JP2008238541A - Gas-barrier film with transparent conductive film and its manufacturing method - Google Patents
Gas-barrier film with transparent conductive film and its manufacturing method Download PDFInfo
- Publication number
- JP2008238541A JP2008238541A JP2007081331A JP2007081331A JP2008238541A JP 2008238541 A JP2008238541 A JP 2008238541A JP 2007081331 A JP2007081331 A JP 2007081331A JP 2007081331 A JP2007081331 A JP 2007081331A JP 2008238541 A JP2008238541 A JP 2008238541A
- Authority
- JP
- Japan
- Prior art keywords
- film
- transparent conductive
- layer
- gas barrier
- organic layer
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 230000004888 barrier function Effects 0.000 claims abstract description 103
- 239000010410 layer Substances 0.000 claims abstract description 74
- 239000012044 organic layer Substances 0.000 claims abstract description 55
- 239000002985 plastic film Substances 0.000 claims abstract description 23
- 229920003023 plastic Polymers 0.000 claims abstract description 20
- 238000010030 laminating Methods 0.000 claims abstract description 8
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 6
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 18
- 238000007740 vapor deposition Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 6
- 230000035699 permeability Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 7
- 239000010408 film Substances 0.000 description 131
- 239000007789 gas Substances 0.000 description 49
- 239000000178 monomer Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000203 mixture Substances 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 11
- 229910044991 metal oxide Inorganic materials 0.000 description 10
- 150000004706 metal oxides Chemical class 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910052814 silicon oxide Inorganic materials 0.000 description 8
- 238000004804 winding Methods 0.000 description 8
- 238000005401 electroluminescence Methods 0.000 description 7
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- -1 polyethylene terephthalate Polymers 0.000 description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 5
- 229910001887 tin oxide Inorganic materials 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000001227 electron beam curing Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920006290 polyethylene naphthalate film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QCTJRYGLPAFRMS-UHFFFAOYSA-N prop-2-enoic acid;1,3,5-triazine-2,4,6-triamine Chemical compound OC(=O)C=C.NC1=NC(N)=NC(N)=N1 QCTJRYGLPAFRMS-UHFFFAOYSA-N 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Abstract
Description
本発明は有機エレクトロルミネッセンス（ＥＬ）等のエレクトロニクス素子に用いられるガスバリア性および耐薬品性を付与した透明導電膜付ガスバリアフィルムおよびその製造方法に関するものである。 The present invention relates to a gas barrier film with a transparent conductive film imparted with a gas barrier property and chemical resistance used for an electronic device such as organic electroluminescence (EL) and a method for producing the same.
自発光体である有機ＥＬ素子は、低電圧、且つ低消費電力である、応答速度が速い、視野角が広い、高輝度であるといった多くの利点を持つことから、ブラウン管や液晶ディスプレイに変わるフラットディスプレイパネルとして注目されている。有機ＥＬ表示装置は、一般に陽極、有機発光層、陰極を積層し、有機ＥＬ素子が形成され、両電極間に電圧を印加することにより有機発光層で発光が生じるものである。 Organic EL elements, which are self-luminous elements, have many advantages such as low voltage and low power consumption, fast response speed, wide viewing angle, and high brightness. It is attracting attention as a display panel. In general, an organic EL display device includes an anode, an organic light emitting layer, and a cathode laminated to form an organic EL element, and light is emitted from the organic light emitting layer by applying a voltage between both electrodes.
近年、薄型、且つフラットなディスプレイに加え、折り曲げることが可能なフレキシブルディスプレイに注目が集まっているが、フレキシブルディスプレイを実現させるためには、透明導電層を積層する基板をガラス基板から透明プラスチックフィルム基板へ置き換えることが必須である。しかしながら、透明プラスチックフィルムは酸素、水蒸気等のガスを遮断する能力が大きく欠けており、これが有機ＥＬ素子の劣化の原因となっている。有機ＥＬ素子の長寿命化のためには、透明プラスチックフィルムへのガスバリア性の付与が必要不可欠であり、その方法の一つとして、透明プラスチックフィルム上に酸化珪素や酸化アルミニウム等の金属酸化物層を形成させたガスバリア性フィルム（例えば、特許文献１参照。）が用いられている。 In recent years, attention has been focused on flexible displays that can be bent in addition to thin and flat displays. In order to realize flexible displays, a substrate on which a transparent conductive layer is laminated is changed from a glass substrate to a transparent plastic film substrate. It is essential to replace However, the transparent plastic film is largely lacking in the ability to block gas such as oxygen and water vapor, which causes deterioration of the organic EL element. In order to extend the lifetime of organic EL elements, it is indispensable to provide a gas barrier property to a transparent plastic film. As one of the methods, a metal oxide layer such as silicon oxide or aluminum oxide is formed on the transparent plastic film. A gas barrier film (see, for example, Patent Document 1) in which is formed is used.
表示素子を作製するにあたりフィルムに求められる要求物性として、バリア性だけでなく、耐溶剤性、耐薬品性、擦れ等から金属酸化物層を保護する機能も必要になってくる。このような要求に応える方法の一つとして、金属酸化物層上に有機層を設ける検討がなされている（例えば、特許文献２参照。）。例えば、巻き取り式の成膜装置で成膜を行った場合に問題となるフィルム同士のこすれによるバリアの劣化を抑える検討がなされている。 As a required physical property required for a film for producing a display element, not only a barrier property but also a function of protecting a metal oxide layer from solvent resistance, chemical resistance, rubbing and the like is required. As one of methods for meeting such demands, studies have been made to provide an organic layer on a metal oxide layer (see, for example, Patent Document 2). For example, studies have been made to suppress the deterioration of the barrier due to the rubbing between films, which is a problem when film formation is performed with a winding film forming apparatus.
