CN105835464A - 复合阻气膜 - Google Patents
复合阻气膜 Download PDFInfo
- Publication number
- CN105835464A CN105835464A CN201510015518.7A CN201510015518A CN105835464A CN 105835464 A CN105835464 A CN 105835464A CN 201510015518 A CN201510015518 A CN 201510015518A CN 105835464 A CN105835464 A CN 105835464A
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- China
- Prior art keywords
- layer
- composite membrane
- choke
- inorganic
- surface functional
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 230000004888 barrier function Effects 0.000 title abstract description 17
- 239000010410 layer Substances 0.000 claims abstract description 152
- 239000002346 layers by function Substances 0.000 claims abstract description 61
- 229920001577 copolymer Polymers 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 23
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 20
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims abstract description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 90
- 239000012528 membrane Substances 0.000 claims description 46
- 239000011241 protective layer Substances 0.000 claims description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 24
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 19
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 19
- 229910010272 inorganic material Inorganic materials 0.000 claims description 16
- 239000011147 inorganic material Substances 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 12
- 230000002452 interceptive effect Effects 0.000 claims description 11
- NWAIGJYBQQYSPW-UHFFFAOYSA-N azanylidyneindigane Chemical compound [In]#N NWAIGJYBQQYSPW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 5
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 3
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920002530 polyetherether ketone Polymers 0.000 claims description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000758 substrate Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract 1
