CN117946612A - Packaging material composition, packaging structure and display device - Google Patents
Packaging material composition, packaging structure and display device Download PDFInfo
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- CN117946612A CN117946612A CN202311794158.6A CN202311794158A CN117946612A CN 117946612 A CN117946612 A CN 117946612A CN 202311794158 A CN202311794158 A CN 202311794158A CN 117946612 A CN117946612 A CN 117946612A
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- 239000000203 mixture Substances 0.000 title claims abstract description 87
- 239000005022 packaging material Substances 0.000 title abstract description 30
- 238000004806 packaging method and process Methods 0.000 title abstract description 20
- BPYFPNZHLXDIGA-UHFFFAOYSA-N diphenylsilicon Chemical class C=1C=CC=CC=1[Si]C1=CC=CC=C1 BPYFPNZHLXDIGA-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003085 diluting agent Substances 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 56
- 230000004888 barrier function Effects 0.000 claims description 38
- -1 2, 3-epoxypropoxy Chemical group 0.000 claims description 26
- 238000005538 encapsulation Methods 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 239000003504 photosensitizing agent Substances 0.000 claims description 13
- 238000007641 inkjet printing Methods 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 239000012952 cationic photoinitiator Substances 0.000 claims description 9
- 238000000016 photochemical curing Methods 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 7
- 238000004528 spin coating Methods 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 4
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 claims description 4
- 125000003566 oxetanyl group Chemical group 0.000 claims description 4
- OLPZCIDHOZATMA-UHFFFAOYSA-N 2,2-dioxooxathiiran-3-one Chemical class O=C1OS1(=O)=O OLPZCIDHOZATMA-UHFFFAOYSA-N 0.000 claims description 3
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 3
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 3
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 3
- TZLVUWBGUNVFES-UHFFFAOYSA-N 2-ethyl-5-methylpyrazol-3-amine Chemical compound CCN1N=C(C)C=C1N TZLVUWBGUNVFES-UHFFFAOYSA-N 0.000 claims description 3
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims description 3
- XAYDWGMOPRHLEP-UHFFFAOYSA-N 6-ethenyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCCC2OC21C=C XAYDWGMOPRHLEP-UHFFFAOYSA-N 0.000 claims description 3
- NRJLSUZLHMXXHJ-UHFFFAOYSA-N [4-(7-oxabicyclo[4.1.0]heptane-4-carbonyloxymethyl)cyclohexyl]methyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CCC(COC(=O)C2CC3OC3CC2)CC1 NRJLSUZLHMXXHJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- KTPIWUHKYIJBCR-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohex-4-ene-1,2-dicarboxylate Chemical compound C1C=CCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 KTPIWUHKYIJBCR-UHFFFAOYSA-N 0.000 claims description 3
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000005520 diaryliodonium group Chemical group 0.000 claims description 3
- 239000012954 diazonium Substances 0.000 claims description 3
- 150000001989 diazonium salts Chemical class 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 125000005409 triarylsulfonium group Chemical group 0.000 claims description 3
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 3
- KBCVENKEACAKMN-UHFFFAOYSA-N 2-[[2,3-bis(oxiran-2-ylmethoxy)-1-propoxypropoxy]methyl]oxirane Chemical compound C(C1CO1)OC(C(OCC1CO1)COCC1CO1)OCCC KBCVENKEACAKMN-UHFFFAOYSA-N 0.000 claims description 2
- KYUGRJLPPCDMOH-UHFFFAOYSA-N 6-(7-oxabicyclo[4.1.0]heptan-3-ylmethoxy)-6-oxohexanoic acid Chemical compound C1C(COC(=O)CCCCC(=O)O)CCC2OC21 KYUGRJLPPCDMOH-UHFFFAOYSA-N 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 15
- 239000010410 layer Substances 0.000 description 53
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 40
- 238000012360 testing method Methods 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 238000001723 curing Methods 0.000 description 24
- 239000000178 monomer Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000010408 film Substances 0.000 description 10
- 230000002829 reductive effect Effects 0.000 description 10
- 238000000921 elemental analysis Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000008393 encapsulating agent Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 150000003254 radicals Chemical group 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 3
- MUUOUUYKIVSIAR-UHFFFAOYSA-N 2-but-3-enyloxirane Chemical compound C=CCCC1CO1 MUUOUUYKIVSIAR-UHFFFAOYSA-N 0.000 description 3
- JZQHTTYHPIAPCZ-UHFFFAOYSA-N 2-prop-1-en-2-yloxirane Chemical compound CC(=C)C1CO1 JZQHTTYHPIAPCZ-UHFFFAOYSA-N 0.000 description 3
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 description 3
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 125000005336 allyloxy group Chemical group 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000010943 off-gassing Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DQXKOHDUMJLXKH-PHEQNACWSA-N (e)-n-[2-[2-[[(e)-oct-2-enoyl]amino]ethyldisulfanyl]ethyl]oct-2-enamide Chemical compound CCCCC\C=C\C(=O)NCCSSCCNC(=O)\C=C\CCCCC DQXKOHDUMJLXKH-PHEQNACWSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910004205 SiNX Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- MWJSKDHMQHQUNH-UHFFFAOYSA-N bis(4-bromophenyl)-dimethylsilane Chemical compound C=1C=C(Br)C=CC=1[Si](C)(C)C1=CC=C(Br)C=C1 MWJSKDHMQHQUNH-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XJWOWXZSFTXJEX-UHFFFAOYSA-N phenylsilicon Chemical compound [Si]C1=CC=CC=C1 XJWOWXZSFTXJEX-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004382 potting Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- FUWFDADDJOUNDL-UHFFFAOYSA-N 9,10-diethoxy-2-ethylanthracene Chemical compound CCC1=CC=C2C(OCC)=C(C=CC=C3)C3=C(OCC)C2=C1 FUWFDADDJOUNDL-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Abstract
The invention relates to the technical field of packaging of organic electroluminescent devices, in particular to a packaging material composition, a packaging structure and a display device. The packaging material composition comprises diphenyl silicon compounds, a reactive diluent and an initiator, wherein the diphenyl silicon compounds comprise one or more compounds represented by the general formula (I): X 1、X2 each independently represents a single bond, alkyl, alkoxy, or fluoroalkyl; r 1-R6 and S each independently represent one or more of H, alkyl, alkoxy, fluoroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted aromatic heterocyclic group; y 1 and Y 2 are each independently one or more of the following structures: * Representing the location of the bridge. The packaging material composition has the characteristics of high light transmittance, high light curing rate, low shrinkage, low air output, high heat resistance and the like.
