JP4106931B2 - Transparent gas barrier thin film coating film - Google Patents
Transparent gas barrier thin film coating film Download PDFInfo
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- JP4106931B2 JP4106931B2 JP2002061483A JP2002061483A JP4106931B2 JP 4106931 B2 JP4106931 B2 JP 4106931B2 JP 2002061483 A JP2002061483 A JP 2002061483A JP 2002061483 A JP2002061483 A JP 2002061483A JP 4106931 B2 JP4106931 B2 JP 4106931B2
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- 230000004888 barrier function Effects 0.000 title claims description 32
- 239000010409 thin film Substances 0.000 title claims description 30
- 239000010408 film Substances 0.000 title claims description 21
- 238000009501 film coating Methods 0.000 title description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 20
- 150000002736 metal compounds Chemical class 0.000 claims description 19
- 230000005540 biological transmission Effects 0.000 claims description 14
- 229920006254 polymer film Polymers 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 125000004437 phosphorous atom Chemical group 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 125000004434 sulfur atom Chemical group 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 238000002834 transmittance Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 description 10
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 229920006305 unsaturated polyester Polymers 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
- Laminated Bodies (AREA)
- Physical Vapour Deposition (AREA)
- Liquid Crystal (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、表示装置内の液晶や、有機エレクトロルミネッセンス（以下有機ＥＬ）に対する水蒸気バリア層等として利用するプラスチックフィルムを基材とした水蒸気バリアに優れた透明ガスバリア薄膜被覆フィルムに関する。
【０００２】
【従来の技術】
プラスチックフィルム上にガスバリア機能を有する薄膜をコーティングした透明ガスバリア薄膜被覆フィルムは食品や医薬品などの包装材として従来利用されてきた。最近では液晶や有機ＥＬ素子を用いた表示装置への応用が注目されている。
【０００３】
現状では、これらの表示装置はガラス基材上に前記素子が形成される構造となっている。近年、これら表示装置の小型化・薄型化への要求に伴いその軽量性、易加工性、形態の多様性の観点から、ガラス基材の代替品として透明ガスバリア薄膜コーティングを施したポリマーフィルム基材が注目されている。
【０００４】
