KR102571690B1 - Adhesive film composition and adhesive film for organic electronic device encapsulation, organic electronic device encapsulation material and encapsulation method using the same - Google Patents
Adhesive film composition and adhesive film for organic electronic device encapsulation, organic electronic device encapsulation material and encapsulation method using the same Download PDFInfo
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- KR102571690B1 KR102571690B1 KR1020220062365A KR20220062365A KR102571690B1 KR 102571690 B1 KR102571690 B1 KR 102571690B1 KR 1020220062365 A KR1020220062365 A KR 1020220062365A KR 20220062365 A KR20220062365 A KR 20220062365A KR 102571690 B1 KR102571690 B1 KR 102571690B1
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- 239000000203 mixture Substances 0.000 title claims abstract description 132
- 239000002313 adhesive film Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000005538 encapsulation Methods 0.000 title abstract description 17
- 239000000463 material Substances 0.000 title description 5
- 239000000853 adhesive Substances 0.000 claims abstract description 128
- 230000001070 adhesive effect Effects 0.000 claims abstract description 128
- 239000000178 monomer Substances 0.000 claims abstract description 73
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229920002367 Polyisobutene Polymers 0.000 claims abstract description 52
- 229920005549 butyl rubber Polymers 0.000 claims abstract description 52
- 239000011230 binding agent Substances 0.000 claims abstract description 43
- 239000008393 encapsulating agent Substances 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000010410 layer Substances 0.000 claims description 134
- 239000012790 adhesive layer Substances 0.000 claims description 55
- 238000001179 sorption measurement Methods 0.000 claims description 42
- 230000004888 barrier function Effects 0.000 claims description 30
- 238000010521 absorption reaction Methods 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 238000011156 evaluation Methods 0.000 claims description 21
- 239000004568 cement Substances 0.000 claims description 2
- 239000003463 adsorbent Substances 0.000 claims 2
- 238000004299 exfoliation Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 92
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- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 24
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical class C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 22
- 230000001588 bifunctional effect Effects 0.000 description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 19
- 125000004386 diacrylate group Chemical group 0.000 description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 17
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- 239000011574 phosphorus Substances 0.000 description 17
- 230000035515 penetration Effects 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000002356 single layer Substances 0.000 description 15
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- 239000002250 absorbent Substances 0.000 description 13
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- 230000008859 change Effects 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 230000007774 longterm Effects 0.000 description 11
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- 239000001301 oxygen Substances 0.000 description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 9
- 239000000292 calcium oxide Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
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- 229920002943 EPDM rubber Polymers 0.000 description 7
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- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 6
- -1 Phenoxy benzyl Chemical group 0.000 description 6
- 238000003848 UV Light-Curing Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
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- 230000000704 physical effect Effects 0.000 description 6
- 230000035699 permeability Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
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- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 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 4
- 239000007789 gas Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
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- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
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- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 238000009659 non-destructive testing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 2
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000010074 rubber mixing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 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 description 1
- LAIJAUHBAWLPCO-UHFFFAOYSA-N (4-tert-butylcyclohexyl) prop-2-enoate Chemical compound CC(C)(C)C1CCC(OC(=O)C=C)CC1 LAIJAUHBAWLPCO-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 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
- YMZIFDLWYUSZCC-UHFFFAOYSA-N 2,6-dibromo-4-nitroaniline Chemical compound NC1=C(Br)C=C([N+]([O-])=O)C=C1Br YMZIFDLWYUSZCC-UHFFFAOYSA-N 0.000 description 1
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 1
- BMYFPLOKANOKIT-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C.CC(=C)C(=O)OCCOC(=O)C(C)=C BMYFPLOKANOKIT-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical group C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- MZROTVLXHYSIQB-UHFFFAOYSA-N C(C1CCCO1)C=C(C(=O)O)C.C(C(=C)C)(=O)OCC1CCCO1 Chemical compound C(C1CCCO1)C=C(C(=O)O)C.C(C(=C)C)(=O)OCC1CCCO1 MZROTVLXHYSIQB-UHFFFAOYSA-N 0.000 description 1
- 229910001374 Invar Inorganic materials 0.000 description 1
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 1
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229920001427 mPEG Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- RZFODFPMOHAYIR-UHFFFAOYSA-N oxepan-2-one;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1CCCCCO1 RZFODFPMOHAYIR-UHFFFAOYSA-N 0.000 description 1
- VJMBENQIKAACCI-UHFFFAOYSA-N oxolan-2-ylmethyl prop-2-enoate 2-(oxolan-2-ylmethyl)prop-2-enoic acid Chemical compound C(C1CCCO1)C(C(=O)O)=C.C(C1CCCO1)OC(C=C)=O VJMBENQIKAACCI-UHFFFAOYSA-N 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 229940068886 polyethylene glycol 300 Drugs 0.000 description 1
- 229920005650 polypropylene glycol diacrylate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/08—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms
- C08F255/10—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms on to butene 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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/842—Containers
- H10K50/8426—Peripheral sealing arrangements, e.g. adhesives, sealants
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- H—ELECTRICITY
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- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/846—Passivation; Containers; Encapsulations comprising getter material or desiccants
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
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Abstract
폴리이소부틸렌 및 부틸고무를 9:1 내지 2:8의 중량비로 포함하는 혼합수지 바인더; 연화점이 90℃이상 150℃미만인 점착 부여제; 단관능 아크릴모노머; 다관능 아크릴모노머; 및 광개시제를 포함하고, 상기 바인더 100 중량부에 대하여 상기 점착 부여제가 20 중량부 초과 160 중량부 미만으로 포함되고, 상기 단관능 아크릴모노머가 5 중량부 초과 20 중량부 미만으로 포함되고, 상기 다관능 아크릴모노머가 2.5중량부 초과 15 중량부 미만으로 포함되고, 상기 광개시제가 5 중량부 초과 20 중량부 미만으로 포함되는, 유기전자장치 봉지용 접착제 조성물, 접착 필름, 이를 이용한 유기전자장치 봉지재 및 봉지 방법이 개시된다.A mixed resin binder containing polyisobutylene and butyl rubber in a weight ratio of 9:1 to 2:8; a tackifier with a softening point of 90°C or more and less than 150°C; Monofunctional acrylic monomer; multifunctional acrylic monomers; And a photoinitiator, wherein the tackifier is included in an amount of more than 20 parts by weight and less than 160 parts by weight based on 100 parts by weight of the binder, the monofunctional acrylic monomer is included in an amount of more than 5 parts by weight and less than 20 parts by weight, and the polyfunctional acrylic monomer is included in an amount of more than 5 parts by weight and less than 20 parts by weight An adhesive composition for encapsulation of an organic electronic device, an adhesive film containing more than 2.5 parts by weight and less than 15 parts by weight of an acrylic monomer and less than 20 parts by weight of the photoinitiator, an organic electronic device encapsulant and an encapsulant using the same A method is disclosed.
Description
본 명세서는 유기전자장치 봉지용 접착제 조성물, 접착 필름, 이를 이용한 유기전자장치 봉지재 및 봉지 방법에 관한 것이다. 상세하게는, 낮은 수분침투속도와 낮은 산소투과도 및 우수한 합착성 등을 가지는 유기전자장치 봉지용 접착제 조성물, 접착 필름, 이를 이용한 유기전자장치 봉지재 및 봉지 방법에 관한 것이다.The present specification relates to an adhesive composition for encapsulating an organic electronic device, an adhesive film, an organic electronic device encapsulating material using the same, and a method for encapsulating the organic electronic device. Specifically, it relates to an adhesive composition for encapsulating an organic electronic device having low water permeation rate, low oxygen permeability, and excellent cohesiveness, an adhesive film, and an organic electronic device encapsulant and encapsulation method using the same.
현재 상용화된 OLED는 LCD 등 기존의 디스플레이와 비교해, 자체발광으로 인한 단순한 구조로 패널구성 부품수가 절반 가량 적다는 장점과 함께 자연색에 가까운 색상과 높은 명암비, 소비전력 감소 등 다양한 장점이 있어, LCD에서 OLED로 시장의 니즈가 옮겨가고 있다. Compared to conventional displays such as LCD, OLED, which is currently commercialized, has the advantage of having a simple structure due to self-luminescence and reducing the number of panel component parts by half, as well as various advantages such as colors close to natural colors, high contrast ratio, and reduced power consumption. Market needs are shifting to OLED.
그러나 OLED는 수분, 가스에 취약한 치명적인 문제점이 있어, 이를 극복하기 위한 다양한 봉지 기술이 개발되어 왔다. However, OLED has a fatal problem of being vulnerable to moisture and gas, and various encapsulation technologies have been developed to overcome this problem.
스마트폰과 같은 중소형 OLED에는 박막봉지(TFE, Thin Film Encapsulation)를 수행한다. 박막봉지(TFE)는 무기층과 잉크젯에 의해 형성되는 얇은 필름상의 유기층이 상호 겹쳐진 멀티레이어 구조로서, 무기층이 주로 산소나 수분의 유입을 방지하여 OLED 재료를 보호하는 방법이다. 박막봉지(TFE)용 무기층 형성 방법으로서 플라즈마 CVD(PECVD)나 ALD(Atomic Layer Deposition) 등을 사용한 방법이 있으며, 비교적 낮은 성막 온도에서 고속 성막이 가능하여 생산성이 우수한 PECVD가 무기층 형성에 주로 사용되고 있다. Thin Film Encapsulation (TFE) is performed on small and medium-sized OLEDs such as smartphones. Thin film encapsulation (TFE) is a multi-layer structure in which an inorganic layer and an organic layer on a thin film formed by inkjet overlap each other, and the inorganic layer mainly prevents the inflow of oxygen or moisture to protect the OLED material. As a method of forming an inorganic layer for thin film encapsulation (TFE), there is a method using plasma CVD (PECVD) or ALD (Atomic Layer Deposition). It is being used.
한편 TV 등 대형 디스플레이에는 박막봉지를 위한 금속 박형 배리어층(Barrier Layer)과 OLED 패널을 부착하되 OLED 패널 내에 발생하는 수분과 가스의 제거를 위한 OLED용 봉지(Encapsulation) 접착 필름과 이를 포함하는 봉지재가 현재 채택되고 있는데, 수분이나 산소에 의해 재료 열화를 방지하는 봉지재 및 봉지기술은 OLED 패널 발광특성이나 수명을 크게 좌우하는 중요한 역할을 가진다. On the other hand, a thin metal barrier layer for thin film encapsulation and an OLED panel are attached to a large display such as a TV, but an encapsulation adhesive film for OLED and an encapsulant containing the same are used to remove moisture and gas generated in the OLED panel. Currently being adopted, encapsulants and encapsulation technologies that prevent material deterioration due to moisture or oxygen have an important role in greatly influencing the lifespan or light emitting characteristics of OLED panels.
이러한 흡습제로 주로 금속산화물이나 금속염인 다량의 흡습제 분말이 사용되는데, 본 발명자들의 연구에 의하면, 해당 흡습제 분말로 인하여 접착 필름과 만나는 금속 층 등 기재와의 밀착력 저하가 발생해, 초기에 수분 침투가 빠르게 발생하는 현상을 발견할 수 있으며, 이에 따라 신뢰성에 문제를 일으킬 수 있다. As such a moisture absorbent, a large amount of moisture absorbent powder, which is mainly a metal oxide or metal salt, is used. According to the study of the present inventors, the moisture absorption powder causes a decrease in adhesion to a substrate such as a metal layer that meets the adhesive film, resulting in moisture penetration in the initial stage. A rapidly occurring phenomenon can be discovered, which can cause reliability problems.
또한, 본 발명자들의 연구에 의하면, 종래 유기전자장치 봉지재 필름의 경우 OLED 패널과의 상온에서의 합착성이 저하되는 문제가 발생하고 이에 따라 미합착 부위가 발생하며 장기 신뢰성이 저하되는 문제가 있다. In addition, according to the research of the present inventors, in the case of the conventional organic electronic device encapsulant film, there is a problem that the adhesion at room temperature with the OLED panel is lowered, and accordingly, non-bonded areas are generated and long-term reliability is lowered. .
본 발명의 예시적인 구현예들에서는, 일 측면에서, 수분 흡수층 (이른바 getter 층)의 흡습제 분말로 인하여 해당 수분 흡수층과 만나는 금속 층 등 배리어층과의 밀착력 저하가 발생해 초기 수분 침투가 빠르게 발생하는 현상 및 이에 따른 신뢰성 저하 문제를 방지할 수 있는, 유기전자장치 봉지용 접착제 조성물, 접착 필름, 이를 이용한 유기전자장치 봉지재 및 그 제조 방법을 제공하고자 한다.In exemplary embodiments of the present invention, in one aspect, due to the moisture absorbent powder of the moisture absorbing layer (the so-called getter layer), the adhesion with the barrier layer such as a metal layer meeting the moisture absorbing layer is lowered, resulting in rapid initial moisture penetration. It is intended to provide an adhesive composition for encapsulating an organic electronic device, an adhesive film, an organic electronic device encapsulant using the same, and a method for manufacturing the same, which can prevent development and consequent reliability degradation.
본 발명의 예시적인 구현예들에서는, 다른 일 측면에서, OLED 패널을 봉지한 후에 가속시험 평가 시, 초기의 수분 침투 속도를 감소시키는, 유기전자장치 봉지용 접착제 조성물, 접착 필름, 이를 이용한 유기전자장치 봉지재 및 그 제조 방법을 제공하고자 한다.In exemplary embodiments of the present invention, in another aspect, an adhesive composition for encapsulating an organic electronic device, an adhesive film, and an organic electronic device using the same, which reduce the initial water permeation rate when evaluating an accelerated test after encapsulating an OLED panel It is intended to provide a device encapsulant and a manufacturing method thereof.
본 발명의 예시적인 구현예들에서는, 다른 일 측면에서, 접착 필름과 금속 층 등의 배리어 층 및/또는 유기전자소자장치 봉지재 접착 필름간 밀착력이 높고, 수분 배리어 특성 및 산소 배리어 특성이 모두 우수한, 유기전자장치 봉지용 접착제 조성물, 접착 필름, 이를 이용한 유기전자장치 봉지재 및 그 제조 방법을 제공하고자 한다.In exemplary embodiments of the present invention, in another aspect, adhesion between the adhesive film and a barrier layer such as a metal layer and/or an organic electronic device device encapsulant adhesive film is high, and both moisture barrier properties and oxygen barrier properties are excellent. , To provide an adhesive composition for encapsulating an organic electronic device, an adhesive film, an organic electronic device encapsulant using the same, and a manufacturing method thereof.
본 발명의 예시적인 구현예들에서는, 다른 일 측면에서, 유기전자장치용 접착 필름과 OLED 패널과의 상온에서의 합착성이 저하되는 문제 및 이에 따른 장기 신뢰성 저하 문제를 방지할 수 있는, 유기전자장치 봉지용 접착제 조성물, 접착 필름, 이를 이용한 유기전자장치 봉지재 및 그 제조 방법을 제공하고자 한다.In exemplary embodiments of the present invention, in another aspect, the problem of deterioration in adhesion between the adhesive film for organic electronic devices and the OLED panel at room temperature and the consequent decrease in long-term reliability can be prevented. It is intended to provide an adhesive composition for device encapsulation, an adhesive film, an organic electronic device encapsulant using the same, and a manufacturing method thereof.
본 발명의 예시적인 구현예들에서는, 유기전자장치 봉지용 접착제 조성물로서, 폴리이소부틸렌 및 부틸고무를 9:1 내지 2:8의 중량비로 포함하는 혼합수지 바인더; 연화점이 90℃이상 150℃미만인 점착 부여제; 단관능 아크릴모노머; 다관능 아크릴모노머; 및 광개시제를 포함하는 유기전자장치 봉지용 접착제 조성물을 제공한다.In exemplary embodiments of the present invention, as an adhesive composition for encapsulating an organic electronic device, a mixed resin binder containing polyisobutylene and butyl rubber in a weight ratio of 9:1 to 2:8; a tackifier with a softening point of 90°C or more and less than 150°C; Monofunctional acrylic monomer; multifunctional acrylic monomers; And it provides an adhesive composition for encapsulating an organic electronic device containing a photoinitiator.
상기 바인더 100 중량부에 대하여, 상기 점착 부여제는 20 중량부 초과 160 중량부 미만으로 포함되고, 상기 단관능 아크릴모노머는 5 중량부 초과 20 중량부 미만으로 포함되고, 상기 다관능 아크릴모노머는 2.5중량부 초과 15 중량부 미만으로 포함되고, 상기 광개시제는 5 중량부 초과 20 중량부 미만으로 포함된다.With respect to 100 parts by weight of the binder, the tackifier is included in more than 20 parts by weight and less than 160 parts by weight, the monofunctional acrylic monomer is included in more than 5 parts by weight and less than 20 parts by weight, and the multifunctional acrylic monomer is included in 2.5 parts by weight. It is included in more than 15 parts by weight and less than 15 parts by weight, and the photoinitiator is included in more than 5 parts by weight and less than 20 parts by weight.
