Electro Luminescence Display; OLED) 등이 있다. 평판표시장치는 디스플레이 패널과 광학 필름을 포함한다. 상기 광학 필름으로는, 편광 필름, 위상차 필름, 눈부심 방지 필름, 광시야각 보상 필름, 휘도 향상 필름 등이 사용되고 있다. 이러한 광학 필름들을 서로 적층하거나 광학 필름을 디스플레이 패널에 부착하는 경우, 광학 투명 점착제(Optically Clear Adhesive, OCA)가 사용되고 있다. Flat panel displays include a liquid crystal display (LCD), a plasma display panel (PDP), and an organic electroluminescence display (OLED). The flat panel display device includes a display panel and an optical film. As the optical film, a polarizing film, a retardation film, an anti-glare film, a wide viewing angle compensation film, and a brightness enhancing film are used. When such optical films are laminated to each other or an optical film is attached to a display panel, an optically clear adhesive (OCA) is used.
이러한 광학용 투명 점착제는 높은 투과율과 낮은 헤이즈가 요구되며, 다양한 기재와의 밀착성, 내열 및 내습열 내구성과 같은 물성을 만족시켜야 한다. 또한, 디스플레이 패널 또는 광학 필름 표면에 결함이 발생하는 경우 원활한 교체를 위해 리워크성도 필요하다.These optically transparent pressure-sensitive adhesives require high transmittance and low haze, and must satisfy physical properties such as adhesion to various substrates, heat resistance, and moisture resistance. In addition, when a defect occurs on the surface of a display panel or an optical film, reworkability is also required for smooth replacement.
한편, 최근에는 플렉서블 디스플레이 장치가 경쟁적으로 개발되고 있다. 플렉서블 디스플레이 장치는 장치 자체가 굽혀지거나(bending), 말아지거나(rolling), 접히게(folding) 되므로, 장치 내에 포함된 디스플레이 패널 및 광학필름들도 굽힘 응력을 받게 된다. 따라서, 휘거나 구부러진 부분에서도 밀착성이 우수하고 내구성이 뛰어난 광학용 투명 점착제에 대한 개발이 요구되고 있다. 또한, 필요에 따라, 이와 같은 디스플레이에 적용하기 위해, 점착과 박리가 용이한 점착시트의 개발이 필요한 실정이며, 예를 들어, 가열 또는 UV 조사에 따라 점착력과 박리력을 조절할 수 있는 가변특성을 갖는 점착시트의 개발이 필요하다. Meanwhile, in recent years, flexible display devices are being developed competitively. In the flexible display device, since the device itself is bent, rolled, or folded, the display panel and optical films included in the device are also subjected to bending stress. Accordingly, there is a need for development of an optically transparent pressure-sensitive adhesive having excellent adhesion and excellent durability even in bent or bent portions. In addition, if necessary, in order to apply to such a display, it is necessary to develop a pressure-sensitive adhesive sheet that is easy to adhere and peel. For example, it has a variable property that can adjust the adhesive force and peel force according to heating or UV irradiation. It is necessary to develop a self-adhesive sheet.
한국 공개특허공보 제10-2016-0114399호에는 융점 이상의 온도에서 우수한 점착력 및 밀착력을 나타내며, 융점 미만의 온도에서 기재와 쉽게 박리가 이루어지는 감온성 점착제 조성물 및 이를 포함하는 감온성 점착 테이프에 관한 기술이 개시되어 있다. 또한, 한국 등록특허공보 제10-1600686호에는 발포미립자를 사용하며, 가열 전에는 높은 점착력을 제공하면서도 가열 후에는 용이하게 박리되는 UV 경화시스템을 이용한 가열 박리형 점착시트 또는 테이프의 제조방법에 관한 기술이 개시되어 있다. 그러나, 상기와 같은 종래기술들은 물성의 온도 의존성이 크거나, 내부 헤이즈 존재로 광학용으로의 적용이 어려운 문제가 있다.Korean Patent Laid-Open Publication No. 10-2016-0114399 discloses a technology related to a temperature-sensitive adhesive composition and a temperature-sensitive adhesive tape including the same, which exhibits excellent adhesion and adhesion at a temperature above the melting point and easily peels off from a substrate at a temperature below the melting point. have. In addition, Korean Patent Publication No. 10-1600686 uses foamed fine particles, and technology related to a method of manufacturing a heat-release type adhesive sheet or tape using a UV curing system that provides high adhesive strength before heating but easily peels off after heating. Is disclosed. However, the prior art as described above has a problem that it is difficult to apply it to optical applications due to a large temperature dependence of physical properties or the presence of internal haze.
본 발명은 가변 점착 특성이 우수한 광학투명점착시트를 제공하는 것을 목적으로 한다.An object of the present invention is to provide an optically transparent adhesive sheet having excellent variable adhesive properties.
또한, 본 발명은 상기 광학투명점착시트를 이용한 표시장치를 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a display device using the optically transparent adhesive sheet.
본 발명은 기재 필름 및 상기 기재 필름의 적어도 일면에 적층된 점착 필름을 포함하고, 상기 점착 필름은 경화시에 1.0 내지 30N의 박리력을 나타내고, 400 내지 450nm의 UV파장에서 100mW이상 조도로 광량 1J이상의 자외선 처리 후 0.01 내지 0.5N의 박리력을 나타내는 것인, 광학투명점착시트를 제공한다. The present invention includes a base film and an adhesive film laminated on at least one side of the base film, wherein the adhesive film exhibits a peel force of 1.0 to 30N upon curing, and an amount of light of 1J at an illuminance of 100mW or more at a UV wavelength of 400 to 450nm It provides an optically transparent adhesive sheet that exhibits a peeling force of 0.01 to 0.5N after the above ultraviolet treatment.
또한, 본 발명은 상기 광학투명점착시트를 이용한 표시장치를 제공한다.In addition, the present invention provides a display device using the optically transparent adhesive sheet.
본 발명은 경화시에 우수한 고점착성을 나타내고, 특정 조도 이상의 UV광 처리에 의해 저점착성을 나타내는 가변 점착 특성으로 인해 재박리가 용이하여 우수한 리워크성 효과를 제공할 수 있을 뿐만 아니라, UV 차단 특성을 가짐으로써, 자외선과 같은 일상생활 또는 가혹조건에도 우수한 내구성을 나타낼 수 있는 광학투명점착시트를 제공할 수 있다.The present invention exhibits excellent high adhesiveness upon curing, and is easy to re-peel due to the variable adhesive property showing low adhesiveness by UV light treatment of a specific illuminance or higher, thereby providing an excellent rework effect, as well as UV blocking properties. By having a, it is possible to provide an optically transparent adhesive sheet capable of exhibiting excellent durability even in everyday life such as ultraviolet rays or harsh conditions.
도 1 은 본 발명의 일 실시예에 의한 광학투명점착시트를 나타내는 개략적인 도면이다.1 is a schematic view showing an optically transparent adhesive sheet according to an embodiment of the present invention.
본 발명은 기재 필름 및 상기 기재 필름의 적어도 일면에 적층된 점착 필름을 포함하고, 상기 점착 필름은 경화시에 1.0 내지 30N의 박리력을 나타내고, 400 내지 450nm의 UV파장에서 100mW이상 조도로 광량 1J이상의 자외선(UV) 처리 후 0.01 내지 0.5N의 박리력을 나타내는, 광학투명점착시트 및 이를 이용한 표시장치에 관한 것이다.The present invention includes a base film and an adhesive film laminated on at least one side of the base film, wherein the adhesive film exhibits a peel force of 1.0 to 30N upon curing, and an amount of light of 1J at an illuminance of 100mW or more at a UV wavelength of 400 to 450nm It relates to an optically transparent adhesive sheet and a display device using the same, which exhibits a peel force of 0.01 to 0.5N after the above ultraviolet (UV) treatment.
이하, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
<광학투명점착시트><optical transparent adhesive sheet>
도 1 은 본 발명의 일 실시예에 의한 광학투명점착시트를 나타내는 개략적인 도면이다.1 is a schematic view showing an optically transparent adhesive sheet according to an embodiment of the present invention.
도 1을 참조하면, 본 발명에 따른 광학투명점착시트는 기재 필름(2) 및 상기 기재 필름의 적어도 일면에 적층된 점착 필름(3)을 포함한다. 상기 광학투명점착시트는 기재 필름의 일면에 점착 필름이 적층되고, 상기 점착 필름이 적층되지 않은 기재필름의 일면에 하드코팅층(1)이 형성 될 수 있다. Referring to FIG. 1, the optically transparent adhesive sheet according to the present invention includes a
필요에 따라, 상기 점착 필름의 일면에는 세퍼레이터가 형성될 수도 있다.If necessary, a separator may be formed on one surface of the adhesive film.
본 발명에 있어서, 상기 점착 필름은 경화시에 고점착성을 나타내고, 400 내지 450nm의 UV파장에서 100mW이상 조도로 광량 1J 이상의 UV광 처리시 저점착성을 나타내는 것이 특징이다.In the present invention, the adhesive film is characterized in that it exhibits high adhesiveness upon curing, and exhibits low adhesiveness when UV light treatment with an amount of light of 1J or more with an illuminance of 100mW or more at a UV wavelength of 400 to 450nm.
상기 고점착성은 1.0내지 30N의 박리력을 나타내는 것을 의미하며, 상기 저점착성은 0.01 내지 0.5N의 박리력을 나타내는 것을 의미할 수 있다. The high-tackiness means exhibiting a peeling force of 1.0 to 30N, and the low-tackiness may mean exhibiting a peeling force of 0.01 to 0.5N.
본 발명의 일 실시예에 있어서, 상기 광학투명점착시트는 기재 필름 상에 본 발명에 따른 점착제 조성물로부터 점착 필름이 형성된 것이거나, 2매의 기재 필름 사이에 본 발명에 따른 점착제 조성물로부터 형성된 점착 필름이 개재된 것 일 수 있다.In one embodiment of the present invention, the optically transparent adhesive sheet is an adhesive film formed from the adhesive composition according to the present invention on a base film, or an adhesive film formed from the adhesive composition according to the present invention between two base films This may be intervening.