ポリマーフィルム基材に透明バリア薄膜コーティングを施した例としては、特開平０７−２３３４６３や特開平１１−２６２９６９に見られるような酸化ケイ素（ＳｉＯX ）、酸化アルミ（ＡｌＯX ）薄膜のコーティングが良く知られており、高い透明性であり、かつ水蒸気透過速度２〜５ｇｍ-2ｄａｙ-1程度のバリア性を有している。しかしながら、この範囲の水蒸気バリア性は、基材をガラスとした場合と比較して非常に低い。液晶や有機ＥＬの素子は、水蒸気劣化し易いため、表示機能の劣化を引き起こすことがわかってきた。したがって、従来に比べより高い水蒸気バリア性を有する薄膜のコーティングを施す必要があり、様々な提案がなされてきた。
【０００５】
水蒸気バリア性を高めるため、ＳｉＯX 、ＡｌＯX 薄膜より、従来の網状構造の緻密さを高め、透過する水分子を低下させることが考えられた。例えば特開平８−６２５９０に見られるように窒素原子を含有させた酸窒化物（例えばＳｉＯX ＮY ）が提案された。この提案により、バリア性が著しく高くなり、水蒸気透過速度０．２〜０．６ｇｍ-2ｄａｙ-1、酸素透過速度０．１〜０．４ｃｃｍ-2ｄａｙ-1まで高くなった。しかし表示装置の水蒸気バリア層としては依然として不充分なバリア性であった。
【０００６】
【発明が解決しようとする課題】
本発明の目的は、これらの問題を解決し、従来の透明ガスバリア薄膜に比べ水蒸気バリアがより高く、かつ透明性を有する透明ガスバリア薄膜被覆フィルムを提供することにある。
【０００７】
本発明は、これらの問題を解決するにあたり検討した結果、以下のことを見出した。酸素を始めとするガスの透過速度は、コーティングする薄膜の欠陥（空孔やクラック）の密度、サイズに強く寄与しており、すなわち膜の網状構造が緻密であるほど高いガスバリア性を示す。しかし水蒸気透過速度については、いまだはっきりしたことは解明されていないが、薄膜の欠陥（あるいは緻密さ）を制御するだけでなく、薄膜と水蒸気（水分子）との相互作用を高めることが重要であることがわかった。したがって水蒸気（水分子）相互作用が強い硫黄原子あるいはリン原子を組成として含有させた金属酸化物薄膜のコーティングにより、劇的に高い水蒸気バリア性を得ることができた。
【０００８】
【課題を解決するための手段】
すなわち本発明の請求項１に係る発明は、金属化合物を少なくとも片面に被覆したポリマーフィルムであって、その金属化合物が、シリコン（Ｓｉ）、アルミニウム（Ａｌ）のいずれかからなる金属原子（Ｍ）、酸素原子（Ｏ）、硫黄原子（Ｓ）より構成され、かつ金属化合物ＭＯＸＳＹにおいて、その組成比Ｘ／Ｙが、（１．２〜１．７）／（０．３〜０．８）であることを特徴とする透明ガスバリア薄膜被覆フィルムである。
【００１０】
本発明の請求項２に係る発明は、金属化合物を少なくとも片面に被覆したポリマーフィルムであって、その金属化合物が、インジウム（Ｉｎ）、シリコン（Ｓｉ）のいずれかからなる金属原子（Ｍ）、酸素原子（Ｏ）、リン原子（Ｐ）より構成され、かつ金属化合物ＭＯＸＰＹにおいて、その組成比Ｘ／Ｙが、（１．５〜２．０）／（０．３〜１．０）であることを特徴とする透明ガスバリア薄膜被覆フィルムである。
【００１３】
本発明の請求項３に係る発明は、上記請求項１または請求項２に係る透明ガスバリア薄膜被覆フィルムの発明において、前記金属化合物を被覆したポリマーフィルムの水蒸気透過速度が、０．１ｇｍ−２ｄａｙ−１以下であり、かつ酸素透過速度が、０．０５ｃｃｍ−２ｄａｙ−１以下であり、かつ光波長５５０ｎｍにおける光線透過率が、８５％以上であることを特徴とする透明ガスバリア薄膜被覆フィルムである。
【００１４】
【発明の実施の形態】
本発明で使用する上記ポリマーフィルム基材としては、不飽和ポリエステル（ポリエチレンテレフタレート）、ポリオレフィン、ポリイミド、ポリビニルアルコール、ポリエーテルサルファイドなど、透明性が高く、かつその厚さが、５０〜２００μｍのフィルムであれば、本発明の目的を逸脱するものではない。またポリマーフィルム基材上に、表面処理あるいはラミネートが施してあっても構わない。
【００１５】
上記金属化合物の形成方法としては、真空蒸着法、イオンプレーティング法、スパッタリング法、化学気相堆積法（ＣＶＤ）などが挙げられる。
【００１６】
例えば、金属化合物ＭＯX ＳY においては、その酸素原子Ｏと硫黄原子（Ｓ）の組成比Ｘ／Ｙは、（１．２〜１．７）／（０．３〜０．８）であることが望ましい。硫黄原子の割合が、この範囲以上になると、薄膜への光吸収が増加し、透明性が低下し、また、この範囲以下では、水蒸気バリア性が低下するという欠点をもつ。
【００１７】