更に、透明導電膜付ガスバリアフィルムとするには、透明導電層を形成しなければならないが、この透明導電層を形成する際のプラズマダメージやストレス、透明導電層のパターン化の際に用いる薬品、例えば、レジスト現像工程やレジスト剥離工程で用いられるアルカリ水溶液から金属酸化物層を保護する必要があり、この際にも有機層が有効であると考えられている。 Furthermore, to make a gas barrier film with a transparent conductive film, a transparent conductive layer must be formed, but plasma damage and stress when forming this transparent conductive layer, chemicals used for patterning the transparent conductive layer, For example, it is necessary to protect a metal oxide layer from an alkaline aqueous solution used in a resist development process or a resist stripping process, and an organic layer is considered to be effective also in this case.
このようにバリア層である金属酸化物層と透明導電層との間に有機層を設けることにより、高いバリア性と耐薬品性をフィルムに付与することができる。 Thus, by providing an organic layer between the metal oxide layer, which is a barrier layer, and the transparent conductive layer, high barrier properties and chemical resistance can be imparted to the film.
以下に先行技術文献を示す。
しかしながら、バリア層と透明導電層との間に有機層を設けたフィルムの場合、バリア層と有機層との密着強度が透明導電層の応力より弱いとクラックが生じ、外観不良になるという問題が生じており、使用可能な透明性を維持することが難しい。 However, in the case of a film in which an organic layer is provided between the barrier layer and the transparent conductive layer, there is a problem that if the adhesion strength between the barrier layer and the organic layer is weaker than the stress of the transparent conductive layer, a crack occurs and the appearance is poor. Has occurred and it is difficult to maintain usable transparency.
本発明は、このような従来技術の問題点を解決しようとするものであり、透明導電層の応力以上の密着強度をバリア層と有機層との間に付与することにより優れた透明性を有し、バリア性並びに耐薬品性に優れた透明導電膜付ガスバリアフィルムおよびその製造方法を提供することを目的とする。 The present invention is intended to solve such problems of the prior art, and has excellent transparency by imparting adhesion strength greater than the stress of the transparent conductive layer between the barrier layer and the organic layer. And it aims at providing the gas barrier film with a transparent conductive film excellent in barrier property and chemical-resistance, and its manufacturing method.
本発明は、上記の課題を解決するために成されたものであり、本発明の請求項１に係る発明は、透明プラスチックフィルム（１）の少なくとも、一方の面に無機化合物からなるバリア層（２）、有機層（３）、透明導電層（４）を順次積層した透明導電膜付ガスバリアフィルムにおいて、前記透明導電層（４）を積層する前のバリア層（２）と有機層（３）との密着強度が２Ｎ／１５ｍｍ以上であることを特徴とする透明導電膜付ガスバリアフィルムである。 The present invention has been made to solve the above-mentioned problems, and the invention according to claim 1 of the present invention is a barrier layer comprising an inorganic compound on at least one surface of a transparent plastic film (1). 2) In the gas barrier film with a transparent conductive film in which the organic layer (3) and the transparent conductive layer (4) are sequentially stacked, the barrier layer (2) and the organic layer (3) before the transparent conductive layer (4) is stacked The gas barrier film with a transparent conductive film is characterized in that the adhesion strength with the transparent conductive film is 2 N / 15 mm or more.
本発明の請求項２に係る発明は、請求項１記載の透明導電膜付ガスバリアフィルムにおいて、前記有機層（３）の膜厚が０．０５〜５．０μｍの範囲内であることを特徴とする透明導電膜付ガスバリアフィルムである。 The invention according to claim 2 of the present invention is the gas barrier film with a transparent conductive film according to claim 1, wherein the thickness of the organic layer (3) is in the range of 0.05 to 5.0 μm. It is a gas barrier film with a transparent conductive film.
本発明の請求項３に係る発明は、請求項１又は２記載の透明導電膜付ガスバリアフィルムにおいて、前記透明導電層（４）を積層する前の透明プラスチックフィルム（１）と、バリア層（２）と、有機層（３）とを順次積層した積層体の水蒸気透過率が０．１ｇ／ｍ2／ｄａｙ（４０℃、９０％ＲＨ）以下であることを特徴とする請求項１又は２記載の透明導電膜付ガスバリアフィルムである。 The invention according to claim 3 of the present invention is the gas barrier film with transparent conductive film according to claim 1 or 2, wherein the transparent plastic film (1) before the transparent conductive layer (4) is laminated, and the barrier layer (2 ) And an organic layer (3) are sequentially laminated, the water vapor transmission rate is 0.1 g / m 2 / day (40 ° C., 90% RH) or less. It is a gas barrier film with a transparent conductive film.
本発明の請求項４に係る発明は、請求項１乃至３のいずれか１項記載の透明導電膜付ガスバリアフィルムの製造方法であって、前記バリア層（２）および前記有機層（３）を成膜する工程が、真空雰囲気下において連続して行われることを特徴とする透明導電膜付ガスバリアフィルムの製造方法である。 Invention of Claim 4 of this invention is a manufacturing method of the gas barrier film with a transparent conductive film of any one of Claims 1 thru | or 3, Comprising: The said barrier layer (2) and the said organic layer (3) are made. It is a manufacturing method of the gas barrier film with a transparent conductive film characterized by performing the film-forming process continuously in a vacuum atmosphere.
