CN101848912A - Organic metal compound, composition for trapping moisture and oxygen, cured body, and organic EL device - Google Patents
Organic metal compound, composition for trapping moisture and oxygen, cured body, and organic EL device Download PDFInfo
- Publication number
- CN101848912A CN101848912A CN200880114950A CN200880114950A CN101848912A CN 101848912 A CN101848912 A CN 101848912A CN 200880114950 A CN200880114950 A CN 200880114950A CN 200880114950 A CN200880114950 A CN 200880114950A CN 101848912 A CN101848912 A CN 101848912A
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- Prior art keywords
- organic
- compound
- oxygen
- composition
- moisture
- Prior art date
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000001301 oxygen Substances 0.000 title claims abstract description 54
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 150000002736 metal compounds Chemical class 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- -1 3-cyclo-dodecyl propyl Chemical group 0.000 claims description 50
- 229910052782 aluminium Inorganic materials 0.000 claims description 49
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 48
- 239000004411 aluminium Substances 0.000 claims description 47
- 150000002902 organometallic compounds Chemical class 0.000 claims description 44
- 239000000126 substance Substances 0.000 claims description 29
- 239000003595 mist Substances 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 abstract description 39
- 125000006165 cyclic alkyl group Chemical group 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 40
- 229920001577 copolymer Polymers 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 36
- 238000005984 hydrogenation reaction Methods 0.000 description 36
- 239000010410 layer Substances 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical class C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 17
- 150000001336 alkenes Chemical class 0.000 description 17
- 239000002904 solvent Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 13
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- 238000000576 coating method Methods 0.000 description 9
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
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- 239000005977 Ethylene Substances 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- 238000005457 optimization Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 7
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- 230000000052 comparative effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000007818 Grignard reagent Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 150000004795 grignard reagents Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 150000003440 styrenes Chemical class 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 239000003566 sealing material Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 238000003747 Grignard reaction Methods 0.000 description 3
- 150000001339 alkali metal compounds Chemical class 0.000 description 3
- 125000001118 alkylidene group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- 239000010422 internal standard material Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 150000002899 organoaluminium compounds Chemical class 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- RQHZDJUTSGQPAO-UHFFFAOYSA-N C1CCCCCCCCCCC1.[Br] Chemical compound C1CCCCCCCCCCC1.[Br] RQHZDJUTSGQPAO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KEVYVLWNCKMXJX-ZCNNSNEGSA-N Isophytol Natural products CC(C)CCC[C@H](C)CCC[C@@H](C)CCC[C@@](C)(O)C=C KEVYVLWNCKMXJX-ZCNNSNEGSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 238000012661 block copolymerization Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000013086 organic photovoltaic Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 108091008695 photoreceptors Proteins 0.000 description 2
- 125000001189 phytyl group Chemical group [H]C([*])([H])/C([H])=C(C([H])([H])[H])/C([H])([H])C([H])([H])C([H])([H])[C@@](C([H])([H])[H])([H])C([H])([H])C([H])([H])C([H])([H])[C@@](C([H])([H])[H])([H])C([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])C([H])([H])[H] 0.000 description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 2
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- YXFVVABEGXRONW-JGUCLWPXSA-N toluene-d8 Chemical compound [2H]C1=C([2H])C([2H])=C(C([2H])([2H])[2H])C([2H])=C1[2H] YXFVVABEGXRONW-JGUCLWPXSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
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- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- DVPBTNIOSMPQCJ-UHFFFAOYSA-N 1,1,2,2,3,3-hexabromocyclododecane hydrobromide Chemical compound BrC(CCCCCCCCCC1(Br)Br)(C1(Br)Br)Br.Br DVPBTNIOSMPQCJ-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- UOZJTJVTHVKRNK-UHFFFAOYSA-N 3-ethenyl-2-ethylaniline Chemical compound CCC1=C(N)C=CC=C1C=C UOZJTJVTHVKRNK-UHFFFAOYSA-N 0.000 description 1
- OCTVDLUSQOJZEK-UHFFFAOYSA-N 4,5-diethylocta-1,3-diene Chemical compound CCCC(CC)C(CC)=CC=C OCTVDLUSQOJZEK-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- CBZMQWPBAUBAPO-UHFFFAOYSA-N 4-ethenyl-n,n-diethylaniline Chemical compound CCN(CC)C1=CC=C(C=C)C=C1 CBZMQWPBAUBAPO-UHFFFAOYSA-N 0.000 description 1
- UGWOAPBVIGCNOV-UHFFFAOYSA-N 5-ethenyldec-5-ene Chemical compound CCCCC=C(C=C)CCCC UGWOAPBVIGCNOV-UHFFFAOYSA-N 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
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- 206010018612 Gonorrhoea Diseases 0.000 description 1
- 244000153234 Hibiscus abelmoschus Species 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- IADKAKQBSKWITE-UHFFFAOYSA-N bromocyclododecane Chemical compound BrC1CCCCCCCCCCC1 IADKAKQBSKWITE-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- VPCAAUUIFCAFRZ-UHFFFAOYSA-N butylalumane Chemical compound CCCC[AlH2] VPCAAUUIFCAFRZ-UHFFFAOYSA-N 0.000 description 1
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XHEDLZYGAQSNTR-UHFFFAOYSA-N ethene;hexanedioic acid Chemical compound C=C.C=C.OC(=O)CCCCC(O)=O XHEDLZYGAQSNTR-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- SPRIOUNJHPCKPV-UHFFFAOYSA-N hydridoaluminium Chemical compound [AlH] SPRIOUNJHPCKPV-UHFFFAOYSA-N 0.000 description 1
- GPHZOCJETVZYTP-UHFFFAOYSA-N hydroperoxycyclododecane Chemical compound OOC1CCCCCCCCCCC1 GPHZOCJETVZYTP-UHFFFAOYSA-N 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- GQEZCXVZFLOKMC-UHFFFAOYSA-N n-alpha-hexadecene Natural products CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- IPNPIHIZVLFAFP-UHFFFAOYSA-N phosphorus tribromide Chemical class BrP(Br)Br IPNPIHIZVLFAFP-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000000207 volumetry Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
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-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/32—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal
- C09K15/326—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal containing only metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/062—Al linked exclusively to C
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/20—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the material in which the electroluminescent material is embedded
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
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- 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
- H10K50/846—Passivation; Containers; Encapsulations comprising getter material or desiccants
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- Chemical & Material Sciences (AREA)
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Abstract
Disclosed is at least one organic metal compound selected from the group consisting of compounds represented by the formulae (I) and (II) below. Also disclosed is a composition for trapping moisture and oxygen, which contains such a compound and a polymer. (I) (II) (In the formula (II), R1's independently represent at least one selected from a hydrogen atom, a linear alkyl group having 0-6 carbon atoms, a branched alkyl group, a cyclic alkyl group and a combination of them; l represents an integer of 1-10; m represents an integer of 5-15; and n represents an integer of 0-14).
Description
Technical field
The present invention relates to and to have the novel organometallic compound of the big alkyl of volume as catching the composition components that moisture and oxygen are used.And, the present invention relates to contain the seizure moisture of specific organometallic compound and composition that oxygen is used, the cured article that forms by said composition and the organic EL that contains this cured article.
Background technology
In recent years, because under DC low-voltage, drive and slimming becomes possibility, get most of the attention as the organic EL of thin display.And, carrying out that, efficient higher than organic EL brightness is higher to be the research and development of purpose.Organic EL generally has charge transport layer (electron supplying layer, hole transporting layer) and the organic luminous layer between anode and negative electrode.Organic luminous layer be by from anode injected electrons hole and from the negative electrode injected electrons in conjunction with the time energy excite, the energy difference when this excited state is got back to ground state comes luminous.