また、金属化合物ＭＯX ＰY においては、その酸素原子（Ｏ）とリン原子（Ｐ）の組成比Ｘ／Ｙは、（１．５〜２．２）／（０．３〜１．０）であることが望ましい。リン原子（Ｐ）の割合が、この範囲以上になると、薄膜への光吸収が増加し、透明性が低下し、また、この範囲以下では、水蒸気バリア性が低下するという欠点をもつ。
【００１８】
金属化合物の薄膜の厚みとしては、１０〜２００ｎｍが望ましい。この厚みがこの範囲以上では、その圧縮応力のためクラックが生じ易くなり、水蒸気バリア性低下の原因となる。また、この範囲以下では十分な厚さではない。
【００１９】
【実施例】
以下に、本発明の具体的実施例について説明する。
＜実施例１＞
反応性スパッタリング法により、ポリエステルフィルム上に、それぞれＳｉＯX ＳY 、ＡｌＯX ＳY の薄膜を被覆した。
ターゲットにＳｉ，Ａｌ、反応ガスに硫化水素と酸素の混合ガスを用いた。基材として不飽和ポリエステルフィルム（厚さ１００μｍ）を用いた。
成膜方法としては、真空チェンバー内を１×１０-4Ｐａまで排気した後に、アルゴンガスを２×１０-1Ｐａまで導入し、続いて、酸素ガスを３×１０-1Ｐａまで導入し、さらに硫化水素ガスを全圧が５×１０-1Ｐａになるまで導入して、金属ターゲットのスパッタリングにより、上記基材上に、それぞれＳｉＯX ＳY 、ＡｌＯX ＳY の薄膜を被覆した。
【００２０】
＜実施例２＞
真空蒸着法により、ポリエステルフィルム上に、それぞれＳｉＯX ＰY 、ＩｎＯX ＰY の薄膜を被覆した。
蒸着材料としてＳｉ，Ｉｎを用い、電子ビームにて蒸発させ、また、五酸化リン（Ｐ2 Ｏ5 ）を抵抗加熱にて蒸発させ成膜した。基材として不飽和ポリエステルフィルム（厚さ１００μｍ）を用いた。
成膜方法としては、真空チェンバー内を１×１０-4Ｐａまで排気した後に、電子ビームにより、金属材料を５×１０-2Ｐａになるまで蒸発させ、同時に抵抗加熱により、五酸化リンを７×１０-3Ｐａになるまで蒸発させ、上記基材上に、それぞれＳｉＯX ＰY 、ＩｎＯX ＰY の薄膜を被覆した。
【００２１】
＜比較例１＞
上記実施例１において、ターゲットにＡｌを用い、酸素ガスを３×１０-1Ｐａまで導入し、さらに硫化水素ガスを全圧が３．５×１０-1Ｐａになるまで導入する以外は、実施例１と同様にして、上記基材上に、それぞれＳｉＯX ＳY 、ＡｌＯX ＳY の薄膜を被覆した。
【００２２】
＜比較例２＞
上記実施例２において、蒸着材料にＳｉを用い、金属材料を５×１０-2 Ｐａになるまで蒸発させ、同時に抵抗加熱により、五酸化リンを９×１０-3Ｐａになるまで蒸発させた以外は、実施例２と同様にして、上記基材上に、それぞれＳｉＯX ＰY 、ＩｎＯX ＰY の薄膜を被覆した。
【００２３】
＜測定と結果＞
上記実施例１、実施例２、及び比較例１、比較例２から得られた各々サンプルの水蒸気透過速度を、水蒸気透過速度測定装置（モダンコントロール社製：ＰＥＲＭＡＴＲＡＮ）を用い、湿度９０％ＲＨ、温度４０℃の雰囲気下で測定した。また、前記各々サンプルの酸素透過速度を、酸素透過速度測定装置（モダンコントロール社製：ＯＸＴＲＡＮ）を用い、湿度０％、温度４０℃の雰囲気下で測定した。
また、その各々サンプルの光線透過率を分光光度計にて測定した。また、金属化合物中の組成比Ｘ／Ｙ（組成比Ｘ：Ｙ）は、Ｘ線光電子分光測定装置（島津製作所製）にて測定した。上記測定結果は表１に併せて示した。
【００２４】
【表１】
表１中の第一段記載のＷＶＴＲ、ＯＴＲ、及びＴ％は、それぞれ水蒸気透過速度（単位ｇｍ-2ｄａｙ-1）、酸素透過速度（単位ｃｃｍ-2ｄａｙ-1）、及び光線透過率（単位％、光波長５５０ｎｍ）を表している。また膜厚の単位はｎｍ。
【００２６】
【発明の効果】
本発明の透明ガスバリア薄膜被覆フィルムは、金属酸化物に硫黄原子あるいはリン原子を含有させることで、今までに無い高水蒸気バリア性を持ち、かつ透明性の高いガスバリア薄膜被覆フィルムが得られる[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a transparent gas barrier thin film coated film excellent in a water vapor barrier based on a plastic film used as a water vapor barrier layer or the like for liquid crystal in a display device or organic electroluminescence (hereinafter referred to as organic EL).