本発明の請求項５に係る発明は、請求項４記載の透明導電膜付ガスバリアフィルムの製造方法において、前記有機層（３）の積層方法がフラッシュ蒸着であることを特徴とする透明導電膜付ガスバリアフィルムの製造方法である。 The invention according to claim 5 of the present invention is the method for producing a gas barrier film with a transparent conductive film according to claim 4, wherein the method for laminating the organic layer (3) is flash vapor deposition. It is a manufacturing method of a gas barrier film.
本発明に係る透明導電膜付ガスバリアフィルムは、透明プラスチックフィルムの少なくとも、一方の面に無機化合物からなるバリア層、有機層、透明導電層を順次積層した透明導電膜付ガスバリアフィルムにおいて、前記透明導電層を積層する前のバリア層と有機層との密着強度が２Ｎ／１５ｍｍ以上であることにより、優れた透明性と高いバリア性を有すると共に、耐薬品性にも優れた透明導電膜付ガスバリアフィルムが得られる。 The gas barrier film with a transparent conductive film according to the present invention is the gas barrier film with a transparent conductive film in which a barrier layer made of an inorganic compound, an organic layer, and a transparent conductive layer are sequentially laminated on at least one surface of the transparent plastic film. Gas barrier film with a transparent conductive film that has excellent transparency and high barrier properties as well as excellent chemical resistance due to the adhesion strength between the barrier layer and the organic layer before laminating the layers being 2 N / 15 mm or more Is obtained.
本発明の実施の形態を図１〜図２に基づいて詳細に説明する。 Embodiments of the present invention will be described in detail with reference to FIGS.
図１は本発明に係る透明導電膜付ガスバリアフィルムの層構成の１実施例を示す側断面図であり、図２は本発明に係る透明導電膜付ガスバリアフィルムの製造に使用するプラズマＣＶＤ装置並びにフラッシュ蒸着装置の１実施例を示す説明図である。 FIG. 1 is a side sectional view showing one embodiment of a layer structure of a gas barrier film with a transparent conductive film according to the present invention, and FIG. 2 shows a plasma CVD apparatus used for manufacturing a gas barrier film with a transparent conductive film according to the present invention, and It is explanatory drawing which shows one Example of a flash vapor deposition apparatus.
本発明に係る透明導電膜付ガスバリアフィルムは、図１に示すように、透明プラスチックフィルム（１）の少なくとも、一方の面に無機化合物からなるバリア層（２）、有機層（３）、透明導電層（４）を順次積層した透明導電膜付ガスバリアフィルムにおいて、前
記透明導電層（４）を積層する前のバリア層（２）と有機層（３）との密着強度が２Ｎ／１５ｍｍ以上であることを特徴とする透明導電膜付ガスバリアフィルムである。
As shown in FIG. 1, the gas barrier film with a transparent conductive film according to the present invention has a barrier layer (2), an organic layer (3), and a transparent conductive film made of an inorganic compound on at least one surface of the transparent plastic film (1). In the gas barrier film with a transparent conductive film in which the layers (4) are sequentially laminated, the adhesion strength between the barrier layer (2) and the organic layer (3) before the transparent conductive layer (4) is laminated is 2 N / 15 mm or more. This is a gas barrier film with a transparent conductive film.
前記透明プラスチックフィルム（１）としては、例えば、ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリエチレンナフタレートフィルム、ポリカーボネイトフィルム、ポリアリレートフィルム、ポリエーテルスルホンフィルム、ポリスルフォンフィルム、アモルファスポリオレフィンフィルムなどが挙げられる。また、該透明プラスチックフィルムの厚さは任意であるが、一般的には数十μｍから数百μｍである。 Examples of the transparent plastic film (1) include a polyethylene terephthalate film, a polybutylene terephthalate film, a polyethylene naphthalate film, a polycarbonate film, a polyarylate film, a polyethersulfone film, a polysulfone film, and an amorphous polyolefin film. Further, the thickness of the transparent plastic film is arbitrary, but is generally several tens μm to several hundreds μm.
前記透明プラスチックフィルム（１）上に無機化合物のバリア層（２）としての金属酸化物からなる金属酸化物層を積層する方法としては、種々あり、スパッタリング法、イオンプレーティング法、真空蒸着法、プラズマＣＶＤ法のいずれかによって形成することができる。成膜中の雰囲気温度を考えると、熱に弱いプラスチックフィルムを温度コントロールするには、最も低温で成膜が可能なプラズマＣＶＤ法が好ましいと考えられる。プラズマ発生法としては直流（ＤＣ）プラズマ、低周波プラズマ、高周波（ＲＦ）プラズマ、パルス波プラズマ、３極構造プラズマ、マイクロ波プラズマ、ダウンストリームプラズマ、カラムナープラズマ、プラズマアシステッドエピタキシー等の低温プラズマ発生装置が用いられる。 There are various methods for laminating a metal oxide layer composed of a metal oxide as a barrier layer (2) of an inorganic compound on the transparent plastic film (1), including sputtering, ion plating, vacuum deposition, It can be formed by any of the plasma CVD methods. Considering the atmospheric temperature during film formation, it is considered that a plasma CVD method capable of forming a film at the lowest temperature is preferable to control the temperature of a plastic film that is vulnerable to heat. Plasma generation methods include low temperature plasma generation such as direct current (DC) plasma, low frequency plasma, high frequency (RF) plasma, pulse wave plasma, tripolar structure plasma, microwave plasma, downstream plasma, columnar plasma, plasma assisted epitaxy, etc. A device is used.
また、透明プラスチックフィルム（１）の特徴を活かした巻き取り式による連続蒸着を行うことができる、巻き取り式の真空成膜装置を用いることが好ましい。 Moreover, it is preferable to use a winding-type vacuum film-forming apparatus which can perform continuous vapor deposition by a winding method taking advantage of the characteristics of the transparent plastic film (1).
