JP4314777B2 - Method for producing transparent conductive film laminate - Google Patents

Description

【０１４８】
表１より本発明の透明導電膜積層体は、透過率、抵抗率、炭素含有率、Ｉｎ／Ｓｎ、屈曲性、劣化試験の総てに優れていることが判る。
【０１４９】
実施例１０
実施例１においてプラズマ放電装置を図６に示したものを２つ用意し、基材を日本ゼオン社製ゼオノアＺＦ１６（厚さ１００μｍ）とした２０００ｍの長尺フィルムとし第一の放電装置でプライマー層を、第二の放電装置で透明導電層を形成し、透過率、比抵抗、耐久性、劣化試験を行った。
【０１５０】
比較例９
実施例１０において、比較例１でもちいたプライマー層をコーティングした後、一度巻き取り、ついで実施例１０で用いた透明導電層形成のためのプラズマ放電装置で透明導電層を作製し、透過率、比抵抗、屈曲性、劣化試験を行った。
【０１５１】
比較例１０
実施例１０において、比較例１でもちいたプライマー層をコーティングした後、一度巻き取り、真空槽、スパッタリングターゲット、気体導入系を有する巻き取り式マグネトロンスパッタリング装置を用いプライマー層上に錫ドープ酸化インジウム膜を作製した。装置内にフィルムを導入し、内部を４．０００×１０^-3Ｐａまで減圧した。尚、スパッタリングターゲットは酸化インジウム：酸化錫９５：５の組成のものを用いた。この後でフィルムの巻き返しを行い、脱ガス処理を行った。ついでアルゴンガスと酸素ガスとの混合ガスを（Ａｒ：Ｏ₂＝９８．８：１．２）を１×１０^-3Ｐａとなるまで導入し、メインロールの温度を室温、フィルムの繰り出し速度を０．１ｍ／ｍｉｎ、投入電力密度１Ｗ／ｃｍ²として製膜を行い、実施例１０と同様に評価を行った。
【０１５２】
実施例１０、比較例９、１０の評価結果を表２にまとめる。尚、実施例１０と比較して、比較例９での全製膜時間は３倍、比較例１０では５倍であった。尚、表２における、ＴＥＯＳ、ｘ、ｙ及びＡＰＧはそれぞれ表１の各々と同義である。
【０１５３】
【表２】

【０１５４】
表２より本発明の透明導電膜積層体は、透過率、抵抗率、炭素含有率、Ｉｎ／Ｓｎ、屈曲性、劣化試験の総てに優れていることが判る。
【０１５５】
実施例１１
プライマー層つきＰＥＴフィルムＡ１の作製
１７５μｍのポリエチレンテレフタレートフィルムを基材とし、プラズマ放電装置には、電極が平行平板型のものを用い、この電極間に上記ＰＥＴ基材を載置し、且つ、混合ガスを導入して薄膜形成を行った。
【０１５６】
尚、電極は、以下の物を用いた。２００ｍｍ×２００ｍｍ×２ｍｍのステンレス板に高密度、高密着性のアルミナ溶射膜を被覆し、その後、テトラメトキシシランを酢酸エチルで希釈した溶液を塗布乾燥後、紫外線照射により硬化させ封孔処理を行った。このようにして被覆した誘電体表面を研磨し、平滑にして、Ｒｍａｘ５μｍとなるように加工した。このように電極を作製し、アース（接地）した。
【０１５７】
一方、印加電極としては、中空の角型の純チタンパイプに対し、上記同様の誘電体を同条件にて被覆したものを複数作製し、対向する電極群とした。
【０１５８】
また、プラズマ発生に用いる使用電源は日本電子（株）製高周波電源ＪＲＦ−１００００にて周波数１５０ｋＨｚの電圧で且つ２Ｗ／ｃｍ²の電力を供給した。
【０１５９】
電極間に以下の組成の反応性ガスを流した。
不活性ガス：ヘリウム ９８．５体積％
反応性ガス１：酸素 ０．２５体積％
反応性ガス２：テトラエトキシシラン １．２５体積％
前記基材上に上記反応性ガス、反応条件により大気圧プラズマ処理を行い、プライマー層を形成した。上記方法により作製したプライマー層つきのＰＥＴフィルムををＡ１とする。
【０１６０】
プライマー層つきＰＥＴフィルムＡ２の作製
次に反応性ガスを以下の組成とし、上記方法と同様にしてＰＥＴ上にプライマー層を形成した。これをＡ２とする。
不活性ガス：ヘリウム ９７．７５体積％
反応性ガス１：酸素 ０．２５体積％
反応性ガス２：テトラエトキシシラン ２．００体積％
プライマー層つきＰＥＴフィルムＡ３の作製
反応性ガスを以下の組成とし、上記方法と同様にしてＰＥＴ上にプライマー層を形成した。これをＡ３とする。
不活性ガス：ヘリウム ９９．２５体積％
反応性ガス１：酸素 ０．２５体積％
反応性ガス２：テトラエトキシシラン ０．５０体積％
プライマー層つきＰＥＴフィルムＢの作製
容器外部が水冷された撹拌容器内にビニルトリメトキシシラン（信越化学社製、商品名ＫＢＭ１００３）１４８質量部を入れ、激しく撹拌を行いながら０．０１規定の塩酸水５４部を徐々に添加し、更に３時間ゆっくりと撹拌を行うことによりビニルトリメトキシシランの加水分解液を得た。ついでトリメチロールプロパントリアクリレート（東亞合成化学社製、商品名アロニックスＭ−３０９）５０質量部、前記ビニルトリメトキシシランの加水分解液を１００質量部、未加水分解のビニルトリメトキシシラン１０質量部、光開始剤２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン（メルク社製、商品名ダロキュアー１１７３）８質量部およびレベリング剤としてシリコンオイル（東レ・ダウコーニングシリコン社製、ＳＨ２８ＰＡ）０．０２質量部を混合して塗液とした。この塗液を基材上にバーコーターを用いてコーティングし、６０℃で１分間加熱して塗膜中の残留溶剤を揮発除去した後、１６０Ｗ／ｃｍの高圧水銀灯を用いて、積算光量８００ｍＪ／ｃｍ²の条件で紫外線を照射して塗膜の硬化を行いプライマー層を得た。
【０１６１】
プライマー層つきＰＥＴフィルムＣの作製
水７２０質量部、２−プロパノール１０８０質量部の混合溶媒に、酢酸８８質量部を加えた後、２−（３，４−エポキシシクロヘキシル）エチルトリエトキシシラン７２５質量部と３−アミノプロピルトリメトキシシラン１７６質量部を順次加えて３時間攪拌したものを塗液としてフィルムにロールコーティングして乾燥膜厚約２μｍの樹脂硬化層を形成した。
【０１６２】
ガスバリヤ層の作製
上記方法によりプライマー層を形成したＰＥＴフィルム上にガスバリヤ層を形成した。ガスバリヤ層の形成は以下の方法に依った。
【０１６３】
ガスバリヤ層い１の作製
プライマー層つきＰＥＴフィルムをプライマー層Ａ１を形成したものと同様の装置にて以下の反応ガスをもちいて大気圧プラズマ処理を行い、ガスバリヤ層を形成した。尚プラズマ発生に用いる使用電源は日本電子（株）製高周波電源ＪＲＦ−１００００にて周波数１３．５６ＭＨｚの電圧で且つ５Ｗ／ｃｍ²の電力を供給した。
不活性ガス：ヘリウム ９６．７５体積％
反応性ガス１：酸素 ０．５０体積％
反応性ガス２：テトラエトキシシラン １．２５体積％
ガスバリヤ層い２の作製
ガスバリヤ層い１の作製において反応性ガスを以下の組成とした事以外はガスバリヤ層い１の作製と同様にしてガスバリヤ層い２を作製した。
不活性ガス：ヘリウム ９８．５体積％
反応性ガス１：酸素 ０．２５体積％
反応性ガス２：テトラエトキシシラン １．２５体積％
ガスバリヤ層い３の作製
ガスバリヤ層い１の作製において、周波数１０ｋＨｚの電圧で且つ５Ｗ／ｃｍ²の電力を供給したこと以外はい１と同様にしてプライマー層つき基板上にガスバリヤ層を作製した。
【０１６４】
ガスバリヤ層い４の作製
ガスバリヤ層い１の作製において、特開２００１−７４９０６の実施例１と同様にして波高値１０ｋＶ、放電電流密度１００ｍＡ／ｃｍ²、周波数６ｋＨｚのパルス電界を印加し、且つ５Ｗ／ｃｍ²の電力を供給したこと以外はい１と同様にしてプライマー層つき基板上にガスバリヤ層を作製した。
【０１６５】
ガスバリヤ層い５の形成方法
ガスバリヤ層い１の作製において、投入する電力を０．１Ｗ／ｃｍ²とすること以外はい１と同様にしてプライマー層つき基板上にガスバリヤ層を作製した。
【０１６６】
ガスバリヤ層い６の作製方法
ガスバリヤ層い１の作製において、投入する電力を１０Ｗ／ｃｍ²とすること以外はい１の作製と同様にしてい１と同様にしてプライマー層つき基板上にガスバリヤ層を作製した。
【０１６７】
ガスバリヤ層ろの作製
通常のマグネトロンスパッタ装置にてＢドープしたＳｉターゲットとして４．０００×１０^-4Ｐａまで排気した後、Ｏ₂／Ａｒ＝３：７の混合ガスを１００ｓｃｃｍ導入し、圧力を０．１０６７Ｐａになるように調整した。メインロール温度２５℃、投入電力密度１Ｗ／ｃｍ²、フィルム速度１．０ｍ／分の条件で反応性スパッタリングを行い、約３０ｎｍの厚みの酸化珪素によるガスバリヤ層を形成した。
【０１６８】
ガスバリヤ層はの作製
減圧プラズマＣＶＤ装置を用い、以下の条件でガスバリヤ層を形成した。
印加電力 ３０ｋＷ
圧力 ６６．６６Ｐａ
ＨＭＤＳＯ（ヘキサメチルジシロキサン）流量 １ｓｌｍ
酸素ガス流量 １０ｓｌｍ
成膜用ドラム表面温度（成膜温度） １００℃
上記のガス流量単位ｓｌｍは、ｓｔａｎｄａｒｄ ｌｉｔｅｒ ｐｅｒ ｍｉｎｕｔｅのことである。
【０１６９】
上記の方法にてプライマー層、ガスバリヤ層を形成したＰＥＴフィルム上に以下の方法で透明導電膜を形成した。
【０１７０】
透明導電膜の形成方法
プライマー層、ガスバリヤ層つきＰＥＴフィルムを上に透明導電膜を形成し、透明導電膜積層体を形成した。透明導電膜の形成法は以下に依った。
【０１７１】
透明導電膜１１の形成方法
反応ガスとして以下の組成のガスを用いてプライマー、ガスバリヤ層つき基板上に透明導電膜積層体を作製した。プラズマ発生に用いる使用電源は日本電子（株）製高周波電源ＪＲＦ−１００００にて周波数１３．５６ＭＨｚの電圧で且つ５Ｗ／ｃｍ²の電力を供給した。
不活性ガス：ヘリウム ９８．５体積％
反応性ガス１：酸素 ０．２５体積％
反応性ガス２：トリス（２，４−ペンタンジオナト）インジウム １．２体積％
反応性ガス３：ジブチル錫ジアセテート ０．０５体積％
透明導電膜１２の形成方法
透明導電膜１１の作製において、周波数１０ｋＨｚの電圧で且つ５Ｗ／ｃｍ²の電力を供給したこと以外は１１と同様にしてプライマー、ガスバリヤ層つき基板上に透明導電膜積層体を作製した。
【０１７２】
透明導電膜１３の形成方法
透明導電膜１１の作製において、特開２００１−７４９０６号の実施例１と同様にして波高値１０ｋＶ、放電電流密度１００ｍＡ／ｃｍ²、周波数６ｋＨｚのパルス電界を印加し、且つ５Ｗ／ｃｍ²の電力を供給したこと以外は１１と同様にしてプライマー、ガスバリヤ層つき基板上に透明導電膜積層体を作製した。
【０１７３】
透明導電膜１４の形成方法