- 238000012423 maintenance Methods 0.000 abstract 1
- 230000002265 prevention Effects 0.000 abstract 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 59
- 229920000139 polyethylene terephthalate Polymers 0.000 description 45
- 239000005020 polyethylene terephthalate Substances 0.000 description 44
- 239000010408 film Substances 0.000 description 27
- 229910052593 corundum Inorganic materials 0.000 description 22
- 229910001845 yogo sapphire Inorganic materials 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 230000035515 penetration Effects 0.000 description 15
- 238000010998 test method Methods 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000151 deposition Methods 0.000 description 12
- 230000008021 deposition Effects 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 11
- 239000003292 glue Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 229940106691 bisphenol a Drugs 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- -1 poly-naphthalenedicarboxylic acid Glycol ester Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical compound ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 1
- SJJCQDRGABAVBB-UHFFFAOYSA-N 1-hydroxy-2-naphthoic acid Chemical compound C1=CC=CC2=C(O)C(C(=O)O)=CC=C21 SJJCQDRGABAVBB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DRNSWCJVNHUPHS-UHFFFAOYSA-N 6-hydroxynaphthalene-2-carboxylic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21.C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 DRNSWCJVNHUPHS-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910008114 Zr(OH)3 Inorganic materials 0.000 description 1
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical compound OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- DWCMDRNGBIZOQL-UHFFFAOYSA-N dimethylazanide;zirconium(4+) Chemical compound [Zr+4].C[N-]C.C[N-]C.C[N-]C.C[N-]C DWCMDRNGBIZOQL-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03926—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate
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- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
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Abstract
本发明公开了一种阻气复合膜,包括基底层,表面功能层设置在基底层的一面或两面上,其中该表面功能层包括对羟基苯甲酸与6-羟基-2-萘甲酸的第一共聚物,或者丙烯酸与二氯乙烯的第二共聚物,以及无机堆叠层,设置在表面功能层上。本发明公开的阻气复合膜,可达到可挠曲及有效阻绝水气,保护基板避免水解,维持长期稳定性的有益效果,可应用于柔性电子组件的阻气基材或背板。
Description
技术领域
本发明涉及气体与水气的阻气膜,特别是涉及一种可挠曲的阻气复合膜。
背景技术
柔性电子技术领域是将光电组件制作于柔性基材上的新技术领域。由于其产品具有轻、薄、易携带等人性化的方便特性,近年来逐渐受到全世界高科技界的重视。柔性电子组件一般以塑料或金属薄片为基材,而塑料基材相较于金属薄片基材具有透明及可挠性较高的优点,然而塑料基材对水气、氧气的阻隔效果不佳,将使得光电组件中的作用层及高功函数电极易与空气中的水气、氧气反应,成为了柔性电子产品发展上的限制。所以,柔性电子产品通常需要有一具阻气功能的复合膜来阻隔水气或氧气进入光电组件内部,以维持光电组件的效能及延长其生命周期。
因此,如何开发一种具有透明、可挠曲特性的阻气复合膜,成为柔性电子产品发展中的关键之一。
发明内容
有鉴于此,本发明提供一种阻气复合膜,以期实现可挠曲和有效阻绝水气的目的。
为了实现上述目的,作为本发明的一个方面,本发明提供了一种阻气复合膜,包括:
一基底层;
一表面功能层,设置在该基底层的一面或两面,其中该表面功能层包括对羟基苯甲酸与6-羟基-2-萘甲酸的第一共聚物或者丙烯酸与二氯乙烯的第二共聚物;以及
一无机堆叠层,设置在该表面功能层上。
其中,该基底层的材料包括聚对苯二甲酸乙二醇酯PET、聚萘二甲酸乙二醇酯PEN、聚甲基丙烯酸甲酯PMMA、聚碳酸酯PC、聚醚砜PES、聚醚醚酮PEEK或其组合。
其中,所述第一共聚物是由60-80摩尔%的对羟基苯甲酸与40-20摩尔%的6-羟基-2-萘甲酸共聚而成。
其中,所述第二共聚物是由10-50摩尔%的丙烯酸与90-50摩尔%的二氯乙烯共聚而成。
其中,所述表面功能层的厚度为0.1μm至100μm。
其中,所述表面功能层的厚度为1μm至50μm。
其中,所述无机堆叠层由至少2种选自氧化铝、氧化锌、氧化锆、氧化铪、氧化硅、氮化铟的无机材料交互堆叠而成。
其中,该无机堆叠层包括氧化铝与选自氧化锌、氧化锆、氧化铪、氧化硅、与氮化铟所组成的无机材料中的至少1种材料交互堆叠而成。
其中,所述无机堆叠层中的每一层厚度介于至之间,且所述无机堆叠层的总厚度介于10nm至50nm之间。
其中,所述无机堆叠层包括由氧化铝与氧化锆交互堆叠而成的层。
所述的阻气复合膜更包括一保护层设置于所述无机堆叠层之上,其中所述保护层包括聚氨酯丙烯酸酯、环氧丙烯酸酯、聚丙烯酸酯、聚酯或其组合。
作为本发明的另一个方面,本发明还提供了一种如上任意一项所述的阻气复合膜在柔性电子组件的阻气基材或背板中的应用,其中所述柔性电子组件包括电子纸、有机发光二极管、有机太阳能电池或薄膜太阳能电池。
通过上述技术方案可知,本发明公开的阻气复合膜,可达到可挠曲及有效阻绝水气,保护基板避免水解,维持长期稳定性的有益效果,可应用于柔性电子组件的阻气基材或背板,所述柔性电子组件包括电子纸、有机发光二极管、有机太阳能电池或薄膜太阳能电池等。
附图说明
图1是本发明一实施例的阻气复合膜的结构示意图;
图2是本发明一实施例的无机堆叠层的结构示意图;
图3是本发明一实施例的阻气复合膜的结构示意图。
附图标记的简单说明:
100 阻气复合膜;
110 基底层;
120 表面功能层;
130 无机堆叠层;
131 第一层无机材料层;
132 第二层无机材料层;
133 第三层无机材料层;
200 阻气复合膜;
240 保护层。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白,以下结合具体实施例,并参照附图,对本发明作进一步的详细说明。
根据本发明的一个具体实施例,如图1所示,本发明公开的阻气复合膜100包括基底层110,表面功能层120设置在基底层110的一面或两面;其中,表面功能层120例如可以为包括对羟基苯甲酸(p-hydroxybenzoicacid)与6-羟基-2-萘甲酸(6-hydroxy-2-naphthoic acid)的第一共聚物,或者丙烯酸(acrylic acid)与二氯乙烯(vinylidene dichloride)的第二共聚物;以及无机堆叠层130,设置在表面功能层120上。