前記バリア層（２）である金属酸化物層は、酸化珪素、酸化アルミニウム、酸化マグネシウムあるいはそれらの混合物などの金属酸化物の蒸着膜からなり、透明性を有し、且つ酸素、水蒸気等のガスバリア性を有するものであれば良い。バリア性、密着性の観点から、酸化珪素膜が好適と考えられる。 The metal oxide layer as the barrier layer (2) is made of a vapor-deposited film of a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide or a mixture thereof, has transparency, and has a gas barrier such as oxygen and water vapor. It is sufficient if it has properties. From the viewpoint of barrier properties and adhesion, a silicon oxide film is considered preferable.
前記プラズマＣＶＤ法にて形成される酸化珪素膜は、有機珪素化合物と酸素ガスを加えたもの、場合によってはそれに不活性ガスを加えたものを原料として用いて成膜される。前記有機珪素化合物としては、テトラエトキシシラン（ＴＥＯＳ）、テトラメトキシシラン（ＴＭＯＳ）、テトラメチルシラン（ＴＭＳ）、ヘキサメチルジシラン、ヘキサメチルジシロキサン（ＨＭＤＳＯ）、テトラメチルジシロキサン、メチルトリメトキシシラン、ヘキサメチルジシラザン、テトラメチルジシラザン等の比較的低分子量の有機珪素化合物を選択し、これらのシラン化合物の一つまたは複数を選択してもよい。これらの有機珪素化合物を気化させ、酸素ガスと混合し、上記真空成膜装置の電極へと導入し、温調入りドラムと電極との間にプラズマを発生させ、プラズマＣＶＤ法にて酸化珪素膜をプラスチックフィルム（１）上に成膜する。その中でも特に、酸素と珪素の構成原子数の比率で、１対１から１対２の範囲である酸化珪素が望ましい。 The silicon oxide film formed by the plasma CVD method is formed using, as a raw material, an organic silicon compound and oxygen gas added, and in some cases, an inert gas added thereto. Examples of the organosilicon compound include tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), tetramethylsilane (TMS), hexamethyldisilane, hexamethyldisiloxane (HMDSO), tetramethyldisiloxane, methyltrimethoxysilane, A relatively low molecular weight organosilicon compound such as hexamethyldisilazane or tetramethyldisilazane may be selected, and one or more of these silane compounds may be selected. These organosilicon compounds are vaporized, mixed with oxygen gas, introduced into the electrode of the vacuum film forming apparatus, plasma is generated between the temperature-controlled drum and the electrode, and a silicon oxide film is formed by plasma CVD. Is formed on the plastic film (1). Among these, silicon oxide having a ratio of the number of constituent atoms of oxygen and silicon in the range of 1: 1 to 1: 2 is particularly desirable.
前記バリア層（２）である酸化珪素膜の膜厚は、特に限定されるものではないが、あまり薄すぎるとバリア性の発現が難しいため、５ｎｍ以上は必要であると考えられる。これ以上の膜厚は、透明性が損なわれない範囲において、必要なバリア性能に合わせて膜厚をコントロールすることが可能である。しかし、ある程度の膜厚となると十分なバリア性に達し、柔軟性、経済性の面で問題が生じるため、１０〜２００ｎｍの範囲内が好ましい。 The film thickness of the silicon oxide film as the barrier layer (2) is not particularly limited, but if it is too thin, it is difficult to develop barrier properties, and it is considered that 5 nm or more is necessary. A film thickness greater than this can be controlled in accordance with the required barrier performance as long as the transparency is not impaired. However, when the film thickness reaches a certain level, sufficient barrier properties are reached, and problems arise in terms of flexibility and economy.
ガスバリア性をより一層向上させるため、さらには耐溶剤性、耐薬品性、耐摩擦性等を向上させるために設ける有機層（３）も、バリア層（２）の積層と同一の巻き取り式の真空成膜装置内で連続して成膜されることが望ましいため、積層方法としては真空中でポリマー層を成膜することが可能な有機蒸着や、フラッシュ蒸着、有機材料のスパッタリング
などが挙げられる。その中でも、成膜レート、安定性、モノマーの自由度から、原材料にアクリル系のモノマー若しくは該モノマーとオリゴマーの混合物を用いたフラッシュ蒸着が望ましいと考えられる。
The organic layer (3) provided for further improving the gas barrier property and further improving the solvent resistance, chemical resistance, friction resistance, etc. is also of the same winding type as that of the barrier layer (2). Since it is desirable to form films continuously in a vacuum film forming apparatus, examples of the laminating method include organic vapor deposition that can form a polymer layer in vacuum, flash vapor deposition, and sputtering of organic materials. . Among them, flash deposition using an acrylic monomer or a mixture of the monomer and oligomer as a raw material is considered desirable from the viewpoint of film formation rate, stability, and freedom of monomer.
前記フラッシュ蒸着にて形成される有機層（３）は、アクリル系のモノマー若しくは該モノマーとオリゴマーの混合物を原材料として用いて成膜される。アクリル系のモノマー及びオリゴマーとしては、モノアクリレート、ジアクリレート、トリアクリレートの少なくとも１つを含有していることが好ましく、また、ポリエステルアクリレート、ポリエーテルアクリレート、アクリルアクリレート、ウレタンアクリレート、エポキシアクリレート、シリコーンアクリレート、ポリアセタールアクリレート、ポリブタジエン系アクリレート、メラミンアクリレート等の重合性の高いモノマーあるいはオリゴマーを適宜選定して用いることもできる。 The organic layer (3) formed by the flash vapor deposition is formed using an acrylic monomer or a mixture of the monomer and oligomer as a raw material. The acrylic monomer and oligomer preferably contain at least one of monoacrylate, diacrylate, and triacrylate, and polyester acrylate, polyether acrylate, acrylic acrylate, urethane acrylate, epoxy acrylate, silicone acrylate Highly polymerizable monomers or oligomers such as polyacetal acrylate, polybutadiene acrylate, and melamine acrylate can be appropriately selected and used.