透明導電膜１１の作製において、投入する電力を０．１Ｗ／ｃｍ²とすること以外は１１の作製と同様にしてプライマー、ガスバリヤ層つき基板上に透明導電膜積層体を作製した。
【０１７４】
透明導電膜１５の作製方法
透明導電膜１１の作製において、投入する電力を１０Ｗ／ｃｍ²とすること以外は１１の作製と同様にしてプライマー、ガスバリヤ層つき基板上に透明導電膜積層体を作製した。
【０１７５】
透明導電膜２の形成方法
プライマー、ガスバリヤ層つきＰＥＴ基材をＤＣマグネトロンスパッタ装置に装着し、真空槽内を１．３３３２×１０^-3Ｐａ以下まで減圧した。尚、スパッタリングターゲットは酸化インジウム：酸化錫９５：５の組成のものを用いた。この後、アルゴンガスと酸素ガスとの混合ガスを（Ａｒ：Ｏ₂＝１０００：３）を１×１０^-3Ｐａとなるまで導入し、スパッタ出力１００Ｗ、基板温度１００℃にて透明導電膜積層体を形成した。
【０１７６】
透明導電膜３の形成方法
透明導電層を京都エレックス（株）製有機ＩＴＯペーストニューフロコートＥＣ−Ｌをディップコートして作製すること以外は透明導電膜１１の作製と同様にして透明導電膜積層体を作製した。
【０１７７】
上述した、プライマー層、ガスバリヤ層及び透明導電膜を表３のように組み合わせて透明導電膜積層体を２７個作製した。
【０１７８】
得られた透明導電膜積層体の評価を上述した方法により行った。尚、ガスバリヤ性の評価方法は以下に記す。
【０１７９】
＜ガスバリヤ性＞
酸素透過度をもってガスバリヤ性の指標とした。酸素透過度は、透明導電層を積層する前の、プライマー層とガスバリヤ層が積層された高分子フィルムについて測定した。測定は、ＭＯＣＯＮ社製オキシトラン２／２０型を用いて、４０℃９０％ＲＨの環境下で測定した。
【０１８０】
【表３】

【０１８１】
表３より本発明の透明導電膜積層体は、ガスバリヤ性、透過率、抵抗率、屈曲性、劣化試験の総てに優れていることが判る。
【０１８２】
【発明の効果】
本発明により、高い透明性、導電率、基材への密着性をもつ高性能な透明導電膜を高い生産性で、かつ環境負荷を低くしつつ生産する製造方法を提供することができた。
【図面の簡単な説明】
【図１】本発明の製造方法に用いられるプラズマ放電処理装置に設置されるプラズマ放電処理容器の一例を示す概略図である。
【図２】本発明の製造方法に用いられるプラズマ放電処理装置に設置されるプラズマ放電処理容器の一例を示す概略図である。
【図３】（ａ）、（ｂ）は各々、本発明に係るプラズマ放電処理に用いられる円筒型のロール電極の一例を示す概略図である。
【図４】（ａ）、（ｂ）は各々、本発明に係るプラズマ放電処理に用いられる固定型の円筒型電極の一例を示す概略図である。
【図５】（ａ）、（ｂ）は各々、本発明に係るプラズマ放電処理に用いられる固定型の角柱型電極の一例を示す概略図である。
【図６】本発明の透明導電膜形成方法に用いられるプラズマ放電処理装置の一例を示す概念図である。
【符号の説明】
２５、２５ｃ、２５Ｃ ロール電極
２６、２６ｃ、２６Ｃ、３６、３６ｃ、３６Ｃ 電極
２５ａ、２５Ａ、２６ａ、２６Ａ、３６ａ、３６Ａ 金属等の導電性母材
２５ｂ、２６ｂ、３６ｂ セラミック被覆処理誘電体
２５Ｂ、２６Ｂ、３６Ｂ ライニング処理誘電体
３１ プラズマ放電処理容器
４１ 電源
５１ ガス発生装置
５２ 給気口
５３ 排気口
６０ 電極冷却ユニット
６１ 元巻き基材
６５、６６ ニップローラ
６４、６７ ガイドローラ[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a transparent conductive film laminate and a method for producing the sameTo the lawMore specifically, the transparent conductive film laminate has excellent transparency and conductivity, and also has excellent adhesion and durability of the transparent conductive layer to the substrate.the body'sManufacturing methodTo the lawRelated.
[0002]
[Prior art]
In recent years, a display element represented by a liquid crystal display element has high demands such as a thinner leaf, a lighter weight, a larger size, an arbitrary shape, and a curved display. In particular, with the expansion of the use of so-called personal information terminal devices that are worn and carried by pagers, mobile phones, electronic notebooks, pen input devices, etc., liquid crystal display panels using plastic substrates instead of conventional glass substrates have been studied. It began to be put into practical use in the department. Such a plastic substrate satisfies the demand for weight reduction and thinning compared to a glass substrate. In addition, among plastic substrates, a film-shaped substrate that is not a sheet-shaped rigid substrate and has excellent flexibility is suitably used for this application.
[0003]
In the transparent conductive film laminate formed by laminating a transparent inorganic thin film on the transparent substrate to give conductivity, the substrate is particularly a transparent plastic sheet (a hard coat layer is formed, although the conductivity is excellent. In some cases, there is a problem in the adhesion of the transparent conductive layer to the substrate, and the flexibility of the substrate and the antireflection layer is different. If the transparent conductive layer is partially peeled off and used in a liquid crystal display or the like, disconnection occurs and the commercial value of the liquid crystal display is remarkably increased. I will drop it.
[0004]
As a method for solving such a problem, methods for providing a primer layer are disclosed in JP-A Nos. 9-174747, 10-111500, JP-A No. 2000-338303, and JP-A No. 2001-125079. In the case of forming a primer layer using, it is necessary to remove the solvent, which not only lowers productivity but also has a great environmental impact. Further, even when the plasma CVD method is used, a vacuum process is required, and thus improvement in productivity cannot be expected. Furthermore, when the solvent is not completely removed and is introduced into the next step, for example, a sputtering process widely used as a method for forming a transparent conductive film, the film is formed under a low pressure. It takes a lot of time to evacuate, and productivity is also lowered. Moreover, the solvent which cannot be removed completely deteriorates the characteristics of the transparent conductive film provided thereafter over time. In addition, when the transparent conductive layer is formed after forming the primer layer, an operation of winding the film once on a roll is added, but further consideration is necessary to prevent blocking or the like that occurs at that time.