[0002]
[Prior art]
A transparent gas barrier thin film-coated film obtained by coating a plastic film with a thin film having a gas barrier function has been conventionally used as a packaging material for foods and pharmaceuticals. Recently, application to a display device using a liquid crystal or an organic EL element has attracted attention.
[0003]
At present, these display devices have a structure in which the element is formed on a glass substrate. In recent years, with the demand for miniaturization and thinning of these display devices, a polymer film substrate provided with a transparent gas barrier thin film coating as an alternative to a glass substrate from the viewpoint of lightness, ease of processing, and variety of forms. Is attracting attention.
[0004]
As an example of applying a transparent barrier thin film coating to a polymer film substrate, a silicon oxide (SiO x ) or aluminum oxide (AlO x ) thin film coating as disclosed in JP-A-07-233463 and JP-A-11-262969 is good. It is known, has high transparency, and has a barrier property of a water vapor transmission rate of about 2 to 5 gm −2 day −1 . However, the water vapor barrier property in this range is very low compared to the case where the substrate is made of glass. It has been found that liquid crystal and organic EL elements are liable to cause water vapor deterioration and thus cause display function deterioration. Therefore, it is necessary to apply a thin film coating having a higher water vapor barrier property than before, and various proposals have been made.
[0005]
In order to improve the water vapor barrier property, it has been considered that the density of the conventional network structure is increased and the permeated water molecules are lowered than the SiO x and AlO x thin films. For example, as shown in JP-A-8-62590, an oxynitride containing a nitrogen atom (for example, SiO x N y ) has been proposed. By this proposal, the barrier property is remarkably enhanced, and the water vapor transmission rate is increased to 0.2 to 0.6 gm −2 day −1 and the oxygen transmission rate is 0.1 to 0.4 ccm −2 day −1 . However, it still has an insufficient barrier property as a water vapor barrier layer of a display device.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to solve these problems and provide a transparent gas barrier thin film-coated film having a water vapor barrier higher than that of a conventional transparent gas barrier thin film and having transparency.
[0007]
As a result of investigations to solve these problems, the present invention has found the following. The permeation rate of oxygen and other gases strongly contributes to the density and size of defects (holes and cracks) of the thin film to be coated. That is, the denser the network structure of the film, the higher the gas barrier property. However, the water vapor transmission rate has not yet been clarified, but it is important not only to control the defects (or denseness) of the thin film, but also to increase the interaction between the thin film and water vapor (water molecules). I found out. Therefore, a dramatically high water vapor barrier property can be obtained by coating a metal oxide thin film containing a sulfur atom or phosphorus atom having a strong water vapor (water molecule) interaction as a composition.