これらのアクリル系モノマー若しくは該モノマーとオリゴマーの混合物を、真空成膜装置内の高温の蒸発源中にノズル等から滴下し、気化させて、透明プラスチックフィルム（１）上に未硬化の被膜層を形成させ、電子線照射もしくは紫外線照射により硬化させる。 These acrylic monomers or a mixture of the monomers and oligomers are dropped from a nozzle or the like into a high-temperature evaporation source in a vacuum film forming apparatus and evaporated to form an uncured coating layer on the transparent plastic film (1). It is formed and cured by electron beam irradiation or ultraviolet irradiation.
前記電子線照射により硬化させる場合、被膜層の膜厚と電子線のエネルギー条件、加工速度および除電とのバランスが重要となる。過度のエネルギー供給は帯電を引き起こし、その結果として起こる放電により、ガスバリア性が損なわれる場合があるため、注意を要する。 In the case of curing by irradiation with the electron beam, the balance between the film thickness of the coating layer and the energy condition of the electron beam, the processing speed, and static elimination is important. Excessive energy supply causes electrification, and the resulting electric discharge may impair gas barrier properties, so care must be taken.
また、前記紫外線照射により硬化させる場合、アクリル系のモノマー若しくは該モノマーとオリゴマーの混合物に光重合開始剤を混合したものを用いる。具体的な光重合開始剤としては、ベンゾインエーテル類、ベンゾフェノール類、キサントン類、アセトフェノン誘導体が挙げられ、光重合開始剤をアクリル系のモノマー若しくは該モノマーとオリゴマーの混合物に対して０．０１〜１０重量％、好ましくは０．１〜０．２重量％の割合で混合して使用する。 Moreover, when making it harden | cure by the said ultraviolet irradiation, what mixed the photoinitiator into the acrylic monomer or the mixture of this monomer and an oligomer is used. Specific examples of the photopolymerization initiator include benzoin ethers, benzophenols, xanthones, and acetophenone derivatives. The photopolymerization initiator may be 0.01 to about 0.1 to an acrylic monomer or a mixture of the monomer and the oligomer. It is used by mixing at a ratio of 10% by weight, preferably 0.1 to 0.2% by weight.
前記有機層（３）の厚さは、０．０５〜５．０μｍの範囲内であることが好ましい。厚さが０．０５μｍ未満であるとバリア性の向上は難しく、また、５．０μｍを超えるとバリア層との密着が悪くなるためである。 The thickness of the organic layer (3) is preferably in the range of 0.05 to 5.0 μm. When the thickness is less than 0.05 μm, it is difficult to improve the barrier property, and when it exceeds 5.0 μm, the adhesion with the barrier layer is deteriorated.
更に、フラッシュ蒸着にて有機層（３）を形成する場合には、原材料であるアクリル系のモノマー若しくは該モノマーとオリゴマーの混合物を真空下において高温蒸発源の中に少量ずつ落下させ、蒸発源の直上に瞬間的に蒸発させる必要があり、その場合、アクリル系のモノマー若しくは該モノマーとオリゴマーの混合物の粘度が高すぎると蒸発源の中に少量ずつ一定速度で落下させることが困難となるため、その粘度は２００ｍＰａ・ｓ／２５℃以下、より好ましくは１００ｍＰａ・ｓ／２５℃以下とすることが望ましい。 Further, when the organic layer (3) is formed by flash evaporation, the acrylic monomer as a raw material or a mixture of the monomer and oligomer is dropped little by little into a high-temperature evaporation source under vacuum, and the evaporation source It is necessary to evaporate instantaneously immediately above, and in that case, if the viscosity of the acrylic monomer or the mixture of the monomer and oligomer is too high, it becomes difficult to drop at a constant rate into the evaporation source little by little. The viscosity is desirably 200 mPa · s / 25 ° C. or lower, more preferably 100 mPa · s / 25 ° C. or lower.
次に、前記透明導電層（４）は膜厚の制御が可能であればいかなる成膜方法でも良いが、薄膜の成膜には乾式法が優れている。これには真空蒸着法、スパッタリング等の物理的気相析出法やＣＶＤ法のような化学的気相析出法を用いることができる。 Next, the transparent conductive layer (4) may be formed by any film forming method as long as the film thickness can be controlled, but a dry method is excellent for forming a thin film. For this, a vacuum vapor deposition method, a physical vapor deposition method such as sputtering, or a chemical vapor deposition method such as a CVD method can be used.
該透明導電層（４）は、酸化インジウム、酸化亜鉛、酸化スズのいずれか、または、それらの２種類もしくは３種類の混合酸化物、更には、その他の添加物が加えられた物等が挙げられるが、目的・用途により種々の材料が使用でき、特に限定されるものではない。それら中でも操作性、コスト、エッチング性などを総合的に考慮すると、酸化インジウムスズ（ＩＴＯ）が望ましい。 Examples of the transparent conductive layer (4) include indium oxide, zinc oxide and tin oxide, or two or three kinds of mixed oxides thereof, and those to which other additives are added. However, various materials can be used depending on the purpose and application, and are not particularly limited. Among these, in consideration of operability, cost, etching property, etc., indium tin oxide (ITO) is desirable.