[0005]
Furthermore, when a transparent conductive film laminate is used as a display element such as a liquid crystal element, in consideration of the manufacturing process and use conditions, air, water vapor, etc. permeate the plastic film and enter the liquid crystal layer to generate display defects. In order to prevent the phenomenon, a gas barrier layer (gas barrier layer) needs to be laminated on the film.
[0006]
On the other hand, transparent conductive films are widely used for liquid crystal display elements, organic EL elements, solar cells, touch panels, electromagnetic wave shielding materials, infrared reflective films, and the like. As the transparent conductive film, metal thin films such as Pt, Au, Ag, and Cu, SnO₂, In₂O_Three, CdO, ZnO₂, SnO₂: Sb, SnO₂: F, ZnO: AL, In₂O_Three: Composite oxide film made of oxide such as Sn and dopant, chalcogenide, LaB₆, Non-oxides such as TiN and TiC. Among them, an indium oxide film doped with tin (hereinafter referred to as ITO) is most widely used because of its excellent electrical characteristics and ease of processing by etching. These are formed by vacuum deposition, sputtering, ion plating, vacuum plasma CVD, spray pyrolysis, thermal CVD, sol-gel, or the like.
[0007]
In recent years, flat panel displays such as liquid crystal display elements and organic EL elements have been increased in area and definition, and a higher performance transparent conductive film is required. In liquid crystal elements, the use of a transparent conductive film having a high electron mobility is required in order to obtain an element or device having a high electric field response. In addition, in an organic EL element, a transparent conductive film having a lower resistance is required in order to adopt a current driving method.
[0008]
Among the methods for forming a transparent conductive film, a low resistance transparent conductive film can be obtained by vacuum deposition or sputtering. Industrially, a specific resistance value of 10 can be obtained by using a DC magnetron sputtering apparatus.^-FourAn ITO film having excellent conductivity on the order of Ω · cm can be obtained.
[0009]
However, in these physical fabrication methods (PVD method), a target substance is deposited on a substrate in a gas phase to grow a film, and a vacuum vessel is used. For this reason, the apparatus is large and expensive, and the use efficiency of raw materials is poor, resulting in low productivity. In addition, it was difficult to form a film with a large area. Furthermore, in order to obtain a low resistance product, it is necessary to heat to 200 to 300 ° C. during film formation, and it is difficult to form a low resistance transparent conductive film on a plastic film.
[0010]
The sol-gel method (coating method) not only requires many processes such as dispersion preparation, coating, and drying, but also has a low adhesiveness to the substrate to be treated, and therefore requires a binder resin, resulting in poor transparency. Moreover, the electrical characteristics of the obtained transparent conductive film are also inferior compared with the PVD method.
[0011]
The thermal CVD method forms a film by applying a precursor of a target substance to a substrate by spin coating, dip coating, printing, etc., and firing (pyrolysis) to form a film. It has the advantage that it is excellent in productivity and easy to form a film with a large area, but has a problem that the base material is limited because it requires a high temperature treatment from 400 ° C. to 500 ° C. during normal firing. It was. In particular, film formation on a plastic film substrate is difficult.
[0012]
As a method of overcoming the disadvantages of obtaining a high-performance thin film by the sol-gel method (coating method) and the disadvantage of low productivity by using a vacuum apparatus, discharging is performed at atmospheric pressure or near atmospheric pressure. A method of forming a thin film on a base material by exciting a reactive gas with plasma (hereinafter referred to as an atmospheric pressure plasma CVD method) has been proposed. Japanese Unexamined Patent Publication No. 2000-303175 discloses a technique for forming a transparent conductive film by an atmospheric pressure plasma CVD method. However, the resistance of the obtained transparent conductive film is 10 to 10.^-2Ω · cm, high resistivity 1 × 10^-3It is insufficient as a transparent conductive film for flat panel displays such as liquid crystal elements, organic EL elements, PDPs, and electronic papers that require excellent electrical characteristics of Ω · cm or less. Further, triethylindium is used as a CVD raw material, and this compound has a safety problem such as being ignited and explosive in normal temperature and in the atmosphere.
[0013]
Japanese Patent Laid-Open No. 2001-74906 has a function of preventing infrared rays and electromagnetic waves, has a high adhesion to a hard coat layer / transparent conductive layer / antireflection layer, and has excellent scratch resistance and surface hardness for PDP or FED. Although the example of a transparent conductive layer is disclosed as an antireflection film and a method for producing the same, the transparent conductive layer described in the patent cannot meet the demand for a transparent conductive film having a lower resistance.
[0014]
[Problems to be solved by the invention]
  The object of the present invention is to produce a high-performance transparent conductive film having high transparency, conductivity, and adhesion to a substrate with high productivity and low environmental impactThe lawIt is to provide.
[0015]
[Means for Solving the Problems]
The above object of the present invention has been achieved by the following constitutions.
[0016]
  1. In the method for producing a transparent conductive film laminate formed by laminating a primer layer and a transparent conductive layer on a transparent substrate, under atmospheric pressure or pressure near atmospheric pressure,A high frequency voltage of a continuous sine wave with a frequency of 150 kHz or more, and 1 to 50 W / cm ² The electric field discharged by supplying the electric power is applied to the discharge space when forming the primer layer and the transparent conductive layer,By introducing a mixed gas composed of at least one kind of inert gas, at least one kind of organometallic compound and at least one kind of reactive gas into the discharge space to be in a plasma state and exposing the transparent substrate Forming the primer layer on the transparent substrate, and further, at atmospheric pressure or near atmospheric pressure, at least one inert gas, at least one organometallic compound, and at least one or more. The transparent conductive layer is formed on the primer layer by introducing a mixed gas composed of the reactive gas in the discharge space to a plasma state and exposing the substrate on which the primer layer is formed on the transparent substrate. The manufacturing method of the transparent conductive film laminated body characterized by these.
[0017]
  2. In a method for producing a transparent conductive film laminate in which a primer layer, a gas barrier layer, and a transparent conductive layer are laminated on a transparent substrate, under atmospheric pressure or pressure near atmospheric pressure,A high frequency voltage of a continuous sine wave with a frequency of 150 kHz or more, and 1 to 50 W / cm ² Apply the electric field discharged by supplying the electric power to the discharge space when forming the primer layer, gas barrier layer and transparent conductive layer,By introducing a mixed gas composed of at least one kind of inert gas, at least one kind of organometallic compound and at least one kind of reactive gas into the discharge space to be in a plasma state and exposing the transparent substrate Forming the primer layer on the transparent substrate, and further, at atmospheric pressure or near atmospheric pressure, at least one inert gas, at least one organometallic compound, and at least one or more. The gas barrier layer is formed on the primer layer by introducing a mixed gas composed of a reactive gas into a discharge space to be in a plasma state and exposing the substrate on which the primer layer is formed on the transparent substrate. At least one kind of inert gas, at least one kind of organometallic compound, and By introducing a mixed gas composed of at least one kind of reactive gas into the discharge space to form a plasma state and exposing the base material on which the primer layer and the gas barrier layer are formed on the transparent base material, A method for producing a transparent conductive film laminate, comprising forming the transparent conductive layer.
[0018]
3. 3. The gas barrier layer is an inorganic compound containing at least one element selected from the group consisting of magnesium, silicon, zirconium, titanium, tungsten, tantalum, aluminum, zinc, indium, chromium, vanadium, niobium, and tin. Manufacturing method of transparent conductive film laminated body.
[0019]
4). 4. The method for producing a transparent conductive film laminate according to any one of 1 to 3, wherein the primer layer is a film of the general formula (1).
[0020]
5). 5. The method for producing a transparent conductive film laminate according to any one of 1 to 4, wherein M in the general formula (1) is silicon.
[0021]
6). 1 to 5 above, wherein the organometallic compound introduced into the discharge space to form the transparent conductive film is an organometallic compound represented by the general formula (2) or the general formula (3) The manufacturing method of the transparent conductive film laminated body of any one of Claims 1.
[0022]
7. 1 to 6 above, wherein a mixed gas containing at least one kind of inert gas is introduced into the discharge space forming the primer layer or the transparent conductive film, and the inert gas contains argon or helium. The manufacturing method of the transparent conductive film laminated body of any one of Claims 1.
[0024]
  8. Any one of the items 2 to 6, wherein a mixed gas containing at least one kind of inert gas is introduced into the discharge space forming the gas barrier layer, and the inert gas contains argon or helium. The manufacturing method of the transparent conductive film laminated body of description.
[0026]
  9. The high frequency voltage is 150 MHz.Less thanSaid, characterized in thatAny one of 1-8The manufacturing method of the transparent conductive film laminated body of description.
[0027]
  10. The high frequency voltage is 200 kHz or more,9The manufacturing method of the transparent conductive film laminated body of description.
[0028]
  11. The high-frequency voltage is 800 kHz or more,9Or 10The manufacturing method of the transparent conductive film laminated body of description.
