CN109423221A - Organic electronic device adhesive film used for packing material and organic electronic device encapsulating material including it - Google Patents
Organic electronic device adhesive film used for packing material and organic electronic device encapsulating material including it Download PDFInfo
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- CN109423221A CN109423221A CN201810955610.5A CN201810955610A CN109423221A CN 109423221 A CN109423221 A CN 109423221A CN 201810955610 A CN201810955610 A CN 201810955610A CN 109423221 A CN109423221 A CN 109423221A
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- electronic device
- organic electronic
- adhesive film
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- 239000002313 adhesive film Substances 0.000 title claims abstract description 96
- 239000000463 material Substances 0.000 title claims abstract description 68
- 238000012856 packing Methods 0.000 title claims abstract description 37
- 239000000126 substance Substances 0.000 claims abstract description 47
- -1 moisture Substances 0.000 claims abstract description 14
- 239000012790 adhesive layer Substances 0.000 claims description 165
- 229920005989 resin Polymers 0.000 claims description 159
- 239000011347 resin Substances 0.000 claims description 159
- 239000003230 hygroscopic agent Substances 0.000 claims description 56
- 239000003795 chemical substances by application Substances 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 38
- 239000000758 substrate Substances 0.000 claims description 37
- 239000011521 glass Substances 0.000 claims description 31
- 239000003999 initiator Substances 0.000 claims description 30
- 239000010410 layer Substances 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 27
- 238000005259 measurement Methods 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 229920005604 random copolymer Polymers 0.000 claims description 12
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 239000002390 adhesive tape Substances 0.000 claims description 9
- 238000007334 copolymerization reaction Methods 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- 238000003475 lamination Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 8
- 239000012535 impurity Substances 0.000 abstract description 8
- 230000007423 decrease Effects 0.000 description 77
- 238000001723 curing Methods 0.000 description 45
- 239000010408 film Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 18
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 12
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 12
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 230000008859 change Effects 0.000 description 11
- 230000014509 gene expression Effects 0.000 description 10
- 229910044991 metal oxide Inorganic materials 0.000 description 10
- 238000003860 storage Methods 0.000 description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000007665 sagging Methods 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 101710137710 Thioesterase 1/protease 1/lysophospholipase L1 Proteins 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000005538 encapsulation Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 150000003505 terpenes Chemical class 0.000 description 6
- 235000007586 terpenes Nutrition 0.000 description 6
- 208000037656 Respiratory Sounds Diseases 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 5
- 238000003682 fluorination reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 230000003139 buffering effect Effects 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 3
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 3
- XJHCXCQVJFPJIK-UHFFFAOYSA-M cesium fluoride Substances [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 238000004845 hydriding Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910001631 strontium chloride Inorganic materials 0.000 description 3
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 2
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- HBGPNLPABVUVKZ-POTXQNELSA-N (1r,3as,4s,5ar,5br,7r,7ar,11ar,11br,13as,13br)-4,7-dihydroxy-3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-2,3,4,5,6,7,7a,10,11,11b,12,13,13a,13b-tetradecahydro-1h-cyclopenta[a]chrysen-9-one Chemical compound C([C@@]12C)CC(=O)C(C)(C)[C@@H]1[C@H](O)C[C@]([C@]1(C)C[C@@H]3O)(C)[C@@H]2CC[C@H]1[C@@H]1[C@]3(C)CC[C@H]1C(=C)C HBGPNLPABVUVKZ-POTXQNELSA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- PFRGGOIBYLYVKM-UHFFFAOYSA-N 15alpha-hydroxylup-20(29)-en-3-one Natural products CC(=C)C1CCC2(C)CC(O)C3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 PFRGGOIBYLYVKM-UHFFFAOYSA-N 0.000 description 1
- CXMYWOCYTPKBPP-UHFFFAOYSA-N 3-(3-hydroxypropylamino)propan-1-ol Chemical compound OCCCNCCCO CXMYWOCYTPKBPP-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910019787 NbF5 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- SOKRNBGSNZXYIO-UHFFFAOYSA-N Resinone Natural products CC(=C)C1CCC2(C)C(O)CC3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 SOKRNBGSNZXYIO-UHFFFAOYSA-N 0.000 description 1
- 244000057114 Sapium sebiferum Species 0.000 description 1
- 235000005128 Sapium sebiferum Nutrition 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910004546 TaF5 Inorganic materials 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- ISFLYIRWQDJPDR-UHFFFAOYSA-L barium chlorate Chemical compound [Ba+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O ISFLYIRWQDJPDR-UHFFFAOYSA-L 0.000 description 1
- 229910001638 barium iodide Inorganic materials 0.000 description 1
- 229940075444 barium iodide Drugs 0.000 description 1
- OOULUYZFLXDWDQ-UHFFFAOYSA-L barium perchlorate Chemical compound [Ba+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O OOULUYZFLXDWDQ-UHFFFAOYSA-L 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 210000000795 conjunctiva Anatomy 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000008717 functional decline Effects 0.000 description 1
- 229910000373 gallium sulfate Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- FAQJJMHZNSSFSM-UHFFFAOYSA-N phenylglyoxylic acid Chemical compound OC(=O)C(=O)C1=CC=CC=C1 FAQJJMHZNSSFSM-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- VTQZBGAODFEJOW-UHFFFAOYSA-N selenium tetrabromide Chemical compound Br[Se](Br)(Br)Br VTQZBGAODFEJOW-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- 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
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C09J123/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines
-
- 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
-
- 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
-
- 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
-
- 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
-
- 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
- H10K50/844—Encapsulations
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention relates to organic electronic device adhesive film used for packing material and including its organic electronic device encapsulating material, it is related to following organic electronic device adhesive film and the organic electronic device encapsulating material including it in more detail, i.e., by remove and obstruct the poor prognostic causes substance such as moisture, impurity makes can not be close to organic electronic device, and while the producible splitting phenomenon when removing moisture removal does not occur, have the effect of that moisture-proof and heat resistance are outstanding.
Description
Technical field
The present invention relates to including organic electronic device adhesive film and including its organic electronic device encapsulating material, more
It is related to following organic electronic device adhesive film and the organic electronic device encapsulating material including it in detail, that is, pass through
The poor prognostic causes substance such as removal and barrier moisture, impurity makes cannot be close to organic electronic device, and will not occur when removal
When moisture while producible splitting phenomenon, have the effect of that moisture-proof and heat resistance are outstanding.
Background technique
Organic Light Emitting Diode (OLED:Organic Light Emitting Diode) is luminescent layer by organic compound
The light emitting diode of formation utilizes the electro optical phenomenon for making electric current pass through fluorescence organic compound generation light.It is this organic
Light emitting diode generally passes through to be turned using three colors (red, green, blue (Red, Green, Blue)) independent pixel method, biology
Mode (CCM), green mode etc. are changed to realize primary color, the amount of the organic substance according to included in the luminescent material used
Divide into low molecule Organic Light Emitting Diode and macromolecule Organic Light Emitting Diode.Also, it can be divided into according to driving method
Passive type type driving method and active driving method.
This Organic Light Emitting Diode is characterized in that, based on itself luminous high efficiency, low voltage drive, simple driving
Deng, and have the advantages that HD video can be shown.And, also it is desirable to using organic matter flexible characteristic flexible display and
The application of organic electronic device.
Organic Light Emitting Diode is prepared by the way that the organic compound as luminescent layer to be layered on substrate with film morphology.
But the organic compound due to being used in Organic Light Emitting Diode is very sensitive to impurity, oxygen and moisture, exists external
Exposed or moisture, Oxygen permeation are easy the problem of making its deterioration in characteristics.The degradation phenomena of these organic matters influences organic light-emitting diodes
The characteristics of luminescence of pipe, and shorten the service life.In order to prevent this phenomenon, thin-film package process (Thin Film is needed
Encapsulation the inside of organic electronic device) is flowed into prevent block, moisture etc..
In the past, metal is filled or glass processing is at the slotted lid form of tool, and will be used to absorb the dry and wet agent of moisture with powder
Last form is loaded in its slot, but this method has the following problems: using the organic electronic device of encapsulation using moisture-inhibiting as mesh
Level be removed, it is difficult to obstruct the poor prognostic causes substance such as moisture, impurity close to organic electronic device, and be difficult not send out
Raw splitting phenomenon producible when removing moisture removal, and it is difficult to have the effect of that moisture-proof and heat resistance are outstanding simultaneously.
Existing technical literature
Patent document
KR published patent number the 10-2006-0030718th (publication date: on 04 11st, 2006)
Summary of the invention
The present invention proposes to solve problem as described above, technical problem to be solved by the present invention lies in,
Offer is made by the poor prognostic causes substance such as removal and barrier moisture, impurity cannot be close to organic electronic device, and will not send out
Life while producible splitting phenomenon, has the effect of that moisture-proof and heat resistance are outstanding when removing moisture removal.
In order to realize technical problem as described above, organic electronic device of the invention adhesive film used for packing material includes the
One binder;And it is formed in the second adhesive layer of the one side of first adhesive layer, temperature of first adhesive layer at 25 DEG C
Degree is lower to have (210~390) × 103The tensile modulus of elasticity of pa, second adhesive layer 25 DEG C at a temperature of have (1400
~2600) × 103The tensile modulus of elasticity of pa.
As a preferably embodiment of the invention, first adhesive layer and the second adhesive layer 25 DEG C at a temperature of drawing
The deviation for stretching elasticity modulus can be 1010~2390 × 103Pa.
As a preferably embodiment of the invention, first adhesive layer includes that first adhesive layer includes the first mixing
Resin, tackifier and the first hygroscopic agent, first hybrid resin with the weight ratio of 1:0.1~10 include the first binding resin and
Second binding resin, relative to the first hybrid resin of 100 parts by weight, the tackifier comprising 50~300 parts by weight, relatively
It may include first hygroscopic agent of 1~40 parts by weight in the first hybrid resin of 100 parts by weight.
