JP2011116124A - 積層フィルムの製造方法 - Google Patents
積層フィルムの製造方法 Download PDFInfo
- Publication number
- JP2011116124A JP2011116124A JP2010243445A JP2010243445A JP2011116124A JP 2011116124 A JP2011116124 A JP 2011116124A JP 2010243445 A JP2010243445 A JP 2010243445A JP 2010243445 A JP2010243445 A JP 2010243445A JP 2011116124 A JP2011116124 A JP 2011116124A
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- JP
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- Prior art keywords
- film
- transparent conductive
- barrier
- laminated
- producing
- 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
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
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- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 7
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- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000004544 sputter deposition Methods 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 229910001887 tin oxide Inorganic materials 0.000 claims description 6
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
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- 229910001195 gallium oxide Inorganic materials 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- HRHKULZDDYWVBE-UHFFFAOYSA-N indium;oxozinc;tin Chemical compound [In].[Sn].[Zn]=O HRHKULZDDYWVBE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 2
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- 230000005684 electric field Effects 0.000 description 1
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- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
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- 238000004611 spectroscopical analysis Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
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- 230000037303 wrinkles Effects 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
- C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/503—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using dc or ac discharges
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/54—Apparatus specially adapted for continuous coating
- C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
- H10K77/111—Flexible substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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Abstract
【解決手段】樹脂フィルム上にバリア膜及び透明導電膜を形成することにより、積層フィルムを製造する。バリア膜の形成は、ロール間放電プラズマCVD法により行う。透明導電膜の形成は、物理気相成長法により行うことが好ましい。樹脂フィルムとしては、ポリエステル樹脂フィルムやポリオレフィン樹脂フィルムを用いることが好ましい。