But organic EL is subjected to the influence of moisture and oxygen easily, has low being not suitable for of weather resistance.That is, oxidation or organic sex change that moisture of introducing in the organic EL and oxygen can cause electrode are accompanied by the long-term of driving time, have the significantly reduced problems of the characteristics of luminescence such as brightness, luminous efficiency.
In order to solve such problem, using the countermeasure that in organic EL, disposes the trapping agent of moisture and oxygen.For example, in TOHKEMY 2006-59571 communique, proposed to contain organo-aluminium compound or the organoboron compound of representing by the particular chemical formula, for the good organic EL panel trapping agent of the capturing ability of moisture or oxygen.And, put down in writing in the document above-mentioned organo-aluminium compound or organoboron compound and tackiness agent blended organic EL panel trapping agent.But such trapping agent thermotolerance is insufficient, thereby at (for example about 80 ℃) under the high temperature environment for use, trapping agent meeting heat flow produces such being not suitable for of distortion.
And in the organic EL of last emission type, because must form the trapping agent layer between organic luminous layer and display surface, it is transparent requiring trapping agent.And then normally the liquid trapping agent (trapping agent that for example contains organo-aluminium compound, solvent and tackiness agent etc.) of coating forms the trapping agent layer on the prescribed position of organic EL, and trapping agent requires the viscosity of appropriateness.In addition, also require as the consistency of the organometallic compound of the composition of trapping agent and tackiness agent good.
Consider that from the further viewpoint of improving the desired every characteristic of moisture and oxygen trapping agent the expectation exploitation contains the trapping agent composition of novel organometallic compound.The inventor is conceived to be used as moisture and oxygen trapping agent, and the while is as the trialkylaluminium of the useful organometallic compound of polymkeric substance synthetic catalyzer.
The manufacturing of trialkylaluminium is generally as shown in the formula carrying out like this.
3Al+3/2H
2+3CH＝CH
2-A→3Al(CH
2CH
2-A)
3
(in the formula, A is hydrogen atom or low alkyl group (down together)).
This reaction can be used cheap raw material, and useful because of single step reaction, but reaction must be a high pressure, and this is unaccommodated.But when using higher alkene in raw material, because the boiling point height, control high pressure difficulty is difficult to react reposefully.And, when making senior trialkylaluminium, remove unreacted aluminium difficulty by distillation is refining.Like this, this synthesis method is the synthetic method that is fit to make more rudimentary trialkylaluminium, but is not suitable for making senior trialkylaluminium.This reaction is recorded in No. 2787626 patent specification of the U.S..
On the other hand, be shown below, as starting raw material or intermediate, the method for making trialkylaluminium also is known with dialkyl aluminum hydride.
AlH(CH
2CH
2-A)
2+CH
2＝CH-A→Al(CH
2CH
2-A)
3
This reaction write up is in TOHKEMY 2003-002892 communique.With dialkyl aluminum hydride during, must synthesize this compound with other method arbitrarily as starting raw material.But, because the synthetic very difficulty of dialkyl aluminum hydride can not be referred to as efficient method.And, make the occasion of intermediate via dialkyl aluminum hydride, the same with aforesaid method, the unreacted aluminium when making senior trialkylaluminium is difficult to remove.
And then, be shown below, also have method by the synthetic trialkylaluminium of Ge Liyafa.
AlCl
3+3(A-CH
2-CH
2)MgBr→Al(CH
2CH
2-A)
3+3MgClBr
But, in this method, when on Al, introducing 3 alkyl, from reaction product, remove the MgClBr difficulty, refining difficulty.
The inventor's purpose is to provide the easy and high purity ground of a kind of energy to make the method for senior trialkylaluminium, has formerly proposed TOHKEMY 2007-204457 communique.In view of the above, by under 50～150 ℃ temperature, heating AlR
3(in the formula, R can represent that identical or different carbonatoms is the alkyl of 2～4 straight or branched) the lower trialkyl aluminium of expression and the 1-alkene of carbonatoms 6～18 react under normal pressure, can obtain AlR '
3The senior trialkylaluminium of (in the formula, the identical or different carbonatoms of R ' expression is the alkyl of 6～18 straight or branched) expression.
But, have the trialkylaluminium of cyclic senior alkyl or have branching senior alkyl 1-phytyl (carbonatoms 20) trialkylaluminium and the preparation generally also do not know.Thereby the expectation exploitation is the useful and trialkylaluminium with ring-type senior alkyl or phytyl that can be used as moisture and oxygen trapping agent composition as polymkeric substance synthetic catalyzer.
As the object lesson of the trialkylaluminium of expecting, can enumerate three (3-cyclo-dodecyl propyl group) aluminium with ring-type senior alkyl.In the cyclododecane class, cyclododecane is well known that as the raw material of the useful cyclo-dodecyl hydrogen peroxide of oxygenant (with reference to TOHKEMY 2000-1473 communique), and the 2-cyclo-dodecyl-1-propyl alcohol as the derivative of cyclododecane is the spices (with reference to Japanese Unexamined Patent Application Publication 2002-504129 communique) of Moschus class, so the bromide hexabromocyclododecane of cyclododecane known be to use (with reference to Japanese Unexamined Patent Application Publication 2003-525863 communique) as fire retardant.But the 3-cyclo-dodecyl-1-propylene that uses as the raw material of three (3-cyclo-dodecyl propyl group) aluminium generally is not known.
Like this, the expectation exploitation is a kind of to be used for moisture and oxygen trapping agent, can be used as the useful novel organometallic compound of polymkeric substance synthetic catalyzer simultaneously, and the moisture and the oxygen seizure property composition that have the operability of good thermotolerance, the transparency and coating concurrently.
Summary of the invention
The present invention proposes in view of above-mentioned being not suitable for that prior art exists.Therefore, first purpose of the present invention be to provide a kind of as polymkeric substance synthetic catalyzer useful or can be effectively as the novel organometallic compound of the composition of catching the composition that moisture and oxygen uses.
Second purpose of the present invention is to provide a kind of specific organometallic compound that contains, and can form the seizure moisture of the good cured article (film etc.) of seizure (water absorbability, inhaling of oxygen), thermotolerance and the transparency of moisture and oxygen and the composition that oxygen is used with good operability.
Above-mentioned first purpose is to realize by at least a kind of organometallic compound of the group of the compound formation that is selected from following formula (I) and (II) represents.
[in the formula (II), R
1Respectively independently expression to be selected from hydrogen atom, carbonatoms be at least a of 0～6 straight chained alkyl, branched-chain alkyl, cycloalkyl or their combination, l is 1～10 integer, m is 5～15 integer, n is 0～14 integer.Wherein, R
1Be combined in by (CH
2)
mOn the carbon of the closed chain that forms, constitute by-CHR
1The alkylidene group of-expression.]
Three (3-cyclo-dodecyl propyl group) aluminium of preferred especially following formula (III) expression of the compound of above-mentioned formula (II).
Above-mentioned second purpose is by containing above-mentioned formula (I) or (II) organometallic compound and the seizure moisture of polymkeric substance and the composition that oxygen is used of (preferred especially above-mentioned formula (III)) expression are realized.