[0029]
  12. Electric power is 1.2W / cm²The above is characterized by the aboveAny one of 1-8The manufacturing method of the transparent conductive film laminated body of description.
[0030]
  13. Electric power is 50W / cm²Said, characterized in that12The manufacturing method of the transparent conductive film laminated body of description.
[0031]
  14. Electric power is 20W / cm²Said, characterized in that12Or13The manufacturing method of the transparent conductive film laminated body of description.
[0033]
  15. The above 8 to 1, wherein at least one of the electrodes is covered with a dielectric.4The manufacturing method of the transparent conductive film laminated body of any one of these.
[0034]
  16. The dielectric material 1 is an inorganic material having a relative dielectric constant of 6 to 45.5The manufacturing method of the transparent conductive film laminated body of description.
[0035]
  17. The surface roughness Rmax of the electrode is 10 μm or less, 1 above5Or 16The manufacturing method of the transparent conductive film laminated body of description.
[0036]
  18. Transparent conductive thin film is indium oxide, tin oxide, zinc oxide, F-doped tin oxide, Al-doped zinc oxide, Sb-doped tin oxide, ITO, In₂O₃The main component is at least one selected from —ZnO-based amorphous transparent conductive films.17The manufacturing method of the transparent conductive film laminated body of any one of these.
[0037]
  19. The transparent conductive film is an ITO film, and the ITO film has an In / Sn atomic ratio of 100 / 0.1 to 100/15.18The manufacturing method of the transparent conductive film laminated body of any one of these.
[0039]
  20. When the gas barrier layer is not formed on the transparent substrate, after forming the primer layer, when the gas barrier layer is formed, after forming the gas barrier layer, the transparent conductive film is formed without winding.19The manufacturing method of the transparent conductive film laminated body of any one of these.
[0040]
  21. The above-mentioned 1-2, wherein the carbon content of the transparent conductive film is in the range of 0-5.0 atomic concentration.0The manufacturing method of the transparent conductive film laminated body of any one of these.
[0047]
The present invention will be described in more detail. The above-described production method and the transparent conductive film laminate produced by the production method not only have high transparency, electrical conductivity, and adhesion to the substrate, but also do not contain a solvent in the primer layer. In particular, there is little change in conductivity, and even when a gas barrier layer is provided, a vacuum process is not required, so that it has excellent characteristics that high productivity can be maintained.
[0048]
The present invention provides a primer layer on the substrate by introducing a reactive gas into the discharge space to form a plasma state under atmospheric pressure or a pressure near atmospheric pressure, and exposing the substrate to the reactive gas in the plasma state. And a transparent conductive layer or primer layer, a gas barrier layer, and a transparent conductive layer, wherein the reactive gas contains a reducing gas. This is a film forming method.
[0049]
  In the atmospheric pressure plasma CVD of the present invention, between the opposing electrodes,15High frequency voltage of 0 kHz to 150 MHz and 1.2 to 50 W / cm²The power (power density) is supplied, and the reactive gas is excited to generate plasma.
[0050]
In the present invention, the upper limit of the frequency of the high-frequency voltage applied between the electrodes is preferably 15 MHz or less.
[0051]
The lower limit value of the frequency of the high frequency voltage is preferably 200 kHz or more. More preferably, it is 800 kHz or more.
[0052]
The lower limit value of the power supplied between the electrodes is 1.2 W / cm.²That's it. The upper limit is 50 W / cm²Below, preferably 50 W / cm²It is as follows. The discharge area (cm²) Refers to the area of the electrode where discharge occurs.
[0053]
The high-frequency voltage applied between the electrodes may be an intermittent pulse wave or a continuous sine wave. However, in order to obtain the effect of the present invention, it is a continuous sine wave. It is preferable.
[0054]
In the present invention, it is necessary to employ an electrode capable of maintaining a uniform glow discharge state by applying such a voltage in a plasma discharge processing apparatus.
[0055]
Such an electrode is preferably a metal base material coated with a dielectric. It is preferable to coat a dielectric on at least one side of the opposed application electrode and the ground electrode, and more preferably coat both the opposed application electrode and the ground electrode with a dielectric. The dielectric is preferably an inorganic substance having a relative dielectric constant of 6 to 45. Examples of such a dielectric include ceramics such as alumina and silicon nitride, silicate glass, borate glass, and the like. There are glass lining materials.
[0056]
In addition, when the substrate is placed between electrodes or transported between electrodes and exposed to plasma, it is not only a roll electrode specification that can be transported in contact with one electrode, but also the dielectric surface is polished. Finishing and setting the electrode surface roughness Rmax (JIS B 0601) to 10 μm or less allows the dielectric thickness and the gap between the electrodes to be kept constant, the discharge state to be stabilized, and the heat shrinkage difference In addition, it is possible to greatly improve durability by eliminating distortion and cracking due to residual stress and coating with a highly accurate inorganic dielectric material that is not porous.
[0057]
In addition, when manufacturing electrodes with a dielectric coating on a metal base at a high temperature, at least the dielectric on the side in contact with the substrate is polished and the difference in thermal expansion between the metal base and the dielectric of the electrode is as much as possible. Therefore, it is necessary to make it small, so in the manufacturing method, the surface of the base material is lined with an inorganic material by controlling the amount of bubbles mixed in as a layer that can absorb stress. It is good that the glass is obtained, and further, the amount of bubbles mixed in the lowermost layer in contact with the conductive metal base material is set to 20 to 30 vol%, and the subsequent layers are set to 5 vol% or less. A good electrode can be made.
[0058]
Another method of coating the base material of the electrode with a dielectric material is to perform thermal spraying of the ceramics to a porosity of 10 vol% or less, and to perform a sealing treatment with an inorganic material that is cured by a sol-gel reaction. In order to promote the sol-gel reaction, heat curing or UV curing is good. Further, when the sealing liquid is diluted, and coating and curing are repeated several times in succession, the mineralization is further improved and the dense without deterioration. An electrode is made.
[0059]
A plasma discharge processing apparatus using such an electrode will be described with reference to FIGS. The plasma discharge treatment apparatus of FIGS. 1-6 discharges between the roll electrode which is a ground electrode, and the fixed electrode which is an application electrode arrange | positioned in the position which opposes, and introduces a reactive gas between the said electrodes The thin film is formed by exposing the long film-like substrate wound around the roll electrode to the plasma-state reactive gas, and the primer layer and gas barrier layer of the present invention. And a transparent conductive layer forming method (hereinafter referred to as a thin film forming method of the present invention) is not limited to this, and a reactive gas is used to stably maintain a glow discharge and form a thin film. What is necessary is just to be excited and made into a plasma state. As another method, there is a jet method in which a base material is placed or transported in the vicinity of an electrode that is not between electrodes and a generated plasma is sprayed onto the base material to form a thin film.
[0060]
FIG. 1 is a schematic view showing an example of a plasma discharge processing container of a plasma discharge processing apparatus used in the thin film forming method of the present invention.
[0061]
In FIG. 1, a long film-like substrate F is conveyed while being wound around a roll electrode 25 that rotates in the conveying direction (clockwise in the figure). The fixed electrode 26 is composed of a plurality of cylinders, and is installed facing the roll electrode 25. The substrate F wound around the roll electrode 25 is pressed by the nip rollers 65 and 66, regulated by the guide roller 64, transported to the discharge treatment space secured by the plasma discharge treatment vessel 31, subjected to discharge plasma treatment, and then Then, it is conveyed to the next process via the guide roller 67. Further, the partition plate 54 is disposed in the vicinity of the nip rollers 65 and 66 to suppress the air accompanying the base material F from entering the plasma discharge processing container 31.
[0062]
The entrained air is preferably suppressed to 1% by volume or less, and more preferably 0.1% by volume or less, with respect to the total volume of gas in the plasma discharge processing vessel 31. This can be achieved by the nip rollers 65 and 66.
[0063]
Note that a mixed gas (inert gas, a reducing gas which is a reactive gas, and an organometallic compound) used for the discharge plasma treatment is introduced into the plasma discharge treatment vessel 31 from the supply port 52, and the treated gas is exhausted. The air is exhausted from the port 53.
[0064]
FIG. 2 is a schematic view showing an example of a plasma discharge processing vessel installed in the plasma discharge processing apparatus used in the manufacturing method of the present invention, as in FIG. In this example, the fixed electrode 26 is a columnar electrode 36, whereas a cylindrical electrode is used.
[0065]
Compared to the cylindrical electrode 26 shown in FIG. 1, the prismatic electrode 36 shown in FIG. 2 has an effect of extending the discharge range, and is therefore preferably used in the thin film forming method of the present invention.
[0066]
FIGS. 3A and 3B are schematic views showing examples of the above-described cylindrical roll electrodes, and FIGS. 4A and 4B show examples of electrodes fixed in a cylindrical form. FIG. 5A and FIG. 5A are schematic views each showing an example of an electrode fixed in a prismatic shape.