Description
Technical Field
The invention relates to the technical field of packaging of organic electroluminescent devices, in particular to a packaging material composition, a packaging structure and a display device.
Background
With the expansion of application area of flexible Organic Light-Emitting Diodes (OLED) screens in various fields, the requirements for the use reliability of thin film packaging materials in many emerging fields (such as vehicles and the like) are increasingly higher, such as high Light transmittance (T% > 98%), high temperature resistance (Tg >110 ℃), high Light curing rate (> 90%), low air output (< 50 ppm), low shrinkage (volume shrinkage < 5%), and the like. However, the conventional film packaging materials cannot meet the requirements at the same time, if the light transmittance of the film packaging materials is not high enough, the light transmittance of the packaged devices can be influenced, if the performances of the film packaging materials such as high temperature resistance, contractibility and the like are not enough, the phenomena of peeling of an organic layer and an inorganic layer, ageing and yellowing of the materials and the like often occur during long-time high-temperature exposure, if the light curing rate of the film packaging materials is low, the film packaging materials are difficult to effectively cure in the air, and if the air output of the film packaging materials is too large, the generated gas can adversely influence the quality and the performances of the packaged devices.
Therefore, there is a need for an encapsulant composition that combines the characteristics of high light transmittance, high light curing rate, low shrinkage, low outgassing, and high heat resistance to meet the demands of increasing thin film encapsulant.
Disclosure of Invention
The invention provides a packaging material composition, a packaging structure and a display device, wherein the packaging material composition can simultaneously meet the performance index requirements of high light transmittance, high light curing rate, low shrinkage, low air output, high heat resistance and the like required by a film packaging material.
According to a first aspect of the present invention, there is provided an encapsulating material composition comprising a diphenylsilicon compound comprising one or more compounds represented by the general formula (I):
Wherein each X 1、X2 independently represents a single bond, C 1～C29 alkyl, C 1～C29 alkoxy, or C 1～C29 fluoroalkyl; r 1-R6 and S each independently represent one or more of an alkyl group of H, C 1～C29, an alkoxy group of C 1～C29, a fluoroalkyl group of C 1～C29, an aryl group of substituted or unsubstituted C 1～C29, an aromatic heterocyclic group of substituted or unsubstituted C 1～C29;
Y 1、Y2 each independently represents one or more of the following structures:
* Representing the location of the bridge.
Further, X 1 and X 2 are the same and represent a single bond, alkyl of C 1～C5, alkoxy of C 1～C5 or fluoroalkyl of C 1～C5;
And/or R 1-R6 is the same and represents one or more of a linear alkyl group of H, C 1～C5, a linear alkoxy group of C 1～C5, a linear fluoroalkyl group of C 1～C5, an aryl group of substituted or unsubstituted C 1～C5, an aromatic heterocyclic group of substituted or unsubstituted C 1～C5;
And/or Y 1 and Y 2 are the same.
Further, the compound represented by the general formula (I) is selected from one or more of the following (I-1) to (I-6):
Further, the content of the diphenyl silicon compound is 30wt% to 85wt%, preferably 30wt% to 60wt% of the encapsulating material composition.
Further, the number average molecular weight of the diphenyl silicon compound is 200-2000g/moL, and the viscosity is 10-2000 mPa.s.
Further, the surface tension of the diphenyl silicon compound is 25-45 mN/m.
Further, the functional groups of the reactive diluent include one or more of alicyclic epoxy, oxetanyl, glycidyl ether, or epoxy groups; and/or the reactive diluent is present in an amount of 13wt% to 68wt% of the encapsulating material composition;
Preferably, the reactive diluent is selected from one or more of vinyl cyclohexene oxide, 3, 4-epoxycyclohexylmethyl-3 ',4' -epoxycyclohexylformate, bis ((3, 4-epoxycyclohexylmethyl) adipate, tetrahydrophthalic acid diglycidyl ester, 4, 5-epoxycyclohexane-1, 2-dicarboxyiate diglycidyl ester, dicyclopentadiene diepoxide, 4- (2, 3-epoxypropoxy) -N, N ' -bis (2, 3-epoxypropyl) aniline, 1, 4-cyclohexanedimethanol bis (3, 4-epoxycyclohexane formate) and cyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 1, 4-butanediol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, butyl glycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, propoxyglycerol triglycidyl ether, oxybxt 101, oxybt 212, oxybt 121 and oxybt 221;
and/or, the initiator is a cationic photoinitiator; preferably, the cationic photoinitiator is selected from one or more of diaryliodonium salts, triarylsulfonium salts, diazonium salts, alkyl sulfonium salts, iron arene salts, sulfonyloxy ketones, and triarylsiloxane ethers; more preferably, the cationic photoinitiator is selected from one or more of triaryl hexafluoroantimonate sulfonium salts, triaryl hexafluorophosphate sulfonium salts or diaryl hexafluorophosphate iodonium salts.
Further, the packaging material composition further comprises an auxiliary agent, wherein the auxiliary agent is selected from one or more of a photosensitizing agent, a polymerization inhibitor, a surfactant, an antioxidant, a defoaming agent and a leveling agent;
preferably, the auxiliary agent is contained in an amount of 0.1 wt% to 1wt% of the encapsulating material composition.
According to a second aspect of the present invention, there is also provided an encapsulation structure comprising an organic barrier layer, which is coated with the above-mentioned encapsulation material composition by spin coating or inkjet printing, and is formed by photo-curing.
According to a third aspect of the present invention, there is also provided a display device, the display device including a functional structure and a package structure, the package structure being the above-described package structure.
The packaging material composition provided by the invention comprises a diphenyl silicon compound, wherein the diphenyl silicon compound takes a phenyl silicon polymer as a main body frame, and a high-activity oxetane end group, an alicyclic epoxy end group or an aliphatic epoxy group is introduced and is compounded with a reactive diluent and an initiator, so that the obtained packaging material composition has the characteristics of high light transmittance, high light curing rate, low shrinkage, low air output, high heat resistance and the like, and a polymer film formed by the packaging material composition is used as an organic barrier layer, so that the optical requirement and the curing requirement of a packaging structure can be well met, and the service life of a packaged device is prolonged.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are some embodiments of the invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural diagram of a display device according to embodiment 21 of the present invention.