ＩＴＯを用いる場合、ＩＴＯにドープされる酸化スズの含有比はデバイスに求められる仕様に応じて、任意の割合を選択する。例えば、機械強度を高める目的で薄膜を結晶化させるためには、酸化スズの含有比は１０重量％未満が望ましく、薄膜をアモルファス化し、フレキシブル性を持たせるためには、酸化スズの含有比は１０重量％以上が望ましい。また、薄膜に低抵抗が求められる場合は、酸化スズの含有比は３重量％〜２０重量％の範囲内が望ましい。 In the case of using ITO, the content ratio of tin oxide doped in ITO is arbitrarily selected according to the specifications required for the device. For example, in order to crystallize a thin film for the purpose of increasing mechanical strength, the content ratio of tin oxide is desirably less than 10% by weight. To make the thin film amorphous and flexible, the content ratio of tin oxide is 10% by weight or more is desirable. Moreover, when low resistance is calculated | required by a thin film, the content ratio of a tin oxide is desirable in the range of 3 to 20 weight%.
本発明の透明導電膜付ガスバリアフィルムは、透明プラスチックフィルム（１）の少なくとも片面の最表面に、バリア層（２）、有機層（３）、透明導電層（４）を順次積層することにより得ることができる。 The gas barrier film with a transparent conductive film of the present invention is obtained by sequentially laminating a barrier layer (2), an organic layer (3), and a transparent conductive layer (4) on the outermost surface of at least one surface of the transparent plastic film (1). be able to.
次に、本発明の透明導電膜付ガスバリアフィルムのバリア層（２）ならびに有機層（３）を製造する巻き取り式真空成膜装置の例を示す。図２は、その説明図である。先ず、巻き取り式真空成膜装置（５）には、ウエブ状のプラスチックフィルムの巻出・巻取室（６）に、巻出ロール（７）と巻取ロール（８）を有しており、また、成膜室（９）には、成膜時のフィルム表面の温度をコントロールできる温調入りドラム（１０）、プロセスガスまたは原料ガスを導入するシャワーヘッド（１１）を持つプラズマＣＶＤ用の電極（１２）、アクリル供給ノズル（１３）、電子線硬化ユニット（１４）が配置され、その間を透明プラスチックフィルムが走行している。 Next, an example of a winding type vacuum film forming apparatus for producing the barrier layer (2) and the organic layer (3) of the gas barrier film with a transparent conductive film of the present invention will be shown. FIG. 2 is an explanatory diagram thereof. First, the take-up vacuum film forming apparatus (5) has a take-up roll (7) and a take-up roll (8) in a web-like plastic film unwinding / winding chamber (6). In addition, the film formation chamber (9) has a temperature-controlled drum (10) that can control the temperature of the film surface during film formation, and a shower head (11) that introduces process gas or source gas for plasma CVD. An electrode (12), an acrylic supply nozzle (13), and an electron beam curing unit (14) are arranged, and a transparent plastic film runs between them.
以下に、本発明の透明導電膜付ガスバリアフィルムについて、具体的にいくつかの実施例を挙げて、さらに詳しく説明する。 Hereinafter, the gas barrier film with a transparent conductive film of the present invention will be described in more detail with specific examples.
＜実施例１＞
透明プラスチックフィルムとして、厚さ１００μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムを使用し、このＰＥＴフィルムの片面上に、図２に示した巻き取り式真空成膜装置に設置されたＣＶＤ電極を用い、金属酸化物層としてＨＭＤＳＯを用いて２０ｎｍの酸化珪素膜を成膜し、連続して、フラッシュ蒸着にて前記金属酸化物層上に、２−ヒドロキシ−３−フェノキシプロピルアクリレート／プロポキシ化ネオペンチルグリコールジアクリレート／エトキシ化トリメチロールプロパントリアクリレート＝６０／３０／１０（重量％）の配合比率の混合物からなる有機層を、膜厚が１μｍになるよう滴下速度を調整しながら積層した後、電子線を照射して有機層を硬化させた。
<Example 1>
As a transparent plastic film, a polyethylene terephthalate (PET) film having a thickness of 100 μm is used, and a metal electrode is formed on one side of the PET film by using a CVD electrode installed in the winding type vacuum film forming apparatus shown in FIG. A silicon oxide film having a thickness of 20 nm was formed using HMDSO as a physical layer, and continuously, 2-hydroxy-3-phenoxypropyl acrylate / propoxylated neopentyl glycol diacrylate was formed on the metal oxide layer by flash evaporation. / Ethoxylated trimethylolpropane triacrylate = 60/30/10 (wt%) organic layer composed of a mixture of layers with a drop rate adjusted so that the film thickness becomes 1 μm, and then irradiated with an electron beam The organic layer was cured.
続いて、スパッタリングにてＩＴＯ膜を１５０ｎｍ成膜し、目的とする実施例１の透明導電膜付ガスバリアフィルムを得た。 Subsequently, an ITO film having a thickness of 150 nm was formed by sputtering to obtain a target gas barrier film with a transparent conductive film of Example 1.
＜実施例２＞
実施例１において、有機層の成膜の膜厚を４μｍになるよう、混合物の滴下速度を調整しながら積層した以外は実施例１と同様にして、実施例２の透明導電膜付ガスバリアフィルムを得た。
<Example 2>
In Example 1, the gas barrier film with a transparent conductive film of Example 2 was prepared in the same manner as in Example 1 except that the organic layer was deposited while adjusting the dropping rate of the mixture so that the film thickness of the organic layer was 4 μm. Obtained.