[0067]
3 (a) and 3 (b), a roll electrode 25c, which is a ground electrode, is a ceramic-coated dielectric in which ceramic is sprayed on a conductive base material 25a such as metal and then sealed with an inorganic material. It is comprised with the combination which coat | covered the body 25b. A ceramic-coated dielectric is coated with 1 mm of a single piece, and is manufactured to have a roll diameter of 200φ after coating, and is grounded to ground. Alternatively, a combination of a conductive base material 25A such as metal covered with a lining dielectric 25B provided with an inorganic material by lining, and a roll electrode 25C may be used. As the lining material, silicate glass, borate glass, phosphate glass, germanate glass, tellurite glass, aluminate glass, vanadate glass and the like are preferably used. Of these, borate glass is more preferred because it is easy to process. Examples of the conductive base materials 25a and 25A such as metal include metals such as silver, platinum, stainless steel, aluminum, and iron. Stainless steel is preferable from the viewpoint of processing. As the ceramic material used for thermal spraying, alumina, silicon nitride, or the like is preferably used. Among these, alumina is more preferable because it is easily processed. In the present embodiment, the base material of the roll electrode is a stainless steel jacket roll base material having a cooling means with cooling water (not shown).
[0068]
4 (a), 4 (b), 5 (a), and 5 (b) show a fixed electrode 26c, an electrode 26C, an electrode 36c, and an electrode 36C as application electrodes, and the roll electrode 25c and the roll electrode described above. It is configured in the same combination as 25C. That is, a hollow stainless steel pipe is covered with the same dielectric as described above, and can be cooled with cooling water during discharge. In addition, it is manufactured so that it becomes 12φ or 15φ after coating with the ceramic coating treated dielectric, and the number of the electrodes is 14 along the circumference of the roll electrode.
[0069]
A power source for applying a voltage to the application electrode is not particularly limited, but a high frequency power source (200 kHz) manufactured by Pearl Industry, a high frequency power source (800 kHz) manufactured by Pearl Industry, a high frequency power source manufactured by JEOL (13.56 MHz), and a high frequency power source manufactured by Pearl Industry. A power source (150 MHz) or the like can be used.
[0070]
FIG. 6 is a conceptual diagram showing an example of a plasma discharge treatment apparatus used in the present invention. In FIG. 6, the part of the plasma discharge processing vessel 31 is the same as that shown in FIG. As a coolant for the electrode cooling unit 60, an insulating material such as distilled water or oil is used.
[0071]
The electrodes 25 and 36 shown in FIG. 6 are the same as those shown in FIGS. 3, 4, 5, etc., and the gap between the opposing electrodes is set to about 1 mm, for example.
[0072]
The distance between the electrodes is determined in consideration of the thickness of the solid dielectric placed on the base material of the electrodes, the magnitude of the applied voltage, the purpose of using plasma, and the like. The shortest distance between the solid dielectric and the electrode when a solid dielectric is placed on one of the electrodes, and the distance between the solid dielectrics when a solid dielectric is placed on both of the electrodes is uniform in any case From the viewpoint of discharging, 0.5 mm to 20 mm is preferable, and 1 mm ± 0.5 mm is particularly preferable.
[0073]
A roll electrode 25 and a fixed electrode 36 are arranged in a predetermined position in the plasma discharge processing container 31, and the mixed gas generated by the gas generator 51 is controlled in flow rate, and the plasma discharge processing container is supplied from the air supply port 52. The plasma discharge treatment vessel 31 is filled with a mixed gas used for the plasma treatment and exhausted from the exhaust port 53. Next, a voltage is applied to the electrode 36 by the power source 41, and the roll electrode 25 is grounded to the ground to generate discharge plasma. Here, the base material F is supplied from the roll-shaped original winding base material 61, and the electrodes in the plasma discharge treatment vessel 31 are in a single-sided contact state (in contact with the roll electrode 25) via the guide roller 64. The surface of the base material F is subjected to discharge treatment by discharge plasma during the transport, and then transported to the next process via the guide roller 67. Here, the substrate F is subjected to discharge treatment only on the surface not in contact with the roll electrode 25.
[0074]
The value of the voltage applied to the electrode 36 fixed from the power supply 41 is appropriately determined. For example, the voltage is about 0.5 to 10 kV, and the power supply frequency is adjusted to 0.5 kHz or more and 150 MHz or less. As for the method of applying power, either a continuous sine wave continuous oscillation mode called continuous mode or an intermittent oscillation mode called ON / OFF intermittently called pulse mode may be adopted. A denser and better quality film can be obtained.
[0075]
The plasma discharge treatment vessel 31 is preferably a treatment vessel made of Pyrex (R) glass or the like, but can be made of metal as long as it can be insulated from the electrodes. For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and the metal frame may be subjected to ceramic spraying to provide insulation.
[0076]
Moreover, in order to suppress the influence on the base material at the time of the discharge plasma treatment to a minimum, the temperature of the base material surface at the time of the discharge plasma treatment is adjusted to a temperature of room temperature (15 ° C to 25 ° C) to 300 ° C or less. It is preferable to adjust the temperature from room temperature to 200 ° C or less, more preferably from room temperature to 100 ° C or less. In order to adjust to the above temperature range, the electrode and the substrate are subjected to discharge plasma treatment while being cooled by a cooling means as necessary.
[0077]
In the present invention, the discharge plasma treatment is performed at or near atmospheric pressure. Here, the vicinity of atmospheric pressure represents a pressure of 20 kPa to 110 kPa, but 93 kPa to 104 kPa is preferable in order to preferably obtain the effects described in the present invention.
[0078]
In the discharge electrode according to the thin film forming method of the present invention, the maximum height (Rmax) of the surface roughness defined by JIS B 0601 on the side in contact with at least the substrate is adjusted to 10 μm or less. Although it is preferable from the viewpoint of obtaining the effects described in the present invention, the maximum value of the surface roughness is more preferably 8 μm or less, and particularly preferably adjusted to 7 μm or less.
[0079]
The centerline average surface roughness (Ra) specified by JIS B 0601 is preferably 0.5 μm or less, more preferably 0.1 μm or less.
[0080]
  The primer layer in the present invention is preferably a film of the general formula (1).
[0081]
  The chemical composition of these primer layers is described later in X-ray photoelectron spectroscopy (XPS).)soYou can ask for it.
[0082]
  By the above method, it is possible to obtain a primer layer having good adhesion to the gas barrier layer, the transparent conductive film and the transparent substrate. Specific examples of the reaction gas used for forming the primer layer include the following. Siliconated organometallic compounds, particularly organometallic compounds such as β-diketone metal complexes, metal alkoxides, and alkyl metals are particularly preferably used.ConversionCompounds include tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetrapentaethoxy Silane, tetrapenta-iso-propoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxy Silane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxysilane, dimethyl Rubutokishishiran, methyldimethoxysilane, methyldiethoxysilane, hexyl trimethoxysilane, and the like to. Examples of the titanium compound include titanium alkoxides such as titanium tetra i-propoxide, titanium tetramethoxide, titanium tetraethoxide, titanium tetra n-propoxide, titanium tetra n-butoxide, and titanium tetra t-butoxide. For other metals, metal alkoxides and alkyl metals are preferably used.
[0083]
The film composition and carbon content are measured using an XPS surface analyzer. There is no particular limitation on the XPS surface analyzer, and any model can be used. In this example, ESCALAB-200R manufactured by VG Scientific, Inc. was used. Mg was used for the X-ray anode, and measurement was performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA). The energy resolution was set to be 1.5 to 1.7 eV when defined by the half width of a clean Ag3d5 / 2 peak. Before performing the measurement, it is necessary to etch away a surface layer corresponding to a thickness of 10 to 20% of the thickness of the thin film in order to eliminate the influence of contamination. For the removal of the surface layer, it is preferable to use an ion gun that can use rare gas ions. As the ion species, He, Ne, Ar, Xe, Kr, or the like can be used. In this measurement, the surface layer was removed using Ar ion etching.
[0084]
First, the range of binding energy from 0 eV to 1100 eV was measured at a data acquisition interval of 1.0 eV to determine what elements were detected.
[0085]
Next, with respect to all the detected elements except the etching ion species, the data acquisition interval was set to 0.2 eV, and the photoelectron peak giving the maximum intensity was subjected to narrow scan, and the spectrum of each element was measured. The obtained spectrum is COMMON DATA PROCESSING SYSTEM manufactured by VAMAS-SCA-JAPAN (preferably Ver. 2.3 or later) so as not to cause a difference in the content calculation result due to a difference in measuring apparatus or computer. After transferring to the top, the process was performed with the same software, and the value of the carbon content was determined as the atomic concentration (at%). The ratio of tin to indium was also the ratio of the number concentration of atoms obtained from the above results.
[0086]
Before performing the quantitative process, a calibration of the Scale Scale was performed for each element, and a 5-point smoothing process was performed. In the quantitative process, the peak area intensity (cps × eV) from which the background was removed was used. For the background treatment, the method by Shirley was used.
[0087]
For the Shirley method, see D.C. A. Shirley, Phys. Rev. , B5, 4709 (1972).