Reference numerals: 1: a substrate ITO;2: a functional structure; 21: an anode; 22: a hole transport layer; 23: a light emitting layer; 24: an electron transport layer; 25: a cathode; 26: a cathode protective layer; 27: an inorganic layer; 3: a package structure; 31: an inorganic barrier layer; 32: an organic barrier layer.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As analyzed in the background art, the ink composition in the prior art is difficult to simultaneously meet the performance index requirements of high light transmittance, high light curing rate, low shrinkage, low air output, high heat resistance and the like required by the increasing growth of the film packaging material, and in order to solve the problem, the invention provides a packaging material composition, a packaging structure and a display device.
In a first exemplary embodiment of the present invention, the present invention provides an encapsulating material composition comprising a diphenylsilicon compound, a reactive diluent and an initiator, the diphenylsilicon compound comprising one or more compounds represented by the general formula (I):
Wherein each X 1、X2 independently represents a single bond, C 1～C29 alkyl, C 1～C29 alkoxy, or C 1～C29 fluoroalkyl; r 1-R6 and S each independently represent one or more of an alkyl group of H, C 1～C29, an alkoxy group of C 1～C29, a fluoroalkyl group of C 1～C29, an aryl group of substituted or unsubstituted C 1～C29, an aromatic heterocyclic group of substituted or unsubstituted C 1～C29;
Y 1、Y2 each independently represents one or more of the following structures:
* Representing the location of the bridge.
Note that, X 1 and X 2 described herein each independently represent a single bond: the Si atom may be directly attached to Y 1 or Y 2.
In the scheme, the packaging material composition comprises the diphenyl silicon compound, the diphenyl silicon compound takes a phenyl silicon polymer as a main body frame, a high-activity oxetane end group, an alicyclic epoxy end group or an aliphatic epoxy group is introduced, the diphenyl silicon compound comprises at least one phenyl group which is bonded to a silicon atom and is substituted or unsubstituted by C 6-C30, so that the high resistance to current used in the deposition of an inorganic barrier layer in an OLED packaging structure is realized, at least two phenyl groups are introduced into a molecular main chain of the diphenyl silicon compound, the glass transition temperature of the organic barrier layer is improved by 110 ℃, the heat resistance is improved, the excessive shrinkage volume generated by the packaging material composition during curing is reduced, the shrinkage rate is reduced, and the problem that the organic barrier layer and the inorganic barrier layer in the OLED packaging structure are easy to fall off is effectively avoided. The packaging material composition compounded by the diphenyl silicon compound, the reactive diluent and the initiator has the characteristics of high light transmittance, high light curing rate, low shrinkage, low air output, high heat resistance and the like, and the polymer film formed by the packaging material composition is used as an organic barrier layer, so that the optical requirement and the curing requirement of a packaging structure can be well met.
In order to better enhance the overall performance of the encapsulant composition, in some embodiments of the present invention, X 1 and X 2 are the same and represent a single bond, an alkyl group of C 1～C5, an alkoxy group of C 1～C5, or a fluoroalkyl group of C 1～C5;
And/or R 1-R6 is the same and represents one or more of a linear alkyl group of H, C 1～C5, a linear alkoxy group of C 1～C5, a linear fluoroalkyl group of C 1～C5, an aryl group of substituted or unsubstituted C 1～C5, an aromatic heterocyclic group of substituted or unsubstituted C 1～C5;
And/or Y 1 and Y 2 are the same.
In some embodiments of the present invention, the compound represented by the general formula (I) is selected from one or more of the following (I-1) - (I-6):
in the scheme, the structure of the diphenyl silicon compound is further designed, so that various performances of the packaging material composition can be further improved.
In some embodiments of the present invention, the diphenylsilicon compounds are present in an amount of 30% to 85% by weight, preferably 30% to 60% by weight, of the encapsulating material composition.
Alternatively, the content of the diphenylsilicon compound may be 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, or the like of the encapsulating material composition, but may be other values within the above range, without limitation.
In the scheme, the content of the diphenyl silicon compound is limited within a reasonable range, so that the shrinkage and the air output after curing of the packaging material composition can be obviously reduced, and the heat resistance, the light transmittance and the packaging performance of the device of the organic barrier layer are further improved. If the content of the diphenylsilicon compound is too low (< 30%), the overall performance of the encapsulating material composition may be poor. If the diphenyl silicon-based compound content is too high (> 85%), it can result in an encapsulant composition having excessive viscosity and mismatched surface tension, affecting inkjet printing and spin-coating performance.
In some embodiments of the invention, the diphenylsilicon compounds have a number average molecular weight of 200-2000g/moL and a viscosity of 10-2000 mPa.s.
In the above-mentioned scheme, the number average molecular weight and viscosity of the diphenyl silicon compound are limited within reasonable range values, so that the encapsulating material composition has good inkjet or spin coating performance.
In some embodiments of the invention, the surface tension of the diphenylsilicon compounds is 25-45 mN/m. Suitable surface tension can provide the encapsulating material composition with good ink jet or spin coating properties and also can provide the encapsulating material composition with excellent adhesion properties.
The diphenylsilicon compounds can be obtained in a variety of ways, with a typical multi-step reaction shown in the following equation (1):
Equation (1).
In some embodiments of the invention, the reactive diluent comprises a photocuring functional group that is free of silicon; the reactive diluent may be a monofunctional monomer, a difunctional monomer, a polyfunctional monomer or a mixture, wherein the monofunctional monomer refers to a monomer having one photocurable functional group, the difunctional monomer refers to a monomer having two photocurable functional groups, and the polyfunctional monomer refers to a monomer having three or more photocurable functional groups. The reactive diluents of the present invention preferably contain monomers with two to four photocuring functionalities. The reactive diluent may also be a mixture of monofunctional monomers, difunctional monomers, and multifunctional monomers. In the mixture, the monofunctional monomer and the difunctional monomer or the polyfunctional monomer may be mixed in a mass ratio of 1:0.1 to 1:10. The photocurable functional groups include one or more of alicyclic epoxy, oxetane, glycidyl ether, or epoxy groups.