The composition that above-mentioned seizure moisture and oxygen are used is suitable for organic EL.Said composition can be used with the form of cured article.Preferably in the time of 25 ℃, mist degree is less than 5% under the thickness 0.5mm for this cured article.And, can constitute the organic EL that comprises the cured article that the composition used by above-mentioned seizure moisture and oxygen forms.
Above-mentioned organometallic compound is useful as polymkeric substance synthetic catalyzer, and has good moisture and oxygen seizure characteristic.And, contain the seizure moisture of such organometallic compound and polymkeric substance and the composition that oxygen is used by use, can form water absorbability, inhaling of oxygen, thermotolerance and the good cured article (film etc.) of the transparency.And then the composition that this seizure moisture and oxygen are used is good because of the consistency of above-mentioned organometallic compound and polymkeric substance, and has the viscosity of appropriateness under liquid state, and the operability when forming cured article is good.This cured article is suitable as the sealing material of the organic EL with above-mentioned every characteristic good, and can be used as the parts of the organic EL of the good last emission type of the transparency.
Description of drawings
Fig. 1 is the sectional view that shows according to an example of organic EL of the present invention.
Fig. 2 is 3-cyclo-dodecyl-1-propylene that synthesis example 1 obtains
1H NMR spectrum.
Fig. 3 is three (3-cyclo-dodecyl propyl group) aluminium that embodiment 1 obtains
1H NMR spectrum.
Fig. 4 is three (1-phytyl) aluminium that embodiment 2 obtains
1H NMR spectrum.
Nomenclature
1 organic EL
2 organic EL layers
3 structures
The 3a substrate
The 3b seal cap
The 3c tackiness agent
4 trapping agent layers
Embodiment
The cured article of the composition that the organometallic compound that has ad hoc structure according to the present invention, the composition that can use with polymkeric substance, the seizure moisture that contains these compositions and oxygen that this organometallic compound uses and this seizure moisture and oxygen are used is described below successively.
1. organometallic compound
Organometallic compound of the present invention is to be selected from following formula (I) and (II) trialkylaluminium in the group that constitutes of the compound of expression, that have at least a kind of bulky alkyl.In addition, the compound of following formula (I) expression is called three (1-phytyl) aluminium.
[in the formula (II), R
1Respectively independently expression to be selected from hydrogen atom, carbonatoms be at least a of 0～6 straight chained alkyl, branched-chain alkyl, cycloalkyl or their combination, l is 1～10 integer, m is 5～15 integer, n is 0～14 integer.R
1Be combined in by (CH
2)
mOn the carbon of the closed chain that forms, constitute by-CHR
1The alkylidene group of-expression.]
As the object lesson of the trialkylaluminium with cyclic alkyl of above-mentioned formula (II) expression, can enumerate three (3-cyclo-dodecyl propyl group) aluminium, three (3-cyclopentadecane base propyl group) aluminium, three (3-cyclo-dodecyl butyl) aluminium etc.Preferred especially three (3-cyclo-dodecyl propyl group) aluminium is represented by following formula (III) in them.
Following formula (I)～(III) senior trialkylaluminium expression, that have bulky alkyl distills refining generally difficult than lower trialkyl aluminium boiling point height.Thereby, must selection not make with extra care, can obtain the synthetic method of highly purified as far as possible product.
Three (1-phytyl) aluminium of above-mentioned formula (I) expression can use hydrocarbon solvents such as heptane as required, under normal pressure at AlR
3React with the 1-phytane in the lower trialkyl aluminium of (in the formula, R is the alkyl of the straight or branched of identical or different carbonatoms 2～4) expression and make.
Here, AlR
3The lower trialkyl aluminium of expression can have been enumerated trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, three n-butylaluminum, triisobutyl aluminium etc.The preferred triisobutyl aluminium that uses in them.
1-phytane used herein can synthesize by the decarboxylation reaction of isophytol.And isophytol is commercially available as reagent from Tokyo HuaCheng Industry Co., Ltd, starts with easily.
AlR
3The lower trialkyl aluminium of expression is different according to target product with the reaction mol ratio of 1-phytane, but usually with respect to 1 mole of lower trialkyl aluminium, the usage quantity of 1-phytane is more than 1 mole, below 4.5 moles.With respect to 1 mole of lower trialkyl aluminium, the 1-phytane is difficult to obtain target product less than 1 mole usage quantity, on the other hand, surpasses the further raising that 4.5 moles usage quantity can not obtain the product productive rate.
Above-mentioned reaction system can be used hydrocarbon solvents such as normal hexane, hexanaphthene, normal heptane, octane, benzene, toluene as required.Use solvent in reaction system, temperature of reaction is controlled easily.Solvent phase can use 50～10000 weight parts for 100 weight part lower trialkyl aluminium, the amount about preferred 500～2000 weight parts.
The above-mentioned normal pressure that is reflected at (fully carries out under 0.05～0.15Mpa).Temperature of reaction is usually at 50～150 ℃, preferred 80～120 ℃.Temperature of reaction is during less than 50 ℃, and reaction has carries out inadequate worry.On the other hand, temperature of reaction surpasses 150 ℃, and side reaction meetings such as polymerization take place, and are not preferred.
The reaction times of above-mentioned reaction typically is 1～48 hour, preferred about 3～24 hours.Even special purification operations is not carried out in above-mentioned reaction except heating up in a steamer the solvent that uses, also can obtain three (1-phytyl) aluminium of the high senior trialkylaluminium of conduct of purity.
Three (1-phytyl) aluminium of Huo Deing passes through like this
1Bonded methene proton on the aluminium of δ 0.6～0.2 in the H NMR spectrum is confirmed its structure from the proton of the phytyl of δ 1.7～0.8 etc.
On the other hand, the trialkylaluminium of cyclic alkyl with above-mentioned formula (II) (preferred following formula (III)) expression is the same with three (1-phytyl) aluminium of following formula (I) expression, by the AlR of above-mentioned definition
3Cycloalkyl-1-chain the alkene reaction of the lower trialkyl aluminium of expression and following formula (IV) expression obtains.
[in the formula (IV), R
1Respectively independently expression to be selected from hydrogen atom, carbonatoms be at least a of 0～6 straight chained alkyl, branched-chain alkyl, cycloalkyl or their combination, l is 1～10 integer, m is 5～15 integer, n is 0～14 integer.R
1Be combined in by (CH
2)
mOn the carbon of the closed chain that forms, constitute by-CHR
1The alkylidene group of-expression.]
The olefin(e) compound that the cycloalkyl-1-alkene of following formula (IV) expression preferably descends formula V to represent with cyclododecane basic ring.The R of following formula V
2Be carbonatoms 2～6, preferred 3～4 outer alkene, for example vinyl, 2-propenyl, 3-butenyl, 4-pentenyl, 5-hexenyl etc.
Particularly preferred outer alkene substituent R in the above-mentioned formula V
2It is the 2-propenyl.This olefin(e) compound (3-cyclo-dodecyl-1-propylene) with cyclododecane basic ring is represented by following formula (VI).
The manufacture method of the cycloalkyl-1-alkene of following formula (IV) expression can be used the olefin(e) compound with cyclododecane basic ring that formula V represents and be illustrated.The operation of the Grignard reagent that the olefin(e) compound with cyclododecane basic ring that last formula V is represented can be made cyclododecane by the single halogenide and the MAGNESIUM METAL of cyclododecane; Synthesize with the Grignard reagent of this cyclododecane and the operation of haloolefin reaction.In this reaction,,, use R with the halogenide of CDX (X is the halogen atom of F, Cl, Br or I) representative ring dodecane with CD representative ring dodecane
2Alkylenes such as expression propenyl are expressed as follows successively.