기재 필름Base film
본 발명에서, 기재 필름은 당 업계에서 사용되는 기재라면 특별한 제한 없이 사용될 수 있으며, 구체적으로, 투명성, 기계적 강도, 열안정성, 수분차폐성, 등방성 등에서 우수한 필름이 사용될 수 있다. 보다 구체적으로는, 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 화상표시장치에 적용이 보다 용이하도록 폴리이미드계 수지를 사용할 수 있다.In the present invention, the base film may be used without particular limitation as long as it is a base material used in the art, and specifically, a film excellent in transparency, mechanical strength, thermal stability, moisture shielding property, isotropic property, and the like may be used. More specifically, polyester resins such as polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, and polybutylene terephthalate; Cellulose resins such as diacetyl cellulose and triacetyl cellulose; Polycarbonate resin; Acrylic resins such as polymethyl (meth)acrylate and polyethyl (meth)acrylate; Styrene resins such as polystyrene and acrylonitrile-styrene copolymer; Polyolefin resins such as polyethylene, polypropylene, polyolefin having a cyclo-based or norbornene structure, and ethylene-propylene copolymer; Vinyl chloride resin; Amide resins such as nylon and aromatic polyamide; Imide resin; Sulfone resin; Polyethersulfone resin; Polyether ether ketone resin; Sulfide polyphenylene resin; Vinyl alcohol resin; Vinylidene chloride resin; Vinyl butyral resin; Allylate resin; Polyoxymethylene resin; A film composed of a thermoplastic resin such as an epoxy resin may be mentioned, and a film composed of a blend of the thermoplastic resin may also be used. In addition, a film made of a thermosetting resin such as (meth)acrylic, urethane, acrylic urethane, epoxy, silicone, etc., or ultraviolet curable resin may be used.According to the embodiment of the present invention, it is flexible due to excellent durability against repeated bending. Polyimide-based resins can be used for easier application to an image display device.
점착 필름Adhesive film
본 발명의 일 실시예에 있어서, 상기 점착 필름은 점착제 조성물을 이용하여 점착제층을 형성함으로써 제조될 수 있다.In an embodiment of the present invention, the adhesive film may be prepared by forming an adhesive layer using an adhesive composition.
상기 점착제 조성물은 아크릴계 공중합체, 이소시아네이트계 가교제, 광중합 개시제, 자외선 차단제 및 다관능 아크릴 모노머를 포함한다.The pressure-sensitive adhesive composition includes an acrylic copolymer, an isocyanate crosslinking agent, a photopolymerization initiator, a sunscreen agent, and a polyfunctional acrylic monomer.
아크릴계 공중합체 Acrylic copolymer
본 발명에 따른 점착제 조성물은 점착 및 내구성 발현을 위해 아크릴계 공중합체를 포함한다.The pressure-sensitive adhesive composition according to the present invention includes an acrylic copolymer for adhesion and durability expression.
본 발명의 일 실시예에 있어서, 상기 아크릴계 공중합체는 탄소수 1 내지 12의 직쇄 또는 분지쇄 알킬기를 함유하는 아크릴 단량체 유래의 반복단위를 포함하는 아크릴계 공중합체로써, 예를 들면 탄소수 1 내지 12의 알킬기를 갖는 아크릴계 단량체 및 가교 가능한 관능기를 갖는 중합성 단량체를 포함하는 단량체들의 공중합체일 수 있다. 바람직하게는 탄소수 1 내지 12의 알킬기를 포함하는 단량체, 산 함유 단량체 및 히드록시기, 또는 아마이드기를 함유한 단량체를 공중합하여 제조되는 것일 수 있다.In one embodiment of the present invention, the acrylic copolymer is an acrylic copolymer comprising a repeating unit derived from an acrylic monomer containing a linear or branched alkyl group having 1 to 12 carbon atoms, for example, an alkyl group having 1 to 12 carbon atoms. It may be a copolymer of monomers including an acrylic monomer having a and a polymerizable monomer having a crosslinkable functional group. Preferably, it may be prepared by copolymerizing a monomer containing an alkyl group having 1 to 12 carbon atoms, an acid-containing monomer, and a hydroxy group, or a monomer containing an amide group.
상기 탄소수 1 내지 12의 알킬기를 포함하는 단량체는 이에 한정되는 것은 아니나 (메트)아크릴레이트계 단량체인 것이 바람직하다. The monomer containing an alkyl group having 1 to 12 carbon atoms is not limited thereto, but is preferably a (meth)acrylate-based monomer.
상기 (메트)아크릴레이트계 단량체로는 n-부틸(메트)아크릴레이트, 2-부틸(메트)아크릴레이트, t-부틸(메트)아크릴레이트, 2-에틸헥실(메트)아크릴레이트, 에틸(메트)아크릴레이트, 메틸(메트)아크릴레이트, n-프로필(메트)아크릴레이트, 이소프로필(메트)아크릴레이트, 펜틸(메트)아크릴레이트, n-옥틸(메트)아크릴레이트, 이소옥틸(메트)아크릴레이트, 이소보닐아크릴레이트, 노닐(메트)아크릴레이트, 데실(메트)아크릴레이트, 라우릴(메트)아크릴레이트 등을 들 수 있으며, 이들 중에서 이소보닐아크릴레이트, 2-에틸헥실아크릴레이트 또는 이들의 혼합물이 바람직하다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The (meth)acrylate-based monomers include n-butyl (meth)acrylate, 2-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and ethyl (meth)acrylate. )Acrylate, methyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, pentyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylic Rate, isobornyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, and the like, among which isobornyl acrylate, 2-ethylhexyl acrylate, or Mixtures are preferred. These can be used alone or in combination of two or more.
상기 탄소수 1 내지 12의 알킬기를 갖는 단량체는 상기 아크릴계 공중합체 전체에 대하여 80 내지 97 중량%, 바람직하게는 85 내지 97 중량%, 더욱 바람직하게는 90 내지 97 중량%로 포함될 수 있다. 상기 탄소수 1 내지 12의 알킬기를 갖는 단량체의 범위가 80 중량% 미만인 경우 점착력이 다소 저하될 수 있으며, 97 중량%를 초과하는 경우 응집력이 다소 저하될 수 있다.The monomer having an alkyl group having 1 to 12 carbon atoms may be included in an amount of 80 to 97% by weight, preferably 85 to 97% by weight, more preferably 90 to 97% by weight, based on the entire acrylic copolymer. When the range of the monomer having an alkyl group having 1 to 12 carbon atoms is less than 80% by weight, adhesive strength may be slightly lowered, and when it exceeds 97% by weight, cohesion may be slightly lowered.
상기 산 함유 단량체는, 예를 들면, (메타)아크릴산일 수 있으나, 이에 한정되는 것은 아니다. 상기 산 함유 단량체는 상기 공중합체 전체에 대하여 0.1 내지 15 중량%로 포함될 수 있다. 상기 산 함유 단량체가 0.1 중량% 미만으로 포함되는 경우 저분자 단량체의 블리드 아웃(bleed out) 현상의 억제 효과가 다소 미비하여 내구성이 저하될 수 있으며, 15 중량%를 초과하는 경우 다소 지나친 가교반응으로 인하여 점착제 조성물의 조액 안정성이 저하될 수 있다.The acid-containing monomer may be, for example, (meth)acrylic acid, but is not limited thereto. The acid-containing monomer may be included in an amount of 0.1 to 15% by weight based on the entire copolymer. If the acid-containing monomer is contained in an amount of less than 0.1% by weight, the effect of suppressing the bleed out phenomenon of the low molecular weight monomer may be somewhat inadequate and durability may be reduced.If it exceeds 15% by weight, due to a somewhat excessive crosslinking reaction The stability of the pressure-sensitive adhesive composition may decrease.
상기 히드록시기를 포함하는 단량체로는, 예를 들면 2-히드록시에틸(메타)아크릴레이트, 3-히드록시프로필(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 2-히드록시에틸(메타)아크릴레이트 바람직하다.Examples of the hydroxy group-containing monomer include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (Meth)acrylate, 2-hydroxyethylene glycol (meth)acrylate, 2-hydroxypropylene glycol (meth)acrylate, hydroxyalkylene glycol (meth)acrylate having 2-4 carbon atoms in the alkylene group, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 7-hydroxyheptyl vinyl ether, 8-hydroxyoctyl vinyl ether, 9-hydroxynonyl vinyl ether and 10- And hydroxydecyl vinyl ether, and among these, 2-hydroxyethyl (meth)acrylate is preferable.
상기 아마이드기를 포함하는 단량체는 예컨대 (메타)아크릴아미드, N-이소프로필아크릴아미드, N-3차부틸아크릴아미드, 3-히드록시프로필(메타)아크릴아미드, 4-히드록시부틸(메타)아크릴아미드, 6-히드록시헥실(메타)아크릴아미드, 8-히드록시옥틸(메타)아크릴아미드, 2-히드록시에틸헥실(메타)아크릴아미드 등을 들 수 있으며, 이들 중에서 (메타)아크릴아미드가 바람직하다.The monomer containing the amide group is, for example, (meth)acrylamide, N-isopropylacrylamide, N-tertiary butylacrylamide, 3-hydroxypropyl (meth)acrylamide, and 4-hydroxybutyl (meth)acrylamide. , 6-hydroxyhexyl (meth)acrylamide, 8-hydroxyoctyl (meth)acrylamide, 2-hydroxyethylhexyl (meth)acrylamide, and the like, among which (meth)acrylamide is preferred. .
상기 히드록시기 또는 아마이드기를 포함하는 단량체는 상기 아크릴계 공중합체 전체에 대하여 1 내지 10 중량%로 포함될 수 있다. 상기 함량이 1 중량% 미만인 경우 양생기간 단축 효과가 다소 미비할 수 있으며, 10 중량%를 초과하는 경우에는 지나친 가교반응으로 조액안정성이 저하될 수 있다.The monomer including a hydroxy group or an amide group may be included in an amount of 1 to 10% by weight based on the entire acrylic copolymer. When the content is less than 1% by weight, the effect of shortening the curing period may be somewhat insignificant, and when it exceeds 10% by weight, the stability of the crude liquid may be deteriorated due to excessive crosslinking reaction.
본 발명의 일 실시예에 있어서, 아크릴계 공중합체는 상기 단량체 이외에 가교 가능한 관능기를 갖는 중합성 단량체를 추가로 함유할 수 있다.In one embodiment of the present invention, the acrylic copolymer may further contain a polymerizable monomer having a crosslinkable functional group in addition to the monomer.