＜比較例１＞
実施例１において、有機層の成膜を行わなかった以外は実施例１と同様にして、比較例１の透明導電膜付ガスバリアフィルムを得た。
<Comparative Example 1>
In Example 1, the gas barrier film with a transparent conductive film of the comparative example 1 was obtained like Example 1 except not having formed into an organic layer.
＜比較例２＞
実施例１において、有機層の成膜の膜厚を０．０３μｍになるよう、混合物の滴下速度を調整しながら積層した以外は実施例１と同様にして、比較例２の透明導電膜付ガスバリアフィルムを得た。
<Comparative example 2>
In Example 1, the gas barrier with a transparent conductive film of Comparative Example 2 was used in the same manner as in Example 1 except that the organic layer was deposited while adjusting the dropping rate of the mixture so that the film thickness of the organic layer was 0.03 μm. A film was obtained.
＜比較例３＞
実施例１において、有機層の成膜の膜厚を７μｍになるよう、混合物の滴下速度を調整しながら積層した以外は実施例１と同様にして、比較例３の透明導電膜付ガスバリアフィルムを得た。
<Comparative Example 3>
In Example 1, the gas barrier film with a transparent conductive film of Comparative Example 3 was prepared in the same manner as in Example 1 except that the organic layer was laminated while adjusting the dropping rate of the mixture so that the film thickness of the organic layer was 7 μm. Obtained.
＜比較例４＞
実施例１において、有機層の成膜をマイクログラビアコーティング法で行った以外は実施例１と同様にして、比較例４の透明導電膜付ガスバリアフィルムを得た。
<Comparative Example 4>
In Example 1, the gas barrier film with a transparent conductive film of the comparative example 4 was obtained like Example 1 except having formed the organic layer by the micro gravure coating method.
（評価）
実施例１〜２および比較例１〜４の本発明の透明導電膜付ガスバリアフィルムにおいて、バリア層と有機層との密着性を確認するため、フィルムを１５ｍｍ幅にスリットして試験片を作製し、その試験片の密着強度をテンシロン型万能試験機で測定した。その結果を表１に示す。
(Evaluation)
In the gas barrier films with a transparent conductive film of Examples 1 to 2 and Comparative Examples 1 to 4, in order to confirm the adhesion between the barrier layer and the organic layer, the film was slit to a width of 15 mm to prepare a test piece. The adhesion strength of the test piece was measured with a Tensilon type universal testing machine. The results are shown in Table 1.
実施例１〜２および比較例１〜４の透明導電膜付ガスバリアフィルムについて、外観確認を行い、また、水蒸気透過率をモダンコントロール社製（ＭＯＣＯＮ ＰＥＲＭＡＴＲＡＮ−Ｗ ３／３１）を用いて、４０℃−９０％ＲＨ雰囲気下で測定した。外観の評価基準については次の通りである。○：外観上欠陥はなく、透明であることを確認した。×：クラックが生じ、干渉縞が観察された。それらの結果を表１に示す。 About the gas barrier film with a transparent conductive film of Examples 1-2 and Comparative Examples 1-4, an external appearance confirmation is carried out, and water vapor permeability is 40 degreeC using the modern control company make (MOCON PERMATRAN-W 3/31). Measured in a −90% RH atmosphere. Appearance evaluation criteria are as follows. ○: It was confirmed that there was no defect in appearance and it was transparent. X: Cracks occurred and interference fringes were observed. The results are shown in Table 1.
（評価結果）
表１に示すように、実施例１および実施例２の本発明の透明導電膜付ガスバリアフィルムは、有機層膜厚が０．０５〜５．０μｍの範囲内で密着強度が２Ｎ／１５ｍｍ以上あり、透明導電層の応力以上の密着強度がバリア層−有機層間にあることによって、クラックが生じず外観は透明であった。また、比較例１の有機層が成膜されていない透明導電膜付ガスバリアフィルムと比べて、実施例１および実施例２の透明導電膜付バリアフィルムの水蒸気透過率は小さく、共に０．１ｇ／ｍ2／ｄａｙ以下であることから、有機層の成膜によるバリア性の向上が見られた。
(Evaluation results)
As shown in Table 1, the gas barrier film with a transparent conductive film of the present invention of Example 1 and Example 2 has an adhesion strength of 2 N / 15 mm or more within the range of the organic layer thickness of 0.05 to 5.0 μm. Since the adhesion strength higher than the stress of the transparent conductive layer is between the barrier layer and the organic layer, cracks did not occur and the appearance was transparent. Moreover, compared with the gas barrier film with a transparent conductive film in which the organic layer of Comparative Example 1 was not formed, the water vapor permeability of the barrier film with a transparent conductive film of Example 1 and Example 2 was small, both 0.1 g / Since it was m 2 / day or less, an improvement in barrier properties due to the formation of the organic layer was observed.
一方、有機層膜厚を０．０３μｍにした比較例２の透明導電膜付ガスバリアフィルムは、バリア層−有機層間の密着強度が２Ｎ／１５ｍｍ以上あり、外観も透明であったが、水蒸気透過率は、比較例１と同等で、バリア性の向上は見られなかった。また、有機層膜厚を７μｍにした比較例３の透明導電膜付ガスバリアフィルムは、有機層の膜厚が厚いことにより実施例１と比較して水蒸気透過率は低くなったが、バリア層−有機層間の密着強度が２Ｎ／１５ｍｍ未満であったために、透明導電層が応力に耐え切れず、クラックが生じ、干渉縞が観察され、外観は不透明となった。 On the other hand, the gas barrier film with a transparent conductive film of Comparative Example 2 having an organic layer thickness of 0.03 μm had an adhesion strength between the barrier layer and the organic layer of 2 N / 15 mm or more, and the appearance was also transparent. Was equivalent to Comparative Example 1, and no improvement in barrier properties was observed. In addition, the gas barrier film with a transparent conductive film of Comparative Example 3 having an organic layer thickness of 7 μm had a lower water vapor transmission rate than Example 1 due to the thick film thickness of the organic layer. Since the adhesion strength between the organic layers was less than 2 N / 15 mm, the transparent conductive layer could not withstand the stress, cracks occurred, interference fringes were observed, and the appearance became opaque.