In the above-mentioned scheme, the viscosity of the encapsulating material composition can be reduced by selecting a proper kind of reactive diluent, the workability of the encapsulating material composition can be improved, and the light transmittance of the encapsulating material composition can be further increased.
To further enhance the performance of the encapsulant composition, in some embodiments of the present invention, the reactive diluent is selected from one or more of vinylcyclohexene oxide, 3, 4-epoxycyclohexylmethyl-3 ',4' -epoxycyclohexylformate, bis ((3, 4-epoxycyclohexyl) methyl) adipate, tetrahydrophthalic acid diglycidyl ester, 4, 5-epoxycyclohexane-1, 2-dicarboxyiate diglycidyl ester, dicyclopentadiene diepoxide, 4- (2, 3-epoxypropoxy) -N, N ' -bis (2, 3-epoxypropyl) aniline, 1, 4-cyclohexanedimethanol bis (3, 4-epoxycyclohexane carboxylate), and cyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 1, 4-butanediol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, butyl glycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, propoxytriglycidyl ether, oXT, O101, O212, OXT221, and O121.
For efficient use with the diphenylsilicon compounds and reactive diluents of the present invention, in some embodiments of the present invention, the initiator is a cationic photoinitiator; preferably, the cationic photoinitiator is selected from one or more of diaryliodonium salts, triarylsulfonium salts, diazonium salts, alkyl sulfonium salts, iron arene salts, sulfonyloxy ketones, and triarylsiloxane ethers; more preferably, the cationic photoinitiator is selected from one or more of triaryl hexafluoroantimonate sulfonium salts, triaryl hexafluorophosphate sulfonium salts or diaryl hexafluorophosphate iodonium salts. For a particular photoinitiator to be selected for a given encapsulating material composition, it is first ensured that the photoinitiator is activated at a wavelength that does not damage the OLED material. Thus, the various photoinitiators typically used in the encapsulant composition are compounds that have a relatively large absorption in the 368 to 420nm range, and the light absorption range should match or overlap as much as possible with the output of light sources such as mercury arc lamps and ultraviolet light emitting diodes.
In some embodiments of the present invention, the encapsulating material composition further comprises an auxiliary agent selected from one or more of a photosensitizing agent, a polymerization inhibitor, a surfactant, an antioxidant, a defoaming agent, and a leveling agent. The above-mentioned various auxiliary agents may be selected from corresponding auxiliary agents commonly used in the existing packaging film technology, and are not listed here. Preferably, the content of the auxiliary agent is 0.1 wt% to 1wt% of the encapsulating material composition.
Since the iodonium salt or sulfonium salt has a shorter ultraviolet absorption wavelength and the short wavelength UV contains a higher energy, if the curing time is longer, it may damage the device encapsulated by the encapsulating material composition, and in order to increase the curing speed, it is preferable that the encapsulating material composition of the present invention further comprises a photosensitizing agent, preferably the photosensitizing agent is a radical photoinitiator. The radical photoinitiators useful in the present invention can be selected by those skilled in the art from the radical photoinitiators commonly used in the art.
In some embodiments of the invention, the photosensitizing agent is one or more of a benzophenone-based photosensitizing agent, a thioxanthone-based photosensitizing agent, and a camphorquinone-based photosensitizing agent. The use of the above photosensitizers to absorb long-wave UV increases the UV curable energy without requiring too much short-wave UV to provide curing energy, preferably the photosensitizers are present in an amount of 0.1wt% to 1wt%, more preferably 0.5wt% to 1wt% of the encapsulating material composition.
In a second exemplary embodiment of the present invention, the present invention also provides an encapsulation structure, which includes an organic barrier layer, and the organic barrier layer is formed by applying the above-mentioned encapsulation material composition by spin coating or inkjet printing, and by photo-curing. In view of cost and process control, the coating is preferably performed by an inkjet printing method.
In the scheme, the polymer film formed by the packaging material composition is used as the organic barrier layer, so that the organic barrier layer has the characteristics of high light transmittance, high light curing rate, low shrinkage, low air output, high heat resistance and the like, and can well meet the optical requirement and curing requirement of a packaging structure.
In some embodiments of the invention, the encapsulating material composition is made to a thickness of 0.1 μm to 20 μm by spin coating or ink jet printing, and cured by UV irradiation of 10-500mW/cm 2 for about 1 second to 300 seconds to provide an organic barrier layer.
In some embodiments of the present invention, the package structure further includes inorganic barrier layers, the organic barrier layers alternating with the inorganic barrier layers.
In the scheme, when the organic barrier layer and the inorganic barrier layer are alternately deposited to form the inorganic-organic-inorganic film packaging structure, the smooth property of the inorganic barrier layer can be ensured, the etching of plasma during the formation of the inorganic barrier layer can be born, the inorganic barrier layer is prevented from being diffused to other inorganic barrier layers, and the packaging effect can be improved.
In some embodiments of the present invention, the inorganic barrier layer may be prepared by depositing a layer of SiNx to a thickness of 0.1 μm to 20 μm by PECVD.
In a third exemplary embodiment of the present invention, the present invention also provides a display device, which includes a functional structure and a package structure, and the package structure is the above-described package structure.
The display device can be used for preparing computers, cameras, mobile phones, instruments, telephones, advertising boards, lighting instruments and the like.
In the scheme, the packaging structure is applied to the display device, so that the penetration of water vapor and oxygen to the functional structure is effectively prevented, the packaging effect is good, the light emitting rate of the display device can be improved, and the service life of the display device is prolonged.
The advantageous effects of the present invention will be described below with reference to specific examples and comparative examples.
Preparation of diphenyl silicon compound
1. Preparation of diphenyl silicon compound I-1:
The preparation reaction equation of the diphenyl silicon compound I-1 is shown as follows:
1.1 Synthesis of TM-1
Into a 250mL three-necked flask equipped with a constant pressure dropping funnel, an electric stirrer and a condenser tube, 4.8g (0.2 moL) of magnesium turnings were added, the mixture was replaced with high purity N 2 three times, 40mL of tetrahydrofuran was added under the protection of N 2 to cover the magnesium turnings, a small amount of a mixed solution prepared from 47g (0.2 moL) of p-dibromobenzene and 100mL of tetrahydrofuran was added dropwise at room temperature to initiate a reaction, and then the mixed solution was slowly added dropwise to maintain the reaction in a micro reflux state, after completion of the dropwise addition within 1 hour, the reaction was heated by an oil bath to reflux for 1 hour when no reflux was generated. Cooled to room temperature, and 11.6g (0.09 moL) of dichlorodimethylsilane is dripped into the mixture in a cold water bath at about 10 ℃ and heated in an oil bath for reflux reaction for 1h after the dripping is completed.