상기 가교 가능한 관능기를 갖는 중합성 단량체는 하기 가교제와의 화학 결합에 의해 응집력 또는 점착 강도를 부여하는 작용을 하는 것으로서, 예를 들면, 카르복시기를 갖는 단량체, 또는 3차 아민기를 갖는 단량체 등을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The polymerizable monomer having a crosslinkable functional group has a function of imparting cohesive strength or adhesive strength by chemical bonding with the following crosslinking agent, and examples thereof include a monomer having a carboxyl group or a monomer having a tertiary amine group. have. These can be used alone or in combination of two or more.
상기 아크릴계 공중합체는 카르복실산을 함유하는 중합성 단량체를 더 포함하여 공중합된 것일 수 있다.The acrylic copolymer may be copolymerized by further including a polymerizable monomer containing a carboxylic acid.
상기 카르복시기를 갖는 단량체로는, 예를 들면 (메타)아크릴산, 크로톤산, 카르복시에틸아크릴산 등의 1가산; 말레인산, 이타콘산, 푸마르산 등의 2가산 및 이들의 모노알킬에스테르; 3-(메타)아크릴로일프로피온산; 알킬기의 탄소수가 2 내지 3인 2-히드록시알킬(메타)아크릴레이트의 무수호박산 개환 부가체, 알킬렌기의 탄소수가 2 내지 4인 히드록시알킬렌글리콜(메타)아크릴레이트의 무수 호박산 개환 부가체, 알킬기의 탄소수가 2 내지 3인 2-히드록시알킬(메타)아크릴레이트의 카프로락톤 부가체에 무수 호박산을 개환 부가시킨 화합물 등을 들 수 있으며, 이들 중에서 카르복시에틸아크릴산이 바람직하다.Examples of the monomer having a carboxyl group include monoacids such as (meth)acrylic acid, crotonic acid, and carboxyethylacrylic acid; Diacids such as maleic acid, itaconic acid, and fumaric acid, and monoalkyl esters thereof; 3-(meth)acryloylpropionic acid; Succinic anhydride ring-opening adduct of 2-hydroxyalkyl (meth)acrylate having 2 to 3 carbon atoms in the alkyl group, and succinic anhydride ring-opening adduct of hydroxyalkylene glycol (meth)acrylate having 2 to 4 carbon atoms in the alkylene group And compounds obtained by ring-opening addition of succinic anhydride to the caprolactone adduct of 2-hydroxyalkyl (meth)acrylate having 2 to 3 carbon atoms in the alkyl group, and among them, carboxyethylacrylic acid is preferable.
상기 3차 아민기를 갖는 단량체로는 N,N-(디메틸아미노)에틸(메타)아크릴레이트, N,N-(디에틸아미노)에틸(메타)아크릴레이트, N,N-(디메틸아미노)프로필(메타)아크릴레이트 등을 들 수 있다. As the monomer having a tertiary amine group, N,N-(dimethylamino)ethyl (meth)acrylate, N,N-(diethylamino)ethyl (meth)acrylate, N,N-(dimethylamino)propyl ( Meth)acrylate, etc. are mentioned.
본 발명에서 상기 가교 가능한 관능기를 갖는 중합성 단량체는 아크릴계 공중합체 전체 중량부에 대하여 0.05 내지 10 중량부로 포함되는 것이 바람직하고, 보다 바람직하게는 0.1 내지 8중량부인 것이 좋다. 함량이 0.05중량부 미만인 경우 점착제의 응집력이 작아지게 되어 내구성이 저하될 수 있으며, 10 중량부 초과인 경우 높은 겔분율에 의해 점착력이 떨어지고 내구성에 문제를 야기할 수 있다.In the present invention, the polymerizable monomer having a crosslinkable functional group is preferably contained in an amount of 0.05 to 10 parts by weight, more preferably 0.1 to 8 parts by weight based on the total weight part of the acrylic copolymer. If the content is less than 0.05 parts by weight, the cohesive strength of the pressure-sensitive adhesive becomes small and durability may be deteriorated, and if the content is more than 10 parts by weight, the adhesive strength may decrease due to a high gel fraction and may cause problems in durability.
또한, 상기 단량체들 이외에 다른 중합성 단량체가 점착력을 저하시키지 않는 범위, 예컨대 아크릴계 공중합체의 제조에 사용되는 총 단량체 100 중량부에 대하여 10 중량부 이하로 더 포함될 수 있다.In addition, other polymerizable monomers other than the above monomers may be further included in a range that does not lower the adhesive strength, for example, 10 parts by weight or less based on 100 parts by weight of the total monomers used in the production of the acrylic copolymer.
본 발명에서 상기 아크릴계 공중합체는 중량평균분자량이 30만 이상 내지 200만 이하 일 수 있으며, 더욱 바람직하게는 70만 이상 내지 170만 이하일 수 있다. 본 발명의 아크릴계 공중합체의 중량평균 분자량이 상기 범위를 만족하는 경우 점착특성 및 젖음성, 내구성 향상을 기대할 수 있다. In the present invention, the acrylic copolymer may have a weight average molecular weight of 300,000 or more and 2 million or less, and more preferably 700,000 or more and 1.7 million or less. When the weight average molecular weight of the acrylic copolymer of the present invention satisfies the above range, it can be expected to improve adhesion properties, wettability, and durability.
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 method for preparing the copolymer is not particularly limited, and may be prepared using a method such as bulk polymerization, solution polymerization, emulsion polymerization, or suspension polymerization commonly used in the art, and solution polymerization is preferred. In addition, a solvent commonly used during polymerization, a polymerization initiator, a chain transfer agent for molecular weight control, and the like may be used.
이소시아네이트계 가교제Isocyanate crosslinking agent
본 발명에서 가교제는 상기 아크릴계 공중합체를 적절히 가교함으로써 점착제의 응집력을 강화하기 위하여 사용되는 것으로 이소시아네이트 화합물을 포함한다.In the present invention, the crosslinking agent is used to enhance the cohesive strength of the pressure-sensitive adhesive by appropriately crosslinking the acrylic copolymer, and includes an isocyanate compound.
상기 이소시아네이트 화합물로는 톨릴렌디이소시아네이트, 자일렌디이소시아네이트, 헥사메틸렌디이소시아네이트, 2,4-디페닐메탄디이소시아네트, 4,4-디페닐메탄디이소시아네트, 이소포론디이소시아네이트, 테트라메틸자일렌디이소시아네이트, 나프탈렌디이소시아네이트, 2,4-톨루엔 디이소시아네이트 부가형 삼량체 등의 부가형 삼량체 또는 이소시아누레이트 삼량체를 들 수 있으며 이에 한정되지 않는다. 바람직하게는, 상기 가교제는 2,4-톨루엔 디이소시아네이트 부가형 삼량체일 수 있다.As the isocyanate compound, tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate , Naphthalene diisocyanate, and 2,4-toluene diisocyanate addition-type trimers such as addition-type trimers or isocyanurate trimers, but are not limited thereto. Preferably, the crosslinking agent may be a 2,4-toluene diisocyanate addition type trimer.
상기 가교제는 상기 아크릴계 공중합체 전체 100 중량부에 대하여 0.1 내지 1 중량부, 바람직하게는 0.1 내지 0.5 중량부, 더욱 바람직하게는 0.1 내지 0.3 중량부로 포함되는 것이 점착력 또는 응집성의 면에서 바람직하다. 상기 가교제가 0.1 중량부 미만인 경우 점착제의 점착력 또는 응집력이 다소 저하될 수 있으며, 1 중량부를 초과하는 경우 상용성이 다소 저하되어 표면이행이 일어날 수 있으며, 가교반응이 너무 진행되어 점착력이 다소 저하될 수 있다.The crosslinking agent is preferably contained in an amount of 0.1 to 1 parts by weight, preferably 0.1 to 0.5 parts by weight, and more preferably 0.1 to 0.3 parts by weight, based on the total 100 parts by weight of the acrylic copolymer in terms of adhesion or cohesiveness. If the crosslinking agent is less than 0.1 parts by weight, the adhesive strength or cohesive strength of the pressure-sensitive adhesive may be slightly lowered, and if it exceeds 1 part by weight, the compatibility may be slightly lowered and surface migration may occur. I can.
광중합 개시제Photopolymerization initiator
본 발명의 점착제 조성물은 UV 대역의 광, 예를 들면 400nm파장 이상에서도 라디칼 중합성기의 반응을 효율적으로 유도할 수 있는 광중합성 개시제를 포함한다. The pressure-sensitive adhesive composition of the present invention includes a photopolymerization initiator capable of efficiently inducing a reaction of a radical polymerizable group even in light in the UV band, for example, at a wavelength of 400 nm or more.
상기 광중합 개시제는 상기 점착제 조성물로 이루어진 점착 필름 재박리 시, 점착 필름에 특정 파장영역, 조도 및 광량의 자외선 처리를 통해 다관능 아크릴 모노머의 가교 반응을 효과적으로 개시 시키는 역할을 할 수 있다. 이에 의해 본 발명은 점착제의 가교도를 올리고, 점착제 자체의 응집력을 향상시켜 피착면에 대한 점착 필름의 저점착 특성이 발현되도록 하여 광학투명점착시트의 리워크성을 향상시킬 수 있다.The photopolymerization initiator may play a role of effectively initiating a crosslinking reaction of the polyfunctional acrylic monomer through ultraviolet treatment of a specific wavelength range, illuminance and light amount on the adhesive film when the adhesive film made of the adhesive composition is peeled again. Accordingly, in the present invention, the degree of crosslinking of the pressure-sensitive adhesive is increased, the cohesive force of the pressure-sensitive adhesive itself is improved, so that the low-adhesion property of the pressure-sensitive adhesive film to the adherend surface is expressed, thereby improving the reworkability of the optically transparent adhesive sheet.
본 발명에서 광중합 개시제는 당해 분야에서 통상적으로 사용되는 광중합 개시제가 특별한 제한 없이 사용될 수 있다. 예를 들면, 벤조인 화합물, 벤조페논 화합물, 알킬페논 화합물, 아실포스핀옥사이드 화합물, 트리아진 화합물, 요오드늄염 및 술포늄염을 들 수 있다. In the present invention, the photopolymerization initiator may be used without particular limitation, such as photopolymerization initiators commonly used in the art. For example, a benzoin compound, a benzophenone compound, an alkylphenone compound, an acylphosphine oxide compound, a triazine compound, an iodonium salt, and a sulfonium salt are mentioned.