본 발명의 예시적인 구현예들에서는 또한, 전술한 접착제 조성물로 형성된 접착층을 포함하는, 유기전자장치용 접착 필름을 제공한다.Exemplary embodiments of the present invention also provide an adhesive film for an organic electronic device comprising an adhesive layer formed of the above-described adhesive composition.
본 발명의 예시적인 구현예들에서는 또한, 금속 층 등의 배리어층 및 전술한 유기전자장지용 접착 필름을 포함하는 유기전자장치 봉지재를 제공한다.Exemplary embodiments of the present invention also provide an organic electronic device encapsulant including a barrier layer such as a metal layer and the above-described adhesive film for an organic electronic device.
본 발명의 예시적인 구현예들에서는 또한, 금속 층 등의 배리어층에 전술한 접착제 조성물을 형성하는 단계;를 포함하는 유기전자장치 봉지재 제조 방법을 제공한다.Exemplary embodiments of the present invention also provide a method for manufacturing an organic electronic device encapsulant comprising the step of forming the above-described adhesive composition on a barrier layer such as a metal layer.
본 발명의 예시적인 구현예들에서는 또한, 전술한 유기전자장치 봉지재를 이용한 유기전자장치의 봉지 방법을 제공한다. Exemplary embodiments of the present invention also provide a method of encapsulating an organic electronic device using the organic electronic device encapsulant described above.
본 발명의 예시적인 구현예들에서는 또한, 전술한 유기전자장치 봉지재로 봉지된 유기전자장치를 제공한다.Exemplary embodiments of the present invention also provide an organic electronic device sealed with the organic electronic device encapsulant described above.
본 발명의 예시적인 구현예들에 의하면 수분 흡수층 [이른바 게터(Getter) 층]의 흡습제 분말로 인하여 해당 수분 흡수층과 접하는 금속 층 등 배리어층과의 밀착력 저하가 발생해 초기 수분 침투가 빠르게 발생하는 현상 및 이에 따른 신뢰성 저하 문제를 방지할 수 있다. 또한, OLED 패널을 봉지한 후에 가속시험 평가 시, 초기의 수분 침투 속도를 감소시킬 수 있다. 또한 접착 필름과 배리어 층뿐만 아니라 접착 필름과 유기전자소자장치 봉지재 접착 필름간 상온에서의 합착성이 우수하고 이에 따라 장기 신뢰성이 우수하다. According to exemplary embodiments of the present invention, the moisture absorbent powder of the moisture absorption layer (the so-called getter layer) causes a decrease in adhesion with a barrier layer such as a metal layer in contact with the moisture absorption layer, resulting in rapid initial moisture penetration. And it is possible to prevent a reliability degradation problem caused by this. In addition, when evaluating an accelerated test after sealing the OLED panel, the initial water penetration rate can be reduced. In addition, adhesion between the adhesive film and the barrier layer as well as between the adhesive film and the organic electronic device encapsulant adhesive film at room temperature is excellent, and thus long-term reliability is excellent.
도 1은 본 발명의 일 구현예에 따른 유기전자장치 봉지재용 접착 필름의 각 접착층을 나타내는 개략도이다.1 is a schematic diagram showing each adhesive layer of an adhesive film for an organic electronic device encapsulant according to an embodiment of the present invention.
본 명세서에서 합착성 또는 패널 합착성이란 봉지층 또는 봉지재를 OLED 패널에 상온에서 압력을 주어 부착할 때의 합착성을 의미한다. 봉지층 또는 봉지재는 예컨대 최외면에서 볼 때, 배리어층(4), 수분합착 접착층(또는 수분 흡착층)(1), 완충 접착층(2)을 포함하며, 합착 시에 완충 접착층(2)의 면이 OLED 패널과 합착되는 면이 된다. 합착 시의 기포 (합착 초기 기포 및 합착 후의 진행성 기포)의 생성이 실질적으로 없는 경우 합착성이 우수하고, 나아가 이물, 찍힘과 같은 외관 불량의 문제가 없을 경우에 합착성이 매우 우수하다고 판단한다. In the present specification, adhesion or panel adhesion refers to adhesion when attaching an encapsulation layer or an encapsulant to an OLED panel by applying pressure at room temperature. The encapsulation layer or encapsulant includes, for example, a barrier layer 4, a moisture bonding adhesive layer (or a moisture adsorption layer) 1, and a buffer adhesive layer 2, when viewed from the outermost surface, and the surface of the buffer adhesive layer 2 during bonding. This becomes the surface to be bonded to the OLED panel. It is judged that the adhesion property is excellent when there is substantially no generation of air bubbles (air bubbles in the initial stage of adhesion and advanced air bubbles after adhesion) during adhesion, and furthermore, when there are no problems with appearance defects such as foreign matter or dents.
상기한 기포의 생성이 실질적으로 없는 것이란, 합착 처음부터 기포가 없거나(0개), 합착 초기 기포가 100개/m2 이하로 있으나 72시간 지난 후 10개/m2 이하로 되는 것을 의미한다.Substantially no generation of the above air bubbles means that there are no air bubbles (0) from the beginning of coalescence or that the number of air bubbles at the beginning of coalescence is 100/m 2 or less, but becomes 10/m 2 or less after 72 hours.
본 명세서에서 신뢰성이란 봉지층 또는 봉지재가 디스플레이 패널에 부품으로 내장된 상태에서 패널을 구동할 때, 적용된 패널의 정상 구동에 필요한 물성이 확보되는지 여부의 물성으로, 우수한 패널 합착성, 양호한 접착력, 수분 및 산소 차단 특성, OLED 패널의 베젤 부위 변색 없음을 포함하는 물성을 동시에 확보한 것을 의미한다. In this specification, reliability refers to the physical properties of whether or not the physical properties necessary for normal driving of the applied panel are secured when the panel is driven in a state where the encapsulation layer or encapsulant is embedded as a component in the display panel, excellent panel adhesion, good adhesive strength, moisture And it means that physical properties including oxygen blocking properties and no discoloration of the bezel of the OLED panel are secured at the same time.
본 명세서에서 장기 신뢰성이란 다양한 제반 환경(고온, 고습, 저온 또는 급격한 온도변화 등)에서 적용 제품을 정해진 일정 시간 이상 구동할 경우에도, 상기의 신뢰성을 유지하는지 여부의 물성을 의미한다.In this specification, long-term reliability refers to physical properties of whether or not the above reliability is maintained even when the applied product is driven for a predetermined period of time or more in various environments (high temperature, high humidity, low temperature or rapid temperature change, etc.).
본 명세서에서 어떤 부분이 어떤 구성 요소를 "포함"한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성 요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다.In the present specification, when a part "includes" a certain component, it means that it may further include other components, not excluding other components unless otherwise stated.
이하, 첨부한 도면을 참조하여 본 발명의 예시적인 구현예들을 상세히 설명한다. Hereinafter, exemplary implementations of the present invention will be described in detail with reference to the accompanying drawings.
본 발명의 예시적인 구현예들에서는, 유기전자장치 봉지용 접착제 조성물로서, 폴리이소부틸렌 및 부틸고무를 9:1 내지 2:8의 중량비로 포함하는 혼합수지 바인더; 연화점이 90℃인 점착 부여제; 단관능 아크릴모노머; 다관능 아크릴모노머; 및 광개시제를 포함한다. In exemplary embodiments of the present invention, as an adhesive composition for encapsulating an organic electronic device, a mixed resin binder containing polyisobutylene and butyl rubber in a weight ratio of 9:1 to 2:8; a tackifier with a softening point of 90°C; Monofunctional acrylic monomer; multifunctional acrylic monomers; and photoinitiators.
예시적인 일 구현예에서, 상기 폴리이소부틸렌 및 부틸고무가 혼합된 바인더 수지의 분자량은 10~200만 Mw일 수 있지만, 바람직하게는 50만~160만 Mw, 더 바람직하게는 60만~150만 Mw일 수 있다. In an exemplary embodiment, the molecular weight of the binder resin in which the polyisobutylene and butyl rubber are mixed may be 10 to 2 million Mw, but is preferably 500,000 to 1.6 million Mw, more preferably 600,000 to 150 can only be Mw.
여기서 분자량은 중량평균 분자량을 의미하며, 예컨대 범용적으로 사용되는 GPC(Gel permeation chromatography)와 같은 분자량 측정 기기로 중량평균 분자량이 측정될 수 있다. Here, the molecular weight means the weight average molecular weight, For example, the weight average molecular weight may be measured by a molecular weight measurement instrument such as GPC (Gel permeation chromatography), which is commonly used.
상기 분자량이 50만 Mw 미만으로 낮을 경우 흡습 필러를 바인딩(Binding)하는 특성이 나빠지고, 접착필름의 수분 배리어 특성이 저하되고, 접착력도 저하될 수 있다. 상기 분자량이 160만 Mw 초과일 경우 다른 원료와의 상용성이 저하되고 OLED 패널과의 합착성이 떨어질 수 있다.When the molecular weight is lower than 500,000 Mw, the property of binding the hygroscopic filler may deteriorate, the moisture barrier property of the adhesive film may deteriorate, and the adhesive strength may also deteriorate. When the molecular weight exceeds 1.6 million Mw, compatibility with other raw materials may be deteriorated and adhesion with OLED panels may be deteriorated.
비제한적인 예시에서, 상기 분자량은 50만 Mw 이상, 60만 Mw 이상, 70만 Mw 이상, 80만 Mw 이상, 90만 Mw 이상, 100만 Mw 이상, 110만 Mw 이상, 120만 Mw 이상, 130만 Mw 이상, 140만 Mw 이상, 150만 Mw 이상일 수 있다. 또는, 160만 Mw 이하, 150만 Mw 이하, 140만 Mw 이하, 130만 Mw 이하, 120만 Mw 이하, 110만 Mw 이하, 100만 Mw 이하, 90만 Mw 이하, 80만 Mw 이하, 70만 Mw 이하, 60만 Mw 이하일 수 있다. In non-limiting examples, the molecular weight is 500,000 Mw or more, 600,000 Mw or more, 700,000 Mw or more, 800,000 Mw or more, 900,000 Mw or more, 1 million Mw or more, 1.1 million Mw or more, 1.2 million Mw or more, 130 It may be 10,000 Mw or more, 1.4 million Mw or more, or 1.5 million Mw or more. or 1.6 million Mw or less, 1.5 million Mw or less, 1.4 million Mw or less, 1.3 million Mw or less, 1.2 million Mw or less, 1.1 million Mw or less, 1 million Mw or less, 900,000 Mw or less, 800,000 Mw or less, 700,000 Mw Or less, it may be 600,000 Mw or less.
예시적인 일 구현예에서, 상기 조성물은 연화점이 90℃이상 150℃미만, 또는 바람직하게는 95℃~140℃ 또는 105℃~140℃, 더욱 바람직하게는 95℃~135℃ 또는 95℃~125℃ 또는 105℃~135℃ 또는 105℃~125℃인 점착 부여제를 더 포함할 수 있다. In an exemplary embodiment, the composition has a softening point of greater than or equal to 90°C and less than 150°C, or preferably 95°C to 140°C or 105°C to 140°C, more preferably 95°C to 135°C or 95°C to 125°C. Or 105 ℃ ~ 135 ℃ or 105 ℃ ~ 125 ℃ may further include a tackifier.
비제한적인 예시에서, 상기 연화점은 90℃이상, 91℃이상, 92℃이상, 93℃이상, 94℃이상, 95℃이상, 96℃이상, 97℃이상, 98℃이상, 99℃이상, 100℃이상, 101℃이상, 102℃이상, 103℃이상, 104℃이상, 105℃이상, 106℃이상, 107℃이상, 108℃이상, 109℃이상, 120℃이상, 121℃이상, 122℃이상, 123℃이상, 124℃이상, 125℃이상, 126℃이상, 127℃이상, 128℃이상, 129℃이상, 130℃이상, 131℃이상, 132℃이상, 133℃이상, 134℃이상, 135℃이상, 136℃이상, 137℃이상, 138℃이상, 139℃이상, 140℃이상, 141℃이상, 142℃이상, 143℃이상, 144℃이상, 145℃이상, 146℃이상, 147℃이상, 148℃이상, 149℃이상일 수 있다. 또는, 상기 연화점은 150℃미만, 149℃이하, 148℃이하, 147℃이하, 146℃이하, 145℃이하, 144℃이하, 143℃이하, 142℃이하, 141℃이하, 140℃이하, 139℃이하, 138℃이하, 137℃이하, 136℃이하, 135℃이하, 134℃이하, 133℃이하, 132℃이하, 131℃이하, 130℃이하, 129℃이하, 128℃이하, 127℃이하, 126℃이하, 125℃이하, 124℃이하, 123℃이하, 122℃이하, 121℃이하, 120℃이하, 119℃이하, 118℃이하, 117℃이하, 116℃이하, 115℃이하, 114℃이하, 113℃이하, 112℃이하, 111℃이하, 110℃이하, 109℃이하, 108℃이하, 107℃이하, 106℃이하, 105℃이하, 104℃이하, 103℃이하, 102℃이하, 101℃이하, 100℃이하, 99℃이하, 98℃이하, 97℃이하, 96℃이하, 95℃이하, 94℃이하, 93℃이하, 92℃이하, 91℃이하로 사용될 수 있다.In non-limiting examples, the softening point is 90 ° C or higher, 91 ° C or higher, 92 ° C or higher, 93 ° C or higher, 94 ° C or higher, 95 ° C or higher, 96 ° C or higher, 97 ° C or higher, 98 ° C or higher, 99 ° C or higher, 100 °C or more, 101 °C or more, 102 °C or more, 103 °C or more, 104 °C or more, 105 °C or more, 106 °C or more, 107 °C or more, 108 °C or more, 109 °C or more, 120 °C or more, 121 °C or more, 122 °C or more , 123℃ or more, 124℃ or more, 125℃ or more, 126℃ or more, 127℃ or more, 128℃ or more, 129℃ or more, 130℃ or more, 131℃ or more, 132℃ or more, 133℃ or more, 134℃ or more, 135 °C or more, 136 °C or more, 137 °C or more, 138 °C or more, 139 °C or more, 140 °C or more, 141 °C or more, 142 °C or more, 143 °C or more, 144 °C or more, 145 °C or more, 146 °C or more, 147 °C or more , 148 ° C or higher, may be 149 ° C or higher. Alternatively, the softening point is less than 150 ° C, 149 ° C or less, 148 ° C or less, 147 ° C or less, 146 ° C or less, 145 ° C or less, 144 ° C or less, 143 ° C or less, 142 ° C or less, 141 ° C or less, 140 ° C or less, 139 °C or less, 138 °C or less, 137 °C or less, 136 °C or less, 135 °C or less, 134 °C or less, 133 °C or less, 132 °C or less, 131 °C or less, 130 °C or less, 129 °C or less, 128 °C or less, 127 °C or less , 126℃ or less, 125℃ or less, 124℃ or less, 123℃ or less, 122℃ or less, 121℃ or less, 120℃ or less, 119℃ or less, 118℃ or less, 117℃ or less, 116℃ or less, 115℃ or less, 114 °C or less, 113 °C or less, 112 °C or less, 111 °C or less, 110 °C or less, 109 °C or less, 108 °C or less, 107 °C or less, 106 °C or less, 105 °C or less, 104 °C or less, 103 °C or less, 102 °C or less , 101 ℃ or less, 100 ℃ or less, 99 ℃ or less, 98 ℃ or less, 97 ℃ or less, 96 ℃ or less, 95 ℃ or less, 94 ℃ or less, 93 ℃ or less, 92 ℃ or less, 91 ℃ or less.
비제한적인 예시에서, 상기 점착 부여제는 석유수첨 DCPD(Dicyclopentadiene)계의 90℃ 이상 150℃미만 또는 바람직하게는 95℃~140℃, 더욱 바람직하게는 95℃~135℃의 연화점을 갖는 제품일 수 있다.In a non-limiting example, the tackifier is a product having a softening point of 90 ° C or more and less than 150 ° C or preferably 95 ° C to 140 ° C, more preferably 95 ° C to 135 ° C of a petroleum hydrogenated DCPD (Dicyclopentadiene) system. can
상기 연화점이 90℃ 미만의 경우 접착필름의 수분 배리어 특성이 나빠질 수 있다. 점착부여제의 연화점이 높을수록 수분 배리어 특성이 우수해지는 경향이 있으나, 150℃ 이상인 경우 점도 및 모듈러스가 높아져 합착성과 접착성이 저하될 수 있다. When the softening point is less than 90° C., the moisture barrier properties of the adhesive film may deteriorate. The higher the softening point of the tackifier, the better the moisture barrier properties, but when the temperature is 150° C. or higher, the viscosity and modulus increase, and adhesion and adhesion may deteriorate.