【選択図】なし
Description
すなわち、本発明は、樹脂フィルム上にバリア膜及び透明導電膜を形成することにより積層フィルムを製造する方法であって、前記バリア膜をロール間放電プラズマCVD法により形成することを特徴とする積層フィルムの製造方法を提供する。
[バリア膜の形成]
図1に示す製造装置を用いて樹脂フィルム上にバリア膜を形成した。すなわち、まず、基材となる樹脂フィルム100(2軸延伸ポリエチレンナフタレートフィルム(PENフィルム)、厚み:100μm、幅:350mm、帝人デュポンフィルム(株)製、商品名「テオネックスQ65FA」)の巻体を送り出しロ−ル11に装着した。該巻体から繰り出した樹脂フィルム100を、搬送ロール21、成膜ロール31、搬送ロール22及び23、成膜ロール32、及び搬送ロール24を順次経由させて、巻取りロール71に巻き付けた。そして、樹脂フィルム100を搬送しながら、成膜ロール31と成膜ロール32との間に磁場を印加すると共に、成膜ロール31と成膜ロール32にそれぞれ電力を供給して、成膜ロール31と成膜ロール32との間に放電してプラズマを発生させ、このような放電領域に、成膜ガス(原料ガスとしてのヘキサメチルジシロキサン(HMDSO)と反応ガスとしての酸素ガス(放電ガスとしても機能する)の混合ガス)を供給して、下記条件にてプラズマCVD法による薄膜形成を行い、樹脂フィルム100上にバリア膜が形成された積層フィルムAを得た。
原料ガスの供給量:50sccm(Standard Cubic Centimeter per Minute)(0℃、1気圧基準)
酸素ガスの供給量:500sccm(0℃、1気圧基準)
真空チャンバー内の真空度:3Pa
プラズマ発生用電源からの印加電力:0.8kW
プラズマ発生用電源の周波数:70kHz
フィルムの搬送速度;0.5m/min。
エッチングイオン種:アルゴン(Ar+)
エッチングレート(SiO2熱酸化膜換算値):0.05nm/sec
エッチング間隔(SiO2換算値):10nm
X線光電子分光装置:Thermo Fisher Scientific社製、機種名「VG Theta Probe」
照射X線:単結晶分光AlKα
X線のスポットの形状及びサイズ:長径800μm、短径400μmの楕円形。
上記積層フィルムAのバリア膜上に、ターゲットとして明浄金属製ITO(In:Sn=95:5、高密度品、純度99.99%、粒子径3〜5mm)を用いて、圧力勾配型プラズマガンのイオンプレーティング成膜装置(中外炉工業製:SUPLaDUO、CVP-4111)により透明導電膜を以下の成膜条件で形成し、積層フィルムBを得た。
放電電力:5.0kW
基板温度:室温
Arガス流量:20sccm(0℃、1気圧基準)
O2ガス流量:13.7sccm(0℃、1気圧基準)
成膜圧力:0.06Pa
プレ放電時間:180s
成膜時間:62s
実施例1で得られた積層フィルムAを用いて、積層フィルムAのバリア膜上に、ターゲットとして明浄金属製ITO(In:Sn=95:5、高密度品、純度99.99%、粒子径3〜5mm)を用いて、圧力勾配型プラズマガンのイオンプレーティング成膜装置(中外炉工業製:SUPLaDUO、CVP-4111)により透明導電膜を以下の成膜条件で形成し、積層フィルムCを得た。
放電電力:5.0kW
基板温度:180℃
Arガス流量:20sccm(0℃、1気圧基準)
O2ガス流量:13.7sccm(0℃、1気圧基準)
成膜圧力:0.06Pa
プレ放電時間:180s
成膜時間:62s
実施例1で得られた積層フィルムAを用いて、積層フィルムAのバリア膜上に、ターゲットとしてZTO(Zn2SnO4、酸化亜鉛スズ)を用いて、圧力勾配型プラズマガンのイオンプレーティング成膜装置(中外炉工業製:SUPLaDUO、CVP-4111)により透明導電膜を以下の成膜条件で形成し、積層フィルムDを得た。
なお、ZTOターゲットとしては、酸化亜鉛粉末(高純度化学研究所製、4N)と酸化錫粉末(高純度化学研究所製、4N)とを亜鉛:錫=2:1(モル比)となるように秤量し混合し焼結して焼結体を作製し、それをイオンプレーティングのターゲットとなるように粒子径3〜5mm程度に粉砕したものを用いた。
放電電力:11.2kW
基板加熱温度:室温
Arガス流量:20sccm(0℃、1気圧基準)
O2ガス流量:0sccm(0℃、1気圧基準)
成膜圧力:0.06Pa
プレ放電時間:26s
成膜時間:33s
実施例1で得られた積層フィルムAを用いて、積層フィルムAのバリア膜上に、ターゲットとしてZTO(Zn2SnO4、酸化亜鉛スズ)を用いて、圧力勾配型プラズマガンのイオンプレーティング成膜装置(中外炉工業製:SUPLaDUO、CVP-4111)により透明導電膜を以下の成膜条件で形成し、積層フィルムEを得た。
なお、ZTOターゲットとしては、酸化亜鉛粉末(高純度化学研究所製、4N)と酸化錫粉末(高純度化学研究所製、4N)とを亜鉛:錫=2:1(モル比)となるように秤量し混合し焼結して焼結体を作製し、それをイオンプレーティングのターゲットとなるように粒子径3〜5mm程度に粉砕したものを用いた。
放電電力:11.2kW
基板加熱温度:180℃
Arガス流量:20sccm(0℃、1気圧基準)
O2ガス流量:0sccm(0℃、1気圧基準)
成膜圧力:0.06Pa
プレ放電時間:26s
成膜時間:33s