CDX+Mg→CDMgX
CDMgX+R
2X→CD-R
2+MgX
2
Here, in the halogenide of cyclododecane, for example single bromo cyclododecane can be commercially available as reagent by シ グ マ ア Le De リ Star チ ジ ヤ パ Application Co., Ltd., obtains easily.And haloolefin for example can synthesize with halogenations such as phosphorus tribromides by the alkanol compound of correspondence.In the haloolefin, for example 3-bromo-1-propylene can be commercially available by Kanto Kagaku K. K., obtains easily.
And the halogenide of cyclododecane and the reaction of MAGNESIUM METAL for example can be in anhydrous solvents such as tetrahydrofuran (THF), diethyl ether, in the presence of sheet or granulous MAGNESIUM METAL, the halogenide of this cyclododecane are carried out Grignard reaction.By this reaction, obtain the Grignard reagent of cyclododecane.
Here, the usage quantity with respect to the halid MAGNESIUM METAL of 1 mole of cyclododecane is generally 1～5 mole, preferred 1～1.5 mole in the Grignard reaction.The usage quantity of MAGNESIUM METAL is removed unreacted magnesium easily when this scope.And then the temperature of reaction of this Grignard reaction is generally 30～80 ℃, and preferred 35～65 ℃, the reaction times is generally 5～120 minutes, preferred 20～60 minutes.
Then, in this reaction system, drip haloolefin usually, by the Grignard reagent and the haloolefin reaction of cyclododecane, the olefin(e) compound with cyclododecane basic ring (alkene reaction) that synthetic upward formula V is represented.3-cyclododecane-1-the propylene of following formula (VI) expression can use the 3-bromo-1-propylene as haloolefin to synthesize.
In this alkene reaction, the usage quantity with respect to the haloolefin of 1 mole of Grignard reagent is generally 0.5～5 mole, preferred 1～1.5 mole.The usage quantity of haloolefin is when this scope, and reaction finishes and be refining easily.And the temperature of reaction of alkene reaction is generally-20～80 ℃, preferred 0～65 ℃, and the reaction times is generally 30 minutes～and 24 hours, preferred 2～12 hours.
The olefin(e) compound that alkene reaction synthetic has the cyclododecane basic ring is an example with 3-cyclo-dodecyl-1-propylene (following formula (VI)), according to
1H NMR spectrum can be confirmed that the methene proton of methine protons, the δ 1.34 of terminal olefin proton, the δ 1.98 of alkene proton, the δ 5.03～4.95 of δ 5.79 waits and confirm its structure.
Cycloalkyl-1-the alkene and the AlR of above-mentioned formula (IV) expression that obtains like this
3The lower trialkyl aluminium of expression obtains the trialkylaluminium with cyclic alkyl of following formula (II) expression in (using same solvent, temperature of reaction, pressure, time and component proportions) reaction under same condition when synthetic with above-mentioned three (1-phytyl) aluminium.And, similarly, the 3-cyclo-dodecyl-1-propylene and the AlR of following formula (VI) expression of particularly preferred example of the cycloalkyl-1-alkene by following formula (IV) expression
3The lower trialkyl reactive aluminum of expression can obtain three (3-cyclo-dodecyl propyl group) aluminium that following formula (III) is represented.
The trialkylaluminium with cyclic alkyl that obtains is an example with three (3-cyclo-dodecyl propyl group) aluminium (following formula (III)), according to
1H NMR spectrum can be confirmed that the cyclododecane basic ring of bonded methene proton, δ 1.8～1.1 on the aluminium of δ 0.56 and methene proton wait and confirm its structure.
Trialkylaluminium as the organometallic compound of such manufacturing is useful as polymkeric substance synthetic catalyzer, can bring into play good moisture and oxygen seizure performance simultaneously.And, contain moisture and oxygen trapping agent that cured article form that the composition of this organometallic compound and polymkeric substance described later forms is suitable as organic EL etc.
2. polymkeric substance
The composition that seizure moisture of the present invention and oxygen are used comprises above-mentioned organometallic compound and polymkeric substance.This polymkeric substance is used as the tackiness agent that forms matrix in the cured article of said composition.Polymkeric substance used herein preferably comprises at least a kind of the conjugated diene copolymer that is selected from conjugated diene copolymer, hydrogenation.
Above-mentioned conjugated diene copolymer preferably has based on the polymer blocks A of aromatic ethylene compound with based among the polymer blocks B of conjugated diene compound at least a kind separately.And the conjugated diene copolymer of above-mentioned hydrogenation is preferably to based on the polymer blocks A of aromatic ethylene compound with based on the product behind at least a kind the conjugated diene copolymer hydrogenation separately among the polymer blocks B of conjugated diene compound.The conjugated diene copolymer of such hydrogenation has the hydrogenation polymer blocks A from polymer blocks A
HWith hydrogenation polymer blocks B from polymer blocks B
H
As the aromatic ethylene compound that uses in the conjugated diene copolymer, vinylbenzene, t-butyl styrene, alpha-methyl styrene, alpha-chloro vinylbenzene, p-methylstyrene, Vinylstyrene, 1 can have been enumerated, 1-diphenyl benzene ethene, N, the N-diethyl-to amino-ethyl vinylbenzene, vinyl pyridine, N, N-diethyl-p-aminophenyl ethene etc.In them, optimization styrene, alpha-methyl styrene, special optimization styrene.
As the conjugated diene compound that uses in the conjugated diene copolymer, can enumerate 1,3-divinyl, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl isophthalic acid, 3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene etc.In them, preferred 1,3-butadiene, isoprene and 1,3-pentadiene, preferred especially 1,3-butadiene, isoprene.
The polymer blocks A that constitutes conjugated diene copolymer is the polymer blocks based on aromatic ethylene compound.As the homopolymer block of polymer blocks A optimization aromatic vinyl compound, or contain the polymer blocks of the above aromatic ethylene compound of 95 quality % in the multipolymer of aromatic ethylene compound and conjugated diene compound.
And the polymer blocks B that constitutes conjugated diene copolymer is the polymer blocks based on conjugated diene compound.As polymer blocks B, the homopolymer block of preferred conjugated diene compound, or contain the polymer blocks of the above conjugated diene compound of 95 quality % in the multipolymer of conjugated diene compound and aromatic ethylene compound.
In the conjugated diene copolymer, the ethene of conjugated diolefine part is preferably more than the 60 quality % in conjunction with content, more preferably more than the 70 quality %, and then preferred 80 quality %.Ethene is in conjunction with content during less than 60 quality %, with the consistency variation of above-mentioned specific organometallic compound, is not preferred.Ethene can be tried to achieve by infrared measure in conjunction with content.
As the example of the conjugated diene copolymer that contains polymer blocks A (based on the polymer blocks of aromatic ethylene compound) and polymer blocks B (based on the polymer blocks of conjugated diene compound), can enumerate and had (A-B)
m, (A-B)
m-A, (B-A)
m-B, (A-B-A)
m, (B-A-B)
m, (A-B)
mX, (B-A)
mX, (A-B-A)
mX, (B-A-B)
mThe isostructural segmented copolymer of X.In these formulas, " A " is polymer blocks A, and " B " is polymer blocks B, and " X " is the coupling agent residue, and m is the integer more than 1.