[0091]
The gas barrier layer in the present invention is preferably an inorganic compound containing at least one element of magnesium, silicon, zirconium, titanium, tungsten, tantalum, aluminum, zinc, indium, chromium, vanadium, niobium, and tin. Among these, a barrier film containing a silicon oxide as a main component is preferable in terms of gas barrier properties, transparency, surface smoothness, flexibility, film stress, and cost. More preferably, a metal oxide mainly composed of silicon oxide having a ratio of the number of oxygen atoms to the number of silicon atoms of 1.5 to 2.0 is preferable. In particular, in the present invention, a mixed gas composed of at least one kind of inert gas, at least one kind of organometallic compound, and at least one kind of reactive gas is used in the discharge space at atmospheric pressure or near atmospheric pressure. It is possible to form a film having excellent barrier properties by forming on the substrate by introducing it into a plasma state and exposing the substrate to the mixed gas in the plasma state. The gas barrier layer may be formed according to the method for forming the primer layer, and the conditions for forming the oxide film having the above composition can be found by trial and error.
[0092]
Examples of the organometallic compound introduced into the plasma space for forming the gas barrier film include the following. Organometallic compounds such as siliconized organometallic compounds, β-diketone metal complexes, metal alkoxides, and alkyl metals are preferably used. Specific compounds include tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, Tetrapentaethoxysilane, tetrapenta-iso-propoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, Methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxy Orchids, dimethyl-butoxy silane, methyl dimethoxy silane, methyl diethoxy silane, hexyl trimethoxy silane, and the like to.
[0093]
The gas barrier layer in the present invention is substantially MO._2-xThe preferred range of x is 0.2 to -0.2.
[0094]
A transparent conductive film refers to a thin film that is optically transparent and conductive. Research and development has been conducted for a long time, and typical transparent conductive films include metal thin films, oxides (SnO₂ZnO₂, In₂O_Three), Composite oxides (ITO, IZO, FTO, ATO), non-oxides (chalcogenide, TiN), and the like.
[0095]
In the present invention, a transparent conductive film is formed on the primer layer, or a transparent conductive film is formed on the barrier layer and further on the barrier layer. As a method for forming the barrier layer and the transparent conductive film, a reactive gas is introduced into the discharge space at atmospheric pressure or near atmospheric pressure to form a plasma state, and the substrate is exposed to the reactive gas in the plasma state. Is a method for forming a transparent conductive film by forming a transparent conductive film on the substrate. By this method, a high-performance transparent conductive film laminate with high productivity can be formed. The atmospheric pressure plasma method can be carried out in the same manner as described above for the primer layer.
[0096]
In forming the transparent conductive film of the present invention, the gas used varies depending on the type of transparent conductive film desired to be provided on the substrate, but basically, an inert gas and a plasma state for forming the transparent conductive film. This is a mixed gas of reactive gas. Here, the inert gas includes Group 18 elements of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, and nitrogen gas, and the effect described in the present invention is obtained. For this purpose, argon or helium is particularly preferably used. A plurality of reactive gases can be used in the present invention, but at least one kind contains a component that is in a plasma state in the discharge space and forms a transparent conductive film. Although there is no restriction | limiting in particular as such reactive gas, An organometallic compound is used preferably. The type of the organometallic compound is not limited, but an organometallic compound having oxygen in the molecule is preferable, and in particular, an organometallic compound such as β-diketone metal complex, metal alkoxide, or alkyl metal is preferably used. More preferable is a reaction gas selected from the compounds represented by the general formula (2) or the general formula (3).
[0097]
In the formula, M is at least one metal selected from indium, zinc, and tin. R represents a fluoroalkyl group containing at least one fluorine having 1 to 10 carbon atoms.
[0098]
Preferred examples of the compound represented by the general formula (2) or the general formula (3) include indium hexafluoropentanedionate, indium methyl (trimethyl) acetyl acetate, indium acetylacetonate, indium isoporopoxide, and indium. Trifluoropentanedionate, tris- (2,2,6,6-tetramethyl-3,5-heptanedionate) indium, di-n-butylbis (2,4-pentanedionate) tin, di-n- Examples thereof include butyldiacetoxytin, di-t-butyldiacetoxytin, tetraisopropoxytin, tetrabutoxytin, zinc acetylacetonate and the like.
[0099]
Of these, indium acetylacetonate, tris- (2,2,6,6-tetramethyl 3,5-heptanedionate) indium, zinc acetylacetonate, and di-n-butyldiacetoxytin are particularly preferable. is there. These organometallic compounds are generally commercially available. For example, indium acetylacetonate can be easily obtained from Tokyo Chemical Industry Co., Ltd.
[0100]
In the present invention, in addition to the organometallic compound containing at least one oxygen atom in the molecule, a doping gas used for improving the conductivity can be used. Examples of reactive gas used for doping include aluminum isopropoxide, nickel acetylacetonate, manganese acetylacetonate, boron isopropoxide, n-butoxyantimony, tri-n-butylantimony, di-n-butylbis ( 2,4-pentanedionate) tin, di-n-butyldiacetoxytin, di-t-butyldiacetoxytin, tetraisopropoxytin, tetrabutoxytin, tetrabutyltin, zinc acetylacetonate, propylene hexafluoride, A cyclobutane octafluoride, methane tetrafluoride, etc. can be mentioned.
[0101]
Furthermore, in the present invention, in addition to the reaction gas containing the constituent elements of the transparent conductive film, an oxidizing gas such as oxygen, a reducing gas such as hydrogen, other nitrogen monoxide, nitrogen dioxide, carbon monoxide, Carbon dioxide or the like can be used as appropriate.
[0102]
The amount ratio of the reactive gas used as the main component of the transparent conductive film and the reactive gas used in a small amount for the purpose of doping differs depending on the type of the transparent conductive film to be formed. For example, in the ITO film obtained by doping tin with indium oxide, the reactive gas amount is adjusted so that the In / Sn atomic ratio of the obtained ITO film is in the range of 100 / 0.1 to 100/15. To do. Preferably, it adjusts so that it may become the range of 100 / 0.5-100 / 10. The atomic ratio of In / Sn can be determined by XPS measurement. In a transparent conductive film (referred to as FTO film) obtained by doping fluorine in tin oxide, the reaction is performed so that the Sn / F atomic ratio of the obtained FTO film is in the range of 100 / 0.01 to 100/50. Adjust the quantity ratio of sex gases. The atomic ratio of Sn / F can be determined by XPS measurement. In₂O_ThreeIn the —ZnO-based amorphous transparent conductive film, the amount ratio of the reactive gas is adjusted so that the atomic ratio of In / Zn is in the range of 100/50 to 100/5. The atomic ratio of In / Zn can be determined by XPS measurement.
[0103]
Furthermore, the reactive gas includes a reactive gas that is a main component of the transparent conductive film and a reactive gas that is used in a small amount for the purpose of doping. Further, a reactive gas can be added to adjust the resistance value of the transparent conductive film. Examples of the reactive gas used for adjusting the resistance value of the transparent conductive film include titanium triisopropoxide, tetramethoxysilane, tetraethoxysilane, and hexamethyldisiloxane.
[0104]
The reactive gas is preferably contained in an amount of 0.01 to 10% by volume with respect to the mixed gas. As the film thickness of the transparent conductive film, a transparent conductive film in the range of 0.1 nm to 1000 nm is obtained.
[0105]
In the present invention, the transparent conductive film is formed under a pressure close to atmospheric pressure, but the temperature of the substrate at that time is not particularly limited. It depends on the thermophysical properties of the material used as the substrate. When glass is used as the substrate, it is preferably 500 ° C. or lower, and when used as a polymer, 300 ° C. or lower is preferable.
[0106]
In the method for forming a transparent conductive film of the present invention, a mixed gas comprising at least one kind of inert gas and at least one kind of reactive gas is introduced into the discharge space under atmospheric pressure or a pressure near atmospheric pressure. It is characterized by forming a thin film on the base material by subjecting the base material to a reactive gas in the plasma state, and then performing a heat treatment.
[0107]
The heat treatment temperature is preferably in the range of 50 to 300 ° C. Preferably it is the range of 100-250 degreeC. The atmosphere for heating is not particularly limited. It is possible to select from an air atmosphere, a reducing atmosphere containing a reducing gas such as hydrogen, an oxidizing atmosphere containing an oxidizing gas such as oxygen, or an inert gas atmosphere such as vacuum, nitrogen or a rare gas. It is. When taking a reducing or oxidizing atmosphere, it is preferable to use a reducing gas or oxidizing gas diluted with an inert gas such as a rare gas or nitrogen. In such a case, the concentration of the reducing gas and the oxidizing gas is preferably 0.01 to 5%, more preferably 0.1 to 3%.
[0108]
Moreover, since the transparent conductive film obtained by the method for forming a transparent conductive film of the present invention uses an organometallic compound as a reactive gas, it may contain a trace amount of carbon. In this case, the carbon content is preferably 0 to 5.0 atom concentration. Particularly preferably, it is within the range of 0.01 to 3 atomic number concentration.
[0109]
There is no particular limitation on the material constituting the substrate. Although glass can be used, a resin film can be preferably used because it is under atmospheric pressure or pressure near atmospheric pressure and low-temperature glow discharge.
[0110]
For example, cellulose esters such as film-like cellulose triacetate, polyesters, polycarbonates, polystyrenes, and gelatin, polyvinyl alcohol (PVA), acrylic resins, polyester resins, cellulosic resins and the like coated thereon are used. I can do it. Moreover, these base materials can use what coated the anti-glare layer and the clear hard-coat layer on the support body, and coated the back-coat layer and the antistatic layer.