본 발명의 일 실시예에 있어서, 광중합 개시제로써 시판품을 사용할 수도 있다. 예를 들어, Lucirin_TPO, 이가큐어(Irgacure) 907, 이가큐어 819 (이상, 전부 BASF 재팬(주) 제조), 세이크올 BZ, 세이크올 Z, 세이크올 BEE(이상, 전부 세이코카가쿠(주) 제조), 카야큐어(kayacure) BP100(니혼카야쿠(주) 제조), 사이라큐어(CYRACURE) UVI-6992(다우케미컬 제조), 아데카옵토머 SP-152, 아데카옵토머 SP-170(이상, 전부 (주)ADEKA 제조), TAZ-A, TAZ-PP(이상, DKSH 재팬 제조), TAZ-104(산와케미컬 제조) 등을 들 수 있다. 이들 중에서 실내외 노출 될 수 있는 자외선 에너지의 감도가 낮은 Lucirin_TPO가 바람직하다.In one embodiment of the present invention, a commercial product may be used as the photopolymerization initiator. For example, Lucirin_TPO, Irgacure 907, Igacure 819 (above, all manufactured by BASF Japan Co., Ltd.), Sakeall BZ, Sakeall Z, Sakeall BEE (above, all manufactured by Seiko Chemical Co., Ltd.) ), Kayacure BP100 (manufactured by Nihon Kayaku Co., Ltd.), Cyracure (CYRACURE) UVI-6992 (manufactured by Dow Chemical), Adeka Optomer SP-152, Adeka Optomer SP-170 (more , All of which are manufactured by ADEKA Co., Ltd.), TAZ-A, TAZ-PP (above, manufactured by DKSH Japan), TAZ-104 (manufactured by Sanwa Chemical), etc. are mentioned. Among these, Lucirin_TPO, which has low sensitivity to ultraviolet energy that can be exposed indoors and outdoors, is preferable.
본 발명에 따른 점착제 조성물에서, 상기 광중합 개시제는 상기 아크릴계 공중합체 100중량부에 대하여 0.3 내지 3.0 중량부로 포함될 수 있으며, 바람직하게는 0.5 내지 2.0 중량부로 포함될 수 있다.In the pressure-sensitive adhesive composition according to the present invention, the photopolymerization initiator may be included in an amount of 0.3 to 3.0 parts by weight, and preferably 0.5 to 2.0 parts by weight, based on 100 parts by weight of the acrylic copolymer.
광중합 개시제가 상기 함량범위로 포함되는 경우, 저점착 특성 구현을 위해 점착 필름에 특정 파장영역, 조도 및 광량의 자외선 처리 시 다관능 아크릴 모노머의 가교 반응을 효과적으로 개시시킬 수 있고, 내구성이 발현되면서 가변성이 우수할 수 있다.When the photopolymerization initiator is included in the above content range, it is possible to effectively initiate a crosslinking reaction of the multifunctional acrylic monomer when UV treatment of a specific wavelength range, illuminance, and amount of light is applied to the adhesive film in order to realize low-adhesion properties. This can be excellent.
자외선 차단제Sunscreen
본 발명에 따른 점착제 조성물은, 장시간 외부광에 의해 하부 패널의 소자 수명을 단축시키는 문제를 방지하도록, 실내/외에서 노출되는 자외선을 차단하여 하부패널의 내광성을 높이기 위해 자외선(UV) 차단제를 포함한다. The pressure-sensitive adhesive composition according to the present invention includes an ultraviolet (UV) blocker to increase light resistance of the lower panel by blocking ultraviolet rays exposed indoors/outside to prevent the problem of shortening the device life of the lower panel by external light for a long time. .
본 발명에서 상기 자외선 차단제는 점착 필름을 재박리하기 위해 UV광 조사 시 상기 광중합 개시제의 라디칼 생성을 방해하는 영역 이외의 자외선을 차단할 수 있는 것이 사용될 수 있고, 예를 들어, 상기 광중합성 개시제와의 최대흡수파장 차이가 50nm이상인 것이라면 특별히 제한되지 않고 사용될 수 있다. In the present invention, the sunscreen agent may be used to block ultraviolet rays other than the area that interferes with the generation of radicals of the photopolymerization initiator when irradiated with UV light in order to re-peel the adhesive film. For example, the photopolymerization initiator If the difference in the maximum absorption wavelength is 50 nm or more, it may be used without particular limitation.
일 실시예에 있어서, 상기 자외선 차단제는, 예를 들어 벤조트라이아졸 유도체, 히드록시벤조페논, 히드록시페닐 트라이진, 치환 또는 비치환된 벤조산의 에스테르, 및 이들 중 임의의 것의 혼합물 등을 들 수 있으나, 이들로 제한되지 않는다. In one embodiment, the sunscreen agent is, for example, a benzotriazole derivative, hydroxybenzophenone, hydroxyphenyl triazine, a substituted or unsubstituted ester of benzoic acid, and a mixture of any of these. However, it is not limited to these.
본 발명의 점착제 조성물은 자외선 자단제로 시판품을 사용할 수 도 있으며, 예를 들면, Ciba 사에 의해 제조된 Tinuvin™ P, Tinuvin™ 1130, Tinuvin™ 326, Tinuvin™ 327, Tinuvin™ 328, Tinuvin™ 460, Tinuvin™ 477, Tinuvin™ 571, Tinuvin™ 99-DW, 또는 Chimassorb™ 81, BASF(독일 루드비히샤펜 소재) 사에 의해 제조된 Uvinul™ 3000, Uvinul™ 3008, Uvinul™ 3040, 또는 Uvinul™ 3050, Cytec Industries, Inc.사에 의해 제조된 Cyasorb™ 5411, Songwon 사에서 제조된 Songsorb CS81 등을 들 수 있다. The pressure-sensitive adhesive composition of the present invention may be a commercially available product as an ultraviolet rosewood, for example, Tinuvin™ P manufactured by Ciba, Tinuvin™ 1130, Tinuvin™ 326, Tinuvin™ 327, Tinuvin™ 328, Tinuvin™ 460, Tinuvin™ 477, Tinuvin™ 571, Tinuvin™ 99-DW, or Chimassorb™ 81, Uvinul™ 3000, Uvinul™ 3008, Uvinul™ 3040, or Uvinul™ 3050 manufactured by BASF (Ludwigschaffen, Germany), or Uvinul™ 3050, Cytec Industries , Cyasorb™ 5411 manufactured by Inc., Songsorb CS81 manufactured by Songwon, and the like.
상기 자외선 차단제는 1종 또는 2종 이상을 혼합하여 사용하는 것도 가능하다.It is also possible to use one or two or more types of the sunscreen.
본 발명에 따른 점착제 조성물에서, 상기 자외선 차단제는 아크릴계 공중합체 100중량부에 대하여 0.5 내지 5.0 중량부로 포함될 수 있으며, 바람직하게는 1.0 내지 3.0 중량부로 포함될 수 있다.In the pressure-sensitive adhesive composition according to the present invention, the sunscreen agent may be included in an amount of 0.5 to 5.0 parts by weight, preferably 1.0 to 3.0 parts by weight, based on 100 parts by weight of the acrylic copolymer.
상기 함량범위로 포함되는 경우 하부 패널의 내광성을 효율적으로 높일 수 있다.When included in the above content range, lightfastness of the lower panel can be efficiently increased.
다관능 아크릴 모노머Polyfunctional acrylic monomer
일 실시예에 있어서, 본 발명에 따른 점착제 조성물은 가변성을 위해 다관능 아크릴 모노머를 포함한다. In one embodiment, The pressure-sensitive adhesive composition according to the present invention includes a polyfunctional acrylic monomer for variability.
본 발명은 상기 다관능 아크릴 모노머에 의해 경화시 점착 필름의 점착 물성에 영향을 끼치지 않아 경화된 점착 필름이 고점착 상태로 유지될 수 있도록 할 수 있고, 상기 자외선 차단제의 흡수범위 이상의 파장, 예를 들어 400 내지 450nm의 파장영역에서 UV광 조사 시 점착 필름의 저점착 특성을 유도할 수 있다.The present invention does not affect the adhesive properties of the adhesive film when cured by the multifunctional acrylic monomer, so that the cured adhesive film can be maintained in a high-adhesive state, and a wavelength of more than the absorption range of the UV blocker, eg For example, when irradiated with UV light in a wavelength range of 400 to 450 nm, low-adhesion properties of the adhesive film may be induced.
본 발명에서 상기 다관능 아크릴 모노머는 아크릴 광경화형 (메타)아크릴레이트 모노머(올리고머)로써, 에폭시 (메타)아크릴레이트, 우레탄 (메타)아크릴레이트 및 폴리에스테르 (메타)아크릴레이트로 구성된 군으로부터 선택된 1종 이상을 사용할 수 있으며, 구체적으로 우레탄(메타)아크릴레이트와 폴리에스테르 (메타)아크릴레이트를 혼합하여 사용하거나, 2종의 폴리에스테르 (메타)아크릴레이트를 혼합하여 사용할 수 있다.In the present invention, the polyfunctional acrylic monomer is an acrylic photocurable (meth) acrylate monomer (oligomer), 1 selected from the group consisting of epoxy (meth) acrylate, urethane (meth) acrylate and polyester (meth) acrylate More than one type may be used, and specifically, urethane (meth)acrylate and polyester (meth)acrylate may be mixed and used, or two types of polyester (meth)acrylate may be mixed and used.
상기 다관능 아크릴 모노머는 UV 조사 후 응집력을 극대화시켜 리워크시 점착력을 낮추기 위한 측면에서, 바람직하게는 3관능 이상일 수 있고, 더욱 바람직하게는 3 내지 6관능을 가질 수 있다.The polyfunctional acrylic monomer may be preferably trifunctional or higher, and more preferably 3 to 6 functional, in terms of maximizing cohesion after UV irradiation and lowering adhesion during rework.
상기 우레탄 (메타)아크릴레이트는 분자 내에 하이드록시기를 갖는 다관능 (메타)아크릴레이트와 이소시아네이트기를 갖는 화합물을 당업계에 공지된 방법에 따라 촉매 존재 하에서 반응시켜 제조할 수 있다. The urethane (meth)acrylate may be prepared by reacting a polyfunctional (meth)acrylate having a hydroxyl group in a molecule and a compound having an isocyanate group in the presence of a catalyst according to a method known in the art.