[0008]
[Means for Solving the Problems]
That is, the invention according to claim 1 of the present invention is a polymer film in which a metal compound is coated on at least one surface, and the metal compound is a metal atom (M) made of either silicon (Si) or aluminum (Al 2). , Oxygen atom (O), and sulfur atom (S), and in the metal compound MO X S Y , the composition ratio X / Y is (1.2 to 1.7) / (0.3 to 0.00. 8) A transparent gas barrier thin film-coated film, which is characterized in that
[0010]
The invention according to claim 2 of the present invention is a polymer film in which a metal compound is coated on at least one side, and the metal compound is a metal atom (M) made of either indium (In) or silicon (Si ), It is composed of an oxygen atom (O) and a phosphorus atom (P), and in the metal compound MO X P Y , the composition ratio X / Y is (1.5 to 2.0) / (0.3 to 1.0 It is a transparent gas barrier thin film covering film characterized by these.
[0013]
According to a third aspect of the present invention, in the transparent gas barrier thin film-coated film according to the first or second aspect , the polymer film coated with the metal compound has a water vapor transmission rate of 0.1 gm −2 day. -1 or less, oxygen transmission rate is 0.05 ccm −2 day −1 or less, and light transmittance at a light wavelength of 550 nm is 85% or more, is there.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The polymer film substrate used in the present invention is a film having a high transparency and a thickness of 50 to 200 μm, such as unsaturated polyester (polyethylene terephthalate), polyolefin, polyimide, polyvinyl alcohol, and polyether sulfide. If there is, it does not deviate from the object of the present invention. Further, surface treatment or lamination may be performed on the polymer film substrate.
[0015]
Examples of the method for forming the metal compound include a vacuum deposition method, an ion plating method, a sputtering method, and a chemical vapor deposition method (CVD).
[0016]
For example, in the metal compound MO X S Y , the composition ratio X / Y between the oxygen atom O and the sulfur atom (S) is (1.2 to 1.7) / (0.3 to 0.8). It is desirable. When the ratio of the sulfur atom exceeds this range, light absorption into the thin film increases and the transparency decreases, and when it falls below this range, the water vapor barrier property decreases.
[0017]
Further, in the metal compound MO X P Y , the composition ratio X / Y between the oxygen atom (O) and the phosphorus atom (P) is (1.5 to 2.2) / (0.3 to 1.0). It is desirable that When the ratio of the phosphorus atom (P) exceeds this range, light absorption into the thin film increases and the transparency decreases, and below this range, the water vapor barrier property decreases.
[0018]
The thickness of the metal compound thin film is preferably 10 to 200 nm. If this thickness is above this range, cracks are likely to occur due to the compressive stress, which causes a decrease in water vapor barrier properties. Also, the thickness is not sufficient below this range.
[0019]
【Example】
Specific examples of the present invention will be described below.
<Example 1>
By reactive sputtering, on a polyester film, coated with a thin film of SiO X S Y, AlO X S Y , respectively.
Si, Al was used as a target, and a mixed gas of hydrogen sulfide and oxygen was used as a reaction gas. An unsaturated polyester film (thickness: 100 μm) was used as the substrate.
As a film forming method, after evacuating the inside of the vacuum chamber to 1 × 10 −4 Pa, argon gas is introduced to 2 × 10 −1 Pa, then oxygen gas is introduced to 3 × 10 −1 Pa, Further, hydrogen sulfide gas was introduced until the total pressure reached 5 × 10 −1 Pa, and thin films of SiO x S y and AlO x S y were respectively coated on the base material by sputtering of a metal target.
[0020]
<Example 2>
A thin film of SiO x P y and InO x p y was coated on the polyester film by vacuum deposition.
Si and In were used as the vapor deposition material, evaporated by an electron beam, and phosphorus pentoxide (P 2 O 5 ) was evaporated by resistance heating to form a film. An unsaturated polyester film (thickness: 100 μm) was used as the substrate.
As a film forming method, after evacuating the inside of the vacuum chamber to 1 × 10 −4 Pa, the metal material is evaporated to 5 × 10 −2 Pa by an electron beam, and at the same time, phosphorus pentoxide is 7 × evaporated to 10 -3 Pa, on the base material, coated with a thin film of SiO X P Y, InO X P Y respectively.