예시적인 일 구현예에서, 상기 점착부여제의 함량은 상기 바인더 100 중량 대비 20 중량부 초과 160중량부 미만, 또는 바람직하게는 40~150중량부로 포함된다.In an exemplary embodiment, the content of the tackifier is greater than 20 parts by weight and less than 160 parts by weight, or preferably 40 to 150 parts by weight, based on 100 parts by weight of the binder.
상기 점착부여제가 20중량부 이하로 함유되는 경우 접착력 저하와 수분 배리어 특성 저하가 발생할 수 있으며, 160중량부 이상인 모듈러스와 점도가 너무 커져 합착성이 떨어지고, 접착력은 높은 반면에 층간 박리가 쉽게 발생할 수 있다.When the tackifier is contained in an amount of 20 parts by weight or less, a decrease in adhesive strength and a decrease in moisture barrier properties may occur, and a modulus of 160 parts by weight or more and a viscosity become too large, resulting in poor adhesion, and high adhesive strength, but may easily cause peeling between layers. there is.
비제한적인 예시에서, 상기 점착 부여제는 20중량부 초과, 30중량부 이상, 40중량부 이상, 50중량부 이상, 60중량부 이상, 70중량부 이상, 80중량부 이상, 90중량부 이상, 100중량부 이상, 110중량부 이상, 120중량부 이상, 130중량부 이상, 140중량부 이상, 150중량부 이상일 수 있다. 또는 상기 점착 부여제는 160중량부 미만, 150중량부 이하, 140중량부 이하, 130중량부 이하, 120중량부 이하, 110중량부 이하, 100중량부 이하, 90중량부 이하, 80중량부 이하, 70중량부 이하, 60중량부 이히, 50중량부 이하, 40중량부 이하, 30중량부 이하일 수 있다.In non-limiting examples, the tackifier is greater than 20 parts by weight, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 60 parts by weight or more, 70 parts by weight or more, 80 parts by weight or more, 90 parts by weight or more , 100 parts by weight or more, 110 parts by weight or more, 120 parts by weight or more, 130 parts by weight or more, 140 parts by weight or more, may be 150 parts by weight or more. Or the tackifier is less than 160 parts by weight, 150 parts by weight or less, 140 parts by weight or less, 130 parts by weight or less, 120 parts by weight or less, 110 parts by weight or less, 100 parts by weight or less, 90 parts by weight or less, 80 parts by weight or less , 70 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, may be 30 parts by weight or less.
예시적인 일 구현예에서, 상기 조성물은 단관능 아크릴모노머 및 다관능 아크릴모노머를 포함한다. In an exemplary embodiment, the composition includes a monofunctional acrylic monomer and a multifunctional acrylic monomer.
예시적인 일 구현예에서, 상기 단관능 아크릴모노머는 단관능의 아크릴모노머이면 특별히 제한되지 않는다. 또한, 상기 단관능 아크릴모노머는 바인더 100 중량부에 대하여 5 중량부 초과 20중량부 미만으로 포함될 수 있다. 바인더 100 중량부 대비하여 5중량부 이하 및 20중량부 이상인 경우 접착력 저하가 발생할 수 있고, 20중량부 이상인 경우 점도가 너무 커져 합착성이 떨어지고, 층간박리가 쉽게 발생할 수 있다.In one exemplary embodiment, the monofunctional acrylic monomer is not particularly limited as long as it is a monofunctional acrylic monomer. In addition, the monofunctional acrylic monomer may be included in more than 5 parts by weight and less than 20 parts by weight based on 100 parts by weight of the binder. In the case of 5 parts by weight or less and 20 parts by weight or more compared to 100 parts by weight of the binder, a decrease in adhesive strength may occur.
비제한적인 예시에서, 상기 단관능 아크릴모노머는 5중량부 초과, 6중량부 이상, 7중량부 이상, 8중량부 이상, 9중량부 이상, 10중량부 이상, 11중량부 이상, 12중량부 이상, 13중량부 이상, 14중량부 이상, 15중량부 이상, 16중량부 이상, 17중량부 이상, 18중량부 이상, 19중량부 이상일 수 있다. 또는 상기 단관능 아크릴모노머는 20중량부 미만, 19중량부 이하, 18중량부 이하, 17중량부 이하, 16중량부 이하, 15중량부 이하, 14중량부 이하, 13중량부 이하, 12중량부 이하, 11중량부 이하, 10중량부 이하, 9중량부 이하, 8중량부 이하, 7중량부 이하, 6중량부 이하일 수 있다.In non-limiting examples, the monofunctional acrylic monomer is greater than 5 parts by weight, 6 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, 9 parts by weight or more, 10 parts by weight or more, 11 parts by weight or more, 12 parts by weight Or more, 13 parts by weight or more, 14 parts by weight or more, 15 parts by weight or more, 16 parts by weight or more, 17 parts by weight or more, 18 parts by weight or more, may be 19 parts by weight or more. Alternatively, the monofunctional acrylic monomer is less than 20 parts by weight, 19 parts by weight or less, 18 parts by weight or less, 17 parts by weight or less, 16 parts by weight or less, 15 parts by weight or less, 14 parts by weight or less, 13 parts by weight or less, 12 parts by weight or less Or less, 11 parts by weight or less, 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, may be 6 parts by weight or less.
비제한적인 예시에서, 상기 단관능 아크릴모노머는 트리메틸올프로판 (EO)n 트리아크릴레이트[Trimethylolpropane (EO)n Triacrylate], 카프로락톤 아크릴레이트(Caprolactone Acrylate), 폴리프로필렌글리콜 모노메타크릴레이트(Polypropyleneglycol Monomethacrylate), 사이클릭 트리메틸올프로판 포멀 아크릴레이트(Cyclic trimethylolpropane formal Acrylate), 페녹시 벤질 아크릴레이트(Phenoxy benzyl Acrylate), 3,3,5-트리메틸 사이클로헥실 아크릴레이트(3,3,5-trimethyl cyclohexyl Acrylate), 이소보르닐 아크릴레이트(Isobornyl Acrylate), 오쏘-페닐페놀 EO 아크릴레이트(o-phenylphenol EO Acrylate), 4-터트-부틸사이클로헥실 아크릴레이트(4-tert-butylcyclohexyl acrylate), 벤질 아크릴레이트(Benzyl Acrylate), 벤질 메타크릴레이트(Benzyl Methacrylate), 라우릴 아크릴레이트[Lauryl Acrylate (예컨대, LA-C12,13)], 라우릴메타크릴레이트[Lauryl Methacrylate (예컨대, LMA-C12,13)], 트리데실아크릴레이트(Tridecyl Acrylate), 라우릴 테트라데실 메타크릴레이트(Lauryl Tetradecyl Methacrylate), 이소데실 아크릴레이트(Isodecyl Acrylate), 이소데실 메타크릴레이트(Isodecyl Methacrylate), 페놀 (EO) 아크릴레이트[Phenol (EO) Acrylate], 페녹시에틸 메타크릴레이트(Phenoxyethyl Methacrylate), 페놀 (EO)2 아크릴레이트[Phenol (EO)2 Acrylate], 페놀 (EO)4 아크릴레이트[Phenol (EO)4 Acrylate], 테트라하이드로푸르푸릴 아크릴레이트(Tetrahydrofurfuryl Acrylate), 테트라하이드로푸르푸릴 메타크릴레이트(Tetrahydrofurfuryl Methacrylate), 노닐 페놀 (PO)2 아크릴레이트[Nonyl Phenol (PO)2 Acrylate], 노닐 페놀 (EO)4 아크릴레이트 [Nonyl Phenol (EO)4 Acrylate], 노닐 페놀 (EO)8 아크릴레이트 [Nonyl Phenol (EO)8 Acrylate], 에톡시 에톡시 에틸아크릴레이트 (Ethoxy ethoxy ethyl Acrylate), 스테아릴 아크릴레이트(Stearyl Acrylate), 스테아릴 메타크릴레이트(Stearyl Methacrylate), 메톡시 폴리에틸렌글리콜 메타크릴레이트(Methoxy PEG Methacrylate, 예컨대 Methoxy PEG 600 Methacrylate)일 수 있지만, 이에 제한되지 않는다.In a non-limiting example, the monofunctional acrylic monomer may be trimethylolpropane (EO)n triacrylate, caprolactone acrylate, or polypropylene glycol monomethacrylate. ), Cyclic trimethylolpropane formal Acrylate, Phenoxy benzyl Acrylate, 3,3,5-trimethyl cyclohexyl Acrylate , Isobornyl Acrylate, o-phenylphenol EO Acrylate, 4-tert-butylcyclohexyl acrylate, Benzyl Acrylate ), benzyl methacrylate, lauryl acrylate [Lauryl Acrylate (eg, LA-C12,13)], lauryl methacrylate [Lauryl Methacrylate (eg, LMA-C12,13)], tridecyl Tridecyl Acrylate, Lauryl Tetradecyl Methacrylate, Isodecyl Acrylate, Isodecyl Methacrylate, Phenol (EO) Acrylate Acrylate], Phenoxyethyl Methacrylate, Phenol (EO)2 Acrylate, Phenol (EO)4 Acrylate, Tetrahydrofurfuryl Acrylate (Tetrahydrofurfuryl Acrylate), Tetrahydrofurfuryl Methacrylate (Tetrahydrofurfuryl Methacrylate), Nonyl Phenol (PO)2 Acrylate [Nonyl Phenol (PO)2 Acrylate], Nonyl Phenol (EO)4 Acrylate [Nonyl Phenol (EO) )4 Acrylate], Nonyl Phenol (EO)8 Acrylate [Nonyl Phenol (EO)8 Acrylate], Ethoxy Ethoxy Ethyl Acrylate, Stearyl Acrylate, Stearyl Methacryl Late (Stearyl Methacrylate), methoxy polyethylene glycol methacrylate (Methoxy PEG Methacrylate, for example, Methoxy PEG 600 Methacrylate) may be used, but is not limited thereto.
비제한적인 예시에서, 상기 단관능 아크릴모노머로서 메타크릴레이트 계열 보다는 경화속도가 상대적으로 빠른 아크릴레이트 계열이 더 바람직할 수 있다.In a non-limiting example, as the monofunctional acrylic monomer, an acrylate series having a relatively fast curing rate may be more preferable than a methacrylate series.
예시적인 일 구현예에서, 상기 다관능 아크릴모노머는 예컨대 2관능기, 3관능기, 4관능기, 5관능기, 6관능기의 아크릴모노머를 사용할 수 있고, 수분침투속도의 측면에서 바람직하게는 2관능 아크릴모노머를 사용할 수 있다. In an exemplary embodiment, the multifunctional acrylic monomer may be, for example, bifunctional, trifunctional, tetrafunctional, pentafunctional, or hexafunctional acrylic monomer, and in terms of water permeation rate, a bifunctional acrylic monomer is preferably used. can be used
상기 다관능 아크릴모노머는 바인더 100 중량부에 대하여 2.5 중량부 초과 15중량부 미만으로 포함된다. 2.5중량부 이하 및 15중량부 이상의 조건에서는 접착력 저하가 발생할 수 있고, 15중량부 이상인 경우 점도가 너무 커져 합착성이 떨어지고, 층간박리가 쉽게 발생할 수 있다.The multifunctional acrylic monomer is included in an amount greater than 2.5 parts by weight and less than 15 parts by weight based on 100 parts by weight of the binder. Under the conditions of 2.5 parts by weight or less and 15 parts by weight or more, adhesive strength may decrease, and when it is 15 parts by weight or more, the viscosity becomes too large and the adhesion is poor, and interlayer peeling may easily occur.
비제한적인 예시에서, 상기 다관능 아크릴모노머는 바인더 100 중량부에 대하여 2.5중량부 초과, 3중량부 이상, 4중량부 이상, 5중량부 이상, 6중량부 이상, 7중량부 이상, 8중량부 이상, 9중량부 이상, 10중량부 이상, 11중량부 이상, 12중량부 이상, 13중량부 이상, 14중량부 이상일 수 있다. 또는, 상기 다관능 아크릴모노머는 15중량부 미만, 14중량부 이하, 13중량부 이하, 12중량부 이하, 11중량부 이하, 10중량부 이하, 9중량부 이하, 8중량부 이하, 7중량부 이하, 6중량부, 5중량부 이하, 4중량부 이하, 3중량부 이하일 수 있다.In a non-limiting example, the multifunctional acrylic monomer is greater than 2.5 parts by weight, 3 parts by weight or more, 4 parts by weight or more, 5 parts by weight or more, 6 parts by weight or more, 7 parts by weight or more, 8 parts by weight based on 100 parts by weight of the binder. Part or more, 9 parts by weight or more, 10 parts by weight or more, 11 parts by weight or more, 12 parts by weight or more, 13 parts by weight or more, may be 14 parts by weight or more. Alternatively, the polyfunctional acrylic monomer is less than 15 parts by weight, 14 parts by weight or less, 13 parts by weight or less, 12 parts by weight or less, 11 parts by weight or less, 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less It may be 6 parts by weight or less, 5 parts by weight or less, 4 parts by weight or less, or 3 parts by weight or less.
비제한적인 예시에서, 상기 다관능 아크릴모노머는 1,6-헥산디올 디아크릴레이트(1,6-Hexanediol Diacrylate), 1,6-헥산디올 디메타크릴레이트(1,6-Hexanediol Dimethacrylate), 1,6-헥산디올 (EO)n 디아크릴레이트[1,6-Hexanediol (EO)n Diacrylate], 폴리프로필렌 글리콜 디아크릴레이트(Polypropylene glycol Diacrylate, 예컨대 Polypropylene glycol 400 Diacrylate), 1,4-부탄디올 디메타크릴레이트(1,4-Butanediol Dimethacrylate), 폴리프로필렌 글리콜 (EO)6 디메타크릴레이트 (Polypropylene glycol (EO)6 Dimethacrylate, 예컨대 Polypropylene glycol 700 (EO)6 Dimethacrylate), 하이드록시 피발릭산 네오펜틸 글리콜 다아크릴레이트(Hydroxy pivalic acid neopentyl glycol Diacrylate), 비스페놀 A (EO)10 디아크릴레이트[Bisphenol A (EO)10 Diacrylate], 비스페놀 A (EO)10 디메타크릴레이트[Bisphenol A (EO)10 Dimethacrylate], 네오펜틸글리콜 디메타크릴레이트(Neopentyl glycol Dimethacrylate), 네오펜틸글리콜 (PO)2 디아크릴레이트(Neopentylglycol (PO)2 Diacrylate), 트리플로필렌 글리콜 디아크릴레이트(Tripropylene glycol Diacrylate), 에틸렌글리콜 디메타크릴레이트(Ethylene glycol Dimethacrylate), 디프로로필렌 글리콜 디아크릴레이트(Dipropylene glycol Diacrylate), 비스페놀 A (EO)30 디아크릴레이트[Bisphenol A (EO)30 Diacrylate], 비스페놀 A (EO)30 디메타크릴레이트[Bisphenol A (EO)30 Dimethacrylate], 디에틸렌글리콜 디메타크릴레이트[Diethylene glycol Dimethacrylate], 트리에틸렌글리콜 디아크릴레이트[Triethylene glycol Diacrylate], 트리에틸렌글리콜 디메타크릴레이트[Triethylene glycol Dimethacrylate], 테트라에틸렌글리콜 디메타크릴레이트[Tetraethylene glycol Dimethacrylate], 비스페놀 A(EO)4 디아크릴레이트[Bisphenol A (EO)4 Diacrylate], 비스페놀 A (EO)4 디메타크릴레이트[Bisphenol A (EO)4 Dimethacrylate], 비스페놀 A (EO)3 디아크릴레이트[Bisphenol A (EO)3 Diacrylate], 비스페놀 A (EO)3 디메타크릴레이트[Bisphenol A (EO)3 Dimethacrylate], 1,3-부틸렌글리콜 디메타크릴레이트[1,3-Butylene glycol Dimethacrylate], 트리사이클로데칸 디메탄올 디아크릴레이트(Tricyclodecane dimethanol Diacrylate), 테트라에틸렌 글리콜 디아크릴레이트(Tetraethylene glycol Diacrylate), 폴리에틸렌글리콜 디아크릴레이트(Polyethylene glycol Diacrylate, 예컨대 Polyethylene glycol 400 Diacrylate), 폴리에틸렌글리콜 디메타크릴레이트(Polyethylene glycol Dimethacrylate, 예컨대 Polyethylene glycol 400 Dimethacrylate, 또는 Polyethylene glycol 200 Dimethacrylate, Polyethylene glycol 600 Dimethacrylate), 폴리에틸렌글리콜 디아크릴레이트(Polyethylene glycol Diacrylate, 예컨대 Polyethylene glycol 200 Diacrylate, Polyethylene glycol 300 Diacrylate, Polyethylene glycol 600 Diacrylate), 비스페놀 F (EO)4 디아크릴레이트[Bisphenol F (EO)4 Diacrylate] 일 수 있지만, 이에 제한되지 않는다.In a non-limiting example, the multifunctional acrylic monomer is 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1 ,6-hexanediol (EO)n diacrylate [1,6-Hexanediol (EO)n Diacrylate], polypropylene glycol diacrylate (e.g. Polypropylene glycol 400 Diacrylate), 1,4-butanediol dimetha acrylate (1,4-Butanediol Dimethacrylate), polypropylene glycol (EO)6 dimethacrylate (e.g. Polypropylene glycol 700 (EO)6 Dimethacrylate), hydroxy pivalic acid neopentyl glycol Hydroxy pivalic acid neopentyl glycol Diacrylate, Bisphenol A (EO)10 Diacrylate, Bisphenol A (EO)10 Dimethacrylate, Neopentyl glycol dimethacrylate, Neopentyl glycol (PO)2 diacrylate, Tripropylene glycol diacrylate, Ethylene glycol dimethacrylate Ethylene glycol Dimethacrylate, Dipropylene glycol Diacrylate, Bisphenol A (EO)30 Diacrylate, Bisphenol A (EO)30 Dimethacrylate [Bisphenol A (EO)30 Dimethacrylate], Diethylene glycol Dimethacrylate, Triethylene glycol Diacrylate, Triethylene glycol Dimethacrylate, Tetraethylene Glycol Dimethacrylate [Tetraethylene glycol Dimethacrylate], Bisphenol A (EO)4 Diacrylate [Bisphenol A (EO)4 Diacrylate], Bisphenol A (EO)4 Dimethacrylate [Bisphenol A (EO)4 Dimethacrylate], Bisphenol A (EO)3 Diacrylate [Bisphenol A (EO)3 Diacrylate], Bisphenol A (EO)3 Dimethacrylate [Bisphenol A (EO)3 Dimethacrylate], 1,3-Butylene Glycol Dimethacrylate [1,3-Butylene glycol Dimethacrylate], Tricyclodecane dimethanol Diacrylate, Tetraethylene glycol Diacrylate, Polyethylene glycol Diacrylate (e.g. Polyethylene glycol 400 Diacrylate), polyethylene glycol dimethacrylate (e.g. Polyethylene glycol 400 Dimethacrylate, or Polyethylene glycol 200 Dimethacrylate, Polyethylene glycol 600 Dimethacrylate), polyethylene glycol diacrylate (e.g. Polyethylene glycol 200 Diacrylate, Polyethylene glycol 300 Diacrylate, Polyethylene glycol 600 Diacrylate), or bisphenol F (EO) 4 diacrylate [Bisphenol F (EO) 4 Diacrylate], but is not limited thereto.