분자 내에 하이드록시기를 갖는 다관능 (메타)아크릴레이트의 구체적인 예는, 2-하이드록시에틸(메타)아크릴레이트, 2-하이드록시이소프로필(메타)아크릴레이트, 4-하이드록시부틸(메타)아크릴레이트, 카프로락톤 개환 하이드록시아크릴레이트, 펜타에리스리톨트리/테트라(메타)아크릴레이트(DPHA) 및 디펜타에리스리톨펜타/헥사(메타)아크릴레이트(PETA) 이루어진 군으로부터 선택되는 1종 이상을 포함할 수 있다. Specific examples of the polyfunctional (meth)acrylate having a hydroxy group in the molecule are 2-hydroxyethyl (meth)acrylate, 2-hydroxyisopropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylic Rate, caprolactone ring-opening hydroxyacrylate, pentaerythritol tri/tetra(meth)acrylate (DPHA), and dipentaerythritol penta/hexa(meth)acrylate (PETA) may contain at least one selected from the group consisting of have.
또한 이소시아네이트기를 갖는 화합물의 구체적인 예는, 1,4-디이소시아나토부탄, 1,6-디이소시아나토헥산, 1,8-디이소시아나토옥탄, 1,12-디이소시아나토도데칸, 1,5-디이소시아나토-2-메틸펜탄, 트리메틸-1,6-디이소시아나토헥산, 1,3-비스(이소시아나토메틸)시클로헥산, 트랜스-1,4-시클로헥센디이소시아네이트, 4,4′-메틸렌비스(시클로헥실이소시아네이트), 이소포론디이소시아네이트, 톨루엔-2,4-디이소시아네이트, 톨루엔-2,6-디이소시아네이트, 자일렌-1,4-디이소시아네이트, 테트라메틸자일렌-1,3-디이소시아네이트, 1-클로로메틸-2,4-디이소시아네이트, 4,4′-메틸렌비스(2,6-디메틸페닐이소시아네이트), 4,4′-옥시비스(페닐이소시아네이트), 헥사메틸렌디이소시아네이트로부터 유도되는 3관능 이소시아네이트, 및 트리메탄프로판올어덕트 톨루엔디이소시아네이트로 이루어진 군으로부터 선택된 1종 이상일 수 있다.Further, specific examples of the compound having an isocyanate group include 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,8-diisocyanatooctane, 1,12-diisocyanatododecane, 1,5 -Diisocyanato-2-methylpentane, trimethyl-1,6-diisocyanatohexane, 1,3-bis(isocyanatomethyl)cyclohexane, trans-1,4-cyclohexenediisocyanate, 4,4' -Methylenebis(cyclohexylisocyanate), isophorone diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylene-1,4-diisocyanate, tetramethylxylene-1,3 -Diisocyanate, 1-chloromethyl-2,4-diisocyanate, 4,4'-methylenebis (2,6-dimethylphenyl isocyanate), 4,4'-oxybis (phenyl isocyanate), hexamethylene diisocyanate It may be at least one selected from the group consisting of derived trifunctional isocyanate, and trimethane propanol adduct toluene diisocyanate.
본 발명에 따른 점착제 조성물에서, 상기 다관능 아크릴 모노머는 아크릴계 공중합체 100중량부를 기준으로 5 내지 50중량부로 포함될 수 있으며, 바람직하게는 10 내지 30중량부로 포함될 수 있다.In the pressure-sensitive adhesive composition according to the present invention, the polyfunctional acrylic monomer may be included in an amount of 5 to 50 parts by weight based on 100 parts by weight of an acrylic copolymer, and preferably 10 to 30 parts by weight.
상기 함량범위로 포함되는 경우 효율적인 가변성을 보일 수 있다.When included in the above content range, efficient variability can be shown.
본 발명의 점착제 조성물의 사용형태는 특별히 한정되는 것은 아니나, 예를 들면, 상술한 점착제 조성물을 기재 필름의 한쪽 면 또는 양면에 도포해서 가열 건조한다. 이에 의해 상기 점착제 조성물로 이루어지는 점착제층을 기재 필름의 한면 또는 양면에 형성하여 점착 시트로서 사용할 수 있다. 상기 점착제 조성물을 실리콘이나 불소 등으로 표면이형 처리를 실시한 기재 필름의 표면에 도포하고 가열 건조해서 점착제층을 형성할 수도 있다. 상기 점착제층을, 사용 시에 상기 기재 필름으로부터 박리하면 상기 점착제를 기재가 없는 점착제층으로서 사용할 수도 있다. 또한, 상기 점착제 조성물을 피착체에 직접 도포해서 가열 건조할 수도 있다.The use mode of the pressure-sensitive adhesive composition of the present invention is not particularly limited, but, for example, the pressure-sensitive adhesive composition described above is applied to one side or both sides of a base film, followed by heating and drying. Thereby, the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition can be formed on one side or both sides of the base film and used as a pressure-sensitive adhesive sheet. The pressure-sensitive adhesive composition may be applied to the surface of a base film subjected to a surface release treatment with silicone or fluorine, and then dried by heating to form a pressure-sensitive adhesive layer. When the pressure-sensitive adhesive layer is peeled from the base film during use, the pressure-sensitive adhesive may be used as a pressure-sensitive adhesive layer without a base. In addition, the pressure-sensitive adhesive composition may be applied directly to an adherend and dried by heating.
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 the adhesion to the pressure-sensitive adhesive layer, the surface of the base film may be subjected to corona discharge treatment, plasma treatment, blast treatment, chemical etching treatment, primer treatment, or the like.
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. 기재가 없는 것을 포함하는 상기 점착제층의 두께는 예를 들어, 5 내지 80㎛로 형성할 수 있다. 상기 점착제층의 두께가 상기 범위이면 우수한 내구성을 나타내면서 재박리성이 용이해 질 수 있다.The application may be generally performed by a knife coater, a roll coater, a calender coater, a comma coater, or the like. In addition, depending on the thickness of the coating or the viscosity of the pressure-sensitive adhesive composition, it may be performed by a gravure coater or a rod coater. The thickness of the pressure-sensitive adhesive layer including those without a substrate may be, for example, 5 to 80㎛. When the thickness of the pressure-sensitive adhesive layer is within the above range, excellent durability may be exhibited and re-peelability may be facilitated.
또한, 상기 점착시트는 재박리를 위해 400 내지 450nm의 UV파장에서 100mW이상 조도로 광량 1J 이상의 UV광이 조사되면, 저점착성을 나타낸다. In addition, the pressure-sensitive adhesive sheet exhibits low adhesiveness when irradiated with UV light of 1J or more in an irradiance of 100 mW or more at a UV wavelength of 400 to 450 nm for re-release.
상기 UV광은 조사 방식이 특별히 제한되지 않으나, 예를 들면, 고압 수은 램프, 무전극 램프 또는 크세논 램프(xenon lamp) 등을 이용할 수 있다.The irradiation method of the UV light is not particularly limited, but, for example, a high-pressure mercury lamp, an electrodeless lamp, or a xenon lamp may be used.
따라서, 본발명에 따른 점착제 조성물은 열 경화시에 우수한 고점착성을 나타내고, 특정 조도 이상의 UV처리에 의해 저점착성을 나타내는 가변 점착 특성으로 인해 재박리가 용이하여 우수한 리워크성 효과를 제공할 수 있을 뿐만 아니라, UV 차단 특성을 가짐으로써, 자외선과 같은 일상생활 또는 가혹조건에도 우수한 내구성을 나타낼 수 있는 효과를 제공할 수 있다. Therefore, the pressure-sensitive adhesive composition according to the present invention exhibits excellent high-adhesiveness upon heat curing, and can provide excellent rework properties due to easy re-peelability due to the variable adhesive property showing low-adhesion by UV treatment above a specific illuminance. In addition, by having a UV blocking property, it is possible to provide an effect capable of showing excellent durability even in daily life or harsh conditions such as ultraviolet rays.
하드코팅층Hard coating layer
본 발명에 따른 광학투명점착시트는 하드코팅층을 포함할 수 있으며, 상기 하드코팅층은 하드코팅 조성물의 경화물을 포함할 수 있다. 본 발명의 하드코팅층에 있어서, 하드코팅조성물의 경화물을 포함한다는 것은 하드코팅층이 하드코팅 조성물로 제조된 것을 의미할 수 있다.The optically transparent adhesive sheet according to the present invention may include a hard coating layer, and the hard coating layer may include a cured product of a hard coating composition. In the hard coating layer of the present invention, including the cured product of the hard coating composition may mean that the hard coating layer is made of a hard coating composition.
상기 하드코팅 조성물은 투광성 수지(A), 광개시제(B), 용제(C) 및 첨가제(D)로 이루어진 군으로부터 선택되는 하나 이상을 포함하는 것일 수 있다. The hard coating composition may include at least one selected from the group consisting of a translucent resin (A), a photoinitiator (B), a solvent (C), and an additive (D).
본 발명에 따른 광학점착시트는 플렉서블 디스플레이에 적용 가능하며, 이에 따라 상기 하드코팅층은 연신률을 조절 설계를 통해 연필 경도, 내찰상성, 연신률 및 내굴곡성이 우수한 특성을 갖는 것이 바람직하다. The optical adhesive sheet according to the present invention can be applied to a flexible display, and accordingly, the hard coating layer preferably has excellent characteristics of pencil hardness, scratch resistance, elongation and bending resistance through a design to control elongation.
투광성 수지(A)Translucent resin (A)
본 발명의 일 실시형태에 따르면, 상기 투광성 수지(A)는 광경화형 수지를 의미하는 것일 수 있으며, 상기 광경화형 수지는 광경화형 (메타)아크릴레이트 올리고머 내지 모노머를 포함할 수 있다. According to an embodiment of the present invention, the translucent resin (A) may mean a photocurable resin, and the photocurable resin may include a photocurable (meth)acrylate oligomer or monomer.