Steaming out tetrahydrofuran, adding methanol to neutralize unreacted Grignard reagent, extracting reaction liquid with dichloroethane, separating out an organic layer, filtering, washing once with dilute hydrochloric acid, washing to neutrality, distilling to recover solvent to obtain di (p-bromophenyl) dimethylsilane, recrystallizing with ethanol to obtain 24.59g, and purifying with yield up to 85% (calculated as dichlorodimethylsilane), wherein the purity is as follows: 98.9%. MS: m/z= 367.92, elemental analysis: c 14H14Br2 Si, calculated C:45.43, si:7.59, br:43.17, H:3.81, found C:45.40, si:7.58, br:43.20, H:3.82.
1.2 Synthesis of TM-2
2.88G (0.12 moL) of magnesium turnings are added into a 250mL three-necked flask equipped with a constant pressure dropping funnel, an electric stirrer and a condenser tube, the magnesium turnings are replaced by high-purity N 2 three times, 30mL of tetrahydrofuran is added under the protection of N 2 to cover the magnesium turnings, a small amount of mixed solution prepared from 22.2g (0.06 moL) of bis (p-bromophenyl) dimethylsilane and 100mL of tetrahydrofuran is added dropwise at room temperature to initiate reaction, and then the mixed solution is slowly added dropwise to maintain the reaction in a micro reflux state, after the completion of the dropwise addition in 1 hour, the reflux reaction is heated by an oil bath for 1 hour. Cooled to room temperature, 2.84g (0.03 moL) of dimethylchlorosilane is dripped into the mixture in a cold water bath at about 10 ℃, and the mixture is heated in an oil bath for reflux reaction for 1h after dripping.
Steaming out tetrahydrofuran, adding 20mL of methanol to neutralize unreacted Grignard reagent, extracting the reaction solution with dichloroethane, separating out an organic layer, filtering, washing once with dilute hydrochloric acid, washing to be neutral, distilling to recover solvent to obtain 7.9g of bis (p-bromophenylsilane) dimethylsilane, wherein the yield reaches 80% (calculated by dimethylchlorosilane), and the purity is as follows: 99.6%, MS: m/z= 328.15, elemental analysis: c 18H28Si3, calculated C65.78, si 25.63, H8.59, found C65.79, si 25.60, H8.61.
1.3 Synthesis of TM-3
In a 250mL three-necked flask, a magnetic stirrer was placed, and the system was evacuated using a vacuum pump and a nitrogen balloon. To a three-necked flask, MEHQ (0.05 g), anhydrous toluene (100 mL), the above second step compound (3.28 g,10 mmoL), platinum (0) -1, 3-diethylene-1, 3-tetramethyldisiloxane (0.005 g) were successively added under nitrogen atmosphere. Heating to 40 ℃, and magnetically stirring uniformly.
To a constant pressure titration funnel was added 1, 2-epoxy-4-vinylcyclohexane (2.48 g), anhydrous toluene (20 mL) under nitrogen. And slowly dripping the 1, 2-epoxy-4-vinylcyclohexane solution after the temperature in the reaction system is raised to 40 ℃. Note that controlling the drop rate prevents the temperature from rising too fast, and the drop rate is standard that the system does not rise in temperature after 20min.
After 4 hours of reaction, GC monitors the reaction, and finds that the raw material 1, 2-epoxy-4-vinylcyclohexane has reacted, and stops the reaction. The solvent was removed by rotary evaporation at 40 ℃ under reduced pressure, and column chromatography (petroleum ether: ethyl acetate=3:1 as developing solvent) gave a colorless oily liquid, yield: 91%, GC test purity 99%, MS: m/z= 576.33, elemental analysis: c 34H52O2Si3, calculated C:70.77, H:9.08, O:5.55, si:14.60, measured C:70.81, H:9.05, O:5.54, si:14.60, surface tension: 43.6mN/m, viscosity (25 ℃ C.). 79mPa.s.
2. Preparation of diphenyl silicon compound I-2
The preparation reaction equation of the diphenyl silicon compound I-2 is shown as follows:
in a 250mL three-necked flask, a magnetic stirrer was placed, and the system was evacuated using a vacuum pump and a nitrogen balloon. To a three-necked flask, MEHQ (0.05 g), anhydrous toluene (100 mL), the above second step compound (3.28 g,10 mmoL), platinum (0) -1, 3-diethylene-1, 3-tetramethyldisiloxane (0.005 g) were successively added under nitrogen atmosphere. Heating to 40 ℃, and magnetically stirring uniformly.
To a constant pressure titration funnel was added 3- [ (allyloxy) methyl ] -3-ethyloxetane (3.12 g, aledine), anhydrous toluene (20 mL) under nitrogen. After the temperature in the reaction system is raised to 40 ℃, 3- [ (allyloxy) methyl ] -3-ethyl oxetane solution is slowly added dropwise. Note that controlling the drop rate prevents the temperature from rising too fast, and the drop rate is standard that the system does not rise in temperature after 20 min.
After 4h of reaction, GC monitors the reaction and finds that the starting 3- [ (allyloxy) methyl ] -3-ethyloxetane has reacted, stopping the reaction. The solvent was removed by rotary evaporation at 40 ℃ under reduced pressure, and column chromatography (petroleum ether: ethyl acetate=3:1 as developing solvent) gave a colorless oily liquid, yield: 94%, GC test purity 99.6%, MS: m/z= 640.38, elemental analysis: c 36H60O4Si3, calculated C:67.44, H:9.43, O:9.98, si:13.14, found C:67.49, H:9.43, O:9.93, si:13.14, surface tension: 33.6mN/m, viscosity (25 ℃ C.). 213.5mpa.s.
3. Preparation of diphenyl silicon compound I-3:
the preparation reaction equation of the diphenyl silicon compound I-3 is shown as follows:
in a 250mL three-necked flask, a magnetic stirrer was placed, and the system was evacuated using a vacuum pump and a nitrogen balloon. To a three-necked flask, MEHQ (0.05 g), anhydrous toluene (100 mL), the above second step compound (3.28 g,10 mmoL), platinum (0) -1, 3-diethylene-1, 3-tetramethyldisiloxane (0.005 g) were successively added under nitrogen atmosphere. Heating to 40 ℃, and magnetically stirring uniformly.