As the coupling agent of giving " X " in the above-mentioned formula, diethylene adipate, Vinylstyrene, silicon tetrachloride, butyl trichlorosilicane, tin tetrachloride, butyl tin trichloride, dimethyl chlorination silicon, germanium tetrachloride, 1 can have been enumerated, 2-ethylene dibromide, 1,4-chloromethylbenzene, two (Trichloromonosilane base) ethane, epoxy linseed oil, tolylene diisocyanate, 1,2,4-benzene triisocyanate etc.
Conjugated diene copolymer is considered preferred (A-B) from preventing the heat flow under the hot environment
mOr (A-B)
mThe segmented copolymer that-A represents, preferred (A-B) especially
mThe segmented copolymer that-A represents.In the formula, m is from making easy consideration more preferably 1.That is at least a in the group that constitutes of conjugated diene copolymer optimization styrene butadiene block copolymer, styrene isoprene segmented copolymer, styrene butadiene styrene segmented copolymer and styrene isoprene styrene block copolymer.Wherein, special optimization styrene butadiene styrene block copolymerization thing or styrene isoprene styrene block copolymer.
The conjugated diene copolymer preferable weight-average molecular weight is 5～600,000, more preferably 5～300,000.The weight-average molecular weight of conjugated diene copolymer was difficult to form cured article less than 50,000 o'clock.On the other hand, the weight-average molecular weight of conjugated diene copolymer surpasses 600,000, because the viscosity of composition rises, and coating, operability variation when forming cured article.
And in the conjugated diene copolymer, the content of aromatic ethenyl compound is preferably 10～50 quality %, more preferably 20～50 quality %.The content of aromatic ethenyl compound is during less than 10 quality %, and the thermotolerance of the cured article of acquisition reduces, and can cause heat flow when using under hot environment.On the other hand, the content of aromatic ethenyl compound surpasses 50 quality %, and with the consistency variation of above-mentioned specific organometallic compound, the viscosity of composition rises simultaneously, and the coating when forming cured article, operability reduce.
The weight-average molecular weight of polymer blocks A (aromatic ethenyl compound is the polymer blocks of main body) the preferred polymers block A all (total of one or more polymer blocks A of existence) of formation conjugated diene copolymer is preferred more than 20,000, and polymer blocks A weight-average molecular weight separately is preferably more than 10,000.The all weight-average molecular weight of polymer blocks A is less than 20,000, or when containing the polymer blocks A that has less than 10,000 weight-average molecular weight, the thermotolerance of the cured article of acquisition reduces.The weight-average molecular weight of polymer blocks A integral body is preferred below 300,000, more preferably below 150,000.And polymer blocks A weight-average molecular weight separately is preferred below 150,000.The all weight-average molecular weight of polymer blocks A surpass 300,000, or comprise when having the polymer blocks A that surpasses 150,000 weight-average molecular weight, reduce with the consistency of above-mentioned specific organometallic compound, the viscosity of composition rises simultaneously, and therefore the coating when forming cured article, operability reduce.In addition, one of the weight-average molecular weight here is any all is to be solvent with the tetrahydrofuran (THF), try to achieve according to gel permeation chromatography (GPC), with the weight-average molecular weight of polystyrene conversion.
The manufacture method of conjugated diene copolymer is not particularly limited, and for example can enumerate in organic solvent with organic alkali metal compound as polymerization starter the active anionic polymerization monomer methods.
As the organic solvent that uses in this polyreaction, hydrocarbon system solvents such as pentane, hexane, heptane, octane, methylcyclopentane, hexanaphthene, benzene, dimethylbenzene can have been enumerated.The organic alkali metal compound that uses as polymerization starter preferably uses organolithium compound, for example n-Butyl Lithium.The preferred per 100 mass parts monomers of the usage quantity of polymerization starter are 0.02～0.2 mass parts.The polymeric temperature of reaction is generally-30～150 ℃.During polyreaction, can add various molecular weight regulators as required.As molecular weight regulator, Anaesthetie Ether, tetrahydrofuran (THF), propyl ether, butyl ether etc. can have been enumerated.
The conjugated diene copolymer of above-mentioned hydrogenation (following is called " hydrogenation multipolymer ") is with respect to above-mentioned conjugated diene copolymer, the product that the double-bond hydrogenation from the structural unit of conjugated diene compound is made.Hydrogenation rate in the hydrogenation multipolymer is preferably more than 80%, more preferably more than 90%, more preferably more than 95%.This hydrogenation rate is followed deterioration can cause the decomposition of polymkeric substance, and then is caused gelation easily less than 80%.In addition, hydrogenation rate can be measured by the iodate volumetry.
As the example of hydrogenation multipolymer, will be from the polymer blocks conduct " A of above-mentioned polymer blocks A
H", from the polymer blocks of above-mentioned polymer blocks B as " B
H", can enumerate and had (A
H-B
H)
m, (A
H-B
H)
m-A
H, (B
H-A
H)
m-B
H, (A
H-B
H-A
H)
m, (B
H-A
H-B
H)
m, (A
H-B
H)
mX, (B
H-A
H)
mX, (A
H-B
H-A
H)
mX, (B
H-A
H-B
H)
mThe isostructural segmented copolymer of X.In addition, the same with the formula of the segmented copolymer of expression before the hydrogenation, X represents the coupling agent residue, and m represents the integer more than 1.In them, the preferred (A of hydrogenation multipolymer
H-B
H)
m, (A
H-B
H)
m-A
HThe segmented copolymer of expression, preferred especially (A
H-B
H)
m-A
HThe segmented copolymer of expression.In the formula, m is preferably 1.
At least a in the group that the hydrogenation products of the hydrogenation products of hydrogenation multipolymer optimization styrene butadiene block copolymer, the hydrogenation products of styrene isoprene segmented copolymer, styrene butadiene styrene segmented copolymer and the hydrogenation products of styrene isoprene styrene block copolymer constitute.Wherein, the hydrogenation products of special optimization styrene butadiene styrene block copolymerization thing or the hydrogenation products of styrene isoprene styrene block copolymer.
The weight-average molecular weight of hydrogenation multipolymer is preferably 5～600,000, and more preferably 5～300,000.The weight-average molecular weight of hydrogenation multipolymer was difficult to form cured article less than 50,000 o'clock.On the other hand, the weight-average molecular weight of hydrogenation multipolymer surpasses 600,000, because the viscosity of composition rises, the coating when forming cured article, operability reduce.
And the monomer that constitutes the hydrogenation multipolymer is preferred 10～50 quality % of content of the aromatic ethenyl compound structural unit of aromatic ethenyl compound (perhaps from), more preferably 20～50 quality %.The content of the aromatic ethenyl compound structural unit of aromatic ethenyl compound (perhaps from) is during less than 10 quality %, and the thermotolerance of the cured article of acquisition reduces, and use at high temperature can cause heat flow.On the other hand, when the content of the aromatic ethenyl compound structural unit of aromatic ethenyl compound (perhaps from) surpasses 50 quality %, reduce with the consistency of above-mentioned specific organometallic compound, the viscosity of composition rises simultaneously, and the coating when therefore forming cured article, operability reduce.
Manufacture method as the hydrogenation multipolymer, be not particularly limited, can enumerate and in organic solvent, use organic alkali metal compound as polymerization starter, make monomer carry out active free radical polymerization, obtain segmented copolymer (segmented copolymer before the hydrogenation), again to the method for this segmented copolymer hydrogenation.