As a preferably embodiment of the invention, the tackifier include the first tackifier of the weight ratio of 1:0.5~1.5
And second tackifier, less than the softening point of the second tackifier, first hygroscopic agent can be wrapped for the softening points of first tackifier
Containing silica.
As a preferably embodiment of the invention, first adhesive layer also includes in curing agent and uv initiator
More than one, relative to the first hybrid resin of 100 parts by weight, the curing agent comprising 2~30 parts by weight, relative to 100
First hybrid resin of parts by weight may include the uv initiator of 0.1~5 parts by weight.
As a preferably embodiment of the invention, the viscosity of first adhesive layer can be under the conditions of 50 DEG C of temperature
150000 Pa Secs or less.
As a preferably embodiment of the invention, second adhesive layer includes the second hybrid resin, tackifier and second
Hygroscopic agent, second hybrid resin include the first binding resin and the second binding resin with the weight ratio of 1:0.1~10, relatively
In the second hybrid resin of 100 parts by weight, the tackifier comprising 60~300 parts by weight, second relative to 100 parts by weight
Hybrid resin may include second hygroscopic agent of 50~450 parts by weight.
As a preferably embodiment of the invention, the tackifier include the first tackifier, and second hygroscopic agent includes
Calcium oxide.
As a preferably embodiment of the invention, second adhesive layer also includes in curing agent and uv initiator
More than one, relative to the second hybrid resin of 100 parts by weight, the curing agent comprising 10~40 parts by weight, relative to 100
Second hybrid resin of parts by weight may include the uv initiator of 0.1~8 parts by weight.
As a preferably embodiment of the invention, the viscosity of second adhesive layer is 200000 under the conditions of 50 DEG C of temperature
Pa Sec or more.
As a preferably embodiment of the invention, first hybrid resin and the second hybrid resin include the first bonding tree
Rouge and the second binding resin, first hybrid resin and the second hybrid resin include described the with the weight ratio of 1:0.1~10
One binding resin and the second binding resin.
As a preferably embodiment of the invention, first binding resin may include weight average molecular weight be 30000~
1550000 random copolymer as made of the copolymerization of ethylene, propylene and diolefinic compounds, the second binding resin may include under
The compound of the expression of chemical formula 1 is stated,
Chemical formula 1
In the chemical formula 1, R1For the branched chain type alkenyl of the straight chain type alkenyl or C4~C10 of hydrogen atom or C3~C10,
The n is that the weight average molecular weight of the compound indicated by chemical formula 1 meets 30000~1550000 rational.
As a preferably embodiment of the invention, the weight ratio of 1:0.3~1.4 carries out random copolymerization to ethylene and propylene
It closes, relative to the random copolymer total weight may include the diolefinic compounds of 2~15 weight percent.
As a preferably embodiment of the invention, the glass of adhesive film of the invention measured according to following measuring methods 1
Adhesion be 1500gf/25mm or more, according to following measuring methods 2 measurement metal adhesion can for 1000gf/25mm with
On.
Measuring method 1
Adhesive tape is measured in adhesive film upper side lamination adhesion, after sample is cut with wide 25mm and long 120mm, at 80 DEG C
At a temperature of adhesive film bottom surfaces are laminated to glass after, ready sample is placed at normal temperature 30 minutes, and with
300mm/ minutes velocity determination glass adhesions.
Measuring method 2
80 DEG C at a temperature of adhesive film upper side is laminated to 80 μm thickness nickel alloy, and adhesion is measured into glue
Tape lamination is in adhesive film bottom surfaces, and after examination cuts sample with wide 25mm and long 120mm, ready sample is placed at normal temperature
30 minutes, and with 300mm/ minutes velocity determination metal adhesions.
On the other hand, organic electronic device encapsulating material of the invention includes organic electronic device of the invention above-mentioned
Use adhesive film.
Also, luminaire of the invention includes substrate, organic electronic device and organic electronic device encapsulating material, institute
At least one side that organic electronic device is formed in substrate is stated, the organic electronic device encapsulating material is for being packaged with electromechanical son
Equipment.
Hereinafter, being illustrated to term used in the present invention.
The term hygroscopic agent being used in the present invention includes using objects such as the interface of hygroscopic agent and Van der Waals fors
Reason or chemical bonding carry out adsorption moisture, the not changed water adsorption substance of the ingredient of substance and pass through due to adsorption moisture
Chemical reaction adsorption moisture and the moisture absorption substance for becoming novel substance.
While organic electronic device of the invention adhesive film used for packing material is by barrier oxygen, impurity, moisture, effectively go
Except the moisture of infiltration, so as to significantly prevent moisture from reaching organic electronic device, therefore it is remarkably improved organic electronic device
Service life and durability.Also, while the producible splitting phenomenon when removing moisture removal will not occur, with outstanding resistance to
Moist and heat resistance.
Detailed description of the invention
Fig. 1 and Fig. 2 is cuing open for the organic electronic device adhesive film used for packing material of a preferably embodiment according to the present invention
View.
Fig. 3 and Fig. 4 is the diagrammatic cross-section of the preferably luminaire of an embodiment according to the present invention.
Specific embodiment
It is general so as to the technical field of the invention hereinafter, the embodiment of the present invention is described in detail referring to attached drawing
Logical technical staff is readily able to implement.The present invention can be realized by a variety of different forms, be not limited to described herein
Embodiment.Part unrelated to the invention is omitted in order to clearly state the present invention in the accompanying drawings, it is right throughout the specification
Identical appended drawing reference is added in same or similar structural element.
Specifically, Fig. 1 is the organic electronic device adhesive film used for packing material of a preferably embodiment according to the present invention
Cross-sectional view, organic electronic device of the invention adhesive film 10 used for packing material include adhesive layer 15, may also include base material film 13,
14, such as it is formed in the top of adhesive layer 15 and/or the release film of lower part.Base material film plays support and protection organic electronic device is used
The effect of adhesive film 10.
Adhesive layer 15 can be formed by the inclusion of hybrid resin 15b, tackifier and hygroscopic agent 15a.
Firstly, hybrid resin 15b may include the first binding resin and the second binding resin, it can be with the weight of 1:0.1~10
Than including the first binding resin and the second binding resin, it is preferable that the weight ratio comprising 1:1~9, it is highly preferred that including 1:1.1
~5 weight ratio.If the weight ratio of the first binding resin and the second binding resin is less than 1:0.1, may occur under reliability
If weight ratio is greater than 1:10 the problem of adhesive layer elastic force declines may occur for the problem of drop.
First binding resin may include the random copolymer that ethylene, propylene and diolefinic compounds are carried out with combined polymerization.This
When, random copolymerization may be carried out to ethylene and propylene with the weight ratio of 1:0.3~1.4, it is preferable that be the weight of 1:0.5~1.2
Amount ratio.If the ethylene of combined polymerization and the weight ratio of propylene are less than 1:0.3, can lead to viscous based on modulus and the increased panel of hardness
Conjunction property is bad, and has the problem of causing the physical property under adhesion and low temperature with substrate to decline, thereby increases and it is possible to be unfavorable for based on bullet
Property modulus decline hygroscopic agent volume expansion, if more than 1:1.4, then can lead to based on modulus and hardness decline panel it is sagging,
And the decline of mechanical properties leads to the decline of the mechanical properties of product, and can occur the high filling based on hygroscopic agent it is difficult and can
The problem of by property decline.
Also, there is the random copolymer total weight of ethylene, propylene and diolefinic compounds relative to combined polymerization, comprising 2~
The diolefinic compounds of 15 weight percent, it is preferable that may include 7~11 weight percent.If the dienes chemical combination
Object then can lead to based on low curing rate and cured density and the sagging problem of the panel of modulus decline less than 2 weight percent,
And heat resistance may decline, and due to the hygroscopic agent volume expansion based on flexibility decrease, it may occur however that phenomenon is tilted with substrate, if
Greater than 15 weight percent, causes wetting insufficient based on high solidification density and generate between the decline of the adhesion of substrate, resin
Compatibility decline, the panel adhesiveness based on high-modulus decline problem, and can lead to the yellowing based on heat.
The weight average molecular weight of first binding resin is 30000~1550000, it is preferable that weight average molecular weight can be 40000
~1500000.If the weight average molecular weight of the first binding resin is less than 30000, it may occur however that gelling rate and modulus is followed to decline
Panel sagging problem, heat resistance may decline, and as the fillibility of hygroscopic agent declines, reliability may decline, and mechanical properties
It may decline.If also, weight average molecular weight is greater than 1550000, is potentially based under the adhesion with substrate of wettability decline
Drop, and as gel fraction and modulus increase, the adhesiveness of panel may be declined.
Second binding resin may include the compound indicated by following chemical formula 1.
Chemical formula 1
In the chemical formula 1, R1For the branched chain type alkenyl of hydrogen atom, the straight chain type alkenyl of C3~C10 or C4~C10,
Preferably, R1It can be the branched chain type alkenyl of hydrogen atom, the straight chain type alkenyl of C4~C8 or C4~C8.
The R of chemical formula 11For the branched chain type alkenyl of hydrogen atom, the straight chain type alkenyl of C3~C10 or C4~C10, reliability can
Energy can be more excellent.
Also, in the chemical formula 1, n is the rational that weight average molecular weight meets 30000~1550000, it is preferable that
40000~1500000 rational can be met for weight average molecular weight.If less than 30000, base can occur for weight average molecular weight
In the panel sagging of modulus decline, and heat resistance may decline, as the fillibility of hygroscopic agent declines, reliability may under
Drop, and mechanical properties may decline, thereby increases and it is possible to the hygroscopic agent volume expansion based on flexibility decrease occurs and shows with the tilting of substrate
As.Also, if weight average molecular weight is greater than 1550000, because wettability declines, may decline with the adhesion of substrate, and with
Modulus increases, and may decline to the adhesiveness of panel.