Allyl glycidyl ether (2.29 g), anhydrous toluene (20 mL) was added to the constant pressure titration funnel under nitrogen. Slowly dripping allyl glycidyl ether solution after the temperature in the reaction system is raised to 40 ℃. Note that controlling the drop rate prevents the temperature from rising too fast, and the drop rate is standard that the system does not rise in temperature after 20 min.
After 4h of reaction, GC monitors the reaction, and the reaction is stopped after the reaction of the allyl glycidyl ether as a raw material is completed. The solvent was removed by rotary evaporation at 40 ℃ under reduced pressure, and column chromatography (petroleum ether: ethyl acetate=3:1 as developing solvent) gave a colorless oily liquid, yield: 74%, GC test purity 97.5%, MS: m/z= 556.29, elemental analysis: c 30H48O4Si3, calculated C:64.70, H:8.69, O:11.49, si:15.13, found C:64.68, H:8.70, O:11.50, si:15.13, surface tension: 40.9mN/m, viscosity (25 ℃ C.). 125mPa.s.
4. Preparation of diphenyl silicon compound I-4:
The preparation reaction equation of the diphenyl silicon compound I-4 is shown as follows:
In a 250mL three-necked flask, a magnetic stirrer was placed, and the system was evacuated using a vacuum pump and a nitrogen balloon. MEHQ (0.05 g), anhydrous toluene (100 mL), the second step compound (3.28 g,10 mmoL), platinum (0) -1, 3-diethylene-1, 3-tetramethyldisiloxane (0.005 g) were added to a three-necked flask in sequence under the protection of nitrogen, the temperature was raised to 40℃and the mixture was stirred magnetically. Epoxybutene (1.41 g) and anhydrous toluene (20 mL) were added to a constant pressure titration funnel under nitrogen. And slowly dripping epoxybutene solution after the internal temperature of the reaction system is raised to 40 ℃. Note that controlling the drop rate prevents the temperature from rising too fast, and the drop rate is standard that the system does not rise in temperature after 20 min.
After 4h of reaction, GC monitors the reaction, and the reaction is stopped after the epoxybutene as a raw material is completely reacted. The solvent was removed by rotary evaporation at 40 ℃ under reduced pressure, and column chromatography (petroleum ether: ethyl acetate=3:1 as developing solvent) gave a colorless oily liquid, yield: 95%, GC test purity 98.9%, MS: m/z= 468.23, elemental analysis: c 26H40O2Si3, calculated C:66.61, H:8.60, O:6.82, si:17.97, found C:66.69, H:8.55, O:6.79, si:17.95, surface tension: 38.6mN/m, viscosity (25 ℃ C.). 55.6mPa.s.
5. Preparation of diphenyl silicon compound I-5:
the preparation reaction equation of the diphenyl silicon compound I-5 is shown as follows:
in a 250mL three-necked flask, a magnetic stirrer was placed, and the system was evacuated using a vacuum pump and a nitrogen balloon. To a three-necked flask, MEHQ (0.05 g), anhydrous toluene (100 mL), the above second step compound (3.28 g,10 mmoL), platinum (0) -1, 3-diethylene-1, 3-tetramethyldisiloxane (0.005 g) were successively added under nitrogen atmosphere. Heating to 40 ℃, and magnetically stirring uniformly.
3, 4-Epoxy-2-methyl-1-butene (1.68 g), anhydrous toluene (20 mL) were added to a constant pressure titration funnel under nitrogen. And slowly dropwise adding the 3, 4-epoxy-2-methyl-1-butene solution after the temperature in the reaction system is raised to 40 ℃. Note that controlling the drop rate prevents the temperature from rising too fast, and the drop rate is standard that the system does not rise in temperature after 20 min.
After 4h of reaction, GC monitors the reaction, and finds that the raw material 3, 4-epoxy-2-methyl-1-butene is reacted completely, and stops the reaction. The solvent was removed by rotary evaporation at 40 ℃ under reduced pressure, and column chromatography (petroleum ether: ethyl acetate=3:1 as developing solvent) gave a colorless oily liquid, yield: 90%, GC test purity 96.5%, MS: m/z= 496.26, elemental analysis: c 28H44O2Si3, calculated C:67.68, H:8.93, O:6.44, si:16.96, measured C:67.68, H:8.94, O:6.45, si:16.94, surface tension: 37.9mN/m, viscosity (25 ℃ C.). 63.4mPa.s.
6. Preparation of diphenyl silicon compound I-6:
The preparation reaction equation of the diphenyl silicon compound I-6 is shown as follows:
in a 250mL three-necked flask, a magnetic stirrer was placed, and the system was evacuated using a vacuum pump and a nitrogen balloon. To a three-necked flask, MEHQ (0.05 g), anhydrous toluene (100 mL), the above second step compound (3.28 g,10 mmoL), platinum (0) -1, 3-diethylene-1, 3-tetramethyldisiloxane (0.005 g) were successively added under nitrogen atmosphere. Heating to 40 ℃, and magnetically stirring uniformly.
1, 2-Epoxy-5-hexene (1.96 g) and anhydrous toluene (20 mL) were added to a constant pressure titration funnel under nitrogen. Slowly dripping 1, 2-epoxy-5-hexene solution after the internal temperature of the reaction system is raised to 40 ℃. Note that controlling the drop rate prevents the temperature from rising too fast, and the drop rate is standard that the system does not rise in temperature after 20 min.
After 4h of reaction, GC monitors the reaction, and finds that the raw material 1, 2-epoxy-5-hexene is reacted completely, and stops the reaction. The solvent was removed by rotary evaporation at 40 ℃ under reduced pressure, and column chromatography (petroleum ether: ethyl acetate=3:2 as developing solvent) gave a colorless oily liquid, yield: 91%, GC test purity 95%, MS: m/z= 524.30, elemental analysis: c 30H48O2Si3, calculated C:68.64, H:9.22, O:6.10, si:16.05, found C:68.61, H:9.22, O:6.07, si:16.10, surface tension: 38.2mN/m, viscosity (25 ℃ C.). 69.8mPa.s.