根据本发明的一个具体实施例,基底层110可以为一柔性可挠材料,例如包含聚对苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯(PEN)、聚甲基丙烯酸甲酯(PMMA)、聚碳酸酯(PC)、聚醚砜(PES)、聚醚醚酮(PEEK)或其组合。
根据本发明的一个具体实施例,表面功能层120可以用来增加基底层110的阻气性与稳定性,因此表面功能层可以选择比基底层具有更低透气率且高致密性的材料,并利用例如贴合或涂布的方式设置于基底层上,使表面功能层120和无机堆叠层130形成协同作用(synergy)来增加阻气性。在一个具体实施例中,表面功能层120例如包括60-80摩尔%的对羟基苯甲酸与40-20摩尔%的6-羟基-2-萘甲酸所形成的第一共聚物,当第一共聚物中的对羟基苯甲酸的摩尔分数越高则加工性越好,当第一共聚物中的6-羟基-2-萘甲酸的摩尔分数越高则阻气性越好,但加工性越差。在另一个具体实施例中表面功能层120例如包括10-50摩尔%的丙烯酸与90-50摩尔%的二氯乙烯所形成的第二共聚物。当第二共聚物中的丙烯酸的摩尔分数越高则加工性越好,当二氯乙烯的摩尔分数越高则阻气性越好,但加工性则越差。在一个具体实施例中,表面功能层厚度可为0.1μm至100μm,另一个具体实施例中,表面功能层厚度为1μm至50μm。
根据本发明的另一个具体实施例,无机堆叠层130是由多层无机层所组成,如图2所示,例如是先沉积第一层无机材料层131,再沉积第二层无机材料层132,又沉积第三层无机材料层133,以此类推,可以沉积多达数百层以上,而上述无机堆叠层130可使用两种无机材料进行交替镀膜,形成超低针孔密度、百层以上的原子层厚度的沉积,作为主要的阻气层之一。在本发明的一个具体实施例中,无机堆叠层130由至少2种选自氧化铝、氧化锌、氧化锆、氧化铪、氧化硅、氮化铟组成的无机材料交互堆叠而成。例如也可以由包括一层氧化铝与一层至少1种选自氧化锌、氧化锆、氧化铪、氧化硅、氮化铟组成的无机材料交互堆叠而成,又例如可以是以一层氧化铝与一层氧化锆交互堆叠,而成为数百层以上的无机堆叠层。在一个具体实施例中,无机堆叠层130可以是以化学蒸气沉积(CVD)、脉冲激光蒸镀(PLD)、原子层沉积(ALD)等镀膜方式进行的一层又一层的无机材料层交互堆叠而成的无机堆叠层,在另一个具体实施例中,无机堆叠层可以是以ALD镀膜方式设置在上述的表面功能层之上,利用表面功能层和无机堆积层形成协同作用增加复合膜的阻气性。
根据本发明的一个具体实施例,每一层无机材料层的厚度为至且无机材料层的总厚度约为10nm至50nm。以一层氧化铝与一层氧化锆交互堆叠而成的无机堆叠层130为例,每一层氧化铝与每一层氧化锆的进料时间比介于20∶10至20∶100,在另一个具体实施例中,氧化铝与氧化锆的进料时间比可以为20∶20至20∶30,先沉积一层氧化铝再沉积一层氧化锆,在氧化锆层之上再沉积一层氧化铝,以此类推,而形成数百层无机堆叠层。
根据本发明的一个具体实施例,请参照图3,阻气复合膜200,更包括保护层240设置于该无机堆叠层130之上,其中该保护层包括聚氨酯丙烯酸酯、环氧丙烯酸酯、聚丙烯酸酯、聚酯或其组合。上述保护层240兼具阻气作用和防止无机堆叠层的刮伤,对无机堆叠层有物理性保护效果。在本发明的一个具体实施例中,上述保护层是将一聚氨酯丙烯酸酯UV胶,涂布在上述无机堆叠层之上,并以UV曝光机固化而成的聚丙烯酸酯保护层,形成基底层110/表面功能层120/无机堆叠层130/保护层240的阻气复合膜结构。在一个具体实施例中,上述保护层的厚度可为1μm至8μm,而另一个具体实施例中保护层的厚度亦可为1μm至5μm。
为了让本发明的上述和其他目的、特征和优点能更清楚易懂,下文特举数个具体实施例配合附图,作详细说明如下:
实施例1至3是采用表面功能层为对羟基苯甲酸与6-羟基-2-萘甲酸共聚物所形成的第一共聚物,其中对羟基苯甲酸占73摩尔%,6-羟基-2-萘甲酸占27摩尔%,厚度为50μm。
实施例1:PET/表面功能层/(Al2O3)200层/保护层
在PET的基底层(厚度188μm)上,利用UV胶贴合上述表面功能层(厚度50μm),并进行UV固化,形成PET/表面功能层结构。并以三甲基铝(trimethyl aluminum,TMA)及水为前驱物,进行纯氧化铝无机堆叠层的原子层沉积。实验步骤如下:
(1)导入TMA 20ms,吸附于表面功能层表面,并与表面功能层表面的-OH官能基反应,产生副产物甲烷(CH4)。此步骤的反应式为:
Al(CH3)3(g)+-O-H(s)→-O-Al(CH3)2(s)+CH4。
(2)通入氮气6s,流量为200sccm,以移除未反应的TMA及甲烷。
(3)导入水蒸气20ms,与表面功能层表面的TMA分子中的甲基反应,产生副产物甲烷。此步骤的反应式如下:
2H2O(g)+-O-Al(CH3)2(s)→-O-Al(OH)2(s)+2CH4。
(4)通入氮气6s,流量为200sccm,以移除未反应的水蒸气及甲烷。
以上完成一层Al2O3镀膜周期(cycle),并重复此镀膜周期循环步骤200次,完成PET/表面功能层上的纯氧化铝无机堆积层((Al2O3)200层)沉积。再以旋转涂布机于无机堆叠层表面涂布聚氨酯丙烯酸酯UV胶,并以UV曝光机固化而形成保护层,从而形成PET/表面功能层/(Al2O3)200层/保护层的阻气复合膜结构。将实施例1中完成的阻气复合膜以ASTMD3985测试方法进行测试,其氧气穿透率为0.05cc/m2·天·atm。
实施例2:PET/表面功能层/(ZrO2)200层/保护层
同实施例1中的PET/表面功能层结构,以顺-四(二甲基酰胺基)锆(IV)(tetrakis(dimethylamido)zirconium(IV),TDMAZr)及水为前躯物,进行纯氧化锆无机堆叠层的原子层沉积,实验步骤如下:
(1)导入TDMAZr 20ms,吸附于表而功能层表而,并与表而功能层表面的-OH官能基反应,产生副产物HN(CH3)2。此步骤的反应式为:
Zr[N(CH3)2]4(g)+-O-H(s)→-O-Zr[N(CH3)2]3(s)+HN(CH3)2。
(2)通入氮气6s,流量为200sccm,以移除未反应的TDMAZr及HN(CH3)2。
(3)导入水蒸气20ms,与表面功能层表面的TDMAZr分子中的甲基反应,产生副产物HN(CH3)2。此步骤的反应式如下:3H2O(g)+-O-Zr[N(CH3)2]3(s)→-O-Zr(OH)3(s)+3HN(CH3)2。
(4)通入氮气6s,流量为200sccm。
以上完成一层ZrO2镀膜周期,并重复此镀膜周期循环步骤200次,完成PET/表面功能层上的纯氧化锆无机堆叠层((ZrO2)200层)的沉积。以旋转涂布机于无机堆叠层表面涂布聚氨酯丙烯酸酯UV胶,并以UV曝光机固化而形成保护层,从而形成PET/表面功能层/(ZrO2)200层/保护层的阻气复合膜结构。将实施例2中完成的阻气复合膜以ASTM D3985测试方法进行测试,其氧气穿透率为0.41cc/m2·天·atm。
实施例3:PET/表面功能层/(Al2O3/ZrO2)200层/保护层
同实施例1中的PET/表面功能层结构,以TMA、TDMAZr及水为前躯物,进行氧化锆与氧化铝交错堆叠的原子层沉积,实验中每一镀膜周期固定TMA进料时间为20ms,改变不同氧化锆的进料量(X ms)以观察对阻气性的影响。无机堆叠层的镀膜步骤如下:
(1)导入TMA共20ms。
(2)通入氮气6s,流量为200sccm。
(3)导入水蒸气20ms。
(4)通入氮气6s,流量为200sccm。
(5)导入TDMAZr共X ms(X=2,5,10,20,30,50,100,200,300,500)。
(6)通入氮气6s,流量为200sccm。
(7)导入水蒸气20ms。
(8)通入氮气6s,流量为200sccm。
以上完成一次Al2O3/ZrO2交互镀膜周期,重复此镀膜周期循环步骤200次,完成PET/表面功能层上的氧化铝与氧化锆交错的无机堆叠层((Al2O3/ZrO2)200层)沉积。随后以旋转涂布机于无机堆叠层表面涂布聚氨酯丙烯酸酯UV胶,并以UV曝光机固化而形成保护层,从而形成PET/表面功能层/(Al2O3/ZrO2)200层/保护层的阻气复合膜结构。
氧化铝与氧化锆进料时间可以为20∶20至20∶100,也可以为20∶20至20∶30。其中,当氧化铝与氧化锆进料时间比为20∶30时,根据ASTM D3985测试方法测试的氧气穿透率为0.02cc/m2·天·atm,根据ASTM F1249测试方法测试的水蒸气穿透率为<0.0005g/m2·天。于25℃、60%RH下放置30天后,氧气穿透率为0.05cc/m2·天·atm,水蒸气穿透率为0.001g/m2·天。
将实施例1-3的实验数据整理到表1中。
表1
实施例4-6采用的表面功能层为丙烯酸与二氯乙烯所形成的第二共聚物,其中丙烯酸占30摩尔%,二氯乙烯占70摩尔%,厚度为10μm。
实施例4:PET/表面功能层/(Al2O3)200层/保护层