[0111]
As the above support (also used as a base material), specifically, polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose acetate butyrate film, Cellulose acetate propionate film, cellulose acetate phthalate film, cellulose triacetate, cellulose ester film such as cellulose nitrate, or derivatives thereof, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene series Film, polycarbonate film, norbornene resin film, polymethylpen Film, polyetherketone film, polyimide film, polyethersulfone film, polysulfone film, polyetherketoneimide film, polyamide film, fluororesin film, nylon film, polymethylmethacrylate film, acrylic film or polyarylate film Can be mentioned.
[0112]
These materials can be used alone or in combination as appropriate. Among these, commercially available products such as ZEONEX (manufactured by Nippon Zeon Co., Ltd.) and ARTON (manufactured by Nippon Synthetic Rubber Co., Ltd.) can be preferably used. Furthermore, even for materials with a large intrinsic birefringence, such as polycarbonate, polyarylate, polysulfone, and polyethersulfone, conditions such as solution casting and melt extrusion, as well as stretching conditions in the longitudinal and lateral directions are set as appropriate. Can be obtained. Moreover, the support body which concerns on this invention is not limited to said description. A film thickness of 10 μm to 1000 μm is preferably used as the film thickness.
[0113]
Further, an antifouling layer can be provided on the outermost layer of the film. In addition, a layer for imparting gas barrier properties and solvent resistance may be provided as necessary.
[0114]
The method for forming these layers is not particularly limited, and a coating method, a vacuum deposition method, a sputtering method, an atmospheric pressure plasma CVD method, or the like can be used. Particularly preferred is the atmospheric pressure plasma CVD method.
[0115]
As a method for forming these layers by atmospheric pressure plasma CVD, for example, a method disclosed in Japanese Patent Application No. 2000-021573 can be used as a method for forming an antireflection film.
[0116]
In the present invention, when the transparent conductive film according to the present invention is provided on the substrate surface as described above, it is preferable to provide a film thickness deviation of ± 10% with respect to the average film thickness, more preferably It is preferably within ± 5%, particularly preferably within ± 1%.
[0117]
【Example】
Next, the present invention will be described more specifically with reference to examples and comparative examples. In addition, evaluation of the produced transparent conductive film laminated body was based on the following method.
[0118]
<Transmissivity>
In accordance with JIS-R-1635, measurement was performed using a spectrophotometer U-4000 type manufactured by Hitachi, Ltd. The wavelength of the test light was 550 nm.
[0119]
<Resistivity>
According to JIS-R-1637, it calculated | required by the four terminal method. In addition, Mitsubishi Chemical Loresta-GP and MCP-T600 were used for the measurement.
[0120]
<Measurement of carbon content>
The film composition and carbon content are measured using an XPS surface analyzer. The measurement was performed by the method described in the specification.
[0122]
<Flexibility>
The bending resistance and the degree of disconnection of the sample after the bending resistance test were examined. In addition, the bending endurance is the resistance value R after being deformed for 1 minute by applying a load of 100 g along the circumference of a 6 mm round bar so that the transparent conductive layer is on the outside. It is defined as the ratio R / R0 of the resistance value R0.
[0123]
<Deterioration test>
The transparent conductive film laminate film was cut to a length of 10 cm in length and width. About this film, the surface resistance in room temperature 25 degreeC 50% of relative humidity was measured using Mitsubishi Chemical Loresta-GP and MCP-T600. This surface resistance value is R0. This film was treated with a constant temperature and humidity chamber at a temperature of 80 ° C. and a relative humidity of 40% for 1 week, and the surface resistance value was measured again. This value was taken as R, and the ratio of R / R0 was determined. This ratio is preferably close to 1.
[0124]
Example 1
A 175 μm polyethylene terephthalate film is used as the base material, and the plasma discharge device uses a parallel plate type electrode. The PET base material is placed between the electrodes, and a mixed gas is introduced to form a thin film. went.
[0125]
In addition, the following thing was used for the electrode. A 200 mm x 200 mm x 2 mm stainless steel plate is coated with a high-density, high-adhesion alumina sprayed coating, and then a solution obtained by diluting tetramethoxysilane with ethyl acetate is applied and dried, and then cured by UV irradiation for sealing treatment. It was. The dielectric surface thus coated was polished, smoothed, and processed to have an Rmax of 5 μm. In this way, an electrode was produced and grounded.
[0126]
On the other hand, as the application electrodes, a plurality of hollow rectangular pure titanium pipes coated with the same dielectric material as described above were produced under the same conditions as the opposing electrode group.
[0127]
The power source used for plasma generation is a high frequency power source JRF-10000 manufactured by JEOL Ltd. and a voltage of 13.56 MHz and 5 W / cm.²Power was supplied.
[0128]
A reactive gas having the following composition was allowed to flow between the electrodes.
Inert gas: Helium 98.5% by volume
Reactive gas 1: 0.25% by volume of oxygen
Reactive gas 2: Tetraethoxysilane 1.25% by volume
An atmospheric pressure plasma treatment was performed on the substrate under the reactive gas and reaction conditions to form a primer layer.
[0129]
Next, the reactive gas was switched to the following composition to form a transparent conductive film on the primer layer.
Inert gas: Helium 98.5% by volume
Reactive gas 1: 0.25% by volume of oxygen
Reactive gas 2: Tris (2,4-pentanedionato) indium 1.2% by volume
Reactive gas 3: Dibutyltin diacetate 0.05% by volume
After film formation, it was evaluated by the evaluation method described above, and the results are shown in Table 1.
[0130]
  Example 2
  A primer layer was formed in the same manner as in Example 1 except that the reactive gas was changed to the following composition when forming the primer layer in Example 1, and a tin-doped indium oxide film was formed thereon as in Example 1. Formed and evaluated in the same manner as in Example 1.
Inert gas: Helium 97.75% by volume
Reactive gas 1: 0.25% by volume of oxygen
Reactive gas 2: Tetraethoxysilane 2.00% by volume
  Example 3
  A primer layer was formed in the same manner as in Example 1 except that the reactive gas was changed to the following composition when forming the primer layer in Example 1, and a tin-doped indium oxide film was formed thereon as in Example 1. Formed and evaluated in the same manner as in Example 1.
Inert gas: Helium 99.25% by volume
Reactive gas 1: 0.25% by volume of oxygen
Reactive gas 2: Tetraethoxysilane 0.50% by volume
  ComparisonExample 4a
  In Example 1, when the primer layer and the transparent conductive layer were formed, the voltage was 10 kHz and 5 W / cm.²A transparent conductive film laminate was produced on a PET substrate in the same manner as in Example 1 except that the power was supplied and evaluated in the same manner as in Example 1.
[0131]
  ComparisonExample 5a
  In Example 1, as in Example 1 of Japanese Patent Laid-Open No. 2001-74906, the peak value is 10 kV and the discharge current density is 100 mA / cm.²Apply a pulse electric field with a frequency of 6 kHz and 5 W / cm²A transparent conductive film laminate was produced on a PET substrate in the same manner as in Example 1 except that the power was supplied and evaluated in the same manner as in Example 1.
[0132]
  ComparisonExample 6a
  The electric power input in Example 1 is 0.1 W / cm.²A transparent conductive film laminate was produced on a PET substrate in the same manner as in Example 1 except that, and evaluation was performed in the same manner as in Example 1.
[0133]
Example 7
The power input in Example 1 is 10 W / cm.²A transparent conductive film laminate was produced on a PET substrate in the same manner as in Example 1 except that, and evaluation was performed in the same manner as in Example 1.
[0134]
Comparative Example 1
A transparent conductive film laminate was produced in the same manner as in Example 1 except that the primer layer had the following configuration in Example 1 and evaluated in the same manner as in Example 1.
[0135]
148 parts by mass of vinyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM1003) is put into a stirring vessel whose outside is cooled with water, and 54 parts of 0.01N hydrochloric acid is gradually added while stirring vigorously. Further, the mixture was slowly stirred for 3 hours to obtain a hydrolyzed liquid of vinyltrimethoxysilane. Subsequently, 50 parts by mass of trimethylolpropane triacrylate (trade name Aronix M-309, manufactured by Toagosei Co., Ltd.), 100 parts by mass of the hydrolyzed liquid of vinyltrimethoxysilane, 10 parts by mass of unhydrolyzed vinyltrimethoxysilane, Photoinitiator 2-hydroxy-2-methyl-1-phenylpropan-1-one (Merck, trade name Darocur 1173) 8 parts by weight and silicone oil as a leveling agent (Toray Dow Corning Silicone, SH28PA) 0 0.02 part by mass was mixed to prepare a coating solution. This coating solution was coated on a substrate using a bar coater, heated at 60 ° C. for 1 minute to volatilize and remove the residual solvent in the coating film, and then an integrated light amount of 800 mJ / cm using a 160 W / cm high-pressure mercury lamp. cm²The primer layer was obtained by curing the coating film by irradiating with ultraviolet rays under the conditions described above.
[0136]
Comparative Example 2
A transparent conductive film laminate was produced in the same manner as in Example 1 except that the primer layer had the following configuration in Example 1 and evaluated in the same manner as in Example 1.