Examples 1 to 20 and comparative examples 1 to 2
Examples 1-20 and comparative examples 1-2 each independently provided an encapsulating material composition comprising a diphenylsilicon-based compound, a reactive diluent, an initiator and a photosensitizing agent, the amounts (in weight%) of each component being shown in tables 1 and 2 below.
The detailed descriptions of the components used in examples 1-20 and comparative examples 1-2 are as follows:
(A) Reactive diluents
(A1) Ethylene glycol diglycidyl ether (microphone), (A2) neopentyl glycol diglycidyl ether (microphone), (A3) OXT101 (east asia synthesis).
(B) Diphenyl silicon compound
Examples use diphenyl silicon compounds: (B1) A monomer of formula I-1, (B2) a monomer of formula I-2, (B3) a monomer of formula I-3, (B4) a monomer of formula I-4, (B5) a monomer of formula I-5, and (B6) a monomer of formula I-6.
Comparative examples silicon-containing compounds were used: (B7) is selected from monomers of solid wetting technology, and has the following structural formula:
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(B8) The structural formula of the silicon-containing compound is as follows:
(C) Cationic initiator C1: PAG20101 (strong new material) 4- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, C2: free radical initiator TPO.
(D) Photosensitizers: PSS306 (New Strong Material) 9, 10-diethoxy-2-ethyl anthracene.
The preparation method of the packaging material composition comprises the following steps:
The components of examples and comparative examples were placed in 250mL brown polypropylene bottles in the amounts (unit: weight percent) listed in tables 1 and 2, followed by mixing for 0.5 hour using ultrasonic waves to prepare potting material compositions.
The results of evaluating the properties of the encapsulating material compositions prepared in examples and comparative examples are shown in tables 1 and 2 below.
Evaluation of Performance:
1. Light transmittance test: an ultraviolet visible spectrophotometer test system (Carry 5000, manufactured by Agilent technologies Co., ltd.) was used. The potting material composition was spray-coated or ink-jet printed on a glass substrate and subjected to UV curing by UV irradiation at 200mW/cm 2 for 180 seconds to produce a cured test specimen having a 10 μm thick layer. The light transmittance of the film was measured in the visible light range of 550nm using an ultraviolet-visible spectrophotometer test system (Carry 5000, manufactured by agilent technologies, inc. In the united states).
2. Photo-curing rate:
1) The curing wavelength is 395nm, and the curing energy is 1500mJ/cm 2.
2) The cure rate was measured using infrared spectroscopy and calculated by comparing the change in the area of the absorption peak of the epoxy before and after curing. Wherein 880cm -1 is the absorption peak of ternary epoxy C-O-C, 980cm -1 is the absorption peak of quaternary epoxy C-O-C, 1730cm -1 is the absorption peak of carbonyl. And (3) taking the carbonyl peak as an internal standard, and calculating the reduction of the epoxy peak area to obtain the curing rate.
3. Glass transition temperature test:
Samples on aluminum plates were cut off with a blade into 5mm wide, 20mm long rectangles and tested for average thickness.
The sample was fixed on a clamp of TADMA Q800,800 dynamic thermo-mechanical analyzer and the temperature program was set to rise from room temperature to 180 ℃ at a rate of 10 ℃/min. The width and thickness of the sample are input, and the length is measured by the instrument by itself, so that the test can be started.
4. Out gas (out gas) quantity test:
Taking toluene as an internal standard, weighing 5-10mg, adding 0.5-1g of sample, irradiating under 395nm UV light of 1500mJ/cm 2, curing, heating at 100deg.C for 30min by using HS-GC-MS (high-quality gas chromatography-mass spectrometry), and comparing with the initially weighed toluene and sample mass to obtain the content of out gas in the Fill glue.
5. Curing volume shrinkage test:
The liquid density was calculated by weighing 10mL of the sample in a plastic cup using a 5mL pipette.
The sample was folded into a small box using aluminum foil, added to a thickness of about 1mm, and light cured by irradiation under a 395nm UV LED lamp for about 5 minutes. And taking out the sample after curing, removing the sample from the aluminum foil, and radiating the sample again for 5 minutes with the reverse side upwards to completely cure the sample. To the mass section for sample density testing.
Volume shrinkage = (1-liquid density/solid density) ×100%
6. Viscosity test:
The device comprises: bole Fei DV2T
The testing method comprises the following steps: the Brookfield rotational viscometer is used for testing at 25 ℃, proper rotating speed is selected according to the viscosity of a sample, the torque is relatively accurate in a 40-60% range, and the viscosity at 25 ℃ is tested.
7. Surface tension test
Test equipment: BZY-1 static surface tension tester (Shanghai balance)
The testing method comprises the following steps: the platinum plate is burned by an alcohol lamp and hung on an instrument hook, and then the instrument is cleared. The sample was poured into a plastic cup and placed on a test platform. The instrument is set to an automatic mode for testing. Taking the third test result as a final result.
TABLE 1
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TABLE 2
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As shown in tables 1 and 2, the encapsulation layer prepared from the encapsulation material composition of the present invention showed low outgassing, low shrinkage, and higher light transmittance than the comparative examples. In addition, the encapsulating material composition of the present invention showed significantly high photocuring rate and glass transition temperature as compared to the comparative example.
Meanwhile, the encapsulation layer prepared from the encapsulation material composition of comparative examples 1-2, which does not contain the diphenylsilicon compounds of the present invention, shows high outgassing, shrinkage and relatively low photo-curing rate, and has significantly inferior heat resistance to the encapsulation material composition of the present invention, and thus the encapsulation material composition of the present invention has more excellent encapsulation effect.
Example 21
The present embodiment provides a display device, which is a flexible OLED device, as shown in fig. 1, including: the substrate ITO 1, the functional structure 2 and the packaging structure 3, wherein the functional structure 2 is formed on the substrate ITO 1, and the packaging structure 3 is formed on the functional structure 2.
The functional structure 2 is an organic light emitting diode, specifically, from the substrate ITO 1 to the direction of the package structure 3, the functional structure sequentially includes an anode 21, a hole transport layer 22, a light emitting layer 23, an electron transport layer 24, a cathode 25, a cathode protection layer 26, and an inorganic layer 27 connected to the package structure 3, where the light emitting layer 23 contains color matching layers of three primary colors of RGB and three primary colors matched with each other.