实施例4的实验条件同实施例1,差别在于实施例4的表面功能层为上述丙烯酸与二氯乙烯共聚物(厚度10μm),形成PET/表面功能层结构。并以TMA及水为前驱物,进行纯氧化铝无机堆叠层的原子层沉积,镀膜步骤如实施例1。
以上完成一层Al2O3镀膜周期,并重复此镀膜周期循环步骤200次,完成PET/表面功能层上的纯氧化铝无机堆叠层((Al2O3)200层)沉积。再以旋转涂布机于无机堆叠层表面涂布聚氨酯丙烯酸酯UV胶,并以UV曝光机固化而形成保护层,从而形成PET/表面功能层/(Al2O3)200层/保护层之阻气复合膜结构。将实施例4中完成的阻气复合膜以ASTM D3985测试方法进行测试,氧气穿透率为0.05cc/m2·天·atm。
实施例5:PET/表面功能层/(ZrO2)200层/保护层
同实施例4的PET/表面功能层结构,并以TDMAZr及水为前躯物,进行纯氧化锆无机堆叠层的原子层沉积,镀膜步骤如实施例2。
以上完成一层ZrO2镀膜周期,并重复此镀膜周期循环步骤200次,完成PET/表面功能层上的纯氧化锆无机堆叠层((ZrO2)200层)沉积。并以旋转涂布机于无机堆叠层表面涂布聚氨酯丙烯酸酯UV胶,并以UV曝光机固化而形成保护层,从而形成PET/表面功能层/(ZrO2)200层/保护层的阻气复合膜结构。将实施例5完成的阻气复合膜以ASTM D3985测试方法进行测试,氧气穿透率为4.5cc/m2·天·atm。
实施例6:PET/表面功能层/(Al2O3/ZrO2)200层/保护层
同实施例4的PET/表面功能层结构,并以TMA、TDMAZr及水为前躯物,进行氧化锆与氧化铝交错的无机堆叠层的原子层沉积,实验中每一镀膜周期固定TMA进料时间为20ms,改变不同氧化锆之进料量(X ms)以观察对阻气性的影响。无机堆叠层的镀膜步骤如实施例3。
完成一次Al2O3/ZrO2交互镀膜周期,并重复此镀膜周期循环步骤200次,完成PET/表面功能层上的氧化锆与氧化铝交错的无机堆叠层((Al2O3/ZrO2)200层)沉积。随后以旋转涂布机于无机堆叠层表面涂布聚氨酯丙烯酸酯UV胶,并以UV曝光机同化而形成保护层,从而形成PET/表面功能层/(Al2O3/ZrO2)200层/保护层的阻气复合膜结构。当氧化铝与氧化锆进料时间比为20∶30时,于ASTM D3985测试方法下的氧气穿透率为0.02cc/m2·天·atm,于ASTM F1249测试方法下的水蒸气穿透率为<0.0005g/m2·天。于25℃、60%RH下放置30天后,氧气穿透率为0.04cc/m2·天·atm,水蒸气穿透率为0.001g/m2·天。
将实施例4-6的实验数据整理到表2中。
表2
从表1及表2推知,当无机堆叠层为Al2O3/ZrO2交互堆叠之组合时,其阻气效果优于纯Al2O3或纯ZrO2等单一材料堆叠。
为了证明本发明表面功能层对于阻气的功效,进行了比较例1-6的验证实验,说明如下:
比较例1:PET/Al2O3 200层/保护层
以PET为基底层(厚度188μm)。以TMA及水为前驱物,进行纯氧化铝无机堆叠层的原子层沉积,镀膜步骤如实施例1。
重复此镀膜周期循环步骤200次,完成PET基底层上的纯氧化铝无机堆叠层沉积。并以旋转涂布机于无机堆叠层表面涂布聚氨酯丙烯酸酯UV胶,并以UV曝光机固化而形成保护层,从而形成PET/(Al2O3)200层/保护层的阻气复合膜结构。将比较例1的阻气复合膜结构根据ASTMD3985测试方法进行测试,氧气穿透率为0.06cc/m2·天·atm。
比较例2:PET/ZrO2 200层/保护层
以PET膜为基材,TDMAZr及水为前躯物,进行纯氧化锆无机堆叠层的原子层沉积,镀膜步骤如实施例2。
重复此镀膜周期循环步骤200次,完成PET基材上的纯氧化锆无机堆叠层沉积。并以旋转涂布机于无机堆叠层表面涂布聚氨酯丙烯酸酯UV胶,并以UV曝光机固化而形成保护层,从而形成PET/(ZrO2)200/保护层的阻气复合膜结构。将比较例2的阻气复合膜结构根据ASTM D3985测试方法进行测试,氧气穿透率为8cc/m2·天·atm。
比较例3:PET/(Al2O3/ZrO2)200层/保护层
以PET膜为基材,TMA、TDMAZr及水为前躯物,进行氧化锆与氧化铝交错的无机堆叠层的原子层沉积,实验中每一镀膜周期固定TMA进料时间为20ms,改变不同氧化锆之进料量(X ms)以观察对阻气性的影响。镀膜步骤如实施例3。
以上完成一镀膜周期,重复此镀膜周期循环步骤200次,完成PET基材上氧化锆与氧化铝交错的无机堆叠层沉积。随后以旋转涂布机于无机层表面涂布聚氨酯丙烯酸酯UV胶,并以UV曝光机固化而形成保护层,从而形成PET/(Al2O3/ZrO2)200层/保护层的阻气复合膜结构。当氧化铝与氧化锆进料时间比为20∶30时,于ASTM D3985测试方法下的氧气穿透率为0.03cc/m2·天·atm,于ASTM F1249测试方法下的水蒸气穿透率为<0.0005g/m2·天。于25℃、60%RH下放置30天后,氧气穿透率为0.1cc/m2·天·atm,水蒸气穿透率为0.01g/m2·天。