[0021]
<Comparative Example 1>
In Example 1 described above, Al was used as the target, oxygen gas was introduced up to 3 × 10 −1 Pa, and hydrogen sulfide gas was introduced until the total pressure reached 3.5 × 10 −1 Pa. In the same manner as in Example 1, thin films of SiO X S Y and AlO X S Y were coated on the substrate.
[0022]
<Comparative example 2>
In Example 2 above, Si was used as the evaporation material, the metal material was evaporated to 5 × 10 −2 Pa, and at the same time, phosphorus pentoxide was evaporated to 9 × 10 −3 Pa by resistance heating. , the same procedure as in example 2, on the base material, coated with a thin film of SiO X P Y, InO X P Y respectively.
[0023]
<Measurement and results>
The water vapor transmission rate of each sample obtained from Example 1, Example 2 and Comparative Example 1 and Comparative Example 2 was measured using a water vapor transmission rate measuring device (manufactured by Modern Control: PERMATRAN), with a humidity of 90% RH, Measurement was performed in an atmosphere at a temperature of 40 ° C. In addition, the oxygen transmission rate of each sample was measured in an atmosphere of 0% humidity and 40 ° C. using an oxygen transmission rate measurement device (manufactured by Modern Control Co., Ltd .: OXTRAN).
The light transmittance of each sample was measured with a spectrophotometer. The composition ratio X / Y (composition ratio X: Y) in the metal compound was measured with an X-ray photoelectron spectrometer (manufactured by Shimadzu Corporation). The measurement results are shown in Table 1.
[0024]
[Table 1]
The WVTR, OTR, and T% described in the first row in Table 1 are the water vapor transmission rate (unit: gm -2 day -1 ), oxygen transmission rate (unit: ccm -2 day -1 ), and light transmittance ( (Unit%, light wavelength 550 nm). The unit of film thickness is nm.
[0026]
【The invention's effect】
The transparent gas barrier thin film-covered film of the present invention has an unprecedented high water vapor barrier property and a highly transparent gas barrier thin film-coated film by containing a sulfur atom or phosphorus atom in a metal oxide.
Claims (3)
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| JP2002061483A JP4106931B2 (en) | 2002-03-07 | 2002-03-07 | Transparent gas barrier thin film coating film |
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| JP5732363B2 (en) * | 2011-09-30 | 2015-06-10 | 株式会社クラレ | Composite structure, packaging material and molded product using the same, and method for producing composite structure |
| WO2013183093A1 (en) * | 2012-06-04 | 2013-12-12 | パナソニック株式会社 | Organic el element, method for producing same, organic el panel, organic el light emitting device, and organic el display device |
| US10273379B2 (en) | 2013-02-08 | 2019-04-30 | Kuraray Co., Ltd. | Multilayer structure and method for producing same |
| JP5873957B1 (en) | 2014-03-18 | 2016-03-01 | 株式会社クラレ | Electronic devices |
| WO2016002222A1 (en) | 2014-07-02 | 2016-01-07 | 株式会社クラレ | Multilayer structure and method for manufacturing same, packaging material and product in which same is used, and electronic device |
| JP6533525B2 (en) | 2014-08-13 | 2019-06-19 | 株式会社クラレ | MULTILAYER STRUCTURE, PACKAGING MATERIAL COMPRISING THE SAME, AND METHOD FOR MANUFACTURING THE MULTILAYER STRUCTURE |
| CN106573442A (en) | 2014-08-13 | 2017-04-19 | 株式会社可乐丽 | Antistatic sheet, and packaging material and electronic device including same |
| TWI687313B (en) | 2014-12-24 | 2020-03-11 | 日商可樂麗股份有限公司 | Multi-layer structure and packaging materials using the same |
| TWI687322B (en) | 2014-12-24 | 2020-03-11 | 日商可樂麗股份有限公司 | Electronic device and its manufacturing method |
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