비제한적인 예시에서, 상기 다관능 아크릴모노머로서 메타크릴레이트 계열보다는 경화속도가 상대적으로 빠른 아크릴레이트 계열이 더 바람직할 수 있다.In a non-limiting example, as the multifunctional acrylic monomer, an acrylate based monomer having a relatively fast curing speed may be more preferable than a methacrylate based monomer.
예시적인 일 구현예에서, 상기 조성물은 광 개시제를 더 포함할 수 있다. 광개시제는 자유라디칼을 발생시키는 것으로 종류에 특별히 제한되지 않으며, 200nm의 단파장부터 400nm 장파장 대역에 반응하는 제품을 폭넓게 사용할 수 있다. In an exemplary embodiment, the composition may further include a photoinitiator. The photoinitiator generates free radicals and is not particularly limited in type, and products that react to a short wavelength of 200 nm to a long wavelength of 400 nm can be widely used.
예컨대, 광개시제로는 벤조인메틸에테르, 2,4,6-트리메틸벤조일 디페닐포스핀옥사이드, 비스(2,4,6-트리메틸벤조일) 페닐포스핀옥사이드, α,α-메톡시-α-하이드록시아세토페논, 2-벤조일-2-(디메틸아미노)-1-[4-(4-몰포닐) 페닐]-1-부타논, 2,2-디메톡시-2-페닐아세토페논, 옥심에스터계 등으로 이루어진 군으로부터 선택된 하나 이상을 포함할 수 있다. 또한, 예컨대, 1-Hydroxy-cyclohexyl-phenyl-ketone나 Bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide 일 수 있고, 바람직하게는 Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide(관용명 TPO)일 수 있다. For example, photoinitiators include benzoin methyl ether, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl) phenylphosphine oxide, α,α-methoxy-α-hydride Roxyacetophenone, 2-benzoyl-2-(dimethylamino)-1-[4-(4-morphonyl)phenyl]-1-butanone, 2,2-dimethoxy-2-phenylacetophenone, oxime ester system It may include one or more selected from the group consisting of and the like. Also, for example, it may be 1-Hydroxy-cyclohexyl-phenyl-ketone or Bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, preferably Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (common name TPO). can
UV 조사 시, 자유라디칼을 발생시켜 아크릴레이트의 이중결합에 반응하여 자신도 반응에 참여하며 광경화를 발생시키므로, 아크릴레이트와의 함량비를 계산할 수 있지만, 바인더에 대한 함량비율로도 광 개시제의 사용량을 정할 수 있다. During UV irradiation, free radicals are generated to react to the double bond of acrylate, which itself participates in the reaction and causes photocuring, so the content ratio with acrylate can be calculated, but the content ratio to the binder usage can be determined.
예시적인 일 구현예에서, 상기 광개시제는 바인더 100중량부 대비 5 중량부 초과 20중량부 미만으로 사용한다. 5중량부 이하인 경우에는 가교밀도가 낮아 접착력, 수분 배리어 특성, 장기 신뢰성이 모두 저하되며, 20 중량부 이상의 함량에서는 과경화 및 미경화 잔존물 발생으로 필름 외관 불량이 발생하며, 장기신뢰성 또한 저하될 수 있다.In an exemplary embodiment, the photoinitiator is used in an amount greater than 5 parts by weight and less than 20 parts by weight based on 100 parts by weight of the binder. If it is less than 5 parts by weight, the crosslinking density is low, so adhesive strength, moisture barrier properties, and long-term reliability all decrease. If the content is more than 20 parts by weight, poor film appearance may occur due to overcuring and uncured residues, and long-term reliability may also decrease. there is.
비제한적인 예시에서, 상기 광개시제는 5중량부 초과, 6중량부 이상, 7중량부 이상, 8중량부 이상, 9중량부 이상, 10중량부 이상, 11중량부 이상, 12중량부 이상, 13중량부 이상, 14중량부 이상, 15중량부 이상, 16중량부 이상, 17중량부 이상, 18중량부 이상, 19중량부 이상일 수 있다. 또는 상기 광개시제는 20중량부 미만, 19중량부 이하, 18중량부 이하, 17중량부 이하, 16중량부 이하, 15중량부 이하, 14중량부 이하, 13중량부 이하, 12중량부 이하, 11중량부 이하, 10중량부 이하, 9중량부 이하, 8중량부 이하, 7중량부 이하, 6중량부 이하일 수 있다.In non-limiting examples, the photoinitiator is greater than 5 parts by weight, 6 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, 9 parts by weight or more, 10 parts by weight or more, 11 parts by weight or more, 12 parts by weight or more, 13 It may be 14 parts by weight or more, 15 parts by weight or more, 16 parts by weight or more, 17 parts by weight or more, 18 parts by weight or more, or 19 parts by weight or more. Or the photoinitiator is less than 20 parts by weight, 19 parts by weight or less, 18 parts by weight or less, 17 parts by weight or less, 16 parts by weight or less, 15 parts by weight or less, 14 parts by weight or less, 13 parts by weight or less, 12 parts by weight or less, 11 It may be less than 10 parts by weight, less than 9 parts by weight, less than 8 parts by weight, less than 7 parts by weight, or less than 6 parts by weight.
예시적인 일 구현예에서, 상기 접착 조성물은 OPP(연신 폴리프로필렌, Oriented Polypropylene) 필름 2장을 겹친 경우의 기준 OTR (Oxygen Transmission Rate)수치를 100이라고 할 때, 해당 2장의 OPP 필름 사이에 상기 접착 조성물로 이루어진 접착층이 형성된 경우의 OTR 수치가 18% 이하인 것이 바람직하다.In an exemplary embodiment, the adhesive composition is the adhesion between the two OPP films when the reference OTR (Oxygen Transmission Rate) value when two OPP (Oriented Polypropylene) films are overlapped is 100. It is preferable that the OTR value when the adhesive layer made of the composition is formed is 18% or less.
즉, 상기 OTR 특성 수치는 적용되지 않았을 때의 OTR(기본 조건, OPP 2장 조건)을 100% (예컨대 후술하는 실험예에서 1352 cc/(m2·day))로 볼 때, OTR 수치가 18% 이하 수준 (예컨대 후술하는 실험예에서 243 cc/(m2·day) 이하)이어야 OTR 성능 향상이 구현되며, 18%를 초과하여 가스차단 특성이 낮을 경우 장기 신뢰성 등이 떨어질 수 있다(후술하는 비교예 1~4, 6~16의 경우 18% 초과) That is, when the OTR (basic condition, OPP chapter 2 condition) when the OTR characteristic value is not applied is 100% (eg, 1352 cc / (m 2 · day) in the experimental example described later), the OTR value is 18 % or less (for example, 243 cc/(m 2 · day) or less in the experimental example described later) to improve OTR performance, and if the gas barrier property is low in excess of 18%, long-term reliability may deteriorate (described later In the case of Comparative Examples 1 to 4 and 6 to 16, more than 18%)
예시적인 일 구현예에서, 상기 접착 조성물은 OPP 필름 2장을 겹친 경우의 기준 WVTR (Water Vapor Transmission Rate) 수치를 100이라고 할 때, 해당 2장의 OPP 필름 사이에 상기 접착 조성물로 이루어진 접착 필름이 형성된 경우의 WVTR 수치가 55% 이하인 것이 바람직하다. 후술하는 실험예에서 WVTR 100%(비교예1)가 2.123704 g/(m2·day)이며, 55%는 1.1680372 g/(m2·day)이다.In an exemplary embodiment, when the reference WVTR (Water Vapor Transmission Rate) value when two OPP films are overlapped is 100, the adhesive composition is formed between the two OPP films. It is preferable that the WVTR value of the case is 55% or less. In an experimental example to be described later, 100% of the WVTR (Comparative Example 1) is 2.123704 g/(m 2 · day), and 55% is 1.1680372 g/(m 2 · day).
즉, 상기 WVTR특성 수치는 접착 필름이 적용되지 않았을 때의 WVTR(기본 조건, OPP2장 조건)을 100%(비교예1)로 볼 때, WVTR 수치가 55% 이하 수준이야 WVTR 성능 향상이 구현되며, 55%를 초과하여 수분차단 특성이 낮을 경우 장기 신뢰성 등이 떨어진다(후술하는 실험예의 비교예들 참조).That is, when the WVTR characteristic value is 100% (comparative example 1) when the WVTR (basic condition, OPP 2 sheet condition) when the adhesive film is not applied, WVTR performance improvement is realized when the WVTR value is 55% or less. , When the moisture barrier property is low by exceeding 55%, long-term reliability, etc. are deteriorated (refer to comparative examples of experimental examples described later).
참고로, OLED는 수분에 약하기 때문에 외부에서 침투된 수분을 Getting하는 역할을 할 때, 봉지층 재료의 WVTR이 낮아야 WTV 성능이 우수해질 수 있다.For reference, OLED is weak against moisture. When it plays a role of getting moisture penetrated from the outside, the WVTR of the encapsulation layer material must be low to achieve excellent WTV performance.
예시적인 일 구현예에서, 상기 접착제 조성물은 하기 [식 1]를 만족하는 것이 바람직하다.In an exemplary embodiment, the adhesive composition preferably satisfies the following [Formula 1].
[식 1][Equation 1]
WTV(㎛) = 410α*(ln(T+1)-1.9)WTV(μm) = 410α*(ln(T+1)-1.9)
상기 [식 1]은 다음과 같이 평가한 것이다. 즉, 전술한 접착제 조성물로 구성된 완충 접착층(2)과 상기 조성물에 산화 칼슘을 넣은 수분 흡착층(1)을 각각 이형필름에 코팅하면서 550nm 파장 기준 500mJ의 광량으로 조사하여 UV 경화시킨후 두 필름을 60℃의 온도로 열합착하고, 수분 흡착층(1)의 이형필름을 제거한 후 세정된 메탈층을 100℃을 열로 합착하고 반대면인 완충 접착층(2)의 이형필름을 제거한 후 무알칼리(Alkali free) 유리를 상온에서 합착 한 후에, 온도 85℃, 습도 85%의 신뢰성 챔버에 넣고, 100시간 단위로 1000시간까지의 방치 시간 동안 모서리에서 시작되는 수분의 침투 길이를 현미경을 통해 측정한다.[Equation 1] is evaluated as follows. That is, the buffer adhesive layer 2 composed of the above-described adhesive composition and the moisture adsorption layer 1 containing calcium oxide in the composition are coated on a release film, respectively, and irradiated with a light amount of 500 mJ based on a wavelength of 550 nm to UV cure, and then the two films are After heat bonding at a temperature of 60 ° C, removing the release film of the moisture adsorption layer (1), bonding the cleaned metal layer with heat at 100 ° C, removing the release film of the opposite side, the buffer adhesive layer (2), and then removing the alkali-free (Alkali) After bonding free) glass at room temperature, it is placed in a reliability chamber with a temperature of 85 ° C and a humidity of 85%, and the penetration length of moisture starting from the corner is measured through a microscope for a standing time of up to 1000 hours in units of 100 hours.
상기 [식 1]에서 WTV(㎛)는 85℃, 85% 온습도 챔버에서의 전술한 바와 같이 측정된 수분 침투 길이, T는 85℃, 85% 온습도 챔버에서의 각 방치 시간(hr)이다.In [Equation 1], WTV (μm) is the water penetration length measured as described above in the 85 ° C., 85% temperature and humidity chamber, and T is each standing time (hr) in the 85 ° C. and 85% temperature and humidity chamber.
상기 [식 1]에서 알 수 있듯이, 온습도 챔버에서의 방치 시간의 로그 값과 수분 침투 길이 간에 상관 관계를 표시할 때 계수 α값 (이를 수분침투속도 계수라고 지칭할 수 있다)을 얻을 수 있으며, 해당 계수 α값을 통하여 초기 수분 침투속도를 평가할 수 있다. As can be seen from [Equation 1] above, when displaying the correlation between the log value of the standing time in the temperature and humidity chamber and the moisture penetration length, the coefficient α value (this can be referred to as the moisture penetration rate coefficient) can be obtained, The initial water permeation rate can be evaluated through the corresponding coefficient α value.
α가 0.80를 초과할 경우, 방치 시간 대비 WTV가 지나치게 커져 초기 수분 침투 속도가 커지며 이에 따라 수분에 의한 장기신뢰성이 저하되어 제품의 수명이 단축될 수 있다. 또한 α가 0.80를 초과할 경우, OLED 패널에서 CaO 등 수분 흡착제의 산화에 따른 색변화가 시인되는 등의 악영향을 줄 수 있다. When α exceeds 0.80, the WTV compared to the standing time becomes excessively large, so the initial water penetration rate increases, and accordingly, the long-term reliability due to moisture is lowered, and the life of the product may be shortened. In addition, when α exceeds 0.80, adverse effects such as color change due to oxidation of moisture absorbents such as CaO may be recognized in the OLED panel.
[WTV 평가][WTV evaluation]
전술한 접착제 조성물로 구성된 완충 접착층(2)과 상기 조성물에 산화 칼슘을 넣은 수분 흡착층(1)을 각각 이형필름에 코팅하면서 550nm 파장 기준 500mJ의 광량으로 조사하여 UV 경화시킨후 두 필름을 60℃의 온도로 열합착하고, 수분 흡착층(1)의 이형필름을 제거한 후 세정된 메탈층을 100℃을 열로 합착하고 반대면인 완충 접착층(2)의 이형필름을 제거한 후 무알칼리(Alkali free) 유리를 상온에서 합착 한 후에, 온도 85℃ 습도 85%의 신뢰성 챔버에 넣고, 100시간 단위로 1000시간까지의 방치 시간 동안 모서리에서 시작되는 수분의 침투 길이 WTV(㎛)를 현미경을 통해 측정한다. The buffer adhesive layer (2) composed of the above-described adhesive composition and the moisture adsorption layer (1) containing calcium oxide in the composition are coated on a release film, respectively, and UV cured by irradiation with a light amount of 500 mJ based on a wavelength of 550 nm, and then the two films are heated at 60 ° C. After heat bonding at a temperature of 100° C. after removing the release film of the moisture absorption layer (1), the cleaned metal layer is bonded with heat at 100° C., and after removing the release film of the opposite side, the buffer adhesive layer (2), alkali-free After the glass is bonded at room temperature, it is placed in a reliability chamber at a temperature of 85° C. and a humidity of 85%, and the penetration length WTV (μm) of moisture starting from the edge is measured through a microscope for a standing time of up to 1000 hours in units of 100 hours.