有機層の成膜をマイクログラビアコーティング法で行った比較例４の透明導電膜付ガスバリアフィルムは、バリア層−有機層間の密着強度は２Ｎ／１５ｍｍ以上であったが、バリア層と有機層の成膜工程を分けて行っているため、バリア層表面がダメージを受け、水蒸気透過率は実施例１と比べ非常に大きくなったと推察される。 In the gas barrier film with a transparent conductive film of Comparative Example 4 in which the organic layer was formed by the microgravure coating method, the adhesion strength between the barrier layer and the organic layer was 2 N / 15 mm or more. Since the film process is performed separately, the surface of the barrier layer is damaged, and the water vapor transmission rate is estimated to be very large as compared with Example 1.
１・・・透明プラスチックフィルム
２・・・バリア層
３・・・有機層
４・・・透明導電層
５・・・巻き取り式真空成膜装置
６・・・巻き出し・巻取り室
７・・・巻き出しロール
８・・・巻き取りロール
９・・・成膜室
１０・・・温調入りドラム
１１・・・シャワーヘッド
１２・・・ＣＶＤ電極
１３・・・アクリル供給ノズル
１４・・・電子線硬化ユニット
DESCRIPTION OF SYMBOLS 1 ... Transparent plastic film 2 ... Barrier layer 3 ... Organic layer 4 ... Transparent conductive layer 5 ... Rewind-type vacuum film-forming
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007081331A JP2008238541A (en) | 2007-03-27 | 2007-03-27 | Gas-barrier film with transparent conductive film and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007081331A JP2008238541A (en) | 2007-03-27 | 2007-03-27 | Gas-barrier film with transparent conductive film and its manufacturing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2008238541A true JP2008238541A (en) | 2008-10-09 |
Family
ID=39910465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007081331A Pending JP2008238541A (en) | 2007-03-27 | 2007-03-27 | Gas-barrier film with transparent conductive film and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2008238541A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013062150A (en) * | 2011-09-13 | 2013-04-04 | Nitto Denko Corp | Organic electroluminescent device and method for manufacturing organic electroluminescent device |
| JP2016525234A (en) * | 2013-07-24 | 2016-08-22 | スリーエム イノベイティブ プロパティズ カンパニー | Adhesive barrier film structure |
-
2007
- 2007-03-27 JP JP2007081331A patent/JP2008238541A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013062150A (en) * | 2011-09-13 | 2013-04-04 | Nitto Denko Corp | Organic electroluminescent device and method for manufacturing organic electroluminescent device |
| JP2016525234A (en) * | 2013-07-24 | 2016-08-22 | スリーエム イノベイティブ プロパティズ カンパニー | Adhesive barrier film structure |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4383077B2 (en) | Gas barrier substrate | |
| JP5402818B2 (en) | Gas barrier film and method for producing gas barrier film | |
| JP5135726B2 (en) | Film with transparent conductive film and method for producing the same, substrate for display made of film with transparent conductive film, display and organic EL element | |
| JP5445179B2 (en) | Gas barrier film, method for producing gas barrier film, and organic electronic device | |
| US20140295109A1 (en) | Film with transparent electroconductive membrane and its use | |
| JP5540949B2 (en) | Gas barrier film, organic photoelectric conversion element, organic electroluminescence element | |
| JP2005289041A (en) | Gas barrier film which is prevented from curving | |
| JP2005096108A (en) | Antireflection gas barrier substrate | |
| JP4373270B2 (en) | Gas barrier film, and liquid crystal display element and EL display element formed using the same | |
| WO2014163062A1 (en) | Method for manufacturing gas barrier film, gas barrier film, and electronic device | |
| TW201209849A (en) | Zinc oxide-based conductive multilayer structure, process for producing same, and electronic device | |
| JP2005289052A (en) | Gas barrier laminated film, manufacturing method of it and image displaying element using the film | |
| US20130047889A1 (en) | Formed article, method for producing the same, electronic device member and electronic device | |
| JP6648752B2 (en) | Sealed structure | |
| TW463525B (en) | Organic electroluminescent device and the manufacturing method of the same | |
| JP2015103389A (en) | Organic el device | |
| TW201806773A (en) | Gas barrier film, organic electronic device, substrate for organic electroluminescent devices, and organic electroluminescent device | |
| JP4537093B2 (en) | SUBSTRATE FOR IMAGE DISPLAY ELEMENT AND ORGANIC ELECTROLUMINESCENCE ELEMENT | |
| JP2008238541A (en) | Gas-barrier film with transparent conductive film and its manufacturing method | |
| KR102287519B1 (en) | Electronic devices and organic electroluminescent devices | |
| JP2014141055A (en) | Gas barrier film | |
| JP2016097500A (en) | Gas barrier film, method for producing the same and base material for plasma chemical vapor deposition method | |
| JP4759971B2 (en) | Barrier film with transparent electrode | |
| TW201601914A (en) | Gas barrier film layered product and electronic component having the same | |
| JP2012228786A (en) | Gas barrier film, and method for manufacturing the same |