As the method for hydrotreating that is used to obtain the hydrogenation polymkeric substance, can use known method.For example the segmented copolymer before the hydrogenation that obtains is dissolved in the inert solvent, at 20～150 ℃, 1～100kg/cm
2Pressurized hydrogen under, use the method for hydrotreating of hydrogenation catalyst.Example as this inert solvent can have been enumerated hydrocarbon solvents such as hexane, heptane, hexanaphthene, or methylethylketone, tetrahydrofuran (THF) isopolarity solvent.
As the hydrogenation catalyst that is used for hydrogenation reaction, can enumerate one of any compound that contains periodic table of elements Ib, IVb, Vb, VIb, VIIb, VIII family element, for example can enumerate the compound of Ti, V, Co, Ni, Zr, Ru, Rh, Pd, Hf, Re, Pt element.Concrete; can enumerate the metallocene based compound that contains Ti, Zr, Hf, Co, Ni, Pd, Pt, Ru, Rh, Re etc.; the loading type heterogeneous system catalyzer of metals such as load P d, Ni, Pt, Rh, Ru on carriers such as carbon, silicon-dioxide, aluminum oxide, diatomite; reductive agents such as organic salt such as Ni, Co or Acetyl Acetone salt and organoaluminum combinations evenly be Ziegler-type catalyst, organometallic compound or inner complex such as Ru, Rh and adsorbed the soccerballene of hydrogen or carbon nanotube etc.In them, one of any metallocene compound that contains Ti, Zr, Hf, Co, Ni can be preferred evenly to be hydrogenation reaction in inert organic solvents.
3. catch the composition that moisture and oxygen are used
In the composition that seizure moisture of the present invention and oxygen are used, contain as the above-mentioned specific organometallic compound and the polymkeric substance of tackiness agent as trapping agent.In the composition that this seizure moisture and oxygen are used, can be used in combination above-mentioned specific organometallic compound and other trapping agent.Other trapping agent are not particularly limited so long as can catch the material of moisture and oxygen, also comprise and the material of water molecules react with, the material of physical adsorption water molecules.In addition, the moisture capturing ability of trapping agent and oxygen capturing ability correlate are known.
As with the trapping agent of water molecules chemical reaction, can enumerate organometallic compound beyond metal oxide, vitriol, metal halide, the above-mentioned trialkylaluminium etc.As metal oxide, calcium oxide, barium oxide, magnesium oxide etc. can have been enumerated.As vitriol, Lithium Sulphate, sodium sulfate, calcium sulfate, sal epsom etc. can have been enumerated.As metal halide, calcium chloride, magnesium chloride, strontium chloride etc. can have been enumerated.Organometallic compound beyond the trialkylaluminium can have been enumerated trigalloyl basic ring alkyl boroxane, octyl group boron oxide compound, octyl group aluminum oxide etc.
As the trapping agent of physical adsorption water molecules, zeolite, silica dioxide gel, activated alumina etc. can have been enumerated.In them, consider the dispersiveness to organic solvent, the viewpoint of the transparency when solidifying, preferred octyl group boron oxide compound, octyl group aluminum oxide.
When above-mentioned specific organometallic compound is used in combination with other trapping agent, the ratio of specific organometallic compound adds up among the 100 quality % at this compound and other trapping agent, can use more than the 50 quality %, more than the preferred 70 quality %, more preferably more than the 90 quality %.
In the composition that seizure moisture of the present invention and oxygen are used, except above-mentioned specific organometallic compound and polymkeric substance, can cooperate various additives as required.As various additives, for example tenderizer, compatilizer etc. can have been enumerated.
Contain the seizure moisture of above-mentioned specific organometallic compound, polymkeric substance and other any composition and the composition of oxygen, for example under the dry nitrogen atmosphere gas of dew point-75 ℃, under the solution state in being dissolved in organic solvent nonreactive equably, can be coated on the target object with it.As such organic solvent, can enumerate non-aqueous solvents such as toluene, dimethylbenzene, paraffin, Liquid Paraffin, naphthalane, diglyme is aromatic hydrocarbon solvents, aliphatic hydrocarbon solvent, ether series solvent etc.The use level of organic solvent is not particularly limited, the preferred above-mentioned specific organometallic compound and the amount of polymkeric substance uniform dissolution.
In the composition of catching moisture and oxygen, with respect to preferred 10～70 quality % of blending ratio of the above-mentioned specific organometallic compound of polymkeric substance., can not get sufficient moisture and oxygen and catch performance during with respect to the blending ratio of the organometallic compound of polymkeric substance less than 10 quality %.And when this blending ratio surpassed 70 quality %, polymkeric substance had situation about becoming not as matrix performance function.
The composition that seizure moisture of the present invention and oxygen are used has good water absorbability, inhaling of oxygen, thermotolerance and the transparency, the consistency of specific organometallic compound and polymkeric substance is good simultaneously, and the viscosity that has appropriateness under liquid state, operability is good when forming cured article.And as mentioned above, by mix specific conjugated diene copolymer in composition, every characteristics such as consistency of the thermotolerance under the high temperature environment for use, the patience to deterioration, organometallic compound and polymkeric substance are further improved.Thereby the composition that this seizure moisture and oxygen are used is suitable for being particularly suitable for the sealing material of organic EL in the sealing materials such as organic EL, organic tft, organic photovoltaic cell, organic C MOS photoreceptor.
4, cured article
Cured article of the present invention is coated with the composition that above-mentioned seizure moisture and oxygen are used on base material, form film after, dry this filmed, removing desolvates obtains.As the method for coating, can enumerate the method for using spinner, roller coat device, sprayer, dispenser, ink discharge device etc.
Temperature during dry coating is not particularly limited, and for example is 5 ℃～100 ℃.The cured article that obtains typically has the shape of film.The thickness of the cured article of such film like is not particularly limited, and for example is 0.1～1.0mm.The cured article that obtains has the good transparency.When the thickness of cured article was 0.5mm, mist degree was less than 5%.
Then, with reference to accompanying drawing, the example of the cured article of the composition that seizure moisture and oxygen are used as the sealing material of organic EL is described.Fig. 1 is the schematic section that expression the present invention has the organic EL of trapping agent layer.
Among Fig. 1, organic EL 1 mainly is to be made of organic EL layer 2, the structure 3 that holds the obstruct extraneous gas of organic EL layer 2, the structure 3 inner trapping agent layers 4 that form.Organic EL layer 2 can be the luminous organic material layer that constitutes by organic materials by the structure in the clamping between pair of electrodes staggered relatively, for example can use anode/electric charge (electron hole) agent delivery/luminescent layer/known structures such as negative electrode.
The cured article of the composition that seizure moisture of the present invention and oxygen are used because contain specific organometallic compound, with polymkeric substance as matrix, its water absorbability, inhaling of oxygen, thermotolerance and the transparency are good.Particularly this cured article has good thermotolerance, even also can not cause distortion by heat flow above under 80 ℃ the environment for use.Thereby this cured article is suitable for the closed material of organic EL, and because the transparency is good, can be used for the emission type organic EL.And then this cured article is because the deterioration that the intrusion of outside moisture and oxygen causes is few, and it is good to obtain weather resistance, can not cause the organic EL of distortion etc. under hot environment.
Embodiment
Enumerate embodiment below the present invention is described, but the invention is not restricted to these embodiment.