예시적인 일 구현예에서, 상기 접착 조성물은 접착력이 최소 6kg/25mm 이상인 것이 바람직하다. In one exemplary embodiment, the adhesive composition preferably has an adhesive force of at least 6kg/25mm or more.
여기서의 접착력은 후술하는 180˚박리 접착력이다.The adhesive force here is the 180° peel adhesive force described later.
즉, 전술한 접착제 조성물로 구성된 완충 접착층과 해당 접착제 조성물에 CaO를 고형분 기준으로 40중량% 더 포함하는 접착제 조성물로 구성된 수분 흡착층을 각각 이형필름에 코팅하면서 365nm 파장의 자외선 기준 1000mJ의 광량으로 조사하여 UV 경화시킨후 두 필름을 60℃의 온도로 열합착하고, 수분 흡착층의 이형필름을 제거한 후 세정된 메탈층을 100℃을 열로 합착하고 폭 1인치 x 길이 140mm로 재단 한 후, 반대면인 완충 접착층의 이형필름을 제거 한 후 75mmx 125mm 무알칼리 유리(Alkali free glass)에 상온 합지 후, 만능재료시험기(UTM, AGS-1KNX, SHIMADZU 사)를 이용하여 180°의 각도로 박리시켜 접착력을 평가한 것이다. That is, while coating a release film with a buffer adhesive layer composed of the above-described adhesive composition and an adhesive composition further containing 40% by weight of CaO based on the solid content of the adhesive composition, the release film is irradiated with a light amount of 1000 mJ based on ultraviolet rays having a wavelength of 365 nm. After UV curing, the two films are thermally bonded at a temperature of 60 ° C, the release film of the moisture adsorption layer is removed, and the cleaned metal layer is bonded with heat at 100 ° C. After cutting to 1 inch width x 140 mm length, the opposite side After removing the release film of the phosphorus buffer adhesive layer, laminating on 75mm x 125mm alkali free glass at room temperature, peel off at an angle of 180° using a universal testing machine (UTM, AGS-1KNX, SHIMADZU) to check the adhesive strength. it was evaluated
이와 같이 평가된 접착력이 6kg/25mm 보다 낮을 경우 장기 신뢰성에 문제가 생겨 제품의 수명에 불안정한 요인이 될 수 있다. If the adhesive force evaluated in this way is lower than 6kg/25mm, a problem in long-term reliability may occur, which may become an unstable factor in the life of the product.
예시적인 일 구현예에서, 상기 접착제 조성물은 박리평가에 따른 뜯김폭이 2mm 이상인 것이 바람직하다. In an exemplary embodiment, the adhesive composition preferably has a tear width of 2 mm or more according to peel evaluation.
여기서, 박리 평가는 다음과 같이 수행한 것이다. 즉, 상기 접착제 조성물로 구성된 완충 접착층과 상기 접착제 조성물에 CaO를 고형분 기준으로 40중량% 더 포함하는 접착제 조성물로 구성된 수분 흡착층을 각각 이형필름에 코팅하면서 550nm파장 기준 500mJ의 광량으로 조사하여 UV경화시킨후 두 필름을 60℃의 온도로 열합착하고, 수분 흡착층의 이형필름을 제거한 후 세정된 메탈층을 100℃을 열로 합착하고, 실제 TV 크기인 65인치 또는 55인치 크기로 타발한 후, OLED 패널에 상온 합착한다. 1일 방치 후, 모서리를 강제로 OLED 패널에서 일부 벗겨낸 후, 1M/sec 의 속도로 30kgf의 힘으로 잡아당겨 뜯김폭(OLED 패널에 잔사되어 남은 길이)를 측정한다. Here, peeling evaluation was performed as follows. That is, UV curing by irradiating with a light amount of 500 mJ based on a wavelength of 550 nm while coating the release film with the buffer adhesive layer composed of the adhesive composition and the moisture adsorption layer composed of the adhesive composition further containing 40% by weight of CaO based on the solid content of the adhesive composition, respectively. After that, the two films are thermally bonded at a temperature of 60 ° C, the release film of the moisture adsorption layer is removed, the cleaned metal layer is bonded with heat at 100 ° C, and the actual TV size is 65 inches or 55 inches. Cement to the OLED panel at room temperature. After leaving it for 1 day, the edge is forcibly peeled off from the OLED panel, and then pulled with a force of 30 kgf at a speed of 1 M/sec to measure the tear width (remaining length remaining on the OLED panel).
전술한 뜯김폭이 2mm 미만으로 작아 쉽게 벗겨질 경우 장기 신뢰성에 문제가 생기고, 수분이 쉽게 침투 할 수 있는 가능성이 높아지고 합착 품질이 저하되므로, 뜯김폭은 2mm 미상인 것이 바람직하다.If the above-mentioned tear width is less than 2 mm and easily peeled off, long-term reliability problems arise, the possibility of easy penetration of moisture increases and the bonding quality decreases, so the tear width is preferably 2 mm unknown.
비제한적인 예시에서, 상기 뜯김폭은 2mm 이상, 3mm 이상, 4mm 이상, 5mm 이상, 6mm 이상, 7mm 이상, 8mm 이상, 9mm 이상 또는 10mm 이상일 수 있다. In non-limiting examples, the tearing width may be 2 mm or more, 3 mm or more, 4 mm or more, 5 mm or more, 6 mm or more, 7 mm or more, 8 mm or more, 9 mm or more, or 10 mm or more.
예시적인 일 구현예에서, 상기 접착제 조성물은 OLED 패널 합착 후 72시간 지난 후 기포 발생이 10개/m2 이하로 우수한 것일 수 있다.In an exemplary embodiment, the adhesive composition may have an excellent bubble generation of 10/m 2 or less after 72 hours after bonding the OLED panel.
여기서 합착성은 상기 접착제 조성물로 제조된 완충 접착층과 상기 접착제 조성물에 CaO를 고형분 기준으로 40중량% 더 포함하는 수분 흡착층으로 이루어진 전체 접착층의 수분 흡착층 면의 이형필름을 제거한 후, 메탈층과 100℃의 온도로 롤라미네이터로 합지하여 시료를 제작하여, OLED 패널과 합지 설비를 활용하여 상온에서 합착하고, 합착 직 후, 1일후, 3일(72시간) 후, 나아가 필요에 따라 일주일후의 합착 상태를 육안 및 비파괴검사 장비로 분석하여 평가하는 것이다.Here, the adhesion is achieved by removing the release film on the surface of the moisture adsorption layer of the entire adhesive layer consisting of a buffer adhesive layer made of the adhesive composition and a moisture adsorption layer containing 40% by weight of CaO based on the solid content of the adhesive composition, and then removing the release film from the metal layer and 100 Samples are prepared by laminating with a roll laminator at a temperature of ℃, bonding at room temperature using an OLED panel and laminating equipment, bonding state immediately after bonding, after 1 day, after 3 days (72 hours), or even after a week if necessary is evaluated by analyzing with the naked eye and non-destructive testing equipment.
아울러, 예시적인 일 구현예에서, 상기 접착제 조성물은 위와 같은 기포 외에, 합착 직 후 육안 관찰 시, 이물 및 찍힘(dent)이 없거나, 있더라도 이물, 찍힘(dent) 또는 이물 및 찍힘(dent) 크기(최대 길이)가 25㎛ 이하인 우수한 외관 특성을 달성할 수 있다.In addition, in one exemplary embodiment, the adhesive composition, in addition to the above air bubbles, has no or no foreign matter and dent upon visual observation immediately after bonding, or the size of foreign matter, dents, or foreign matter and dents ( It is possible to achieve excellent appearance characteristics with a maximum length) of 25 μm or less.
한편, 본 발명의 예시적인 구현예들에서는 또한, 전술한 접착제 조성물로 형성된 접착층을 포함하는, 유기전자장치용 접착 필름을 제공한다. Meanwhile, exemplary embodiments of the present invention also provide an adhesive film for an organic electronic device including an adhesive layer formed of the above-described adhesive composition.
예시적인 일 구현예에서, 상기 접착층은 2 층으로 이루어질 수 있으며 상기 접착제 조성물로 이루어지고 수분 흡착제를 더 포함하는 수분 흡착층 및 상기 접착제 조성물로 이루어지고 수분 흡착제를 포함하지 않는 완충 접착층을 포함할 수 있다. In one exemplary embodiment, the adhesive layer may be made of two layers and may include a moisture adsorption layer made of the adhesive composition and further including a moisture absorbent and a buffer adhesive layer made of the adhesive composition and not containing a moisture absorbent. there is.
본 발명의 예시적인 구현예들에서는 또한, 금속 층 등의 배리어층 및 전술한 유기전자장지용 접착 필름을 포함하는 유기전자장치 봉지재를 제공한다.Exemplary embodiments of the present invention also provide an organic electronic device encapsulant including a barrier layer such as a metal layer and the above-described adhesive film for an organic electronic device.
예시적인 일 구현예에서, 상기 접착 필름의 접착층은 상기 접착제 조성물로 이루어진 완충 접착층(이른바 Buffer 층)을 OLED 패널 즉 유기전자장치 측에 배치하고 상기 완층 접착층 상에 수분 흡착층을 형성한 것일 수 있다. In an exemplary embodiment, the adhesive layer of the adhesive film may be formed by placing a buffer adhesive layer (so-called Buffer layer) made of the adhesive composition on the side of an OLED panel, that is, an organic electronic device, and forming a moisture absorption layer on the soft adhesive layer. .
상기 수분 흡착층은 상기 접착제 조성물에 산화 칼슘 등의 금속산화물을 고형분 대비 약 20~60중량%, 또는 30~50중량% 또는 40중량%로 포함하는 것일 수 있다. CaO의 경우 수분함유 시 색상변화가 육안으로 쉽게 관찰되는 장점과 함께, 범용적으로도 다양한 분야에 사용되고 있어 적용이 용이하여 가장 일반적으로 사용되지만 이에 반드시 한정되는 것은 아니다.The moisture absorption layer may include a metal oxide such as calcium oxide in the adhesive composition in an amount of about 20 to 60% by weight, or 30 to 50% by weight or 40% by weight based on solid content. In the case of CaO, it is most commonly used because it is easy to apply because it is widely used in various fields with the advantage that color change is easily observed with the naked eye when water is contained, but it is not necessarily limited thereto.
상기 수분 흡착층은 금속층 등과 같은 배리어층에 접하게 되며, 봉지재는 해당 배리어층 및 접착 필름을 포함한다.The moisture absorption layer comes into contact with a barrier layer such as a metal layer, and the encapsulant includes a corresponding barrier layer and an adhesive film.
도 1은 본 발명의 일 구현예에 따른 유기전자장치 봉지재용 접착 필름을 나타내는 개략도이다.1 is a schematic view showing an adhesive film for an organic electronic device encapsulant according to an embodiment of the present invention.
도 1에 도시된 바와 같이, OLED 봉지용 접착 필름은 2층으로 구성될 수 있으며, 이와 같이 2층으로 구성 시 흡습제가 포함된 접착층인 수분 흡착층(1)이 금속 층과 합착되며, 흡습제가 포함되지 않은 접착력이 향상된 완충 접착층(2)이 OLED 패널에 합착된 구조로 구성되어 있다. As shown in FIG. 1, the adhesive film for encapsulating OLED may be composed of two layers, and when composed of two layers, the moisture adsorption layer 1, which is an adhesive layer containing a moisture absorbent, is bonded to the metal layer, and the moisture absorbent is bonded to the metal layer. It is composed of a structure in which a buffer adhesive layer 2 with improved adhesive strength, which is not included, is bonded to the OLED panel.
여기서 각 층 간 접착력이 우수하고, 수분침투속도가 최소화되어야 제품의 수명을 향상시킬 수 있다. Here, the lifespan of the product can be improved only when the adhesion between each layer is excellent and the water permeation rate is minimized.
코팅액은 내수분 특성이 좋은 폴리올레핀계 바인더를 기반으로 이의 성능을 부가적으로 향상시킬 수 있는 다양한 기능성 첨가제로 구성하였다. 흡습제로는 전술한 바와 같이 금속산화물을 사용하는 것이 바람직하며, 상기 수분 흡착층(1)의 두께는 20~1,000㎛ 이며, 바람직하게는 20~100㎛이다. The coating solution was composed of various functional additives that can additionally improve its performance based on a polyolefin-based binder with good moisture resistance. As the moisture absorbent, it is preferable to use a metal oxide as described above, and the thickness of the moisture absorption layer 1 is 20 to 1,000 μm, preferably 20 to 100 μm.
상기 두께가 20㎛ 미만으로 낮을 경우, 흡습 성능의 저하가 발생할 수 있으며, 100㎛를 초과하여 높을 경우, 패널 전체 두께가 커지게 되므로 바람직하지 않다.When the thickness is less than 20 μm, deterioration in moisture absorption performance may occur, and when the thickness exceeds 100 μm, the overall thickness of the panel increases, which is not preferable.
상기 완충 접착층(2)의 두께는 5~50㎛이며, 바람직하게는 5~20㎛이다. 해당 두께가 5㎛ 미만으로 낮을 경우, 흡습제 등 필러의 영향으로 표면 조도가 커져 부착력이 낮을 수 있으며, 20㎛를 초과하여 높을 경우, 흡습 성능을 저하시킬 수 있다. The thickness of the buffer adhesive layer 2 is 5 to 50 μm, preferably 5 to 20 μm. When the thickness is less than 5 μm, surface roughness may be increased due to the influence of fillers such as moisture absorbents, and thus adhesion may be low, and when the thickness exceeds 20 μm, moisture absorption performance may be deteriorated.
한편, 본 발명의 예시적인 구현예들에서는 또한, 금속 층 등의 배리어층에 전술한 접착 필름을 형성하는 단계;를 포함하는 유기전자장치 봉지재 제조 방법을 제공한다.On the other hand, exemplary embodiments of the present invention also provide a method for manufacturing an organic electronic device encapsulant comprising the step of forming the above-described adhesive film on a barrier layer such as a metal layer.
예시적인 일 구현예에서, 상기 방법은 흡습제를 포함하지 않는 접착제 조성물을 제1 이형 필름(중박리 이형필름)에 코팅하고, 가열 건조 및 경화한 후 제2 이형 필름(경박리 이형 필름)을 합지하여 완충 접착층이 사이에 게재된 예비 접착 필름을 제공하는 단계; In an exemplary embodiment, the method is to coat an adhesive composition that does not contain a moisture absorbent on a first release film (heavy release film), heat dry and cure, and then laminate a second release film (light release film). providing a pre-adhesive film having a buffer adhesive layer interposed therebetween;
제3 이형 필름(경박리 이형 필름)에 흡습제를 포함하는 접착제 조성물을 코팅하고, 가열 건조 및 경화한 후, 상기 제1 예비 접착 필름에서 제2 이형 필름(경박리 이형 필름)을 제거하고 노출된 면에 열 합지하여 수분 흡착층 및 완충 접착층을 포함하는 접착 필름을 제공하는 단계; 및After coating an adhesive composition containing a moisture absorbent on a third release film (light-peel release film), drying and curing by heating, removing the second release film (light-peel release film) from the first pre-adhesive film and exposed providing an adhesive film comprising a moisture adsorption layer and a buffer adhesive layer by thermally laminating the surface; and
상기 접착 필름에서 제3 이형 필름(경박리 이형 필름)을 제거하고 노출된 면과 인바, 알루미늄과 같은 금속층 등의 배리어층을 합지하여 봉지재를 제공하는 단계;를 포함할 수 있다. It may include removing a third release film (light release film) from the adhesive film and providing an encapsulant by laminating the exposed surface with a barrier layer such as invar or a metal layer such as aluminum.
본 발명의 예시적인 구현예들에서는 또한, 전술한 유기전자장치 봉지재를 이용한 유기전자장치의 봉지 방법을 제공한다. Exemplary embodiments of the present invention also provide a method of encapsulating an organic electronic device using the organic electronic device encapsulant described above.
본 발명의 예시적인 구현예들에서는 또한, 전술한 유기전자장치 봉지재로 봉지된 유기전자장치를 제공한다.Exemplary embodiments of the present invention also provide an organic electronic device sealed with the organic electronic device encapsulant described above.