Then, tackifier can include the bonding for being typically used as organic electronic device adhesive film used for packing material without restriction
Resin, it is preferable that may include selected from hydrogenated petroleum resin, hydrogenated rosin resin, hydrogenated rosin ester resin, hydrogenated terpene resin,
One or more of hydriding terpene phenolic resin, polymeric rosin resin and polymeric rosin ester resin.
It may include the increasing included in adhesive layer 15 of 50~300 parts by weight relative to the hybrid resin 15b of 100 parts by weight
Stick, it is preferable that include 80~280 parts by weight.If relative to the hybrid resin of 100 parts by weight, tackifier less than 50 parts by weight,
The bad problem of moisture-proof can then occur, if tackifier are greater than 300 parts by weight, the flexibility decrease based on adhesive layer can occur
(the problem of durability and moisture-proof decline of frangible (Brittle).
Then, hygroscopic agent 15a can include the encapsulating material of the encapsulation commonly used in organic electronic device without restriction, excellent
Selection of land may include hygroscopic agent, metal salt and metal oxygen containing zeolite, titanium dioxide, zirconium oxide or montmorillonite etc. as ingredient
One or more of compound, it is highly preferred that may include metal oxide, it is further preferred that may include in metal oxide
Calcium oxide (CaO).
Metal oxide may include metal oxide, such as silica (SiO2), aluminium oxide (Al2O3), lithia
(Li2O), sodium oxide molybdena (Na2O), barium monoxide (BaO), calcium oxide (CaO) or magnesia (MgO), organo metallic oxide and five oxygen
Change two phosphorus (P2O5One or more of).
Metal salt may include sulfate, such as lithium sulfate (Li2SO4), sodium sulphate (Na2SO4), calcium sulfate (CaSO4), magnesium sulfate
(MgSO4), cobaltous sulfate (CoSO4), gallium sulfate (Ga2(SO4)3), titanium sulfate (Ti (SO4)2) or nickel sulfate (NiSO4), metal halide
Object, such as calcium chloride (CaCl2), magnesium chloride (MgCl2), strontium chloride (SrCl2), yttrium chloride (YCl3), copper chloride (CuCl2), fluorination
Caesium (CsF), fluorination tantalum (TaF5), fluorination niobium (NbF5), lithium bromide (LiBr), calcium bromide (CaBr2), cesium bromide (CeBr3), bromine
Change selenium (SeBr4), bromination vanadium (VBr3), magnesium bromide (MgBr2), barium iodide (BaI2) or magnesium iodide (MgI2) and metal chlorate,
Such as barium perchlorate (Ba (ClO4)2) or magnesium perchlorate (Mg (ClO4)2One or more of).
Preferably, the purity of hygroscopic agent 15a is 95% or more.In the case where purity is less than 95%, not only moisture absorption
Function reduction, and the substance for being included in hygroscopic agent plays the role of impurity and may cause the bad of adhesive film, it is also possible to shadow
Organic electronic device is rung, but not limited to this.
Relative to the hybrid resin 15b of 100 parts by weight, the moisture absorption included in adhesive layer 15 comprising 10~550 parts by weight
Agent 15a, it is preferable that may include 20~520 parts by weight.If hygroscopic agent is less than 10 weight relative to the hybrid resin of 100 parts by weight
Part, then because the durability of organic electronic device declines, and moisture removal significant effect decline etc., and cannot achieve the viscous of institute's purpose
Conjunctiva, if hygroscopic agent be greater than 550 parts by weight, because wettability deficiency due to the adhesion force of adhesive film and organic electronic device, bonding
The Poor cohesions such as power lead to the reliability decrease of organic electronic device, with when moisture absorption based on excessive volume expansion and
The problem of tilting phenomenon, the lost of life of organic electronic device can occur occurs.
On the other hand, adhesive layer 15 of the invention also may include one or more of curing agent and uv initiator.
It include 2 relative to the hybrid resin of 100 parts by weight when including curing agent in adhesive layer 15 of the invention
The curing agent of~50 parts by weight, it is preferable that may include 5~40 parts by weight.If the case where including the curing agent less than 2 parts by weight
Under, then it can not be achieved the gel fraction and modulus of institute's purpose, it may occur however that the problem of elastic force declines, comprising being greater than 50 weight
In the case where part, since panel Poor cohesion may occur for high modulus and hardness, based on the adhesion decline of wettability decline
Problem.
Curing agent can include the substance that usually can be used as curing agent without restriction, it is preferable that may include can be by playing
Crosslinking action ensures the substance of the sufficient crosslink density of adhesive film, it is further preferred that may include selected from by polyurethane
One or more of the group of esters of acrylic acid curing agent and acrylic compounds curing agent composition.
Also, the weight average molecular weight of curing agent can be 100~1500, it is preferable that weight average molecular weight can for 200~
1300.If the weight average molecular weight of curing agent less than 100, based on hardness increase and panel adhesiveness and under the adhesion of substrate
Drop and the degasification (Outgas) that unreacted curing agent may occur, if weight average molecular weight is greater than 1500, due to the property of softening
(Softness) increase the problem of mechanical properties decline may occur.
In the case where including uv initiator in adhesive layer 15 of the invention, relative to the mixed of 100 parts by weight
Resin, the uv initiator comprising 0.1~10 parts by weight, it is preferable that may include 0.5~8 parts by weight.If comprising being less than
The uv initiator of 0.1 parts by weight, it may occur however that the problem of based on ultraviolet curing undesirable poor heat resistance, if comprising being greater than
The problem of 10 parts by weight, the then poor heat resistance that possible generation is declined based on cured density.
Uv initiator can be without restriction comprising being typically used as uv initiator, it is preferable that may include being selected from
Monoacyl phosphine (Mono Acyl Phosphine), double acylphosphanes (Bis Acyl Phosphine), alpha-alcohol ketone (α-
Hydroxyketone), α-amido ketone (α-Aminoketone), acetaldehyde acid phenenyl ester (Phenylglyoxylate), benzyl diformazan
One or more of base ketal (Benzyldimethyl-ketal).
On the other hand, the viscosity including the adhesive layer 15 in organic electronic device adhesive film 10 used for packing material of the invention
For 100000~300000 Pa Secs (50 DEG C), it is preferable that viscosity can be 120000~280000 Pa Secs (50 DEG C).If viscous
Less than 100000 Pa Secs of the viscosity (50 DEG C) of layer 15 is tied, then as adhesiveness (Tack) increases, process is deteriorated, to occur
The problem of release film can not be removed, can as adhesiveness (Tack) declines if viscosity is greater than 300000 Pa Secs (50 DEG C)
The problem of declining with the adhesion of substrate can occur.
Viscosity can be the viscosity measured by common viscosity measurement, it is preferable that with 800~900 μm of thickness
Sample is placed on plate simultaneously after the round punching of the diameter of 8mm using viscosimetric analysis equipment (ARES-G2, TA) by laminated samples
It can measure.At this point, determination condition can 5% strain (strain), 0.05N axial force (Axial Force),
The sensitivity (Sensitivity) of 0.005N, 1rad/ seconds, be measured at a temperature of -5 DEG C~130 DEG C, with 0.5N before measurement
Axial force, 0.05N sensitivity be spaced (gap) adjustment and sample stabilize after, can be measured by the condition, but
It's not limited to that.
On the other hand, it in the case where being equipped with adhesive layer 15 of single layer structure, is encapsulated in organic electronic device of the invention
For material in adhesive film 10, the glass adhesion according to the measurement of following measuring methods 1 is 1500gf/25mm or more, it is preferable that can
Think 1600gf/25mm or more.
Measuring method 1
Adhesion measurement adhesive tape (7475, TESA) is laminated on adhesive film by hand pressure roller (2Kg Hand Roller)
Portion face, after sample is cut with width 25mm and length 120mm, 80 DEG C at a temperature of adhesive film bottom surfaces are laminated to glass
Afterwards, ready sample is placed 30 minutes at normal temperature, and with 300mm/ minutes velocity determination glass adhesions.
Also, in the case where being equipped with adhesive layer 15 of single layer structure, in organic electronic device encapsulating material of the invention
With in adhesive film 10, the metal adhesion according to the measurement of following measuring methods 2 is 1000gf/25mm or more, it is preferable that Ke Yiwei
1100gf/25mm or more.
Measuring method 2
80 DEG C at a temperature of adhesive film upper side is laminated to 80 μm thickness nickel alloy, pass through hand pressure roller (2Kg
Hand Roller) by adhesion measurement adhesive tape (7475, TESA) be laminated to adhesive film bottom surfaces, by sample with wide 25mm and length
After 120mm is cut, the sample prepared is placed 30 minutes at normal temperature, and is sticked together with 300mm/ minutes velocity determination metals
Power.
When meeting the range according to the adhesion of the measuring method 1 and the measurement of measuring method 2, it is suitable for Organic Electricity
When sub- equipment, the removing of adhesive film may be remarkably decreased.
On the other hand, in a preferably example of the invention, as shown in Fig. 2, organic electronic device encapsulating material of the invention
Adhesive layer with adhesive film 10 is multilayered structure, it may include the first adhesive layer 11 and be formed in the first adhesive layer 11 one side
Two adhesive layers 12.That is, adhesive layer of the invention may include being formed in the first adhesive layer 11 and being formed in first as multilayered structure
Second adhesive layer 12 of the one side of adhesive layer 11.
At this point, organic electronic device of the invention adhesive film 10 used for packing material may also include base material film 14, such as it is formed in
The release film of first adhesive layer, 11 bottom surfaces, and may also include base material film 13, be such as formed in 12 upper side of the second adhesive layer from
Type film.