The manufacturing of synthesis example 13-cyclo-dodecyl-1-propylene
15.5g (0.637 mole) sheet magnesium and 600mL anhydrous tetrahydro furan are joined in the reaction vessel of 1000mL, drip the 30g in 150g (0.607 mole) the bromine cyclododecane.Be heated 50 ℃, begin reaction, keep the weak state that refluxes outside bathing, the limit drips remaining bromine cyclododecane.After dripping termination, refluxed 2 hours, under the cool to room temperature.It is cooled off in ice-water bath, and at the 3-bromo-1-of 30 ℃ of following Dropwise 5 7.8mL of interior temperature (0.668 mole) propylene, dropping refluxes an evening after stopping.Behind the cool to room temperature, under ice-water bath, drip the hydrochloric acid of 1N, after the organic layer layering, clean 3 organic layers with 200mL water.Organic layer anhydrous magnesium sulfate drying, filtration, concentrated.The residue that obtains distills, and collects the 3-cyclo-dodecyl-1-propylene 43g as target compound under the condition of 109～110 ℃/3.2mmHg from the cut that obtains, and product is a colourless transparent liquid, productive rate 34%.The compound that obtains
1H NMR spectrum is shown among Fig. 2.
1H NMR spectrum is to use that NEC company makes goes into 300 and measures (too following).Use CDCl in the mensuration
3As solvent, the internal standard material is TMS.
In the three-necked flask of 200mL, in loft drier, add 10g (50.4 mmole) triisobutyl aluminium, 31.9g (153 mmole) 3-cyclo-dodecyl-1-propylene and 50mL heptane, reflux a whole night.Then, be cooled to 55 ℃, reduce pressure with vacuum pump in this temperature bottom, the limit is heated up in a steamer and is desolvated, cool to room temperature, the water white transparency oily thing of acquisition Dian Fentang pulpous state.In loft drier, place this oily matter a few days, obtain 33g white solid three (3-cyclo-dodecyl propyl group) aluminium.Productive rate is quantitative.The compound that obtains
1H NMR spectrum is shown among Fig. 3.Use near toluene-d8 (peak is δ 2.1) as the internal standard material in the mensuration.
Three (the 3-cyclo-dodecyl propyl group) aluminium that obtains adds in the toluene solution with the styrene series elastomer of 25 quality % prepared at concentrations (JSR Corp. makes " ダ イ Na ロ Application "), during solution after the interpolation was all, this elastomerics added and vigorous stirring with the concentration of 20 quality %.The preparation of solution is carried out under the dry nitrogen atmosphere gas of dew point-75 ℃.This solution coat is on substrate, and drying is 20 minutes under 100 ℃, obtains film.
In the three-necked flask of 200mL, in loft drier, add 2.32g (11.7 mmole) triisobutyl aluminium, 10.0g (35.6 mmole) 1-phytane and 15mL heptane, reflux a whole night.Then, be cooled to 55 ℃, reduce pressure with vacuum pump in this temperature bottom, the limit is heated up in a steamer and is desolvated, and cool to room temperature obtains water white transparency oily thing three (1-phytyl) aluminium 10.4g.Productive rate is quantitative.The compound that obtains
1H NMR spectrum is shown among Fig. 4.Use near toluene-d8 (peak is δ 2.1) as the internal standard material in the mensuration.
Three (1-phytyl) aluminium that obtains adds in the toluene solution of the styrene series elastomer (JSR Corp. makes " ダ イ Na ロ Application ") with 25 quality % prepared at concentrations, during solution after the interpolation was all, this elastomerics added and vigorous stirring with the concentration of 20 quality %.The preparation of solution is carried out under the dry nitrogen atmosphere gas of dew point-75 ℃.This solution coat is on substrate, and drying is 20 minutes under 100 ℃, obtains film.
Comparative example 1 contains the manufacturing of the film of three (octadecyl) aluminium
In the three-necked flask of 200mL, in loft drier, add 10g (50.4 mmole) triisobutyl aluminium, 38.9g (154 mmole) 1-octadecylene and 50mL heptane, reflux a whole night.Then, be cooled to 55 ℃, reduce pressure with vacuum pump in this temperature bottom, the limit is heated up in a steamer and is desolvated, and cool to room temperature obtains 40g white solid three (octadecyl) aluminium.Productive rate is quantitative.
Three (octadecyl) aluminium that obtains adds in the toluene solution of the styrene series elastomer (JSR Corp. makes " ダ イ Na ロ Application ") with 25 quality % prepared at concentrations, during solution after the interpolation was all, this elastomerics added and vigorous stirring with the concentration of 20 quality %.The preparation of solution is carried out under the dry nitrogen atmosphere gas of dew point-75 ℃.This solution coat is on substrate, and drying is 20 minutes under 100 ℃, obtains film.
Comparative example 2 contains the manufacturing of the film of three (hexadecyl) aluminium
In the three-necked flask of 200mL, in loft drier, add 10g (50.4 mmole) triisobutyl aluminium, 34.5g (154 mmole) 1-hexadecylene and 50mL heptane, reflux a whole night.Then, be cooled to 55 ℃, reduce pressure with vacuum pump in this temperature bottom, the limit is heated up in a steamer and is desolvated, and cool to room temperature obtains 36g white solid three (hexadecyl) aluminium.Productive rate is quantitative.
Three (hexadecyl) aluminium that obtains adds in the toluene solution of the styrene series elastomer (JSR Corp. makes " ダ イ Na ロ Application ") with 25 quality % prepared at concentrations, during solution after the interpolation was all, this elastomerics added and vigorous stirring with the concentration of 20 quality %.The preparation of solution is carried out under the dry nitrogen atmosphere gas of dew point-75 ℃.This solution coat is on substrate, and drying is 20 minutes under 100 ℃, obtains film.
Comparative example 3 contains the manufacturing of the film of three (dodecyl) aluminium
In the three-necked flask of 200mL, in loft drier, add 10g (50.4 mmole) triisobutyl aluminium, 25.9g (154 mmole) 1-laurylene and 50mL heptane, reflux a whole night.Then, be cooled to 55 ℃, reduce pressure with vacuum pump in this temperature bottom, the limit is heated up in a steamer and is desolvated, and cool to room temperature obtains 27g water white transparency oily thing three (dodecyl) aluminium.Productive rate is quantitative.
Three (dodecyl) aluminium that obtains adds in the toluene solution of the styrene series elastomer (JSR Corp. makes " ダ イ Na ロ Application ") with 25 quality % prepared at concentrations, during solution after the interpolation was all, this elastomerics added and vigorous stirring with the concentration of 20 quality %.The preparation of solution is carried out under the dry nitrogen atmosphere gas of dew point-75 ℃.This solution coat is on substrate, and drying is 20 minutes under 100 ℃, obtains film.
Evaluation method
To the film that obtains in the foregoing description and the comparative example, estimate transparent, membranous and water absorbability according to following method.Evaluation structure is shown in Table 1.In addition, inhaling of oxygen is because known relevant with water absorbability, and it estimates omission.
(1) transparency
Manosil AS sheet glass at the melt-shaping that 2 thickness are 0.7mm (sandwiches film (thickness 0.5mm) between " Corning 1737 " that コ one ニ Application グ Amada Co., Ltd. makes, use total light transmittance mist degree determinator (BYK-Gardner company makes " Haze-Gard plus 4725 "), with the measuring method of JIS K7105 regulation, total light transmittance (%) and mist degree (%) under measuring 25 ℃.As " zero ", mist degree is in the occasion conduct " * " of the transparency difference 5% or more less than 5% transparent good occasion for mist degree.
(2) membranous
Visual observation, film do not exist crack or concavo-convex conduct " zero ", and film observes crack or concavo-convex conduct " * ".