이상과 같이 본 발명의 예시적인 구현예들에 의하면 배리어층과 접합하는 수분 흡착층(Getter 층)에 적용된 금속산화물이나 금속염인 다량의 흡습제 분말에 의하여 초기 수분침투속도가 증가되고 이에 따라 제품 수명이 저하되는 문제를 방지하여 초기 수분침투속도를 최소화하여 신뢰성을 향상하면서, 아울러 낮은 수분/산소 투과도를 갖고 접착력, 상온에서의 합착성 등이 우수하다. As described above, according to exemplary embodiments of the present invention, the initial moisture penetration rate is increased by a large amount of metal oxide or metal salt desiccant powder applied to the moisture adsorption layer (getter layer) bonded to the barrier layer, and thus the product life is increased. It prevents deterioration and minimizes the initial water permeation rate to improve reliability, and also has low water/oxygen permeability and excellent adhesive strength and cohesiveness at room temperature.
이하의 실시예를 통하여 본 발명의 예시적인 구현예들을 더욱 상세하게 설명된다. 본 명세서에 개시된 실시예들은 단지 설명을 위한 목적으로 예시된 것으로서, 본 발명의 실시예들은 다양한 형태로 실시될 수 있으며 본 명세서에 설명된 실시예들에 한정되는 것으로 해석되어서는 안 된다. Exemplary embodiments of the present invention are described in more detail through the following examples. Embodiments disclosed herein are illustrated for purposes of explanation only, and embodiments of the present invention may be implemented in various forms and should not be construed as being limited to the embodiments described herein.
[실험예][Experimental example]
우선 낮은 수분침투속도와 낮은 산소투과도를 갖는 폴리올레핀계 바인더 및 첨가제 선정을 위해, OPP(Oriented Poly Propylene) 필름에 각 원재료를 샌드위치 타입으로 배치한 후 각 원재료 종류별로 OTR과 WVTR을 측정하였다. First, in order to select polyolefin binders and additives with low water penetration rate and low oxygen permeability, OTR and WVTR were measured for each raw material type after placing each raw material in a sandwich type on an OPP (Oriented Poly Propylene) film.
[비교예 1][Comparative Example 1]
비교예 1은 OPP/OPP 기존 구조이다. Comparative Example 1 is an OPP/OPP existing structure.
즉, OPP는 WVTR은 우수하고, OTR은 낮은 것으로 알려져 있다. 기본 조건을 확인하기 위해 12㎛ 두께의 OPP를 두 장 합친 후 OTR, WVTR을 평가하였다. That is, OPP is known to have excellent WVTR and low OTR. To confirm the basic conditions, OTR and WVTR were evaluated after combining two sheets of OPP with a thickness of 12 μm.
[비교예2][Comparative Example 2]
비교예 2는 OPP/OPP 필름 사이에 EPDM 바인더 수지 단독으로 이루어진 조성물로 형성된 50㎛ 필름을 배치한 것이다. 해당 필름 구성 후OTR, WVTR을 분석하였다.In Comparative Example 2, a 50 μm film formed of a composition consisting of an EPDM binder resin alone was disposed between OPP/OPP films. After constructing the corresponding film, OTR and WVTR were analyzed.
[비교예3][Comparative Example 3]
비교예 3은 OPP/OPP 필름 사이에 부틸 고무 바인더 단독으로 이루어진 조성물로 형성된 50㎛ 필름을 배치한 것이다. 해당 필름 구성 후 OTR, WVTR을 분석하였다.In Comparative Example 3, a 50 μm film formed of a composition consisting of only a butyl rubber binder was disposed between OPP/OPP films. After constructing the film, OTR and WVTR were analyzed.
[비교예4][Comparative Example 4]
비교예 4는 OPP/OPP 필름 사이에 폴리이소부틸렌(PIB; Polyisobutene) 바인더 수지 단독으로 이루어진 조성물로 형성된 50㎛ 필름을 배치한 것이다. 해당 필름 구성 후 OTR, WVTR을 분석하였다.In Comparative Example 4, a 50 μm film formed of a composition consisting of only a polyisobutene (PIB) binder resin was disposed between the OPP/OPP films. After constructing the film, OTR and WVTR were analyzed.
[실시예1][Example 1]
실시예 1은 OPP/OPP 필름 사이에, 폴리이소부틸렌(Polyisobutylene)과 부틸 고무(Butyl Rubber)가 7:3의 중량비로 혼합된 바인더 100 중량 기준에, 80중량부의 연화점 125℃의 점착부여제(DCPD), 10중량부의 단관능 아크릴모노머(THFA), 5중량부의 2관능 아크릴모노머(TCDDA), 10중량부의 인계 광개시제(TPO)가 혼합된 접착제 조성물로 형성된 50㎛ 필름(접착제 조성물 단층 필름)을 배치한 것이다. 해당 필름 구성 후 OTR, WVTR을 분석하였다.Example 1 is based on 100 weight of a binder in which polyisobutylene and butyl rubber are mixed at a weight ratio of 7: 3 between OPP / OPP films, 80 parts by weight of a tackifier with a softening point of 125 ° C. (DCPD), 10 parts by weight of a monofunctional acrylic monomer (THFA), 5 parts by weight of a bifunctional acrylic monomer (TCDDA), and 10 parts by weight of a phosphorus-based photoinitiator (TPO). will be placed After constructing the film, OTR and WVTR were analyzed.
한편, 상기 접착제 조성물을 이용하여 완충 접착층(2) 10㎛을 제조하고, 상기 접착제 조성물에 전체 고형분의 40wt%가 되도록 CaO(산화칼슘)를 넣은 접착제 조성물을 이용하여 수분흡수 흡착층(1) 40㎛을 제조하였다. On the other hand, a buffer adhesive layer (2) of 10 μm was prepared using the adhesive composition, and the moisture absorbing adsorption layer (1) 40 μm was prepared.
각 층은 용매에 녹여진 코팅액으로 제조된 후 슬롯 다이(Slot die) 코터에서 코팅 후, 용매를 제거한 후, UV 365nm 파장대 기준으로 500mJ의 광량으로 조사한 후 두 층을 60℃온도로 열로 합지하여 접착 필름(완충 접착층 및 수분 흡수 흡착층을 포함하는 접착 필름)을 형성하였다. Each layer is prepared with a coating liquid dissolved in a solvent, coated in a slot die coater, the solvent removed, and then irradiated with a light amount of 500 mJ based on the UV 365 nm wavelength range, and then the two layers are thermally laminated at 60 ° C and bonded. A film (adhesive film comprising a buffer adhesive layer and a moisture absorption adsorption layer) was formed.
[실시예2][Example 2]
접착제 조성물에서 점착 부여제(DCPD)의 연화점이 105℃인 것을 사용한 것을 제외하고는 실시예 1과 동일하게 잡착제 조성물 단층 필름, 완충 접착층 및 수분 흡수 흡착층을 포함하는 접착 필름을 제조 및 분석하였다. An adhesive film including a single layer film of the adhesive composition, a buffer adhesive layer, and a moisture absorption adsorption layer was prepared and analyzed in the same manner as in Example 1, except that the softening point of the tackifier (DCPD) in the adhesive composition was used. .
즉, 실시예 2의 접착제 조성물은 폴리이소부틸렌과 부틸 고무가 7:3의 중량비로 혼합된 바인더 100 중량 기준에, 80중량부의 연화점 105℃의 점착부여제(DCPD), 10중량부의 단관능 아크릴모노머, 5중량부의 2관능 아크릴모노머, 10중량부의 인계 광개시제가 혼합된 접착제 조성물이다.That is, the adhesive composition of Example 2 is based on 100 weight of a binder in which polyisobutylene and butyl rubber are mixed at a weight ratio of 7:3, 80 parts by weight of a tackifier (DCPD) having a softening point of 105 ° C., 10 parts by weight of a monofunctional It is an adhesive composition in which an acrylic monomer, 5 parts by weight of a bifunctional acrylic monomer, and 10 parts by weight of a phosphorus-based photoinitiator are mixed.
[실시예 3][Example 3]
접착제 조성물에서 폴리이소부틸렌과 부틸고무의 혼합 중량비를 9:1로 한 것을 제외하고는 실시예 1과 동일하게 잡착제 조성물 단층 필름, 완충 접착층 및 수분 흡수 흡착층을 포함하는 접착 필름을 제조 및 분석하였다. An adhesive film including a single layer film of the adhesive composition, a buffer adhesive layer, and a moisture absorption adsorption layer was prepared in the same manner as in Example 1, except that the mixed weight ratio of polyisobutylene and butyl rubber in the adhesive composition was 9: 1, and analyzed.
즉, 실시예 3의 접착제 조성물은 폴리이소부틸렌과 부틸 고무가 9:1의 중량비로 혼합된 바인더 100 중량 기준에, 80중량부의 연화점 125℃의 점착부여제(DCPD), 10중량부의 단관능 아크릴모노머, 5중량부의 2관능 아크릴모노머, 10중량부의 인계 광개시제가 혼합된 접착제 조성물이다.That is, the adhesive composition of Example 3 is based on 100 weight of a binder in which polyisobutylene and butyl rubber are mixed at a weight ratio of 9: 1, 80 parts by weight of a tackifier with a softening point of 125 ° C. (DCPD), 10 parts by weight of a monofunctional It is an adhesive composition in which an acrylic monomer, 5 parts by weight of a bifunctional acrylic monomer, and 10 parts by weight of a phosphorus-based photoinitiator are mixed.
[실시예 4][Example 4]
접착제 조성물에서 폴리이소부틸렌과 부틸고무의 혼합 중량비를 2:8로 한 것을 제외하고는 실시예 1과 동일하게 접착제 조성물 단층 필름, 완충 접착층 및 수분 흡수 흡착층을 포함하는 접착 필름을 제조 및 분석하였다. Preparation and analysis of an adhesive film including a single layer film of the adhesive composition, a buffer adhesive layer and a moisture absorption adsorption layer in the same manner as in Example 1, except that the mixed weight ratio of polyisobutylene and butyl rubber in the adhesive composition was 2:8 did
즉, 실시예 4의 접착제 조성물은 폴리이소부틸렌과 부틸 고무가 2:8의 중량비로 혼합된 바인더 100 중량 기준에, 80중량부의 연화점 125℃의 점착부여제(DCPD), 10중량부의 단관능 아크릴모노머, 5중량부의 2관능 아크릴모노머, 10중량부의 인계 광개시제가 혼합된 접착제 조성물이다.That is, the adhesive composition of Example 4 is based on 100 weight of a binder in which polyisobutylene and butyl rubber are mixed at a weight ratio of 2:8, 80 parts by weight of a tackifier (DCPD) with a softening point of 125 ° C., 10 parts by weight of a monofunctional It is an adhesive composition in which an acrylic monomer, 5 parts by weight of a bifunctional acrylic monomer, and 10 parts by weight of a phosphorus-based photoinitiator are mixed.
[비교예 5][Comparative Example 5]
접착제 조성물에서 부틸 고무 사용하지 않고 폴리이소부틸렌만 사용한 것을 제외하고는 실시예 1과 동일하게 잡착제 조성물 단층 필름, 완충 접착층 및 수분 흡수 흡착층을 포함하는 접착 필름을 제조 및 분석하였다. An adhesive film including a single layer film of the adhesive composition, a buffer adhesive layer, and a moisture absorption adsorption layer was prepared and analyzed in the same manner as in Example 1, except that butyl rubber was not used in the adhesive composition and only polyisobutylene was used.
즉, 비교예 5의 접착제 조성물은 폴리이소부틸렌 바인더 100 중량 기준에, 80중량부의 연화점 125℃의 점착부여제(DCPD), 10중량부의 단관능 아크릴모노머, 5중량부의 2관능 아크릴모노머, 10중량부의 인계 광개시제가 혼합된 접착제 조성물이다. That is, the adhesive composition of Comparative Example 5 contains 80 parts by weight of a tackifier (DCPD) having a softening point of 125° C., 10 parts by weight of a monofunctional acrylic monomer, 5 parts by weight of a bifunctional acrylic monomer, 10 parts by weight based on 100 parts by weight of a polyisobutylene binder. An adhesive composition in which a phosphorus-based photoinitiator is mixed by weight.
[비교예 6][Comparative Example 6]
접착제 조성물에서 폴리이소부틸렌은 사용하지 않고 부틸 고무만 사용한 것을 제외하고는 실시예 1과 동일하게 잡착제 조성물 단층 필름, 완충 접착층 및 수분 흡수 흡착층을 포함하는 접착 필름을 제조 및 분석하였다. An adhesive film including a single-layer adhesive composition, a buffer adhesive layer, and a moisture absorption adsorption layer was prepared and analyzed in the same manner as in Example 1, except that polyisobutylene was not used in the adhesive composition and only butyl rubber was used.
즉, 비교예 6의 접착제 조성물은 부틸 고무 바인더 100 중량 기준에, 80중량부의 연화점 125℃의 점착부여제(DCPD), 10중량부의 단관능 아크릴모노머, 5중량부의 2관능 아크릴모노머, 10중량부의 인계 광개시제가 혼합된 접착제 조성물이다. That is, the adhesive composition of Comparative Example 6 is based on 100 weight of butyl rubber binder, 80 parts by weight of a tackifier (DCPD) with a softening point of 125 ° C, 10 parts by weight of a monofunctional acrylic monomer, 5 parts by weight of a bifunctional acrylic monomer, 10 parts by weight It is an adhesive composition in which a phosphorus-based photoinitiator is mixed.
[비교예 7] [Comparative Example 7]
접착제 조성물에서 바인더 수지로 EPDM을 사용한 것을 제외하고는 실시예 1과 동일하게 잡착제 조성물 단층 필름, 완충 접착층 및 수분 흡수 흡착층을 포함하는 접착 필름을 제조 및 분석하였다. An adhesive film including a single layer film of the adhesive composition, a buffer adhesive layer, and a moisture absorption adsorption layer was prepared and analyzed in the same manner as in Example 1, except that EPDM was used as the binder resin in the adhesive composition.
즉, 비교예 7의 접착제 조성물은 EPDM 바인더 100 중량 기준에, 80중량부의 연화점 125℃의 점착부여제(DCPD), 10중량부의 단관능 아크릴모노머, 5중량부의 2관능 아크릴모노머, 10중량부의 인계 광개시제가 혼합된 접착제 조성물이다. That is, the adhesive composition of Comparative Example 7 contains 80 parts by weight of a tackifier (DCPD) having a softening point of 125° C., 10 parts by weight of a monofunctional acrylic monomer, 5 parts by weight of a bifunctional acrylic monomer, and 10 parts by weight of a phosphorus based on 100 parts by weight of the EPDM binder. It is an adhesive composition in which a photoinitiator is mixed.
[비교예 8] [Comparative Example 8]
접착제 조성물에서 폴리이소부틸렌과 부틸고무의 혼합 중량비를 1:9로 한 것을 제외하고는 실시예 1과 동일하게 잡착제 조성물 단층 필름, 완충 접착층 및 수분 흡수 흡착층을 포함하는 접착 필름을 제조 및 분석하였다. An adhesive film including a single layer film of the adhesive composition, a buffer adhesive layer and a moisture absorption adsorption layer was prepared in the same manner as in Example 1, except that the mixed weight ratio of polyisobutylene and butyl rubber in the adhesive composition was 1:9, and analyzed.
즉, 실시예 3의 접착제 조성물은 폴리이소부틸렌과 부틸 고무가 1:9의 중량비로 혼합된 바인더 100 중량 기준에, 80중량부의 연화점 125℃의 점착부여제(DCPD), 10중량부의 단관능 아크릴모노머, 5중량부의 2관능 아크릴모노머, 10중량부의 인계 광개시제가 혼합된 접착제 조성물이다.That is, the adhesive composition of Example 3 is based on 100 weight of a binder in which polyisobutylene and butyl rubber are mixed at a weight ratio of 1:9, 80 parts by weight of a tackifier with a softening point of 125 ° C. (DCPD), 10 parts by weight of a monofunctional It is an adhesive composition in which an acrylic monomer, 5 parts by weight of a bifunctional acrylic monomer, and 10 parts by weight of a phosphorus-based photoinitiator are mixed.
[비교예 9] [Comparative Example 9]
접착제 조성물에서 점착 부여제로 연화점이 150℃인 것(연화점 150℃의 방향족 C9계 석수수지 점착부여제)을 사용한 것을 제외하고는 실시예 1과 동일하게 잡착제 조성물 단층 필름, 완충 접착층 및 수분 흡수 흡착층을 포함하는 접착 필름을 제조 및 분석하였다. In the adhesive composition, the adhesive composition monolayer film, the buffer adhesive layer and the moisture absorption adsorption were the same as in Example 1 except that the one having a softening point of 150 ° C. (aromatic C9-based mason resin tackifier with a softening point of 150 ° C.) was used as the tackifier. An adhesive film comprising the layers was prepared and analyzed.