First adhesive layer 11 is the layer being directly in contact with organic electronic device (not shown), can be by the inclusion of the first mixing
Resin 11b, tackifier and the first hygroscopic agent 11a are formed.At this point, the first hybrid resin 11b may include the first binding resin and
Second binding resin, tackifier may include the first tackifier, also may include the second tackifier.
Second adhesive layer 12 may include the second hybrid resin 12b, tackifier and the second hygroscopic agent 12a.At this point, the second mixing
Resin 12b may include the first binding resin and the second binding resin, and tackifier also may include the first tackifier.
Firstly, being illustrated to the first adhesive layer 11.
First hybrid resin 11b of the first adhesive layer may include the first binding resin and the second binding resin, the first bonding
Resin and the second binding resin may include the first binding resin and the second binding resin with hybrid resin 15b (Fig. 1) above-mentioned
Identical substance.
The first binding resin and the second binding resin with the weight ratio of 1:0.1~10 comprising the first hybrid resin 11b, it is excellent
Selection of land, the weight ratio comprising 1:1~9, it is highly preferred that may include the weight ratio of 1:1.1~5.If the first binding resin and second
The problem of weight ratio of binding resin is less than 1:0.1, then reliability decrease may occur may if weight ratio is greater than 1:10
The problem of elastic force decline of adhesive layer occurs.
The tackifier of first adhesive layer 11 may include the first tackifier, also may include the second tackifier.First tackifier and
Second tackifier can include the tackifier for being typically used in organic electronic device adhesive film used for packing material without restriction, preferably
Ground may include the tackifier that can be improved reliability, it is highly preferred that may include selected from hydrogenated petroleum resin, hydrogenated rosin resin,
In hydrogenated rosin ester resin, hydrogenated terpene resin, hydriding terpene phenolic resin, polymeric rosin resin and polymeric rosin ester resin
More than one, it is further preferred that may include the different hydrogenated petroleum resin of softening point.As an example, comprising softening point not
In the case where same hydrogenated petroleum resin, the softening point of the first tackifier is smaller than the softening point of the second tackifier, but and unlimited
Due to this.
The first tackifier and the second tackifier of first adhesive layer 11 include hydrogenated petroleum resin, when the first tackifier use
When hydrogenated petroleum resin comprising the softening point less than the second tackifier, the non-hydrogenated petroleum tree of the weight ratio comprising 1:0.5~1.5
Rouge, it is preferable that may include the weight ratio of 1:0.6~1.4.If the weight ratio of the first tackifier and the second tackifier is less than 1:0.5,
The problem of decline of heat-resisting maintenance energy may then occur, may since adhesive wettability declines if weight ratio is greater than 1:1.5
The problem of adhesion decline occurs.
First hybrid resin 11b of the first adhesive layer 11 relative to 100 parts by weight, comprising 50~300 parts by weight
The tackifier of one adhesive layer 11, it is preferable that may include 80~280 parts by weight.If the first compound tree relative to 100 parts by weight
Comprising the tackifier less than 50 parts by weight the problem of moisture-proof is deteriorated may then occur for rouge, if comprising being greater than 300 parts by weight
The problem of tackifier, the then possible durability that the flexibility decrease (Brittle) based on the first adhesive layer occurs and moisture-proof decline.
First hygroscopic agent 11a of the first adhesive layer 11 can be excellent without restriction using the substance that usually can be used as hygroscopic agent
Silica can be used in selection of land.When using silica as the first hygroscopic agent 11a, moisture removal excellent performance, and can prevent
The only separation of organic electronic device and encapsulating material, and the durability of organic electronic device can be dramatically increased.
The BET specific surface area of first hygroscopic agent 11a of the first adhesive layer 11 is 2~20m2/ g, it is preferable that BET specific surface
Product is 3~14m2/ g, it is highly preferred that BET specific surface area can be 4~8m2/g.Specific surface area is measured using BET method, tool
Body, added in pipe sample the first hygroscopic agent of 1g and -195 DEG C at a temperature of using ASAP2020
(Micromeritics, the U.S.) is measured, without carrying out pre-treatment.It, can be by measuring three times for identical sample
To obtain average value.If the BET specific surface area of the first hygroscopic agent 11a is greater than 20m2/ g, not only and under the adhesion of substrate
Drop, and the decline of resin flowing (resin flow) is brought, so as to cause Poor cohesion.Also, in rough surface or more
The problem of in the case where permeability, BET specific surface area is possible to become larger, and panel breakage may occur due to rough surface.Therefore, originally
First hygroscopic agent of invention has low BET specific surface area, so as to high spherical rate.
First hybrid resin 11b of the first adhesive layer 11 relative to 100 parts by weight, first comprising 1~40 parts by weight
First hygroscopic agent 11a of adhesive layer 11, it is preferable that may include 5~35 parts by weight.If including the first moisture absorption less than 1 parts by weight
Moisture removal effect in the case where agent 11a, by being unable to reach in the first adhesive layer of purpose, it is thus possible to which there are organic
The problem of durability decline of electronic equipment, due to wettability deficiency, and bonds comprising being greater than 40 parts by weight
The Poor cohesions such as adhesion force, cohesive force between film and organic electronic device, it is understood that there may be under the reliability of organic electronic device
The problem of drop.
On the other hand, the first adhesive layer 11 of the invention also may include one of curing agent and uv initiator with
On.
When including curing agent in the first adhesive layer 11 of the invention, relative to the first hybrid resin of 100 parts by weight,
Curing agent comprising 2~30 parts by weight, it is preferable that may include 5~25 parts by weight.If including the curing agent less than 2 parts by weight
In the case of, it is impossible to reach the gel fraction and modulus of institute's purpose, it may occur however that the problem of elastic force declines, comprising being greater than 30 weights
In the case where measuring part, since panel Poor cohesion may occur for high modulus and hardness, the adhesion strength based on wettability declines
Problem.
Curing agent can include the substance that usually can be used as curing agent without restriction, it is preferable that may include can be by playing
The substance for acting on ensuring the sufficient crosslink density of adhesive film of crosslinking agent, it is highly preferred that may include selected from by polyurethane third
One or more of the group of olefin(e) acid esters curing agent and acrylic compounds curing agent composition.
Also, the weight average molecular weight of curing agent can be 100~1500, it is preferable that weight average molecular weight can for 200~
1300.If the weight average molecular weight of curing agent less than 100, adhesiveness based on the increased panel of hardness and with the adhesion of substrate
Decline and the degasification problem that unreacted curing agent may occur, if weight average molecular weight is greater than 1500, since property of softening increase can
The problem of mechanical properties decline can occur.
The first mixing when in the first adhesive layer 11 of the invention including uv initiator, relative to 100 parts by weight
Resin, the uv initiator comprising 0.1~5 parts by weight, it is preferable that may include 0.5~4 parts by weight.If comprising less than 0.1 weight
Measure the uv initiator of part, it may occur however that the problem of based on ultraviolet curing undesirable poor heat resistance, if comprising being greater than 5 weight
The problem of part, the then poor heat resistance that possible generation is declined based on cured density.
Uv initiator can be without restriction comprising being typically used as uv initiator, it is preferable that may include being selected from
One or more of monoacyl phosphine, double acylphosphanes, alpha-alcohol ketone, α-amido ketone, acetaldehyde acid phenenyl ester, benzyl dimethyl ketal.
On the other hand, including the first adhesive layer 11 in organic electronic device adhesive film 10 used for packing material of the invention
Viscosity be 150000 Pa Secs (50 DEG C) below, it is preferable that viscosity can be 10000~130000 Pa Secs (50 DEG C).If the
The viscosity of one adhesive layer 11 is greater than 150000 Pa Secs (50 DEG C), then as adhesiveness increases, it may occur however that with sticking together for substrate
The problem of power declines.
Viscosity can be the viscosity measured by common viscosity measurement, it is preferable that with 800~900 μm of thickness
Sample is placed on plate simultaneously after the round punching of the diameter of 8mm using viscosimetric analysis equipment (ARES-G2, TA) by laminated samples
It can measure.At this point, determination condition can be in 5% strain, the axial force of 0.05N, the sensitivity of 0.005N, 1rad/ seconds, -5
DEG C~130 DEG C at a temperature of be measured, interval adjustment and sample carried out with the axial force of 0.5N, the sensitivity of 0.05N before measurement
After product stabilize, it can be measured by the condition, but not limited to this.
Then, the second adhesive layer 12 of the one side for being formed in the first adhesive layer 11 of the invention is illustrated.
Second hybrid resin 12b of the second adhesive layer 12 may include the first binding resin and the second binding resin, and first is viscous
Knot resin and the second binding resin may include setting with the first binding resin of hybrid resin 15b (Fig. 1) above-mentioned and the second bonding
The identical substance of rouge.
The first binding resin and the second binding resin with the weight ratio of 1:0.1~10 comprising the second hybrid resin 12b, it is excellent
Selection of land, the weight ratio comprising 1:1~9, it is highly preferred that may include the weight ratio of 1:1.1~5.If the first binding resin and second
The problem of weight ratio of binding resin is less than 1:0.1, then reliability decrease may occur may if weight ratio is greater than 1:10
The problem of elastic force decline of adhesive layer occurs.
The tackifier of second adhesive layer 12 may include the first tackifier.First tackifier can be without restriction comprising usually making
Binding resin for organic electronic device adhesive film, it is preferable that may include selected from hydrogenated petroleum resin, hydrogenated rosin tree
Rouge, hydrogenated rosin ester resin, hydrogenated terpene resin, hydriding terpene phenolic resin, polymeric rosin resin and polymeric rosin ester resin
One or more of.
Second hybrid resin 12b of the second adhesive layer 12 relative to 100 parts by weight, comprising 60~300 parts by weight
First tackifier of two adhesive layers 12, it is preferable that may include 90~280 parts by weight.If relative to 100 the second compound trees of parts by weight
Rouge, comprising the first tackifier less than 60 parts by weight, then the problem of poor moisture resistance may occur, if comprising being greater than 300 parts by weight
The first tackifier, then may occur the flexibility decrease based on the second adhesive layer durability and moisture-proof decline the problem of.