The encapsulation structure 3 includes the inorganic barrier layers 31 and the organic barrier layers 32 alternately arranged, wherein the organic barrier layers 32 are formed by coating the encapsulation material composition of example 1 by inkjet printing and curing with UV irradiation of 150mW/cm 2 for about 10 seconds. The thickness of the inorganic barrier layer 31 is 1 μm, the inorganic barrier layer 31 is specifically SiNx, and the thickness of the organic barrier layer 32 is 10 μm.
Comparative examples 3 to 4
The organic barrier layer 32 was formed by coating the encapsulating material composition of comparative examples 1 to 2 by inkjet printing and photo-curing, unlike example 21.
The flexible OLED devices of example 21 and comparative examples 3-4 were tested for performance by a test method comprising: the device double 85 test sees the memory life, the light area duty ratio, and the black dot count duty ratio, and the test results are shown in tables 3 and 4 below.
TABLE 3 area ratio of bright areas (%)
As can be seen from the comparison results of table 3, the display device using the encapsulation material composition of the present invention as an organic barrier layer has a larger bright area ratio than the display device using the encapsulation material compositions of comparative examples 1 to 2 as an organic barrier layer, wherein example 21> comparative example 3> comparative example 4.
TABLE 4 area ratio of black dots (%)
As can be seen from the comparison results of table 4, the display device using the encapsulation material composition of the present invention as an organic barrier layer has a smaller black dot chip count area ratio than the display device using the encapsulation material compositions of comparative examples 1 to 2 as an organic barrier layer, wherein example 21 < comparative example 3 < comparative example 4.
As can be seen from the above results of the device double 85 test, the encapsulation performance of the display device encapsulated by using the encapsulation material composition of the present invention as an organic barrier layer is excellent, which is significantly better than that of comparative examples 3 and 4.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. An encapsulating material composition, characterized in that the encapsulating material composition comprises a diphenyl silicon compound, a reactive diluent and an initiator, wherein the diphenyl silicon compound comprises one or more compounds represented by the general formula (I):
Wherein each X 1、X2 independently represents a single bond, C 1～C29 alkyl, C 1～C29 alkoxy, or C 1～C29 fluoroalkyl; r 1-R6 and S each independently represent one or more of an alkyl group of H, C 1～C29, an alkoxy group of C 1～C29, a fluoroalkyl group of C 1～C29, an aryl group of substituted or unsubstituted C 1～C29, an aromatic heterocyclic group of substituted or unsubstituted C 1～C29;
Y 1、Y2 each independently represents one or more of the following structures:
* Representing the location of the bridge.
2. The encapsulating material composition according to claim 1, wherein X 1 and X 2 are the same and represent a single bond, an alkyl group of C 1～C5, an alkoxy group of C 1～C5 or a fluoroalkyl group of C 1～C5;
And/or R 1-R6 is the same and represents one or more of a linear alkyl group of H, C 1～C5, a linear alkoxy group of C 1～C5, a linear fluoroalkyl group of C 1～C5, an aryl group of substituted or unsubstituted C 1～C5, an aromatic heterocyclic group of substituted or unsubstituted C 1～C5;
And/or Y 1 and Y 2 are the same.
3. The encapsulating material composition according to claim 2, wherein the compound represented by the general formula (I) is selected from one or more of the following (I-1) to (I-6):
4. encapsulating material composition according to claim 1, characterized in that the content of diphenyl silicon compound is 30-85 wt%, preferably 30-60 wt% of the encapsulating material composition.
5. The encapsulating material composition according to claim 1, wherein the diphenyl silicon compound has a number average molecular weight of 200 to 2000g/moL and a viscosity of 10 to 2000mpa.s.
6. The encapsulating material composition according to any one of claims 1 to 5, wherein the surface tension of the diphenyl silicon compound is 25 to 45mN/m.
7. The encapsulating material composition of any of claims 1-6, wherein the functional groups of the reactive diluent comprise one or more of alicyclic epoxy, oxetanyl, glycidyl ether, or epoxy groups; and/or the reactive diluent is present in an amount of 13wt% to 68wt% of the encapsulating material composition;
Preferably, the reactive diluent is selected from one or more of vinyl cyclohexene oxide, 3, 4-epoxycyclohexylmethyl-3 ',4' -epoxycyclohexylformate, bis ((3, 4-epoxycyclohexylmethyl) adipate, tetrahydrophthalic acid diglycidyl ester, 4, 5-epoxycyclohexane-1, 2-dicarboxyiate diglycidyl ester, dicyclopentadiene diepoxide, 4- (2, 3-epoxypropoxy) -N, N ' -bis (2, 3-epoxypropyl) aniline, 1, 4-cyclohexanedimethanol bis (3, 4-epoxycyclohexane formate) and cyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 1, 4-butanediol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, butyl glycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, propoxyglycerol triglycidyl ether, oxybxt 101, oxybt 212, oxybt 121 and oxybt 221;
and/or, the initiator is a cationic photoinitiator; preferably, the cationic photoinitiator is selected from one or more of diaryliodonium salts, triarylsulfonium salts, diazonium salts, alkyl sulfonium salts, iron arene salts, sulfonyloxy ketones, and triarylsiloxane ethers; more preferably, the cationic photoinitiator is selected from one or more of triaryl hexafluoroantimonate sulfonium salts, triaryl hexafluorophosphate sulfonium salts or diaryl hexafluorophosphate iodonium salts.
8. The encapsulating material composition according to claim 1, further comprising an auxiliary agent selected from one or more of a photosensitizing agent, a polymerization inhibitor, a surfactant, an antioxidant, a defoaming agent, a leveling agent;
preferably, the auxiliary agent is contained in an amount of 0.1 wt% to 1wt% of the encapsulating material composition.
9. An encapsulation structure, characterized in that the encapsulation structure comprises an organic barrier layer, which is formed by spin coating or inkjet printing using the encapsulation material composition according to any one of claims 1 to 8 and by photo-curing.
10. A display device comprising a functional structure and a package structure, wherein the package structure is the package structure of claim 9.
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| CN202311794158.6A CN117946612A (en) | 2023-12-22 | 2023-12-22 | Packaging material composition, packaging structure and display device |
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| CN202311794158.6A CN117946612A (en) | 2023-12-22 | 2023-12-22 | Packaging material composition, packaging structure and display device |
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