상기 광경화형 (메타)아크릴레이트 올리고머는 에폭시 (메타)아크릴레이트, 우레탄 (메타)아크릴레이트등을 통상적으로 사용하며 우레탄 (메타)아크릴레이트가 보다 바람직하다. 우레탄 (메타)아크릴레이트는 분자내에 히드록시기를 갖는 다관능 (메타)아크릴레이트와 이소시아네이트기를 갖는 화합물을 촉매 존재 하에서 제조할 수 있다. 상기 분자내에 히드록시기를 갖는 (메타)아크릴레이트의 구체적인 예로는 2-히드록시에틸(메타)아크릴레이트, 2-히드록시이소프로필(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 카프로락톤 개환 히드록시아크릴레이트, 펜타에리스리톨트리/테트라(메타)아크릴레이트 혼합물 및 디펜타에리스리톨펜타/헥사(메타)아크릴레이트 혼합물로 이루어진 군으로부터 선택되는 1종 이상 선택될 수 있다. 또한 상기 이소시아네이트기를 갖는 화합물의 구체적인 예로는, 1,4-디이소시아나토부탄, 1,6-디이소시아나토헥산, 1,8-디이소시아나토옥탄, 1,12-디이소시아나토도데칸, 1,5-디이소시아나토-2-메틸펜탄, 트리메틸-1,6-디이소시아나토헥산, 1,3-비스(이소시아나토메틸)시클로헥산, 트랜스-1,4-시클로헥센디이소시아네이트, 4,4'-메틸렌비스(시클로헥실이소시아네이트), 이소포론디이소시아네이트, 톨루엔-2,4-디이소시아네이트, 톨루엔-2,6-디이소시아네이트, 자일렌-1,4-디이소시아네이트, 테트라메틸자일렌-1,3-디이소시아네이트, 1-클로로메틸-2,4-디이소시아네이트, 4,4'-메틸렌비스(2,6-디메틸페닐이소시아네이트), 4,4'-옥시비스(페닐이소시아네이트), 헥사메틸렌디이소시아네이트로부터 유도되는 3관능 이소시아네이트, 및 트리메탄프로판올어덕트톨루엔디이소시아네이트로 이루어진 군으로부터 1종 이상 선택될 수 있다.The photo-curable (meth) acrylate oligomer is usually an epoxy (meth) acrylate, urethane (meth) acrylate, and the like, and urethane (meth) acrylate is more preferable. Urethane (meth)acrylate can be prepared in the presence of a catalyst polyfunctional (meth)acrylate having a hydroxy group in the molecule and a compound having an isocyanate group. Specific examples of the (meth)acrylate having a hydroxy group in the molecule include 2-hydroxyethyl (meth)acrylate, 2-hydroxyisopropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, capro One or more selected from the group consisting of lactone ring-opening hydroxyacrylate, pentaerythritol tri/tetra (meth) acrylate mixture, and dipentaerythritol penta/hexa (meth) acrylate mixture may be selected. In addition, specific examples of the compound having an isocyanate group include 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,8-diisocyanatooctane, 1,12-diisocyanatododecane, 1, 5-diisocyanato-2-methylpentane, trimethyl-1,6-diisocyanatohexane, 1,3-bis(isocyanatomethyl)cyclohexane, trans-1,4-cyclohexenediisocyanate, 4,4 '-Methylenebis (cyclohexylisocyanate), isophorone diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylene-1,4-diisocyanate, tetramethylxylene-1, 3-diisocyanate, 1-chloromethyl-2,4-diisocyanate, 4,4'-methylenebis (2,6-dimethylphenyl isocyanate), 4,4'-oxybis (phenyl isocyanate), hexamethylene diisocyanate Trifunctional isocyanate derived from, and trimethane propanol adduct toluene diisocyanate may be selected from the group consisting of one or more.
상기 모노머는 통상적으로 사용하는 것으로 광경화형 관능기로 (메타)아크릴로일기, 비닐기, 스티릴기, 알릴기 등의 불포화 기를 분자내 갖는 것으로, 그 중에서도 (메타)아크릴로일기가 보다 바람직하다. The monomer is usually used and has an unsaturated group such as a (meth)acryloyl group, a vinyl group, a styryl group, and an allyl group as a photocurable functional group, and among them, a (meth)acryloyl group is more preferable.
상기 (메타)아크릴로일기를 갖는 모노머는 구체적인 예로 네오펜틸글리콜아크릴레이트, 1,6-헥산디올(메타)아크릴레이트, 프로필렌글리콜디(메타)아크릴레이트, 트리에틸렌글리콜디(메타)아크릴레이트, 디프로필렌글리콜디(메타)아크릴레이트, 폴리에틸렌글리콜디(메타)아크릴레이트, 폴리프로필렌글리콜디(메타)아크릴레이트, 트리메틸올프로판트리(메타)아크릴레이트, 트리메틸올에탄트리(메타)아크릴레이트, 1,2,4-시클로헥산테트라(메타)아크릴레이트, 펜타글리세롤트리(메타)아크릴레이트, 펜타에리스리톨테트라(메타)아크릴레이트, 펜타에리스리톨트리(메타)아크릴레이트, 에톡실레이티드 펜타에리스리톨 트리아크릴레이트, 디펜타에리스리톨트리(메타)아크릴레이트, 디펜타에리스리톨펜타(메타)아크릴레이트, 디펜타에리스리톨테트라(메타)아크릴레이트, 디펜타에리스리톨헥사(메타)아크릴레이트, 에톡실레이티드 디펜타에리스리톨 헥사아크릴레이트, 트리펜타에리스리톨트리(메타)아크릴레이트, 트리펜타에리스리톨헥사트리(메타)아크릴레이트, 비스(2-하이드록시에틸)이소시아누레이트디(메타)아크릴레이트, 하이드록시에틸(메타)아크릴레이트, 하이드록시프로필(메타)아크릴레이트, 하이드록시부틸(메타)아크릴레이트, 이소옥틸(메타)아크릴레이트, 이소-덱실(메타)아크릴레이트, 스테아릴(메타)아크릴레이트, 테트라하이드로퍼푸릴(메타)아크릴레이트, 페녹시에틸(메타)아크릴레이트,이소보네올(메타)아크릴레이트로 이루어진 군으로부터 1종 이상 선택될 수 있다.The monomer having the (meth)acryloyl group is specific examples of neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, 1 ,2,4-cyclohexanetetra(meth)acrylate, pentaglycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol triacrylate , Dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethoxylated dipentaerythritol hexaacrylic Rate, tripentaerythritol tri(meth)acrylate, tripentaerythritol hexatri(meth)acrylate, bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, hydroxyethyl(meth)acrylate , Hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isooctyl (meth) acrylate, iso-decyl (meth) acrylate, stearyl (meth) acrylate, tetrahydroperfuryl (meth) ) It may be selected from the group consisting of acrylate, phenoxyethyl (meth) acrylate, isoborneol (meth) acrylate.
전술한 광경화형 (메타)아크릴레이트 올리고머 내지 모노머는 각각 단독으로 또는 둘 이상을 조합하여 사용될 수 있다.The above-described photocurable (meth)acrylate oligomer or monomer may be used alone or in combination of two or more.
광개시제(B)Photoinitiator (B)
본 발명에서 광개시제(B)는 특별히 한정하지 않으며, 당 업계에서 사용되는 것이라면 제한 없이 사용될 수 있다. 구체적으로, 하이드록시케톤류, 아미노케톤류, 수소탈환형 광개시제 및 이들의 조합으로 이루어진 군으로부터 선택되는 하나 이상을 사용할 수 있으며, 보다 구체적으로는, 2-메틸-1-[4-(메틸티오)페닐]2-모폴린프로판온-1, 디페닐케톤, 벤질디메틸케탈, 2-하이드록시-2-메틸-1-페닐-1-온, 4-하이드록시시클로페닐케톤, 2,2-디메톡시-2-페닐-아세토페논, 안트라퀴논, 플루오렌, 트리페닐아민, 카바졸, 3-메틸아세토페논, 4-크놀로아세토페논, 4,4-디메톡시아세토페논, 4,4-디아미노벤조페논, 1-하이드록시시클로헥실페닐케톤, 벤조페논, 디페닐(2,4,6-트리메틸벤조일)포스핀옥사이드 및 이들의 조합으로로 이루어진 군으로부터 선택된 1종 이상을 사용할 수 있으나, 이에 한정되는 것은 아니다.In the present invention, the photoinitiator (B) is not particularly limited, and any one used in the art may be used without limitation. Specifically, one or more selected from the group consisting of hydroxy ketones, amino ketones, hydrogen decyclic photoinitiators, and combinations thereof may be used, and more specifically, 2-methyl-1-[4-(methylthio)phenyl ]2-morpholine propanone-1, diphenyl ketone, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-1-one, 4-hydroxycyclophenyl ketone, 2,2-dimethoxy- 2-phenyl-acetophenone, anthraquinone, fluorene, triphenylamine, carbazole, 3-methylacetophenone, 4-chronoloacetophenone, 4,4-dimethoxyacetophenone, 4,4-diaminobenzophenone , 1-hydroxycyclohexylphenyl ketone, benzophenone, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, and combinations thereof, one or more selected from the group consisting of, but are limited thereto no.
상기 광개시제(B)의 함량은 본 발명에서 특별히 한정하지는 않으나, 이를 포함하는 하드코팅 조성물 전체 100중량부에 대하여 0.1 내지 10중량부, 구체적으로 1 내지 5중량부로 포함될 수 있다. 상기 광개시제(B)의 함량이 상기 범위 내로 포함되는 경우 하드코팅 조성물의 경화 속도를 단축시켜도 미경화의 발생 확률이 감소하여 이로 인한 기계적 물성의 저하를 방지할 수 있으며, 크랙의 발생을 억제할 수 있는 이점이 있다.The content of the photoinitiator (B) is not particularly limited in the present invention, but may be included in an amount of 0.1 to 10 parts by weight, specifically 1 to 5 parts by weight, based on 100 parts by weight of the total hard coating composition including the same. When the content of the photoinitiator (B) is included within the above range, the probability of occurrence of uncured decreases even if the curing speed of the hard coating composition is shortened, thereby preventing a decrease in mechanical properties and suppressing the occurrence of cracks. There is an advantage.
용제(C)Solvent (C)
본 발명에서 용제(C)는 특별히 한정하지 않으며, 당 업계에서 사용되는 용제라면 특별한 제한 없이 사용할 수 있다. 구체적으로, 알코올계(메탄올, 에탄올, 이소프로판올, 부탄올, 메틸셀루소브, 에틸솔루소브 등), 케톤계(메틸에틸케톤, 메틸부틸케톤, 메틸이소부틸케톤, 디에틸케톤, 디프로필케톤, 시클로헥사논 등), 헥산계(헥산, 헵탄, 옥탄 등), 벤젠계(벤젠, 톨루엔, 자일렌 등) 등을 들 수 있으나, 이에 한정되는 것은 아니다. In the present invention, the solvent (C) is not particularly limited, and any solvent used in the art may be used without particular limitation. Specifically, alcohol-based (methanol, ethanol, isopropanol, butanol, methylcellulose, ethylsolusob, etc.), ketone-based (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, cyclo Hexanone, etc.), hexane-based (hexane, heptane, octane, etc.), benzene-based (benzene, toluene, xylene, etc.), and the like, but are not limited thereto.