Second hygroscopic agent 12a of the second adhesive layer 12 can be excellent without restriction using the substance that usually can be used as hygroscopic agent
Selection of land, it includes zeolite, titanium dioxide, zirconium oxide or montmorillonite etc. as ingredient, metal salt and metal oxidation that hygroscopic agent, which can be used,
One or more of object, it is highly preferred that may include metal oxide, it is further preferred that may include the oxygen in metal oxide
Change calcium (CaO).
Metal oxide may include metal oxide, such as silica, aluminium oxide, lithia, sodium oxide molybdena, barium monoxide, oxygen
Change calcium or magnesia, organo metallic oxide and phosphorus pentoxide (P2O5One or more of).
Metal salt may include sulfate, such as lithium sulfate, sodium sulphate, calcium sulfate, magnesium sulfate, cobaltous sulfate, gallium sulfate, titanium sulfate
Or nickel sulfate, metal halide, such as calcium chloride, magnesium chloride, strontium chloride, yttrium chloride, copper chloride, cesium fluoride, fluorination tantalum, fluorination
Niobium, lithium bromide, calcium bromide, cesium bromide, selenium bromide, bromination vanadium, magnesium bromide, barium iodide or magnesium iodide and metal chlorate are such as high
One or more of barium chlorate or magnesium perchlorate.
Preferably, the purity of the second hygroscopic agent 12a is 95% or more.In the case where purity is less than 95%, not only moisture
Absorption function decline, and the substance for being included in hygroscopic agent plays the role of impurity and may cause the bad of adhesive film, also may be used
Organic electronic device can be influenced, but not limited to this.
Second hybrid resin 12b of the second adhesive layer 12 relative to 100 parts by weight, comprising 50~450 parts by weight
Second hygroscopic agent 12a of two adhesive layers 12, it is preferable that may include 70~430 parts by weight.If including second less than 50 parts by weight
In the case where hygroscopic agent 12a, then it can not be achieved the adhesive film of institute's purpose there may be moisture removal significant effect decline etc.
Problem, comprising being greater than 450 parts by weight, then the caking property of the second adhesive layer 12 is remarkably decreased, and absorbs moisture
When due to volume expansion it is excessive, include that the first adhesive layer 11 and the second adhesive layer 12 and/or second are viscous in organic electronic device
The adhesive layer for tying layer 12 and the first adhesive layer 11 tilts, and moisture penetrates between it rapidly, shortens Organic Electricity so as to exist
The problem of service life of sub- equipment.
On the other hand, the shape of the second hygroscopic agent 12a of the second adhesive layer 12 or partial size are unrestricted, it is, however, preferable that
In order to improve dispersibility in the second adhesive layer, it can be achieved that average grain diameter is the spherical shape of 5nm~8 μm, it is preferable that can be achieved average
Partial size is the spherical shape of 10nm~6 μm.Be conducive to have the function of as a result, to carry out adhesive film while the moisture removal of institute's purpose thin
Membranization.
On the other hand, the second adhesive layer 12 of the invention also may include one of curing agent and uv initiator with
On.
It include 10~40 relative to 100 the second hybrid resins of parts by weight when including curing agent in the second adhesive layer 12
The curing agent of parts by weight, it is preferable that may include 12~35 parts by weight.If in the case where comprising the curing agent less than 10 parts by weight,
It can not be achieved the gel fraction and modulus of institute's purpose, thereby increases and it is possible to the problem of elastic force decline occurs, comprising being greater than 40 parts by weight
In the case where, due to high modulus and hardness, it may occur however that panel Poor cohesion, the adhesion decline based on wettability decline are asked
Topic.
Curing agent can include the substance that usually can be used as curing agent without restriction, it is preferable that may include can be by playing
Crosslinking action ensures the substance of the sufficient crosslink density of adhesive film, it is further preferred that may include selected from by polyurethane
One or more of the group of esters of acrylic acid curing agent and acrylic compounds curing agent composition.
Also, the weight average molecular weight of curing agent can be 100~1500, it is preferable that weight average molecular weight can for 200~
1300.If the weight average molecular weight of curing agent less than 100, based on hardness increase and panel adhesiveness and under the adhesion of substrate
Drop and the degasification that unreacted curing agent may occur, if weight average molecular weight is greater than 1500, since property of softening increase may occur
The problem of mechanical properties decline.
When including uv initiator in the second adhesive layer 12 of the invention, second relative to 100 parts by weight is mixed
Resin, the uv initiator comprising 0.1~8 parts by weight, it is preferable that may include 0.5~6 parts by weight.If comprising less than 0.1
The problem of uv initiator of parts by weight, then poor heat resistance undesirable based on ultraviolet curing occurs for possibility, if comprising being greater than 8
The problem of parts by weight, the then poor heat resistance that possible generation is declined based on cured density.
Uv initiator can be without restriction comprising being typically used as uv initiator, it is preferable that may include being selected from
One or more of monoacyl phosphine, double acylphosphanes, alpha-alcohol ketone, α-amido ketone, acetaldehyde acid phenenyl ester, benzyl dimethyl ketal.
On the other hand, including the second adhesive layer 12 in organic electronic device adhesive film 10 used for packing material of the invention
Viscosity is 200000 Pa Secs (50 DEG C) or more, it is preferable that viscosity can be 220000~1000000 Pa Secs (50 DEG C).If
Less than 200000 Pa Secs of the viscosity of second adhesive layer 12 (50 DEG C), then as caking property declines, it may occur however that glutinous with substrate
The problem of putting forth effort decline.
Viscosity can be the viscosity measured by common viscosity measurement, it is preferable that with 800~900 μm of thickness
Sample is placed on plate simultaneously after the round punching of the diameter of 8mm using viscosimetric analysis equipment (ARES-G2, TA) by laminated samples
It can measure.At this point, determination condition can be in 5% strain, the axial force of 0.05N, the sensitivity of 0.005N, 1rad/ seconds, -5
DEG C~130 DEG C at a temperature of be measured, interval adjustment and sample carried out with the axial force of 0.5N, the sensitivity of 0.05N before measurement
After product stabilize, it can be measured by the condition, but not limited to this.
On the other hand, it is being equipped with the adhesive layer for including the case where the multilayered structure of the first adhesive layer 11 and the second adhesive layer 12
Under, in organic electronic device adhesive film 10 used for packing material of the invention, it is according to the adhesion that following measuring methods 1 measure
1500gf/25mm or more, it is preferable that can be 1600gf/25mm or more.
Measuring method 1
Adhesion measurement adhesive tape (7475, TESA) is laminated on adhesive film by hand pressure roller (2Kg Hand Roller)
Portion face, after sample is cut with width 25mm and length 120mm, 80 DEG C at a temperature of adhesive film bottom surfaces are laminated to glass
Afterwards, the sample prepared is placed 30 minutes at normal temperature, and with 300mm/ minutes velocity determination glass adhesions.
Also, in the case where being equipped with the adhesive layer of the multilayered structure including the first adhesive layer 11 and the second adhesive layer 12,
In organic electronic device adhesive film 10 used for packing material of the invention, according to the metal adhesion of following measuring methods 2 measurement
For 1000gf/25mm or more, it is preferable that can be 1100gf/25mm or more.
Measuring method 2
80 DEG C at a temperature of adhesive film upper side is laminated to 80 μm thickness nickel alloy, pass through hand pressure roller (2Kg
Hand Roller) adhesion measurement adhesive tape (7475, TESA) is laminated to adhesive film bottom surfaces, by sample with width 25mm and
After length 120mm is cut, the sample prepared is placed 30 minutes at normal temperature, and with 300mm/ minutes velocity determination metals
Adhesion.
When meeting the range according to the adhesion of the measuring method 1 and the measurement of measuring method 2, it is suitable for Organic Electricity
When sub- equipment, the removing of adhesive film may be remarkably decreased.
On the other hand, in adhesive layer 15 including the first adhesive layer 11 and the second adhesive layer including the single layer structure
In the case where the adhesive layer of the multilayered structure of 12 structure, since size or thickness equal-specification can be different according to purpose,
The present invention is not particularly limited to this.
Also, the adhesive layer 15 of single layer structure, multilayered structure including the first adhesive layer 11 and the second adhesive layer 12 is viscous
Tying layer can be the adhesive layer of drying regime or the adhesive layer of solid state.
On the other hand, as described above, when adhesive layer of the invention including the first adhesive layer 11 and is formed in the first adhesive layer
When the second adhesive layer 12 of 11 one side, the first adhesive layer 11 can have (210~390) × 10 in 25 DEG C of temperature3Pa
Tensile modulus of elasticity, it is preferable that (240~360) × 103The tensile modulus of elasticity of pa, it is further preferred that (270~330) ×
103The tensile modulus of elasticity of pa.If the tensile modulus of elasticity of the first adhesive layer 11 is less than 210 × 103, then durability may occur
The problem of decline, if more than 390 × 103Pa, then volume expansion due to reaction of moisture, and may occur and substrate (glass, gold
Belong to etc.) tilting and/or crackle.
Also, the second adhesive layer 12 has (1400~2600) × 10 under the conditions of 25 DEG C of temperature3The tensile elasticity of pa
Modulus, it is preferable that (1600~2400) × 103The tensile modulus of elasticity of pa, it is further preferred that (1800~2200) × 103Pa
Tensile modulus of elasticity.If the tensile modulus of elasticity of the second adhesive layer 12 is less than 1400 × 103, then durability decline may occur
The problem of, if more than 2600 × 103Pa, then volume expansion due to reaction of moisture, it may occur however that with substrate (glass, metal etc.)
Tilting and/or crackle.