比较例4:PET/表面功能层(双酚A与碳酰氯共聚物)/(Al2O3)200层/保护层
同实施例4的阻气复合膜结构,比较例4仅将表面功能层改为双酚A与光气的共聚物(bisphenol A-phosgene copolymer)(厚度80μm),根据ASTM D3985测试方法测试的氧气穿透率为3cc/m2·天·atm。
比较例5:PET/表面功能层(双酚A与碳酰氯共聚物)/(ZrO2)200层/保护层
同实施例5的阻气复合膜结构,比较例5仅将表面功能层改为双酚A与光气的共聚物(厚度80μm),根据ASTM D3985测试方法测试的氧气穿透率为8cc/m2·天·atm。
比较例6:PET/表面功能层(双酚A与碳酰氯共聚物)/(Al2O3/ZrO2)200层/保护层
同实施例6的阻气复合膜结构,比较例6仅将表面功能层改为双酚A与光气的共聚物(厚度80μm),根据ASTM D3985测试方法测试的氧气穿透率为1.5cc/m2·天·atm。
将使用不同表面功能层制作阻气复合膜,根据ASTM D3985测试方法测试的氧气穿透率的影响数据整理如表3所示。
表3
氧气穿透率(OTR)单位cc/m2·天·atm
当PET在长时间置放过程中会造成表面水解,使PET与无机层接触面产生缺陷,因而降低阻气性。本发明通过引入比PET具更高阻气性与亲和性之表面功能层,来避免PET水解造成的缺陷,且进一步提高阻气性,增加长期存放稳定性。
下面将实施例及比较例的实验数据整理如表4所示。
表4
作为本发明的另一个方面,本发明还提供了一种如上所述的阻气复合膜在柔性电子组件的阻气基材或背板中的应用,其中所述柔性电子组件包括电子纸、有机发光二极管、有机太阳能电池或薄膜太阳能电池。
综上所述,本发明公开的阻气复合膜,可达到可挠曲及有效阻绝水气,保护基板避免水解,维持长期稳定性的有益效果,可应用于柔性电子组件的阻气基材或背板,所述柔性电子组件包括电子纸、有机发光二极管、有机太阳能电池或薄膜太阳能电池等。
以上所述的具体实施例,对本发明的目的、技术方案和有益效果进行了进一步详细说明,应理解的是,以上所述仅为本发明的具体实施例而已,并不用于限制本发明,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (12)
1.一种阻气复合膜,包括:
一基底层;
一表面功能层,设置在该基底层的一面或两面,其中该表面功能层包括对羟基苯甲酸与6-羟基-2-萘甲酸的第一共聚物或者丙烯酸与二氯乙烯的第二共聚物;以及
一无机堆叠层,设置在该表面功能层上。
2.如权利要求1所述的阻气复合膜,其中该基底层的材料包括聚对苯二甲酸乙二醇酯PET、聚萘二甲酸乙二醇酯PEN、聚甲基丙烯酸甲酯PMMA、聚碳酸酯PC、聚醚砜PES、聚醚醚酮PEEK或其组合。
3.如权利要求1所述的阻气复合膜,其中所述第一共聚物是由60-80摩尔%的对羟基苯甲酸与40-20摩尔%的6-羟基-2-萘甲酸共聚而成。
4.如权利要求1所述的阻气复合膜,其中所述第二共聚物是由10-50摩尔%的丙烯酸与90-50摩尔%的二氯乙烯共聚而成。
5.如权利要求1所述的阻气复合膜,其中所述表面功能层的厚度为0.1μm至100μm。
6.如权利要求5所述的阻气复合膜,其中所述表面功能层的厚度为1μm至50μm。
7.如权利要求1所述的阻气复合膜,其中所述无机堆叠层由至少2种选自氧化铝、氧化锌、氧化锆、氧化铪、氧化硅、氮化铟的无机材料交互堆叠而成。
8.如权利要求7所述的阻气复合膜,其中该无机堆叠层包括氧化铝与选自氧化锌、氧化锆、氧化铪、氧化硅、与氮化铟所组成的无机材料中的至少1种材料交互堆叠而成。
9.如权利要求7所述的阻气复合膜,其中所述无机堆叠层中的每一层厚度介于至之间,且所述无机堆叠层的总厚度介于10nm至50nm之间。
10.如权利要求8所述的阻气复合膜,其中所述无机堆叠层包括由氧化铝与氧化锆交互堆叠而成的层。
11.如权利要求1所述的阻气复合膜,更包括一保护层设置于所述无机堆叠层之上,其中所述保护层包括聚氨酯丙烯酸酯、环氧丙烯酸酯、聚丙烯酸酯、聚酯或其组合。
12.一种如权利要求1至11任意一项所述的阻气复合膜在柔性电子组件的阻气基材或背板中的应用,其中所述柔性电子组件包括电子纸、有机发光二极管、有机太阳能电池或薄膜太阳能电池。
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