즉, 비교예 9의 접착제 조성물은 폴리이소부틸렌과 부틸 고무가 7:3의 중량비로 혼합된 바인더 100 중량 기준에, 80중량부의 연화점 150℃의 방향족 C9계 석수수지 점착부여제, 10중량부의 단관능 아크릴모노머, 5중량부의 2관능 아크릴모노머, 10중량부의 인계 광개시제가 혼합된 접착제 조성물이다.That is, the adhesive composition of Comparative Example 9 is based on 100 weight of a binder in which polyisobutylene and butyl rubber are mixed at a weight ratio of 7:3, 80 parts by weight of an aromatic C9-based mason resin tackifier with a softening point of 150 ° C., 10 parts by weight An adhesive composition in which a monofunctional acrylic monomer, 5 parts by weight of a bifunctional acrylic monomer, and 10 parts by weight of a phosphorus-based photoinitiator are mixed.
[비교예10][Comparative Example 10]
접착제 조성물에서 단관능 아크릴모노머를 20중량부로 과량 사용한 것을 제외하고는 실시예 1과 동일하게 잡착제 조성물 단층 필름, 완충 접착층 및 수분 흡수 흡착층을 포함하는 접착 필름을 제조 및 분석하였다. An adhesive film including a single layer film of the adhesive composition, a buffer adhesive layer, and a moisture absorption adsorption layer was prepared and analyzed in the same manner as in Example 1, except that 20 parts by weight of the monofunctional acrylic monomer was excessively used in the adhesive composition.
즉, 비교예 10의 접착제 조성물은 폴리이소부틸렌과 부틸 고무가 7:3의 중량비로 혼합된 바인더 100 중량 기준에, 80중량부의 연화점 125℃의 점착부여제(DCPD), 20중량부의 단관능 아크릴모노머, 5중량부의 2관능 아크릴모노머, 10중량부의 인계 광개시제가 혼합된 접착제 조성물이다.That is, the adhesive composition of Comparative Example 10 is based on 100 weight of a binder in which polyisobutylene and butyl rubber are mixed at a weight ratio of 7: 3, 80 parts by weight of a tackifier (DCPD) having a softening point of 125 ° C., 20 parts by weight of a monofunctional It is an adhesive composition in which an acrylic monomer, 5 parts by weight of a bifunctional acrylic monomer, and 10 parts by weight of a phosphorus-based photoinitiator are mixed.
[비교예11][Comparative Example 11]
접착제 조성물에서 다관능 아크릴모노머를 2.5중량부로 과소량 사용한 것을 제외하고는 실시예 1과 동일하게 잡착제 조성물 단층 필름, 완충 접착층 및 수분 흡수 흡착층을 포함하는 접착 필름을 제조 및 분석하였다. An adhesive film including a single layer film of the adhesive composition, a buffer adhesive layer, and a moisture absorption adsorption layer was prepared and analyzed in the same manner as in Example 1, except that 2.5 parts by weight of the polyfunctional acrylic monomer was used in the adhesive composition in an excessive amount.
즉, 비교예 11의 접착제 조성물은 폴리이소부틸렌과 부틸 고무가 7:3의 중량비로 혼합된 바인더 100 중량 기준에, 80중량부의 연화점 125℃의 점착부여제(DCPD), 10중량부의 단관능 아크릴모노머, 2.5중량부의 2관능 아크릴모노머, 10중량부의 인계 광개시제가 혼합된 접착제 조성물이다.That is, the adhesive composition of Comparative Example 11 is based on 100 weight of a binder in which polyisobutylene and butyl rubber are mixed at a weight ratio of 7:3, 80 parts by weight of a tackifier (DCPD) having a softening point of 125 ° C., 10 parts by weight of a monofunctional It is an adhesive composition in which an acrylic monomer, 2.5 parts by weight of a bifunctional acrylic monomer, and 10 parts by weight of a phosphorus-based photoinitiator are mixed.
[비교예12][Comparative Example 12]
접착제 조성물에서 다관능 아크릴모노머를 15중량부로 과량 사용한 것을 제외하고는 실시예 1과 동일하게 잡착제 조성물 단층 필름, 완충 접착층 및 수분 흡수 흡착층을 포함하는 접착 필름을 제조 및 분석하였다. An adhesive film including a single-layer adhesive composition, a buffer adhesive layer, and a moisture absorption adsorption layer was prepared and analyzed in the same manner as in Example 1, except that 15 parts by weight of the multifunctional acrylic monomer was excessively used in the adhesive composition.
즉, 비교예 12의 접착제 조성물은 폴리이소부틸렌과 부틸 고무가 7:3의 중량비로 혼합된 바인더 100 중량 기준에, 80중량부의 연화점 125℃의 점착부여제(DCPD), 10중량부의 단관능 아크릴모노머, 15중량부의 2관능 아크릴모노머, 10중량부의 인계 광개시제가 혼합된 접착제 조성물이다.That is, the adhesive composition of Comparative Example 12 is based on 100 weight of a binder in which polyisobutylene and butyl rubber are mixed at a weight ratio of 7:3, 80 parts by weight of a tackifier (DCPD) having a softening point of 125 ° C., 10 parts by weight of a monofunctional It is an adhesive composition in which an acrylic monomer, 15 parts by weight of a bifunctional acrylic monomer, and 10 parts by weight of a phosphorus-based photoinitiator are mixed.
[비교예13][Comparative Example 13]
접착제 조성물에서 광개시제를 5중량부로 과소량 사용한 것을 제외하고는 실시예 1과 동일하게 잡착제 조성물 단층 필름, 완충 접착층 및 수분 흡수 흡착층을 포함하는 접착 필름을 제조 및 분석하였다. An adhesive film including a single layer film of the adhesive composition, a buffer adhesive layer, and a moisture absorption adsorption layer was prepared and analyzed in the same manner as in Example 1, except that the photoinitiator was used in an excessive amount of 5 parts by weight in the adhesive composition.
즉, 비교예 13의 접착제 조성물은 폴리이소부틸렌과 부틸 고무가 7:3의 중량비로 혼합된 바인더 100 중량 기준에, 80중량부의 연화점 125℃의 점착부여제(DCPD), 10중량부의 단관능 아크릴모노머, 5중량부의 2관능 아크릴모노머, 5중량부의 인계 광개시제가 혼합된 접착제 조성물이다.That is, the adhesive composition of Comparative Example 13 is based on 100 weight of a binder in which polyisobutylene and butyl rubber are mixed at a weight ratio of 7:3, 80 parts by weight of a tackifier (DCPD) with a softening point of 125 ° C., 10 parts by weight of a monofunctional It is an adhesive composition in which an acrylic monomer, 5 parts by weight of a bifunctional acrylic monomer, and 5 parts by weight of a phosphorus-based photoinitiator are mixed.
[비교예14][Comparative Example 14]
접착제 조성물에서 광개시제를 20중량부로 과량 사용한 것을 제외하고는 실시예 1과 동일하게 잡착제 조성물 단층 필름, 완충 접착층 및 수분 흡수 흡착층을 포함하는 접착 필름을 제조 및 분석하였다. An adhesive film including a single-layer adhesive composition film, a buffer adhesive layer, and a moisture absorption adsorption layer was prepared and analyzed in the same manner as in Example 1, except that the photoinitiator was used in excess of 20 parts by weight in the adhesive composition.
즉, 비교예 14의 접착제 조성물은 폴리이소부틸렌과 부틸 고무가 7:3의 중량비로 혼합된 바인더 100 중량 기준에, 80중량부의 연화점 125℃의 점착부여제(DCPD), 10중량부의 단관능 아크릴모노머, 5중량부의 2관능 아크릴모노머, 20중량부의 인계 광개시제가 혼합된 접착제 조성물이다.That is, the adhesive composition of Comparative Example 14 is based on 100 weight of a binder in which polyisobutylene and butyl rubber are mixed at a weight ratio of 7: 3, 80 parts by weight of a tackifier (DCPD) having a softening point of 125 ° C., 10 parts by weight of a monofunctional It is an adhesive composition in which an acrylic monomer, 5 parts by weight of a bifunctional acrylic monomer, and 20 parts by weight of a phosphorus-based photoinitiator are mixed.
[비교예15][Comparative Example 15]
접착제 조성물에서 점착부여제를 20중량부로 과소량 사용한 것을 제외하고는 실시예 1과 동일하게 잡착제 조성물 단층 필름, 완충 접착층 및 수분 흡수 흡착층을 포함하는 접착 필름을 제조 및 분석하였다. An adhesive film including a single layer film of the adhesive composition, a buffer adhesive layer, and a moisture absorption adsorption layer was prepared and analyzed in the same manner as in Example 1, except that the tackifier was used in an excessive amount of 20 parts by weight in the adhesive composition.
즉, 비교예 15의 접착제 조성물은 폴리이소부틸렌과 부틸 고무가 7:3의 중량비로 혼합된 바인더 100 중량 기준에, 20중량부의 연화점 125℃의 점착부여제(DCPD), 10중량부의 단관능 아크릴모노머, 5중량부의 2관능 아크릴모노머, 10중량부의 인계 광개시제가 혼합된 접착제 조성물이다.That is, the adhesive composition of Comparative Example 15 is based on 100 weight of a binder in which polyisobutylene and butyl rubber are mixed in a weight ratio of 7: 3, 20 parts by weight of a tackifier (DCPD) having a softening point of 125 ° C., 10 parts by weight of a monofunctional It is an adhesive composition in which an acrylic monomer, 5 parts by weight of a bifunctional acrylic monomer, and 10 parts by weight of a phosphorus-based photoinitiator are mixed.
[비교예16][Comparative Example 16]
접착제 조성물에서 점착부여제를 160중량부로 과량 사용한 것을 제외하고는 실시예 1과 동일하게 잡착제 조성물 단층 필름, 완충 접착층 및 수분 흡수 흡착층을 포함하는 접착 필름을 제조 및 분석하였다. An adhesive film including a single layer film of the adhesive composition, a buffer adhesive layer, and a moisture absorption adsorption layer was prepared and analyzed in the same manner as in Example 1, except that the tackifier was used in an excessive amount of 160 parts by weight in the adhesive composition.
즉, 비교예 16의 접착제 조성물은 폴리이소부틸렌과 부틸 고무가 7:3의 중량비로 혼합된 바인더 100 중량 기준에, 160중량부의 연화점 125℃의 점착부여제(DCPD), 10중량부의 단관능 아크릴모노머, 5중량부의 2관능 아크릴모노머, 10중량부의 인계 광개시제가 혼합된 접착제 조성물이다.That is, the adhesive composition of Comparative Example 16 is based on 100 weight of a binder in which polyisobutylene and butyl rubber are mixed at a weight ratio of 7: 3, 160 parts by weight of a tackifier (DCPD) having a softening point of 125 ° C., 10 parts by weight of a monofunctional It is an adhesive composition in which an acrylic monomer, 5 parts by weight of a bifunctional acrylic monomer, and 10 parts by weight of a phosphorus-based photoinitiator are mixed.
이상의 실시예 및 비교예들의 구성을 정리하면 다음 표와 같다.The configuration of the above examples and comparative examples is summarized in the following table.
* 상기 표에서 조성물은 바인더 수지 외에 점착 부여제, 단관능 아크릴 모노머, 다관능 아크릴모노머, 광개시제를 포함하는 것이다. * In the above table, the composition includes a tackifier, a monofunctional acrylic monomer, a multifunctional acrylic monomer, and a photoinitiator in addition to the binder resin.
[실험 1: 산소투과도(OTR; Oxygen Trans. Rate), 수증기 투과도(WVTR; Water Vapor Trans. Rate) 평가][Experiment 1: Oxygen Trans. Rate (OTR), Water Vapor Trans. Rate (WVTR) Evaluation]
Mocon사의 산소투과도, 수분투과도 장비를 활용하여, 각각 ASTM D3985, KS M ISO 15106규격에 맞게 평가하였다. OTR은 Mocon사의 Mocon OX-Tran 2/61, WVTR은 MOCON PERMATRAN-W 3/61로 분석하였다.Using Mocon's oxygen permeability and moisture permeability equipment, they were evaluated according to ASTM D3985 and KS M ISO 15106 standards, respectively. OTR was analyzed with Mocon OX-Tran 2/61 from Mocon, and WVTR was analyzed with MOCON PERMATRAN-W 3/61.
[실험 2: 수분침투길이(WTV; Water Transmission Velocity) 평가][Experiment 2: Water Transmission Velocity (WTV) Evaluation]
완충 접착층(2)과 수분 흡착층(1)을 각각 이형필름에 코팅하면서 550nm파장 기준 500mJ의 광량으로 조사하여 UV 경화시킨후 두 필름을 60℃의 온도로 열합착하고, 수분 흡착층(1)의 이형필름을 제거한 후 세정된 메탈층을 100℃을 열로 합착하고 반대면인 완충 접착층(2)의 이형필름을 제거한 후 무알칼리(Alkali free) 유리를 상온에서 합착 한 후에, 온도 85℃, 습도 85%의 신뢰성 챔버에 넣고, 100시간 단위로 1000시간까지 모서리에서 시작되는 수분의 침투 길이를 현미경을 통해 측정하였다. While coating the release film with the buffer adhesive layer (2) and the moisture adsorption layer (1), respectively, UV curing by irradiation with a light amount of 500 mJ based on a wavelength of 550 nm, the two films are thermally bonded at a temperature of 60 ° C, and the moisture adsorption layer (1) After removing the release film, the cleaned metal layer is bonded with heat at 100 ° C, and after removing the release film of the buffer adhesive layer (2), which is the opposite side, after bonding the alkali-free glass at room temperature, the temperature is 85 ° C, and the humidity is 85 ° C. It was placed in a reliability chamber of 85%, and the penetration length of moisture starting from the edge was measured through a microscope until 1000 hours in 100 hour increments.
한편, 1000시간 기준 OLED 패널 베젤 인접 부위 색변화 측정을 위하여, 상기 무알칼리(Alkali free) 유리 대신 OLED 패널을 상온에서 합착하고, 온도 85℃, 습도 85%의 신뢰성 챔버에 넣고, 1000시간일 때를 기준으로 OLED 패널의 베젤 인접 부위의 색 변화를 육안으로 관찰하였다.On the other hand, in order to measure the color change of the area adjacent to the OLED panel bezel based on 1000 hours, the OLED panel was bonded at room temperature instead of the alkali-free glass, placed in a reliability chamber with a temperature of 85 ° C and a humidity of 85%, and at 1000 hours Based on this, the color change of the area adjacent to the bezel of the OLED panel was observed with the naked eye.
[실험 3: 180° 박리 접착력 평가] [Experiment 3: 180° Peel Adhesion Evaluation]
완충 접착층(2)과 수분 흡착층(1)을 각각 이형필름에 코팅하면서 550nm 파장 기준 500mJ의 광량으로 조사하여 UV 경화시킨후 두 필름을 60℃의 온도로 열합착하고, 수분 흡착층(1)의 이형필름을 제거한 후 세정된 메탈층을 100℃을 열로 합착하고 폭 1인치 x 길이 140mm로 재단 한 후, 반대면인 완충 접착층(2)의 이형필름을 제거 한 후 75mmx 125mm Alkali free glass에 상온 합지 후, 만능재료시험기(UTM, AGS-1KNX, SHIMADZU社)를 이용하여 180°의 각도로 박리시켜 접착력을 평가하였다. While coating the buffer adhesive layer (2) and the moisture adsorption layer (1) on the release film, irradiation with a light amount of 500 mJ based on a wavelength of 550 nm and UV curing, the two films are thermally bonded at a temperature of 60 ° C, and the moisture adsorption layer (1) After removing the release film, the cleaned metal layer is bonded with heat at 100 ° C, cut to 1 inch wide x 140 mm long, and after removing the release film of the opposite side, the buffer adhesive layer (2), it is placed on 75 mm x 125 mm Alkali free glass at room temperature. After laminating, adhesive strength was evaluated by peeling at an angle of 180 ° using a universal testing machine (UTM, AGS-1KNX, SHIMADZU).
[실험 4: 박리(Decapsulation) 평가 - 뜯김폭 평가] [Experiment 4: Decapsulation evaluation - tear width evaluation]
완충 접착층(2)과 수분 흡착층(1)을 각각 이형필름에 코팅하면서 550nm파장 기준 500mJ의 광량으로 조사하여 UV 경화시킨후 두 필름을 60℃의 온도로 열합착하고, 수분 흡착층(1)의 이형필름을 제거한 후 세정된 메탈층을 100℃을 열로 합착하고, 실제 TV 크기인 65인치 또는 55인치 크기로 타발 한 후, OLED 패널에 상온 합착하였다. 1일 방치 후, 모서리를 강제로 OLED 패널에서 일부 벗겨낸 후, 일정 힘으로 잡아당겨 박리 특성을 평가하고, 뜯김폭(OLED 패널의 베젤부에 잔사되어 남은 길이)를 측정하였다. While coating the buffer adhesive layer (2) and the moisture adsorption layer (1) on the release film, UV curing by irradiation with a light amount of 500 mJ based on a wavelength of 550 nm, the two films are thermally bonded at a temperature of 60 ° C, and the moisture adsorption layer (1) After removing the release film, the cleaned metal layer was bonded with heat at 100 ° C, punched out to a size of 65 inches or 55 inches, which is the size of an actual TV, and then bonded to an OLED panel at room temperature. After leaving for 1 day, the edges were forcibly peeled off from the OLED panel, and then pulled with a certain force to evaluate the peeling characteristics, and the tear width (remaining length remaining on the bezel of the OLED panel) was measured.