Also, the first adhesive layer 11 and the second adhesive layer 12 of the invention be under conditions of 25 DEG C, tensile modulus of elasticity
Deviation can be 2390 × 103Below pa, it is preferable that 1010 × 103Pa~2040 × 103Pa, it is further preferred that 1530 ×
103Pa~1870 × 103Pa.If deviation is greater than 2390 × 103Pa then passes through the contraction and/or expansion of adhesive layer, it may occur however that
The rupture of part film and crackle.
On the other hand, as described above, when adhesive layer of the invention including the first adhesive layer 11 and is formed in the first adhesive layer
In the case where second adhesive layer 12 of 11 one side, the first adhesive layer 11 is 8.4 according to the calculated measured value of following mathematical expressions 1
~15.8%, it is therefore preferable to 9.68~14.52%, it more preferably can be 10.89~13.31%.If the first adhesive layer 11
According to the measured value of mathematical expression 1 less than 8.4%, then since heat resistance is deteriorated, it may occur however that resin overflow (resin over
Flow), if more than 15.8%, then the problem of declining with the adhesion of substrate (glass, metal etc.) may occur.
Mathematical expression 1
Measured value (%)=100 × S2/S1
S1To utilize advanced Rheometric Expansion System in stress relaxation mould in the state of preparing adhesive layer with 600 μm of thickness
Under formula, by using the parallel-plate that diameter is 8mm 85 DEG C at a temperature of be applicable in the vertical force of 200gf, to the adhesive film
Apply the maximum stress value measured when 30% strain, S2To keep 180 in the state of applying the strain to the adhesive film
The stress value measured after second.
It also, is 1~20%, preferably 7.32 in the measured value according to mathematical expression 1 of the second adhesive layer 12 of the invention
~10.98%, it more preferably can be 8.23~10.07%.If the measured value according to mathematical expression more than 1 of the second adhesive layer 12 is small
In 1%, then since heat resistance is deteriorated, it may occur however that resin overflow may then occur and substrate (glass, metal if more than 20%
Deng) adhesion decline the problem of.
Also, the deviation of the measured value according to mathematical expression 1 of the first adhesive layer 11 and the second adhesive layer 12 of the invention is
11.6% or less, it is therefore preferable to 0.39~6.29%, it more preferably can be 2.36~3.54%.If deviation is greater than 11.6%,
The problem of reliability decrease of contraction and/or expansion based on adhesive layer may then occur in thermal process.
Further, adhesive layer of the invention can be all satisfied following conditions (1) and condition (2).
As condition (1),It can preferably be
Also, as condition (2),It can preferably be
In the condition (1), a1And a2For respectively 25 DEG C at a temperature of storage elastic modulus (pa) and loss resilience
Modulus (pa), b1And b2For respectively 50 DEG C at a temperature of storage elastic modulus (pa) and loss elastic modulus (pa).
If in the condition (1)Less than 5.28, then as panel sagging occurs, it may occur however that can not
The problem of preventing volume expansion, if more than 7.16, then with based on external impact buffering effect decline, durability may under
Drop.
If also, in the condition (2)Less than 4.22, then act in an unreasonable way overflow (Over in bonding process
Flow), it is possible to create bubble and/or reliability decrease, can then due to that can not make up the difference in height of panel if more than 5.6
Adhesion decline and/or splitting phenomenon can occur.
Also, adhesive layer of the invention can meet following conditions (3).
As condition (3),It can preferably be
In the condition (3), c1And c2For respectively 100 DEG C at a temperature of storage elastic modulus (pa) and loss bullet
Property modulus (pa).
If in the condition (3)Less than 3.46, then due to the mobility of binder, it may occur however that heat resistance
If more than 5.02 may then occur for the problem of decline the problem of declining based on the insufficient adhesion decline of wettability and heat resistance.
It is 7 × 10 in 25 DEG C of at a temperature of storage elastic modulus also, to make adhesive layer of the invention meet condition (1)6
~1.5 × 108Pa can preferably be 8 × 106~1 × 108Pa is 10 in 25 DEG C of at a temperature of loss elastic modulus7~2 ×
108Pa can preferably be 1.2 × 107~1.5 × 108Pa.If 25 DEG C at a temperature of storage elastic modulus less than 7 × 106
Pa, then with the generation of panel sagging, it may occur however that the problem of volume expansion can not be prevented, if more than 1.5 × 108Pa,
Then as the buffering effect based on external impact declines, durability may decline.If also, in 25 DEG C of at a temperature of loss resilience
Modulus is less than 107Pa, then with the generation of panel sagging, it may occur however that the problem of volume expansion can not be prevented, if more than 2
×108Pa then declines with the buffering effect based on external impact, and durability may decline.
It is 10 in 50 DEG C of at a temperature of storage elastic modulus also, to make adhesive layer of the invention meet condition (2)6~
1.5×107Pa can preferably be 1.2 × 106~9 × 106Pa is 8 × 10 in 50 DEG C of at a temperature of loss resilience mould5~
1.5×107Pa can preferably be 9 × 105~1 × 107Pa.If storage elastic modulus is less than 10 at 50 °C6Pa, then
With overflow occurs in bonding process, it is possible to create bubble and/or reliability decrease, if more than 1.5 × 107Pa, then with
The difference in height of panel can not be made up, it may occur however that adhesion decline and/or splitting phenomenon.If also, in 50 DEG C of temperature
Lower loss elastic modulus is less than 8 × 105Pa, then with overflow occurs in bonding process, it is possible to create bubble and/or reliability
Decline, if more than 1.5 × 107Pa is then with the difference in height that can not make up panel, it may occur however that adhesion decline and/or interlayer stripping
From phenomenon.
Also, to make adhesive layer of the invention meet condition (3), 100 DEG C of at a temperature of storage elastic modulus be 2 ×
105~8 × 106Pa can preferably be 3 × 105~6 × 106Pa is 5 × 10 in 100 DEG C of at a temperature of loss elastic modulus4
~2 × 106Pa can preferably be 6 × 104~1.5 × 106Pa.If 100 DEG C at a temperature of storage elastic modulus less than 2 ×
105Pa, then due to the mobility of binder, it may occur however that the problem of heat resistance declines, if more than 8 × 106Pa may then occur
The problem of being declined based on the insufficient adhesion decline of wettability and heat resistance.If also, in 100 DEG C of at a temperature of loss resilience mould
Amount is less than 5 × 104Pa, then due to the mobility of binder, it may occur however that the problem of heat resistance declines, if more than 2 × 106Pa is then
The problem of declining based on the insufficient adhesion decline of wettability and heat resistance may occur.
On the other hand, the gel fraction (gel content) according to the measurement of following mathematical expressions 2 of adhesive layer of the invention is 45
~95%, it can preferably be 50~90%.
Mathematical expression 2:
In the mathematical expression 2, dry bonding layer weight refers to the cross of 100mm × 25mm × perpendicular cutting adhesive layer,
After being put into the adhesive layer of cutting in the bottle of the toluene equipped with 5g and placing 15 minutes, adhesive layer is filtered with filter, is passed through
160 DEG C at a temperature of heated-air drying filtering adhesive layer 30 minutes completely remove the weight measured after toluene.
If less than 45%, panel sagging occurs for the gel fraction of the adhesive layer, it is impossible to prevent from causing because of moisture
Expansion, in bonding process occur overflow there may be bubble and/or reliability decreases, due to the flowing of binder
Property, it may occur however that the problem of heat resistance declines.If also, the gel fraction of the adhesive layer is greater than 95%, with based on outside
The buffering effect of impact declines, and durability may decline, and with the difference in height for not making up panel, it may occur however that under adhesion
Drop and/or splitting phenomenon, due to wettability deficiency, possible the problem of adhesion decline and heat-resisting decline occurs.
Further, adhesive layer of the invention can be all satisfied following conditions (4) and condition (5), so as to solve institute as above
The problem of stating.
As condition (4),It can preferably beDo Ei condition
(5),It can preferably be
But the d indicates that the thickness (μm) of adhesive layer, the e indicate the average grain diameter (μm) of hygroscopic agent.
If according in the condition (4)Less than 8, then the bonding of organic electronic device adhesive film used for packing material
Property may decline, thereby increases and it is possible to occur the tie layer surface prominent hygroscopic agent the problem of, due to from tie layer surface it is viscous go out moisture absorption
Agent, reliability may decline.If also, in the condition (5)Less than 0.01, then may occur viscous out from tie layer surface
The problem of hygroscopic agent, reliability and caking property may decline, ifGreater than 0.9, then organic electronic device bonding used for packing material
The caking property of film may decline, thereby increases and it is possible to occur the problem of tie layer surface protrudes hygroscopic agent.
At this point, adhesive layer of the invention with a thickness of 8~85 μm, so as to meet the condition (4) and condition (5), preferably
Ground thickness can be 10~80 μm.If the thickness of adhesive layer, less than 8 μm, organic electronic device adhesive film used for packing material glues
Knot property may decline, thereby increases and it is possible to occur the problem of tie layer surface protrudes hygroscopic agent, if thickness is greater than 85 μm, may occur
The problem of reliability decrease of organic electronic device adhesive film used for packing material.
On the other hand, the present invention includes organic electronic device encapsulating material and luminaire, the organic electronic device
It include organic electronic device as described above adhesive film used for packing material with encapsulating material, the luminaire includes described organic
Electronic equipment encapsulating material.
The luminaire include substrate, be formed in the substrate at least one side organic electronic device and encapsulation described in
The organic electronic device encapsulating material according to the present invention of organic electronic device.
As shown in figure 3, a preferably embodiment according to the present invention, luminaire 100 of the invention can be equipped with containing mixed
The adhesive layer 115 of the single layer structure of resin 115b and hygroscopic agent 115a, in preferably another embodiment according to the present invention, such as
Shown in Fig. 4, luminaire 100 of the invention can be equipped with the multilayered structure for including the first adhesive layer 111 and the second adhesive layer 112
Adhesive layer, first adhesive layer 111 contain the first hybrid resin 111b and the first hygroscopic agent 111a, include the second compound tree
Rouge 112b and the second hygroscopic agent 112a.