상기 용제(C)의 함량은 본 발명에서는 특별히 한정하지 않으나, 이를 포함하는 하드코팅층 형성용 조성물 전체 100중량부에 대하여 10 내지 95중량부 포함될 수 있다. 상기 용제(C)가 상기 범위 내로 포함될 경우, 점도를 적절히 조절하여 작업성을 향상시킬 수 있으며, 경화 시간을 단축시킬 수 있는 이점이 있다. The content of the solvent (C) is not particularly limited in the present invention, but may be included in an amount of 10 to 95 parts by weight based on 100 parts by weight of the total composition for forming a hard coating layer including the same. When the solvent (C) is included within the above range, the viscosity can be appropriately adjusted to improve workability, and there is an advantage of shortening the curing time.
첨가제(D)Additive (D)
상기 첨가제(D)는 본 발명에서 특별히 한정하는 것은 아니나, 예를 들면 무기산화물미립자, 레벨링제 등을 포함할 수 있다. The additive (D) is not particularly limited in the present invention, but may include, for example, inorganic oxide fine particles, leveling agents, and the like.
상기 무기산화물미립자는 도막 내에 균일하게 형성되어 내마모성, 내스크래치성, 연필 경도 등의 기계적 물성을 향상시킬 수 있는 이점이 있다. The inorganic oxide fine particles are uniformly formed in the coating film, thereby improving mechanical properties such as abrasion resistance, scratch resistance, and pencil hardness.
상기 무기산화물미립자는 입경이 100nm이하인 것을 사용할 수 있으며, 이 경우 조성물 내에 응집이 발생하는 현상을 방지하여 균일한 도막의 형성을 가능하게 하여 기계적 물성이 저하되는 것을 방지할 수 있다. The inorganic oxide fine particles may have a particle diameter of 100 nm or less, and in this case, it is possible to prevent a phenomenon in which aggregation occurs in the composition to form a uniform coating film, thereby preventing deterioration of mechanical properties.
상기 무기산화물미립자는 예를 들면, 산화규소(실리카), 산화티탄, 산화알루미늄, 산화아연, 산화주석, 산화지르코늄 등을 들 수 있으나 이에 한정되는 것은 아니다. The inorganic oxide fine particles may include, for example, silicon oxide (silica), titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, etc., but are not limited thereto.
상기 레벨링제는 실리콘계 레벨링제, 불소계 레벨링제 및 아크릴계 레벨링제 등을 들 수 있으나, 이에 한정되는 것은 아니다. 이와 같이 레벨링제를 함께 포함하는 경우 도막 형성시 평활성 및 코팅성의 부여가 가능한 이점이 있다. The leveling agent may be a silicone-based leveling agent, a fluorine-based leveling agent, and an acrylic leveling agent, but is not limited thereto. In the case of including a leveling agent as described above, there is an advantage that smoothness and coating properties can be imparted when forming a coating film.
본 발명의 광학투명점착시트를 도포하는 방법은 특별히 제한되지 않으며, 광학투명점착시트를 도포 한 후, 이를 열경화를 통해 경화시킨다. 본 출원에서, 예를 들어, 자외선 조사 방식을 적용할 경우에, 상기 자외선 조사는, 고압 수은 램프, 무전극 램프 또는 크세논 램프(xenon lamp) 등의 수단을 사용하여 수행할 수 있다. The method of applying the optically transparent adhesive sheet of the present invention is not particularly limited, and after applying the optically transparent adhesive sheet, it is cured through thermal curing. In the present application, for example, when the ultraviolet irradiation method is applied, the ultraviolet irradiation may be performed using a means such as a high-pressure mercury lamp, an electrodeless lamp, or a xenon lamp.
또한, 광조사 공정의 전 또는 후에 조성물 내의 가교제의 작용기와 중합체의 열경화성 관능기의 반응을 유도하는 적절한 숙성 공정을 진행할 수도 있고, 그 과정에서의 조건은 적절한 가교 반응이 일어날 수 있다면, 특별히 제한되지 않는다. In addition, before or after the light irradiation process, an appropriate aging process for inducing a reaction between the functional group of the crosslinking agent in the composition and the thermosetting functional group of the polymer may be performed, and the conditions in the process are not particularly limited as long as an appropriate crosslinking reaction can occur. .
본 발명의 광학투명점착시트는 예를 들면, 편광필름, 위상차 필름, 눈부심 방지 필름, 광시야각 보상 필름 또는 휘도 향상 필름 등의 광학 필름을 서로 적층하거나, 상기 광학 필름 또는 그 적층체를 디스플레이 패널 등과 같은 피착체에 부착하기 위한 용도로 사용될 수 있다. In the optically transparent adhesive sheet of the present invention, for example, optical films such as a polarizing film, a retardation film, an anti-glare film, a wide viewing angle compensation film, or a luminance enhancing film are stacked on each other, or the optical film or a stack thereof is It can be used for attachment to the same adherend.
특히, 본 발명의 광학투명점착시트는 플렉서블 디스플레이 장치에 바람직하게 사용될 수 있다. 예를 들면, 상기 광학투명점착시트는 플렉서블 디스플레이 장치의 최외곽 보호용 광학필름으로 사용될 수 있다.In particular, the optically transparent adhesive sheet of the present invention can be preferably used in a flexible display device. For example, the optically transparent adhesive sheet may be used as an outermost protective optical film of a flexible display device.
또한, 광학투명점착시트의 제조방법은 이 분야에 공지된 방법이 제한 없이 사용될 수 있다. In addition, the method of manufacturing the optically transparent adhesive sheet may be used without limitation any method known in the art.
본 발명은 상기 광학투명점착 시트를 포함하는 평판표시장치를 제공할 수 있다. 상기에서 상기에서 평판표시장치는 플렉서블 디스플레이 장치인 것이 더욱 바람직하다. The present invention can provide a flat panel display device including the optically transparent adhesive sheet. In the above, it is more preferable that the flat panel display device is a flexible display device.
이하, 본 발명을 실시예 및 비교예를 이용하여 더욱 상세하게 설명한다. 그러나 하기 실시예는 본 발명을 예시하기 위한 것으로서 본 발명은 하기 실시예에 의해 한정되지 않고 다양하게 수정 및 변경될 수 있다.Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples. However, the following examples are intended to illustrate the present invention, and the present invention is not limited by the following examples and may be variously modified and changed.
실시예 및 비교예: 점착제 조성물 및 광학 투명 점착시트의 제조Examples and Comparative Examples: Preparation of an adhesive composition and an optically transparent adhesive sheet
(1) 점착제 조성물의 제조(1) Preparation of pressure-sensitive adhesive composition
하기 표 1의 조성으로 실시예 1 내지 7 및 비교예 1 및 2의 점착제 조성물을 제조하였다(단위: 중량부).To prepare the pressure-sensitive adhesive compositions of Examples 1 to 7 and Comparative Examples 1 and 2 with the composition of Table 1 (unit: parts by weight).
IBOA: 이소보닐아크릴레이트
HEA: 2-하이드록시에틸아크릴레이트
AA: 아크릴산
Coronate-L: 닛폰우레탄品
TPO: Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide
Songsorb CS81: 송원산업品
Songsorb 3260: 송원산업品
DPHA: MIRAMER M500, 미원케미컬
PETA: MIRAMER M420, 미원케미컬EHA 2-ethylhexyl acrylate
IBOA: isobornyl acrylate
HEA: 2-hydroxyethylacrylate
AA: acrylic acid
Coronate-L: Nippon Urethane Product
TPO: Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide
Songsorb CS81: Songwon Industrial Products
Songsorb 3260: Songwon Industrial Products
DPHA: MIRAMER M500, Miwon Chemical
PETA: MIRAMER M420, Miwon Chemical
(2) 광학투명점착시트의 제조(2) Preparation of optically transparent adhesive sheet
상기에서 제조된 점착제 조성물을 실리콘 이형제가 코팅된 이형필름 상에 50㎛의 두께로 도포하고 100℃에서 1분 동안 건조시켜 점착제층을 형성하고 그 위에 이형필름을 접합하여 점착 시트를 완성하였다.The pressure-sensitive adhesive composition prepared above was applied to a thickness of 50 μm on a release film coated with a silicone release agent and dried at 100° C. for 1 minute to form a pressure-sensitive adhesive layer, and the release film was bonded thereon to complete the pressure-sensitive adhesive sheet.
실험예Experimental example
실시예 1 내지 7 및 비교예 1 내지 2의 광학투명점착시트의 물성을 하기의 방법으로 측정하고, 그 결과를 하기 표 2에 나타내었다.The physical properties of the optically transparent adhesive sheets of Examples 1 to 7 and Comparative Examples 1 to 2 were measured by the following method, and the results are shown in Table 2 below.
(1) 점착력(1) adhesion
제조된 점착시트 한 면의 이형필름을 박리하고 38um의 PET필름과 점착제면에 코로나처리하고 접합한 후 폭이 25 mm이고, 길이가 200mm가 되도록 재단하여 시편을 제조하였다. 이어서, PET/점착제층 구성에 부착된 이형필름을 박리하고, JIS Z 0237의 규정에 따라 2 kg의 롤러를 사용하여 점착시트를 무알칼리 강화 글라스에 부착 후, 오토클레이브(50℃, 5 기압)에서 약 20분 동안 압착 처리하였다.After peeling off the release film on one side of the prepared adhesive sheet, corona treatment and bonding to the 38um PET film and the adhesive side, the specimen was prepared by cutting so that the width was 25 mm and the length was 200 mm. Subsequently, the release film adhered to the PET/adhesive layer structure was peeled off, and the adhesive sheet was attached to the alkali-free reinforced glass using a 2 kg roller according to JIS Z 0237, and then autoclaved (50° C., 5 atm). It was pressed for about 20 minutes at.
이 후, 실시예 1 내지 7 및 비교예 1 내지 2의 광학투명점착시트를 항온 항습 조건(23℃, 50% 상대습도(RH))에서 1시간 동안 보관한 다음, 오토 그라프(AG-1S, SHIMADZU사)를 이용하여, 상기 점착시트를 무알칼리 강화 글라스로부터 0.3m/min의 박리 속도 및 180도의 박리 각도로 100mm박리하면서 통상 점착력을 측정하였다.Thereafter, the optically transparent adhesive sheets of Examples 1 to 7 and Comparative Examples 1 to 2 were stored for 1 hour under constant temperature and humidity conditions (23° C., 50% relative humidity (RH)), and then autograph (AG-1S, SHIMADZU) was used to measure the adhesive strength while peeling the adhesive sheet from the alkali-free reinforced glass by 100 mm at a peel rate of 0.3 m/min and a peel angle of 180 degrees.