実施例1で用いた基材(PENフィルム)に、実施例1のプラズマCVD法による成膜の代わりにシリコンをターゲットとして反応スパッタ法で酸化珪素膜の成膜を行い、積層フィルムFを得た。実施例1と同様にして、酸化珪素膜のXPSデプスプロファイル測定を行ったところ、酸化珪素膜は、珪素及び酸素を含む膜であるが、炭素を含まない膜であることが確認できた。
得られた酸化珪素膜の厚みは100nmであった。また、得られた積層フィルムFにおいて、温度40℃、低湿度側の湿度10%RH、高湿度側の湿度100%RHの条件における水蒸気透過度は1.3g/(m2・day)であり、基材のPENの水蒸気透過度の1.3g/(m2・day)と同じであり酸化珪素膜のバリア性は確認されなかった。
実施例1と同様にして求めた透明導電膜の膜厚は150nmで、可視光の透過率は79%だった。得られた積層フィルムGは、バリア性に乏しく、有機ELなどのフレキシブル基板としては不適であった。
Claims (11)
- 樹脂フィルム上にバリア膜及び透明導電膜を形成することにより積層フィルムを製造する方法であって、前記バリア膜をロール間放電プラズマCVD法により形成することを特徴とする積層フィルムの製造方法。
- 前記樹脂フィルムがポリエステル樹脂フィルム又はポリオレフィン樹脂フィルムである請求項1に記載の積層フィルムの製造方法。
- 前記バリア膜が珪素、酸素及び炭素を含む膜である請求項1又は2に記載の積層フィルムの製造方法。
- 前記透明導電膜を物理気相成長法により形成する請求項1〜3のいずれかに記載の積層フィルムの製造方法。
- 前記物理気相成長法がイオンプレーティング法である請求項4に記載の積層フィルムの製造方法。
- 前記イオンプレーティング法が圧力勾配型プラズマガンを用いるイオンプレーティング法である請求項5に記載の積層フィルムの製造方法。
- 前記物理気相成長法がスパッタ法である請求項4に記載の積層フィルムの製造方法。
- 前記透明導電膜がインジウム、スズ、亜鉛及びチタンからなる群から選ばれる少なくとも1種の元素を含む膜である請求項1〜7のいずれかに記載の積層フィルムの製造方法。
- 前記透明導電膜がインジウム−スズ酸化物、亜鉛−スズ酸化物、インジウム−亜鉛酸化物、インジウム−ガリウム酸化物、インジウム−亜鉛−スズ酸化物、インジウム−ガリウム−亜鉛酸化物、アルミニウムドープ亜鉛酸化物、ガリウムドープ亜鉛酸化物、アンチモンドープスズ酸化物、フッ素ドープスズ酸化物、ニオブドープ酸化チタン(NTO)、タンタルドープ酸化チタン(TTO)及びバナジウムドープ酸化チタン(VTO)からなる群から選ばれる少なくとも1種の酸化物の膜である請求項1〜7のいずれかに記載の積層フィルムの製造方法。
- 前記樹脂フィルム上に前記バリア膜を形成した後、前記バリア膜上に前記透明導電膜を形成する請求項1〜9のいずれかに記載の積層フィルムの製造方法。
- 前記バリア膜上に直接、前記透明導電膜を形成する請求項10に記載の積層フィルムの製造方法。
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- 2010-10-26 KR KR1020127010602A patent/KR101697806B1/ko active IP Right Grant
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- 2010-10-26 EP EP10826894.7A patent/EP2495738A4/en not_active Withdrawn
- 2010-10-26 WO PCT/JP2010/069394 patent/WO2011052764A1/ja active Application Filing
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JPWO2015029732A1 (ja) * | 2013-08-27 | 2017-03-02 | コニカミノルタ株式会社 | ガスバリアフィルムおよびガスバリアフィルムの製造方法 |
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JP2015047823A (ja) * | 2013-09-03 | 2015-03-16 | Jnc株式会社 | ガスバリアフィルム積層体とそれを用いた電子部品 |
Also Published As
Publication number | Publication date |
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CN102598158A (zh) | 2012-07-18 |
KR20120091121A (ko) | 2012-08-17 |
WO2011052764A1 (ja) | 2011-05-05 |
TWI495744B (zh) | 2015-08-11 |
KR101697806B1 (ko) | 2017-01-18 |
EP2495738A4 (en) | 2013-11-13 |
CN102598158B (zh) | 2016-11-02 |
EP2495738A1 (en) | 2012-09-05 |
TW201131003A (en) | 2011-09-16 |
JP5601153B2 (ja) | 2014-10-08 |
US20120269988A1 (en) | 2012-10-25 |
US9011985B2 (en) | 2015-04-21 |
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