뜯김폭을 측정하는 박리 평가는 배리어층인 금속면과 수분 흡착층(1), 수분 흡착층(1)과 완충 접착층(2), 완충 접착층(2)과 OLED 패널 간의 접착특성 및 접착제의 응집특성에 따라 영향을 받으며, OLED 패널에서도 유기물과 무기물의 종류와 계면특성(표면에너지, 표면조도, 패턴폭, 패턴높이 등)에 따라서도 달라져 실제로는 매우 복합적인 요인들이 작용하는 것으로 여겨진다. Peeling evaluation, which measures the tearing width, is the barrier layer, the metal surface and the moisture adsorption layer (1), the moisture adsorption layer (1) and the buffer adhesive layer (2), the adhesive characteristics between the buffer adhesive layer (2) and the OLED panel, and the cohesion characteristics of the adhesive Depending on the type of organic and inorganic materials and interface characteristics (surface energy, surface roughness, pattern width, pattern height, etc.)
해당 뜯김폭을 측정하는 박리 평가는 180° 접착력 평가와 근소하게 비례하는 관계에 있으나, 반드시 일치하지 않는다. 180° 접착력 평가와 유사한 물성으로 90° 접착력 평가를 아래와 같이 추가 평가하였다.The peel evaluation, which measures the tear width, has a slightly proportional relationship with the 180° adhesive strength evaluation, but does not necessarily match. With physical properties similar to those of the 180 ° adhesive force evaluation, the 90 ° adhesive force evaluation was additionally evaluated as follows.
[실험 5: 90 ° 박리 접착력 평가] [Experiment 5: 90 ° Peel Adhesion Evaluation]
전술한 바와 같이, 뜯김폭은 매우 복합적인 요인들이 작용할 수 있으며, 180° 접착력 평가와 반드시 비례하지 않기 때문에, 보다 유사한 물성으로서 90° 박리 접착력 평가를 수행하여 비교 평가하였다. As described above, since the tear width can be affected by very complex factors and is not necessarily proportional to the 180 ° adhesive force evaluation, the 90 ° peel adhesive force evaluation was performed and compared as a more similar physical property.
즉, 완충 접착층(2)과 수분 흡착층(1)을 각각 이형필름에 코팅하면서 550nm파장 기준 500mJ의 광량으로 조사하여 UV 경화시킨후 두 필름을 60℃의 온도로 열합착하고, 수분 흡착층(1)의 이형필름을 제거한 후 세정된 메탈층을 100℃을 열로 합착하고 폭 1인치 x 길이 140mm로 재단 한 후, 반대면인 완충 접착층(2)의 이형필름을 제거 한 후 75mmx 125mm Alkali free glass에 상온 합지 후, 만능재료시험기(UTM, AGS-1KNX, SHIMADZU社)를 이용하여 90°의 각도로 박리시켜 접착력을 평가하였다. That is, while coating the release film with the buffer adhesive layer 2 and the moisture adsorption layer 1, respectively, UV curing by irradiation with a light amount of 500 mJ based on a wavelength of 550 nm, the two films are thermally bonded at a temperature of 60 ° C, and the moisture adsorption layer ( After removing the release film of 1), the cleaned metal layer is bonded with heat at 100 ° C, cut to a width of 1 inch x length of 140 mm, and after removing the release film of the opposite side, the buffer adhesive layer (2), 75 mm x 125 mm Alkali free glass After lamination at room temperature, adhesive force was evaluated by peeling at an angle of 90 ° using a universal testing machine (UTM, AGS-1KNX, SHIMADZU).
[실험 6: 합착성 평가][Experiment 6: Adhesion evaluation]
앞서 제조된 전체 접착층(3)의 수분 흡착층(1) 면의 이형필름을 제거한 후, 메탈층(4)과 100℃의 온도로 롤라미네이터로 합지하여 시료를 제작하여, OLED 패널과 합지 설비를 활용하여 상온에서 합착하였다. After removing the release film on the surface of the moisture adsorption layer (1) of the entire adhesive layer (3) prepared previously, a sample was prepared by laminating with the metal layer (4) with a roll laminator at a temperature of 100 ° C., OLED panel and laminating equipment It was bonded at room temperature using
합착 직 후, 1일후, 3일(72시간) 후의 합착 상태를 육안 및 비파괴검사 장비로 분석하여 종합 평가하였다.The bonding state immediately after bonding, 1 day later, and 3 days (72 hours) later was analyzed with the naked eye and non-destructive testing equipment for comprehensive evaluation.
OLED 패널 합착 후 72시간 지난 후, 육안 및 비파괴 검사 장비로 분석 시, 기포 발생이 10개/m2 이하로 우수한 경우 합착성을 O로 평가하고, 72시간 지난 후 기포 발생이 0개/m2를 초과하는 경우 합착성을 X로 평가하였다.After 72 hours after OLED panel bonding, when analyzed with the naked eye and non-destructive inspection equipment, if the bubble generation is excellent at 10/m 2 or less, the bonding property is evaluated as O, and after 72 hours, the bubble generation is 0/m 2 If it exceeds, the adhesion property was evaluated as X.
아울러, 기포 외에, 합착 직 후 육안 관찰 시, 이물 및 찍힘(dent)이 없거나, 있더라도 이물, 찍힘(dent) 또는 이물 및 찍힘(dent) 크기(최대 길이)가 25㎛ 이하의 우수한 외관 특성을 달성하는지 확인하였다. In addition, in addition to air bubbles, when visually observed immediately after bonding, foreign matter and dents are absent, or even if there are, foreign matter, dents, or foreign matter and dent size (maximum length) achieve excellent appearance characteristics of 25 μm or less confirmed that it does.
이와 같이 외관 특성까지 우수한 경우 ◎로 평가하였다.In this way, when the appearance characteristics were excellent, it was evaluated as ◎.
이상의 실시예들 및 비교예들의 OTR, WVTR 특성 결과를 다음 표에 도시하였다.The OTR and WVTR characteristic results of the above examples and comparative examples are shown in the following table.
(층분리, 합착 X)Unmeasured due to film problem
(layer separation, cementation X)
(접착력 저하)Unmeasured due to film problem
(decreased adhesion)
(접착력 저하)Unmeasured due to film problem
(decreased adhesion)
(접착력 저하)Unmeasured due to film problem
(decreased adhesion)
(가교 문제 발생)Unmeasured due to film problem
(Crosslinking problem occurred)
(미반응 잠재물 발생)Unmeasured due to film problem
(Generation of unreacted potential)
(접착력 저하)Unmeasured due to film problem
(decreased adhesion)
(합착불량)Unmeasured due to film problem
(Poor adhesion)
이상으로부터 알 수 있듯이, 폴리이소부틸렌 및 부틸 고무의 혼합 조성물을 포함하는 실시예들의 경우 OTR, WVTR 특성이 높아 우수한 수분/가스 배리어 특성을 가지고 있음을 확인할 수 있다. 또한 일정 범위(90℃이상 150℃미만)에서 가급적 높은 연화점의 점착부여제를 사용할 경우 예상외로 OTR과 WVTR의 특성이 같이 향상되는 것을 확인할 수 있다. 앞서 살펴본 바와 같이 연화점이 150℃이상인 경우 또는 점착 부여제의 양이 전술한 범위 보다 많은 경우 층분리가 발생하고 합착이 불량하게 될 수 있다. 한편, 조성물의 바인더로 부틸고무를 단독 사용하는 경우에는 OTR, WVTR이 크게 감소하였다. As can be seen from the above, in the case of the examples including the mixed composition of polyisobutylene and butyl rubber, it can be seen that OTR and WVTR characteristics are high and have excellent moisture / gas barrier properties. In addition, when using a tackifier with a softening point as high as possible within a certain range (90 ° C or more and less than 150 ° C), it can be confirmed that the characteristics of OTR and WVTR are unexpectedly improved together. As described above, when the softening point is 150° C. or more or when the amount of the tackifier is greater than the above range, layer separation may occur and adhesion may be poor. On the other hand, when butyl rubber was used alone as a binder in the composition, OTR and WVTR were greatly reduced.
한편, 실시예들 및 비교예들의 WTV 특성 결과를 다음 표에 도시하였다.On the other hand, the WTV characteristic results of Examples and Comparative Examples are shown in the following table.
이상에서 알 수 있듯이, EPDM에 비해 폴리이소부틸렌과 부틸 고무의 경우 WTV 수치가 낮은데, 부틸 고무 함량이 클수록 WTV 길이가 커지는 경향성을 확인할 수 있다. 또한 높은 연화점의 점착부여제를 사용할 경우, WVTR 결과와 같이 WTV 특성도 향상되는 것을 확인할 수 있다. 실험적으로 α 파라미터의 값이 0.8 를 초과할 경우, 아래 표 4에서와 같이 OLED 패널의 베젤 인접 부위에 CaO의 산화에 따른 색변화가 시인되었다. 따라서 0.8 이하의 값을 가져야 수분 배리어 특성이 우수한 것을 알 수 있다.As can be seen from the above, the WTV values of polyisobutylene and butyl rubber are lower than those of EPDM, and the WTV length tends to increase as the content of butyl rubber increases. In addition, when using a tackifier with a high softening point, it can be seen that the WTV characteristics are also improved, as shown in the WVTR results. Experimentally, when the value of the α parameter exceeded 0.8, as shown in Table 4 below, a color change due to the oxidation of CaO was recognized in the area adjacent to the bezel of the OLED panel. Therefore, it can be seen that the moisture barrier properties are excellent only when the value is 0.8 or less.
한편, 각 실시예들 및 비교예들의 조성물 중 접착력, 뜯김폭, 합착성 측정이 가능한 실시예 및 비교예에 대하여 각 특성을 측정하고 아래 표에 기재하였다.On the other hand, among the compositions of Examples and Comparative Examples, each characteristic was measured for Examples and Comparative Examples capable of measuring adhesive force, tear width, and cohesiveness, and listed in the table below.
(kgf/inch)180° Peel
(kgf/inch)
(kgf/inch)90° Peel
(kgf/inch)
(mm)tear width length
(mm)
합착성OLED panel
adhesion
이상에서 알 수 있듯이, 폴리이소부틸렌의 ?t량이 커지고 부틸고무의 함량이 낮을수록 180°, 90° 접착력의 저하가 발생하고, 뜯김폭 길이도 작아지는 경향이 나타났다. 그러나, 비교예 5와 같이 180°, 90° 접착력이 선형적으로 비례하지는 않으며 오히려 90° 접착력이 뜯김폭과 연관성이 더 큰 것을 알 수 있다. 한편, 실시예들과 달리 비교예들의 경우 비교예 6을 제외하고는 OLED 패널과의 상온 합착성이 저조하다. 비교예 6의 경우에는 상온 합착성은 우수하나, 전술한 바와 같이, OTR, WVTR 값이 크고 WTV 길이가 커진다.As can be seen from the above, as the ?t amount of polyisobutylene increases and the content of butyl rubber decreases, the 180 ° and 90 ° adhesive strength decreases, and the tear width tends to decrease. However, as in Comparative Example 5, it can be seen that the 180 ° and 90 ° adhesive forces are not linearly proportional, but rather the 90 ° adhesive force has a greater correlation with the tear width. On the other hand, unlike the Examples, in the case of Comparative Examples, except for Comparative Example 6, room temperature adhesion with the OLED panel is poor. In the case of Comparative Example 6, room temperature adhesion is excellent, but as described above, the OTR and WVTR values are large and the WTV length is increased.
요컨대 전체적인 평가를 통해 폴리이소부틸렌, 부틸 고무의 혼합 바인더를 일정 중량비로 사용하는 경우 수분/산소 배리어 특성, 초기수분침투속도에서 우수하고, 점착부여제의 연화점이 높을수록 본 수분침투속도가 낮아지는 경향을 확인 할 수 있다. 폴리이소부틸렌 단독의 경우 뜯김폭 특성 구현이 미미하고 OLED 패널과의 상온 합착성이 저조하므로 유기전자장치 접착제 조성물에서 폴리이소부틸렌 외에 부틸고무를 일정 범위로 제한하여 혼합하는 한편, 기타 단광능 아크릴모노머, 다관능아크릴모노머, 광개시제의 함량을 함께 조절하는 것이 필요하다는 것을 알 수 있다.In short, through the overall evaluation, when a mixed binder of polyisobutylene and butyl rubber is used at a certain weight ratio, it is excellent in moisture / oxygen barrier properties and initial moisture penetration rate, and the higher the softening point of the tackifier, the lower the water penetration rate. A losing trend can be observed. In the case of polyisobutylene alone, the tear width characteristics are insignificant and the room temperature adhesion with the OLED panel is poor, so in the organic electronic device adhesive composition, butyl rubber in addition to polyisobutylene is limited to a certain range and mixed, while other briquetting properties It can be seen that it is necessary to adjust the contents of the acrylic monomer, the multifunctional acrylic monomer, and the photoinitiator together.
이상 본 발명의 비제한적이고 예시적인 구현예들을 설명하였으나, 본 발명의 기술 사상은 첨부 도면이나 상기 설명 내용에 한정되지 않는다. 본 발명의 기술 사상을 벗어나지 않는 범위 내에서 다양한 형태의 변형이 가능함이 이 분야의 통상의 지식을 가진 자에게는 자명하며, 또한, 이러한 형태의 변형은 본 발명의 특허청구범위에 속한다고 할 것이다.Although non-limiting and exemplary implementations of the present invention have been described above, the technical idea of the present invention is not limited to the accompanying drawings or the above description. It is obvious to those skilled in the art that various types of modifications are possible within the scope of the technical spirit of the present invention, and also, these types of modifications will fall within the scope of the claims of the present invention.
Claims (4)
하기 박리 평가 방법에 따른 뜯김폭이 2mm 이상이고,
상기 접착제 조성물은 폴리이소부틸렌 및 부틸고무를 9:1 내지 2:8의 중량비로 포함하는 혼합수지 바인더; 연화점이 90℃인 점착 부여제; 단관능 아크릴모노머; 다관능 아크릴모노머; 및 광개시제를 포함하는 것이되, 상기 점착부여제의 함량은 상기 바인더 100 중량 대비 20 중량부 초과 160중량부 미만으로 포함하는 것을 특징으로 하는 유기전자장치용 접착 필름.
[박리 평가 방법]
수분 흡착층의 이형필름을 제거한 후 배리어층으로서 세정된 메탈층을 100℃열로 합착하고, 반대면인 완충 접착층의 이형필름을 제거 한 후 실제 TV 크기인 65인치 또는 55인치 크기로 타발한 후, OLED 패널에 상온 합착한다. 1일 방치 후, 모서리를 강제로 OLED 패널에서 일부 벗겨낸 후, 1M/sec 의 속도로 30kgf의 힘으로 잡아당겨 뜯김폭 - OLED 패널에 잔사되어 남은 길이 - 를 측정한다.
a moisture adsorption layer made of an adhesive composition and further including a moisture adsorbent and positioned on the side of the barrier layer; And an adhesive film for an organic electronic device comprising a buffer adhesive layer made of the adhesive composition and not containing a moisture adsorbent and located on the organic electronic device side,
The tear width according to the following peel evaluation method is 2 mm or more,
The adhesive composition includes a mixed resin binder containing polyisobutylene and butyl rubber in a weight ratio of 9:1 to 2:8; a tackifier with a softening point of 90°C; Monofunctional acrylic monomer; multifunctional acrylic monomers; And a photoinitiator, wherein the content of the tackifier is more than 20 parts by weight and less than 160 parts by weight based on 100 parts by weight of the binder.
[Exfoliation evaluation method]
After removing the release film of the moisture absorption layer, the metal layer cleaned as a barrier layer is bonded with 100 ° C heat, and after removing the release film of the buffer adhesive layer, which is the opposite side, it is punched out to a size of 65 inches or 55 inches, which is the size of an actual TV, Cement to the OLED panel at room temperature. After leaving it for 1 day, the edge is forcibly peeled off from the OLED panel, and then pulled with a force of 30 kgf at a speed of 1M/sec to measure the tear width - the remaining length remaining on the OLED panel.
제1항의 유기전자장치용 접착 필름을 포함하는 것을 특징으로 하는 유기전자장치 봉지재.
barrier layer; and
An organic electronic device encapsulant comprising the adhesive film for an organic electronic device of claim 1.
A method of encapsulating an organic electronic device, characterized in that the organic electronic device is encapsulated with the organic electronic device encapsulant of claim 2.
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