한편 재박리를 위해 UV조사 후의 점착력은 상기와 같은 샘플 제작 후 400nm 내지 450nm 파장의 자외선을 조도 5mW로 광량 1J 조사한 샘플과 조도 100mW로 광량 1J조사한 샘플의 점착력을 측정하였다. 그 결과를 하기 표 2에 나타내었다.On the other hand, the adhesive strength after UV irradiation for re-peelation was measured by measuring the adhesive strength of a sample irradiated with an amount of light of 1J at an illuminance of 5mW and a sample irradiated with an amount of light of 1J at an illuminance of 100mW after preparing the sample as described above. The results are shown in Table 2 below.
(2) 리워크성 (2) Rework
점착 시트의 한 면의 이형필름을 박리하고 점착제면에 코로나 처리를 한 후 50㎛의 PET 필름과 접합하였다. 상기 점착 시트를 90㎜×170㎜ 크기로 절단하고, 다른 한 면의 이형필름을 박리한 후 유리 기판(110㎜Х190㎜Х0.7㎜)에 부착하여 시편을 제작하였다. 이때, 가해진 압력은 5㎏/㎠이며 기포나 이물이 생기지 않도록 크린룸 작업을 하였다. 상기 시편을 80℃에서 10 시간 동안, 60℃, 90% RH 조건에서 12 시간 동안 에이징하였다. 그 다음, 400nm 내지 450nm 파장의 자외선을 조도 5mW로 광량1J 조사한 샘플과 조도100mW로 광량1J 조사 후 점착시트를 유리에서 박리시켜 하기의 평가기준에 따라 리워크성을 측정하였다. 그 결과를 하기 표 2에 나타내었다.The release film on one side of the pressure-sensitive adhesive sheet was peeled off, corona treatment was performed on the pressure-sensitive adhesive side, and then bonded with a 50 μm PET film. The adhesive sheet was cut into a size of 90 mm×170 mm, the release film on the other side was peeled off, and then attached to a glass substrate (110 mm×190 mm×0.7 mm) to prepare a specimen. At this time, the applied pressure was 5 kg/
○: 재박리시 점착제가 남김없이 떨어지는 경우○: When the adhesive falls off completely when peeling again
X : 재박리시 점착제가 떨어지지 않고 남음X: The adhesive does not fall off when peeling again.
점착력After UV irradiation
adhesiveness
리워크 성 After UV irradiation
Rework Castle
표 2를 참조하면, 본 발명에 따른 실시예 1 내지 7의 광학투명점착시트는, 특정의 UV광 처리를 하지 않은 경화된 상태에서는 상대적으로 높은 박리력을 나타냄에 따라 본 발명에 따른 광학투명점착시트가 고점착력을 나타낼 수 있음을 확인할 수 있었다. 또한, 일상 생활의 통상적인 자외선 조건(5mW 조도)에서는 크게 영향을 받지 않고 고점착력을 유지할 수 있음을 확인할 수 있었다.Referring to Table 2, the optically transparent adhesive sheet of Examples 1 to 7 according to the present invention exhibits a relatively high peeling force in the cured state without specific UV light treatment, so that the optically transparent adhesive according to the present invention It was confirmed that the sheet can exhibit high adhesion. In addition, it was confirmed that high adhesive strength can be maintained without being significantly affected under normal ultraviolet conditions (5mW illuminance) in daily life.
또한, 실시예 1 내지 7의 광학투명점착시트에 대해, 400 내지 450nm 파장에서, 100mW 조도로 광량 1J의 자외선(UV)을 조사하면 상대적으로 낮은 박리력을 나타내는 것으로부터 저점착력을 나타냄을 확인할 수 있으며, 이러한 저참착력에 의해 재박리시 기판으로부터 점착제가 남김없이 떨어져 우수한 리워크성을 나타내는 것을 확인할 수 있었다.In addition, with respect to the optically transparent adhesive sheets of Examples 1 to 7, it can be confirmed that when irradiating ultraviolet (UV) of 1J of light at a wavelength of 400 to 450 nm and with a 100 mW illuminance, it exhibits a relatively low peeling force and thus a low adhesive force. In addition, it was confirmed that the pressure-sensitive adhesive completely fell from the substrate upon re-peeling due to this low adhesion force and exhibited excellent rework property.
반면, 비교예 1 및 2의 광학투명점착시트는, 400 내지 450nm 파장에서 100mW 조도로 광량 1J의 자외선(UV)을 조사하여도, UV 조사전 및 일상 생활의 통상적인 자외선 조건에서와 같이 여전히 고점착력을 나타내어, 리워크성 역시 우수하지 못한 것을 확인할 수 있었다.On the other hand, the optically transparent adhesive sheet of Comparative Examples 1 and 2, even when irradiated with ultraviolet rays (UV) of 1J light intensity at 100 mW at a wavelength of 400 to 450 nm, is still high as before UV irradiation and in normal ultraviolet conditions of daily life. It was confirmed that the adhesive strength was exhibited, and the rework property was also not excellent.
상기 결과로부터, 본 발명의 광학투명점착시트는 경화시에 우수한 고점착성을 나타내고, 특정 조도 이상의 UV광 처리에 의해 저점착성을 나타내는 가변 점착 특성으로 인해 재박리가 용이하여 우수한 리워크성 효과를 제공할 수 있음을 알 수 있다. 또한, 본 발명의 광학투명점착시트는 UV 차단 특성을 가져 자외선과 같은 일상생활 또는 가혹조건에서도 우수한 내구성을 나타낼 수 있음을 확인할 수 있다.From the above results, the optically transparent adhesive sheet of the present invention exhibits excellent high adhesiveness upon curing, and is easy to re-peel due to the variable adhesive property showing low adhesiveness by UV light treatment of a specific illuminance or higher, providing excellent rework properties. You can see that you can. In addition, it can be seen that the optically transparent adhesive sheet of the present invention has UV blocking properties and can exhibit excellent durability in daily life such as ultraviolet rays or even under severe conditions.
1: 하드코팅층
2: 기재 필름
3: 점착 필름1: hard coating layer
2: base film
3: adhesive film
Claims (14)
상기 기재 필름의 적어도 일면에 적층된 점착 필름을 포함하고,
상기 점착 필름은 경화시에 1.0 내지 30N 의 박리력을 나타내고, 400 내지 450nm의 UV파장에서 100mW이상 조도로 광량 1J이상의 자외선 처리 후 0.01 내지 0.5N의 박리력을 나타내는 것인, 광학투명점착시트.Base film; And
Including an adhesive film laminated on at least one side of the base film,
The adhesive film exhibits a peel force of 1.0 to 30N upon curing, and exhibits a peeling force of 0.01 to 0.5N after UV treatment with an amount of light of 1J or more with an illuminance of 100mW or more at a UV wavelength of 400 to 450nm.
이소시아네이트계 가교제;
광중합 개시제;
상기 광중합 개시제와의 최대 흡수파장 차이가 50nm 이상인 자외선 차단제; 및
에폭시 (메타)아크릴레이트, 우레탄 (메타)아크릴레이트 및 폴리에스테르(메타)아크릴레이트로 구성된 군으로부터 선택되는 1종 이상을 포함하는 다관능 아크릴 모노머를 포함하는 조성물로 제조되는, 광학투명점착시트. The method according to claim 1, wherein the pressure-sensitive adhesive film is an acrylic copolymer containing a repeating unit derived from an acrylic monomer containing a C1-C12 linear or branched alkyl group;
An isocyanate crosslinking agent;
Photopolymerization initiator;
A UV blocking agent having a maximum absorption wavelength difference of 50 nm or more from the photopolymerization initiator; And
Epoxy (meth) acrylate, urethane (meth) acrylate and polyester (meth) acrylate prepared from a composition comprising a polyfunctional acrylic monomer comprising at least one selected from the group consisting of acrylate, optically transparent adhesive sheet.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20220081418A (en) * | 2020-12-08 | 2022-06-16 | (주)트러스 | Repeelable adhesive including photo curable adhesive and heat foaming agent and repeelable adhesive tape including the same |
| CN115820170A (en) * | 2022-12-28 | 2023-03-21 | 苏州凡赛特材料科技有限公司 | Optical-grade transparent glue capable of blocking ultraviolet light and glue film thereof |
| CN116376478A (en) * | 2023-03-24 | 2023-07-04 | 太仓斯迪克新材料科技有限公司 | Ultraviolet cured OCA and preparation method thereof |
| WO2023158026A1 (en) * | 2022-02-17 | 2023-08-24 | 엘지전자 주식회사 | Transparent antenna |
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| KR101600686B1 (en) | 2014-05-21 | 2016-03-08 | 주식회사 대현에스티 | Manufacturing method of heat-peelable adhesive sheet or adhesive tape using uv curing system |
| KR20160114399A (en) | 2015-03-24 | 2016-10-05 | 동우 화인켐 주식회사 | Heat-Sensitive Adhesive Composition and Heat-Sensitive Adhesive Tape Comprising the Same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101600686B1 (en) | 2014-05-21 | 2016-03-08 | 주식회사 대현에스티 | Manufacturing method of heat-peelable adhesive sheet or adhesive tape using uv curing system |
| KR20160114399A (en) | 2015-03-24 | 2016-10-05 | 동우 화인켐 주식회사 | Heat-Sensitive Adhesive Composition and Heat-Sensitive Adhesive Tape Comprising the Same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20220081418A (en) * | 2020-12-08 | 2022-06-16 | (주)트러스 | Repeelable adhesive including photo curable adhesive and heat foaming agent and repeelable adhesive tape including the same |
| WO2023158026A1 (en) * | 2022-02-17 | 2023-08-24 | 엘지전자 주식회사 | Transparent antenna |
| CN115820170A (en) * | 2022-12-28 | 2023-03-21 | 苏州凡赛特材料科技有限公司 | Optical-grade transparent glue capable of blocking ultraviolet light and glue film thereof |
| CN116376478A (en) * | 2023-03-24 | 2023-07-04 | 太仓斯迪克新材料科技有限公司 | Ultraviolet cured OCA and preparation method thereof |
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