Aftermentioned content is illustrated on the basis of the luminaire 100 of the adhesive layer of the multilayered structure equipped with Fig. 4.
Luminaire 100 according to the present invention includes substrate 101, organic electronic device 102, organic electronic device encapsulation
Material 111,112, the machine electronic equipment 102 are formed in at least one side of the substrate 101, the organic electronic device envelope
Package material 111,112 is formed in 102 top of the substrate 101 and organic electronic device.The organic electronic device package material
Material includes: the first adhesive layer 111, includes the first hybrid resin 111b and hygroscopic agent 111a, the first hybrid resin 111b packet
Containing the first binding resin and the second binding resin, the hygroscopic agent 111a includes silica;And second adhesive layer 112, shape
The one side of first adhesive layer described in Cheng Yu, and include the second hybrid resin 112b and the second adhesive layer 112, second compound tree
Rouge 112b includes the first binding resin and the second bonding tree, second adhesive layer 112 include hygroscopic agent 112a.
Preferably, glass substrate, quartz wafer, sapphire substrate, plastic base and flexible can be used in the substrate 101
It is any in flexible polymeric film.
The organic electronic device 102 for being formed in at least one side of the substrate 101 can be formed, in the substrate
Film is carried out to lower electrode on 101 and stacks gradually n-type semiconductor layer, active layer, p-type semiconductor layer, top electricity on it
It is extremely formed afterwards by etching, or is placed on the substrate 101 and is formed by additional substrate manufacture.It will be this organic
Electronic equipment 102 is formed in the specific method on substrate 101 and can be carried out by method well-known in the art, and in the present invention
In be not particularly limited to this, the organic electronic device 102 can be Organic Light Emitting Diode.
Then, it is encapsulated including the organic electronic device according to the present invention for encapsulating the organic electronic device 102
The specific method of material 111,112, the encapsulation can be carried out according to well known commonsense method, and not limited especially in the present invention
In this.As the non-limiting example to this, used in the organic electronic device 102 being formed on substrate 101 in organic electronic device
First adhesive layer 111 of encapsulating material 111,112 can be by using vacuum in the state of directly contacting with organic electronic device 102
Press machine or vacuum laminator etc. execute to apply heat and/or pressure.Also, in order to which the solidification of adhesive layer can apply heat
Amount, can be by being moved to further progress in the chamber of irradiation light in the case where the binder comprising binding resin of photocuring
Solidification process.
Hereinafter, examples illustrate the present invention by following, at this point, following embodiments be only used for illustrating the present invention and
It proposes, invention of the invention is claimed range and is not limited to following embodiments.
Embodiment 1: the manufacture of organic electronic device adhesive film used for packing material
The formation of (1) first adhesive layer
In order to form the first adhesive layer, it is copolymerized with the weight ratio mixing of 1:2.33 by ethylene, propylene and diolefinic compounds
Made of random copolymer (the first binding resin) and the compound (the second binding resin) indicated by following chemical formula 1 prepare
After first hybrid resin, relative to first hybrid resin of 100 parts by weight, the first tackifier (SU- of 80 parts by weight is put into
90, Cologne industry) and the second tackifier (SU-100, Cologne industry) of 50 parts by weight, 11 parts by weight the weight as curing agent
Average molecular weight be 226 acrylic acid (M200, rice source speciality chemical (Miwon Specialty Chemical)), 3 parts by weight
Uv initiator (irgacure TPO, Ciba) and the average grain diameters of 24 parts by weight be to carry out after 0.5 μm of silica
Stirring.
After the completion of stirring, mixture is set to pass through capsule filters come after removing foreign matter, using slot-die coater coated in thickness
Then the heavy antistatic abnormal shape polyethylene terephthalate (PET) (RT81AS, SKCHass) that degree is 75 μm utilizes 120
It DEG C is dried and is prepared for the first adhesive layer that final thickness is 20 μm after removing solvent.
By with the copolymerization weight ratio ethylene and propylene monomer of 1:0.85 and relative to random copolymer total weight, with 9 weights
Amount percentage is copolymerized diolefinic compounds to be prepared for first binding resin, and the diolefinic compounds are to use ethylidene
The random copolymer that the weight average molecular weight of norbornene (ethylidene norbornene) preparation is 500000.
Chemical formula 1
In the chemical formula 1, the R1 is isoprene, and the n is the weight for meeting the compound indicated by chemical formula 1
The rational of average molecular weight 400000.
The formation of (2) second adhesive layers
In order to form the second adhesive layer, it is copolymerized with the weight ratio mixing of 1:2.33 by ethylene, propylene and diolefinic compounds
Made of random copolymer (the first binding resin) and the compound (the second binding resin) indicated by following chemical formula 1 prepare
After second hybrid resin, relative to second hybrid resin of 100 parts by weight, the first tackifier of 150 parts by weight are put into
(M200, rice source are special for the acrylic acid that the weight average molecular weight as curing agent of (SU-90, Cologne industry), 17 parts by weight is 226
Chemicals), the average grain diameters of the uv initiator (irgacure TPO, Ciba) of 3 parts by weight and 100 parts by weight be 3 μm
It is stirred after calcium oxide.
After completing stirring, 20 DEG C at a temperature of viscosity is adjusted to 800cps and to make it through capsule filters different to remove
After object, using slot-die coater be coated in a thickness of 38um light removing abnormal shape polyethylene terephthalate (RF02,
SKCHass), then it is dried and is removed with 120 DEG C and is prepared for the second adhesive layer that final thickness is 30 μm after solvent.
By with the copolymerization weight ratio ethylene and propylene monomer of 1:0.85 and relative to random copolymer total weight, combined polymerization
The diolefinic compounds of 9 weight percent are prepared for first binding resin, and the diolefinic compounds are using sub- second
The random copolymer that the weight average molecular weight of base norbornene preparation is 500000.
Chemical formula 1
In the chemical formula 1, the R1For isoprene, the n is the weight for meeting the compound indicated by chemical formula 1
The rational of average molecular weight 400000.
First adhesive layer of the manufacture is bonded in a manner of towards the second adhesive layer and makes it through 70 DEG C of layer
Pressure roller has manufactured adhesive film.
Embodiment 2~11 and comparative example 1~8
It manufactures same as Example 1ly, but the weight average molecular weight by changing the first binding resin and the second binding resin,
Content, uv initiator content of curing agent etc. manufacture the adhesive film such as following table 1~table 4.
Experimental example 1
It is directed to the organic electronic device adhesive film prepared according to Examples and Comparative Examples, by being laminated the first adhesive layer
Or second adhesive layer, to prepare the coated film with a thickness of 40 μm.For prepared coated film, coating direction when preparing is made
For length direction, after cutting preparation test piece with the size of 50mm × 10mm (length x width), it is towards length that the test piece, which is pasted,
Degree direction only leaves 25mm.Then catch adhesive portion, and 25 DEG C at a temperature of, with 18mm/ minutes speed tensiles, and survey
Determine tensile modulus of elasticity.
Experimental example 2
For the adhesive film manufactured by the Examples and Comparative Examples, following physical property are measured, such as following table 1 to 4 institute of table
Show.
1. the moisture penetration of adhesive film is evaluated
After cutting test piece with the size of 95mm × 95mm, the alkali-free glass of 100mm × 100mm with remove after protective film with
After so that test piece is located at and is aligned from the mode of the edge on four sides of alkali-free glass 2.5mm inwardly, using being heated to 65 DEG C
Roll laminating is adhered to.After remaining release film in the test piece of removal attachment, the alkali-free glass of another 100mm × 100mm is covered
Glass is made without the sample of the bonding of bubble in 65 DEG C of temperature laminated one minute using vacuum laminator.To having bonded
At sample be set as 85 DEG C, observing the length of moisture penetration under the reliability chamber that relative humidity is 85% with 1000 hours units
Degree.
2. the volume expansion of adhesive film is evaluated
The layer of rolls press removal examination for being heated to about 65 DEG C is utilized in the SUS plate of 50 μm of the thickness cut with 30mm × 20mm
Adhered to after the release film of piece.After the test piece of attachment is cut into SUS size using knife, in 40mm × 30mm 0.7T alkali-free
Glass is adhered to using the layer of rolls press for being heated to 65 DEG C.Confirmation test piece does not have hole between glass (Glass) and SUS
(Void) after bonding is good, be set as 85 DEG C, in the reliability chamber that relative humidity is Figure 85 % to be within 100 hours that interval is observed
1000 hours, by height change on the basis of SUS by the test piece of optical microphotograph sem observation in the position of hygroscopic moisture.
Observation in the case where the height change at moisture moisture absorption position is less than 1 μm with ◎ as a result, indicated, moisture moisture absorption position
Height change be 1~less than 3 μm in the case where indicated with zero, the height change at moisture moisture absorption position for 3~feelings less than 5 μm
It is indicated under condition with Δ, the height change at moisture moisture absorption position is used in the case where being 5 μm or more × indicated.
3. the Evaluation of Heat Tolerance of adhesive film
With the cutting test piece of 50mm × 80mm size, after the protective film for removing test piece, in the nickel of the 0.08T of 60mm × 150mm
In alloy, 80 DEG C, notch be (Gap) be 1mm, speed (Speed) is 1 under conditions of adhered to using layer of rolls press.It goes
After the release film (Linerfilm) of the test piece of the attachment, in the alkali-free glass of the 5T of 30mm × 70mm, 80 DEG C, cut
Adhered under conditions of mouth is 1mm, speed is 1 using layer of rolls press.The test piece for being attached to the glass is vertically fixed on
After 130 DEG C of chamber (Chamber), the hammer of 1kg is hung up to grasp whether binder (adhesive) is flowing.