(3) water absorbability
Configuration thickness is adjusted to the film of 0.6mm on the glass dish of internal diameter 3cm, is 800cm having thermometer and hygroscopic internal volume
3Vacuum drier in put into the glass disc that has disposed this film, observe vacuum drier humidity inside and temperature variation.Observe the value of relative humidity (Hr, %), centigradetemperature (Tc, ℃), try to achieve absolute humidity (Ha, %) based on this value and following formula.Absolute humidity after 2 hours is compared the degree of initial stage absolute humidity minimizing and is estimated as water absorbability (%).
Ha＝4.0×10
-3{exp(6.4×10
-2·Tc)}Hr
[table 1]
From the result of table 1 as can be seen, the embodiment 1 that forms of the composition of using according to seizure moisture of the present invention and oxygen and 2 cured article film demonstrate the good membranous and good transparency, water absorbability.Relative therewith, comparative example 1 and 2 cured article film are membranous poor, and mist degree is more than 5%, and outward appearance shows gonorrhoea.The cured article film water absorbability maximum of comparative example 3, membranous remarkable variation are seen the crack.
Industrial applicibility
The composition that seizure moisture of the present invention and oxygen are used is when having good hygroscopicity, inhaling of oxygen, heat resistance and the transparency, and the compatibility of specific organo-metallic compound and polymer is good, and liquid lower viscosity with appropriateness. Cause with these good characteristics, said composition can be used for the encapsulants such as organic EL, organic tft, organic photovoltaic cell, organic C MOS photoreceptor, is particularly suitable for the encapsulant of organic EL. And, said composition transparent good, thereby can be as the parts of upper emission type organic EL.
Claims (7)
1. at least a organometallic compound of the group that the compound that is selected from following formula (I) and (II) represents constitutes,
In the formula (II), R
1Respectively independently expression to be selected from hydrogen atom, carbonatoms be at least a of 0～6 straight chained alkyl, branched-chain alkyl, cycloalkyl or their combination, l is 1～10 integer, m is 5～15 integer, n is 0～14 integer.
2. organometallic compound as claimed in claim 1, the compound of wherein above-mentioned formula (II) are three (3-cyclo-dodecyl propyl group) aluminium of following formula (III) expression,
3. contain the seizure moisture of organometallic compound as claimed in claim 1 or 2 and polymkeric substance and the composition that oxygen is used.
4. the composition that seizure moisture as claimed in claim 3 and oxygen are used, it is used for organic EL.
5. the cured article that forms by the composition of using as claim 3 or 4 described seizure moisture and oxygen.
6. cured article as claimed in claim 5, its under 25 ℃, the mist degree of thickness 0.5mm is less than 5%.
7. comprise organic EL as claim 5 or 6 described cured articles.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007-288467 | 2007-11-06 | ||
| JP2007288466 | 2007-11-06 | ||
| JP2007288465 | 2007-11-06 | ||
| JP2007288467 | 2007-11-06 | ||
| JP2007288468 | 2007-11-06 | ||
| JP2007-288466 | 2007-11-06 | ||
| JP2007-288468 | 2007-11-06 | ||
| JP2007-288465 | 2007-11-06 | ||
| PCT/JP2008/068213 WO2009060681A1 (en) | 2007-11-06 | 2008-10-07 | Organic metal compound, composition for trapping moisture and oxygen, cured body, and organic el device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101848912A true CN101848912A (en) | 2010-09-29 |
Family
ID=40625581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880114950A Pending CN101848912A (en) | 2007-11-06 | 2008-10-07 | Organic metal compound, composition for trapping moisture and oxygen, cured body, and organic EL device |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPWO2009060681A1 (en) |
| KR (1) | KR20100087151A (en) |
| CN (1) | CN101848912A (en) |
| TW (1) | TW200927752A (en) |
| WO (1) | WO2009060681A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103378302A (en) * | 2012-04-23 | 2013-10-30 | 海洋王照明科技股份有限公司 | Organic light-emitting device and encapsulating method thereof |
| CN103378295A (en) * | 2012-04-23 | 2013-10-30 | 海洋王照明科技股份有限公司 | Organic light-emitting device and encapsulating method thereof |
| CN103378294A (en) * | 2012-04-23 | 2013-10-30 | 海洋王照明科技股份有限公司 | Organic light-emitting device and encapsulating method thereof |
| CN103378304A (en) * | 2012-04-23 | 2013-10-30 | 海洋王照明科技股份有限公司 | Organic light-emitting device and encapsulating method thereof |
| CN105307753A (en) * | 2013-07-04 | 2016-02-03 | Jsr株式会社 | Organic el element |
| TWI582099B (en) * | 2015-01-28 | 2017-05-11 | Futaba Denshi Kogyo Kk | A compound, a desiccant, a sealing structure, and an organic EL element |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5262964B2 (en) * | 2008-07-16 | 2013-08-14 | Ｊｓｒ株式会社 | Moisture and oxygen scavenging composition, cured body, and organic EL device |
| JP5262963B2 (en) * | 2008-07-16 | 2013-08-14 | Ｊｓｒ株式会社 | Moisture and oxygen scavenging composition, cured body, and organic EL device |
| JP5408418B2 (en) * | 2009-07-17 | 2014-02-05 | Ｊｓｒ株式会社 | Organic EL device |
| JP5716921B2 (en) * | 2009-09-03 | 2015-05-13 | Jsr株式会社 | Composition, cured body and electronic device, and tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum and method for producing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5756416A (en) * | 1995-11-28 | 1998-05-26 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst composition having improved comonomer reactivity |
| JP5596250B2 (en) * | 2005-03-02 | 2014-09-24 | スリーエム イノベイティブ プロパティズ カンパニー | Moisture-reactive composition and organic EL device |
| JP2007214015A (en) * | 2006-02-10 | 2007-08-23 | Kokusai Kiban Zairyo Kenkyusho:Kk | Capture agent of water and oxygen, and organic electronic device |
-
2008
- 2008-10-07 JP JP2009539991A patent/JPWO2009060681A1/en active Pending
- 2008-10-07 CN CN200880114950A patent/CN101848912A/en active Pending
- 2008-10-07 KR KR1020107009869A patent/KR20100087151A/en not_active Application Discontinuation
- 2008-10-07 WO PCT/JP2008/068213 patent/WO2009060681A1/en active Application Filing
- 2008-11-03 TW TW097142351A patent/TW200927752A/en unknown
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103378302A (en) * | 2012-04-23 | 2013-10-30 | 海洋王照明科技股份有限公司 | Organic light-emitting device and encapsulating method thereof |
| CN103378295A (en) * | 2012-04-23 | 2013-10-30 | 海洋王照明科技股份有限公司 | Organic light-emitting device and encapsulating method thereof |
| CN103378294A (en) * | 2012-04-23 | 2013-10-30 | 海洋王照明科技股份有限公司 | Organic light-emitting device and encapsulating method thereof |
| CN103378304A (en) * | 2012-04-23 | 2013-10-30 | 海洋王照明科技股份有限公司 | Organic light-emitting device and encapsulating method thereof |
| CN105307753A (en) * | 2013-07-04 | 2016-02-03 | Jsr株式会社 | Organic el element |
| TWI582099B (en) * | 2015-01-28 | 2017-05-11 | Futaba Denshi Kogyo Kk | A compound, a desiccant, a sealing structure, and an organic EL element |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200927752A (en) | 2009-07-01 |
| KR20100087151A (en) | 2010-08-03 |
| WO2009060681A1 (en) | 2009-05-14 |
| JPWO2009060681A1 (en) | 2011-03-17 |
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