At this point, being indicated in the case where evaluation result does not have exception with zero, if using × indicating shaking and making a movement.
4. glass adhesion is evaluated
For the adhesive film manufactured according to Examples and Comparative Examples, adhesion is measured by adhesive tape by the hand pressure roller of 2kg
(7475, TESA) are laminated to the upper surface of adhesive film, after sample is cut into width 25mm and length 120mm, in 80 DEG C of temperature
It is lower will be laminated to alkali-free glass below adhesive film after, sample is placed at normal temperature 30 minutes, by universal testing machine (UTM) with
300mm/ minutes velocity determination glass adhesions.
5. metal adhesion flat fare
For the adhesive film prepared according to Examples and Comparative Examples, 80 DEG C at a temperature of will be laminated to thickness above adhesive film
The nickel alloy that degree is 80 μm, and adhesion measurement adhesive tape (7475, TESA) is laminated to adhesive film in the following, sample is cut into width
After spending 25mm and length 120mm, ready sample is placed at normal temperature 30 minutes, by universal testing machine (UTM) with
300mm/ minutes velocity determination glass adhesions.
Experimental example 3
Organic luminescent device (hole transmission layer NPD/ thickness is deposited on the substrate with electro-conductive glass (ITO) pattern
800A, luminescent layer Alq3/ thickness 300A, electron injecting layer LiF/ thickness 10A, cathode Al+Liq/ thickness 1000A) after, it is manufacturing
Device in normal temperature layer at all according to the adhesive film of Examples and Comparative Examples after, manufactured the Organic Light Emitting Diode of luminous green
(OLED) unit test piece.Then, following evaluation of physical property are carried out for test piece, as shown in table 1 to table 7.
1. pair according to the durability evaluation of the organic luminescent device of the moisture penetration of adhesive film
By test piece be set as 85 DEG C, relative humidity be 85% in the environment of, with × 100 digit microscope with 100 hours
Observe pixel shrinkage (Pixel shrinkage) in illumination region hourly and stain (Dark spot) for unit
It generates and/or grows, the time required to 50% or more and/or stain generation occur for measurement pixel shrinkage.
At this point, being used in the case where being 1000 or more the time required to pixel shrinkage occurs 50% or more and/or stain generates
◎ is indicated, for less than 1000 hours~800 hours or more the time required to pixel shrinkage occurs 50% or more and/or stain generates
In the case where indicated with zero, pixel shrinkage occur 50% or more and/or stain generate the time required to for less than 800 hours~
Indicated in the case where 600 hours or more with Δ, pixel shrinkage occur 50% or more and/or stain generate the time required to for less than
600 it is small in the case of with × indicate.
2. the durability evaluation of adhesive film
By test piece be set as 85 DEG C, relative humidity be 85% reliability chamber in be within 100 hours that spacing observation 1000 is small
When, by generating gas in interfacial separation, crackle or the adhesive film between optical microphotograph sem observation organic electronic device and adhesive film
It is evaluated whether bubble, bonding interlaminar separation etc. are come to physical damage.Evaluation result, with zero table in the case where no exception
Show, used with any one of bubble, bonding interlaminar separation etc. is generated in interfacial separation, crackle or adhesive film ×
Indicate,
Table 1
Table 2
Table 3
Table 4
From the table 1 to table 4 it is found that be all satisfied tensile modulus of elasticity of the invention, preferred first binding resin and
The embodiment 1 of weight average molecular weight, the content of curing agent, uv initiator content and the bonding layer number of second binding resin etc.
Even if~7, embodiment 9, embodiment 10 with miss one of them embodiment 8, embodiment 11, embodiment 19, embodiment 22 and
Comparative example 1~14 is compared, and moisture removal and barrier are effective, therefore moisture penetration length is short, and the volume expansion of adhesive film is several
Do not have, the durability evaluation result of heat resistance and organic luminescent device is very well and the durability of adhesive film is very outstanding, adhesion
It is outstanding.
Those skilled in the art may be easy to implement simple deformation or change of the invention, can be considered as
This deformation or change belong in the field of the invention.
Claims (16)
1. a kind of organic electronic device adhesive film used for packing material, which is characterized in that
The second adhesive layer including the first adhesive layer and the one side for being formed in first adhesive layer,
First adhesive layer 25 DEG C at a temperature of have (210~390) × 103The tensile modulus of elasticity of pa, described second is viscous
Tie layer 25 DEG C at a temperature of have (1400~2600) × 103The tensile modulus of elasticity of pa.
2. organic electronic device adhesive film used for packing material according to claim 1, which is characterized in that first bonding
Layer and the second adhesive layer 25 DEG C at a temperature of tensile modulus of elasticity deviation be 1010~2390 × 103Pa.
3. organic electronic device adhesive film used for packing material according to claim 1, which is characterized in that
First adhesive layer includes the first hybrid resin, tackifier and the first hygroscopic agent,
First hybrid resin includes the first binding resin and the second binding resin with the weight ratio of 1:0.1~10,
Relative to the first hybrid resin of 100 parts by weight, the tackifier comprising 50~300 parts by weight,
Relative to the first hybrid resin of 100 parts by weight, first hygroscopic agent comprising 1~40 parts by weight.
4. organic electronic device adhesive film used for packing material according to claim 3, which is characterized in that
The tackifier include the first tackifier and the second tackifier of the weight ratio of 1:0.5~1.5,
The softening point of first tackifier less than the second tackifier softening point,
First hygroscopic agent includes silica.
5. organic electronic device adhesive film used for packing material according to claim 3, which is characterized in that
First adhesive layer also includes one or more of curing agent and uv initiator,
Relative to the first hybrid resin of 100 parts by weight, the curing agent comprising 2~30 parts by weight,
Relative to the first hybrid resin of 100 parts by weight, the uv initiator comprising 0.1~5 parts by weight.
6. organic electronic device adhesive film used for packing material according to claim 3, which is characterized in that first bonding
The viscosity of layer is 150000 Pa Secs or less under the conditions of 50 DEG C of temperature.
7. organic electronic device adhesive film used for packing material according to claim 1, which is characterized in that
Second adhesive layer includes the second hybrid resin, tackifier and the second hygroscopic agent,
Second hybrid resin includes the first binding resin and the second binding resin with the weight ratio of 1:0.1~10,
Relative to the second hybrid resin of 100 parts by weight, the tackifier comprising 60~300 parts by weight,
Relative to the second hybrid resin of 100 parts by weight, second hygroscopic agent comprising 50~450 parts by weight.
8. organic electronic device adhesive film used for packing material according to claim 7, which is characterized in that
The tackifier include the first tackifier,
Second hygroscopic agent includes calcium oxide.
9. organic electronic device adhesive film used for packing material according to claim 7, which is characterized in that
Second adhesive layer also includes one or more of curing agent and uv initiator,
Relative to the second hybrid resin of 100 parts by weight, the curing agent comprising 10~40 parts by weight,
Relative to the second hybrid resin of 100 parts by weight, the uv initiator comprising 0.1~8 parts by weight.
10. organic electronic device adhesive film used for packing material according to claim 7, which is characterized in that described second is viscous
The viscosity for tying layer is 200000 Pa Secs or more under the conditions of 50 DEG C of temperature.
11. organic electronic device adhesive film used for packing material according to claim 3 or 7, which is characterized in that
First hybrid resin and the second hybrid resin include the first binding resin and the second binding resin,
It include first binding resin and the second binding resin with the weight ratio of 1:0.1~10.
12. organic electronic device adhesive film used for packing material according to claim 11, which is characterized in that
First binding resin includes that weight average molecular weight is 30000~1550000 by ethylene, propylene and diolefinic compounds
Random copolymer made of copolymerization,
Second binding resin includes the compound indicated by following chemical formula 1,
Chemical formula 1:
In the chemical formula 1, R1For the branched chain type alkenyl of the straight chain type alkenyl or C4~C10 of hydrogen atom or C3~C10, the n
Meet 30000~1550000 rational for the weight average molecular weight of the compound indicated by chemical formula 1.
13. according to right want 12 described in organic electronic device adhesive film used for packing material, which is characterized in that
Random copolymerization is carried out to the ethylene and propylene with the weight ratio of 1:0.3~1.4,
Relative to the random copolymer total weight, the diolefinic compounds comprising 2~15 weight percent.
14. organic electronic device adhesive film used for packing material according to claim 1, which is characterized in that
The glass adhesion according to the measurement of following measuring methods 1 of the adhesive film is 1500gf/25mm or more,
Metal adhesion according to the measurement of following measuring methods 2 is 1000gf/25mm or more,
Measuring method 1: adhesive tape is measured in adhesive film upper side lamination adhesion, sample is cut out with width 25mm and length 120mm
After cutting, 80 DEG C at a temperature of adhesive film bottom surfaces are laminated to glass after, the sample prepared is placed 30 points at normal temperature
Clock, and with 300mm/ minutes velocity determination glass adhesions,
Measuring method 2: 80 DEG C at a temperature of adhesive film upper side is laminated to 80 μm thickness nickel alloy, and by adhesion
Measurement adhesive tape is laminated to adhesive film bottom surfaces, and after sample is cut with width 25mm and length 120mm, the sample prepared is existed
It is placed 30 minutes under room temperature, and with 300mm/ minutes velocity determination metal adhesions.
15. a kind of organic electronic device encapsulating material, which is characterized in that including described in any one of claims 1 to 14
Organic electronic device adhesive film used for packing material.
16. a kind of light emitting device characterized by comprising
Substrate;
Organic electronic device is formed in at least one side of the substrate;And
Organic electronic device encapsulating material described in claim 15, for encapsulating the organic electronic device.
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CN103998238A (en) * | 2012-01-06 | 2014-08-20 | Lg化学株式会社 | Encapsulation film |
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