Epoxy acrylate prepolymer having a molecular weight of about 1040 and a melting point of 55 ° C. (VR-60, Showa Polymer Co., Ltd.); 100 parts by mass
200 parts by mass of diethylene glycol
Ethyl acetate; 100 parts by mass
Benzene ethyl ether; 2 parts by mass
Silane coupling agent (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.); 1 part by mass
Is stirred and dissolved at 50 ° C. to obtain a uniform solution, applied by dipping, heated at 80 ° C. for 10 minutes, and then irradiated with ultraviolet light to form a primer layer on one side of the polymer film. Formed.
[0137]
Example 8
A transparent conductive film laminate was prepared in the same manner as in Example 1 except that polyethylene terephthalate was changed to an amorphous cyclopolyolefin resin film (ARTON film manufactured by JSR: thickness 100 μm) in Example 1. Evaluation was performed in the same manner as above.
[0138]
Example 9
A transparent conductive film laminate was prepared in the same manner as in Example 1 except that a polycarbonate film (pure ace manufactured by Teijin Limited: thickness 100 μm) formed by casting a polyethylene terephthalate in Example 1 was used. Evaluation was performed in the same manner as above.
[0139]
Comparative Example 3
A transparent conductive film laminate was prepared in the same manner as in Comparative Example 1 except that polyethylene terephthalate was changed to an amorphous cyclopolyolefin resin film (ARTON film manufactured by JSR: thickness: 100 μm) in Comparative Example 1. Example 1 Evaluation was performed in the same manner as above.
[0140]
Comparative Example 4
A transparent conductive film laminate was prepared in the same manner as in Comparative Example 1 except that a polycarbonate film (Pure Ace manufactured by Teijin Limited: thickness 100 μm) formed by casting the polyethylene terephthalate in Comparative Example 1 was used. Example 1 Evaluation was performed in the same manner as above.
[0141]
Comparative Example 5
A transparent conductive film laminate was prepared in the same manner as in Comparative Example 2 except that polyethylene terephthalate was changed to an amorphous cyclopolyolefin resin film (ARTON film manufactured by JSR: thickness of 100 μm) in Comparative Example 2. Example 1 Evaluation was performed in the same manner as above.
[0142]
Comparative Example 6
A transparent conductive film laminate was formed in the same manner as in Example 1 except that the transparent conductive layer was produced by the following method in Example 1 and evaluated in the same manner as in Example 1.
[0143]
A PET substrate is mounted on a DC magnetron sputtering apparatus, and the inside of the vacuum chamber is 1.33322 × 10^-3The pressure was reduced to Pa or lower. A sputtering target having a composition of indium oxide: tin oxide 95: 5 was used. Thereafter, a mixed gas of argon gas and oxygen gas is used (Ar: O₂= 1000: 3) is 1 × 10^-3It introduced until it became Pa, formed into a film with sputter | spatter output 100W and the substrate temperature of 100 degreeC, and evaluated.
[0144]
Comparative Example 7
In Example 1, a transparent conductive layer was produced in the same manner as in Example 1 except that the transparent conductive layer was prepared by dip coating organic ITO paste Neufrocoat EC-L manufactured by Kyoto Elex Co., Ltd. Evaluation was performed in the same manner as in Example 1.
[0145]
Comparative Example 8
A transparent conductive film laminate was formed in the same manner as in Comparative Example 1 except that the primer layer was prepared in the same manner as in Comparative Example 1 in Comparative Example 6, and evaluation was performed in the same manner as in Example 1.
[0146]
  From Example 1From 3 and 79,Comparative Examples 4a to 6a andThe evaluation results of Comparative Examples 1 to 8 are summarized in Table 1. In Table 1, TEOS is tetraethoxysilane (SiO_x(OEt)_y). Ratio of x and y of tetraethoxysilane usedRateDescribed. APG (Atmospheric Pressure Glow Plasma)Means atmospheric pressure glow discharge.
[0147]
[Table 1]

[0148]
From Table 1, it can be seen that the transparent conductive film laminate of the present invention is excellent in all of transmittance, resistivity, carbon content, In / Sn, flexibility, and deterioration test.
[0149]
Example 10
In Example 1, two plasma discharge devices shown in FIG. 6 were prepared, and a 2000 m long film having ZEONOR ZF16 (thickness: 100 μm) made by Nippon Zeon Co., Ltd. was used as a primer layer in the first discharge device. A transparent conductive layer was formed with a second discharge device, and transmittance, specific resistance, durability, and deterioration tests were performed.
[0150]
Comparative Example 9
In Example 10, after coating the primer layer used in Comparative Example 1, it was wound up once, and then a transparent conductive layer was produced with the plasma discharge device for forming the transparent conductive layer used in Example 10, and the transmittance, Specific resistance, flexibility and deterioration tests were performed.
[0151]
Comparative Example 10
In Example 10, after coating the primer layer used in Comparative Example 1, it was wound up once, and a tin-doped indium oxide film was formed on the primer layer using a winding-type magnetron sputtering apparatus having a vacuum chamber, a sputtering target, and a gas introduction system. Was made. Film is introduced into the device, and the inside is 4.000 × 10^-3The pressure was reduced to Pa. A sputtering target having a composition of indium oxide: tin oxide 95: 5 was used. Thereafter, the film was rewound and degassed. Then, a mixed gas of argon gas and oxygen gas (Ar: O₂= 98.8: 1.2) to 1 × 10^-3It is introduced until it reaches Pa, the temperature of the main roll is room temperature, the feeding speed of the film is 0.1 m / min, and the input power density is 1 W / cm.²As in Example 10, evaluation was performed.
[0152]
  Table 2 summarizes the evaluation results of Example 10 and Comparative Examples 9 and 10. In comparison with Example 10, the total film forming time in Comparative Example 9 was 3 times, and in Comparative Example 10, it was 5 times. In Table 2, TEOS, x,y andAnd APGIs synonymous with each of Table 1.
[0153]
[Table 2]

[0154]
From Table 2, it can be seen that the transparent conductive film laminate of the present invention is excellent in all of transmittance, resistivity, carbon content, In / Sn, flexibility, and deterioration test.
[0155]
Example 11
Preparation of PET film A1 with primer layer
A 175 μm polyethylene terephthalate film is used as the base material, and the plasma discharge device uses a parallel plate type electrode. The PET base material is placed between the electrodes, and a mixed gas is introduced to form a thin film. went.
[0156]
In addition, the following thing was used for the electrode. A 200 mm x 200 mm x 2 mm stainless steel plate is coated with a high-density, high-adhesion alumina sprayed coating, and then a solution obtained by diluting tetramethoxysilane with ethyl acetate is applied and dried, and then cured by UV irradiation for sealing treatment. It was. The dielectric surface thus coated was polished, smoothed, and processed to have an Rmax of 5 μm. In this way, an electrode was produced and grounded.
[0157]
On the other hand, as the application electrodes, a plurality of hollow rectangular pure titanium pipes coated with the same dielectric material as described above were produced under the same conditions as the opposing electrode group.
[0158]
The power source used for plasma generation is a high frequency power source JRF-10000 manufactured by JEOL Ltd. and a voltage of 150 kHz and 2 W / cm.²Power was supplied.
[0159]
A reactive gas having the following composition was allowed to flow between the electrodes.
Inert gas: Helium 98.5% by volume
Reactive gas 1: 0.25% by volume of oxygen
Reactive gas 2: Tetraethoxysilane 1.25% by volume
An atmospheric pressure plasma treatment was performed on the substrate under the reactive gas and reaction conditions to form a primer layer. A PET film with a primer layer produced by the above method is designated as A1.
[0160]
Preparation of PET film A2 with primer layer
Next, the reactive gas was made into the following composition, and the primer layer was formed on PET like the said method. This is A2.
Inert gas: Helium 97.75% by volume
Reactive gas 1: 0.25% by volume of oxygen
Reactive gas 2: Tetraethoxysilane 2.00% by volume
Preparation of PET film A3 with primer layer
The reactive gas was made into the following composition, and the primer layer was formed on PET like the said method. This is A3.
Inert gas: Helium 99.25% by volume
Reactive gas 1: 0.25% by volume of oxygen
Reactive gas 2: Tetraethoxysilane 0.50% by volume
Preparation of PET film B with primer layer
148 parts by mass of vinyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM1003) is put into a stirring vessel whose outside is cooled with water, and 54 parts of 0.01N hydrochloric acid is gradually added while stirring vigorously. Further, the mixture was slowly stirred for 3 hours to obtain a hydrolyzed liquid of vinyltrimethoxysilane. Subsequently, 50 parts by mass of trimethylolpropane triacrylate (trade name Aronix M-309, manufactured by Toagosei Co., Ltd.), 100 parts by mass of the hydrolyzed liquid of vinyltrimethoxysilane, 10 parts by mass of unhydrolyzed vinyltrimethoxysilane, Photoinitiator 2-hydroxy-2-methyl-1-phenylpropan-1-one (Merck, trade name Darocur 1173) 8 parts by weight and silicone oil as a leveling agent (Toray Dow Corning Silicone, SH28PA) 0 0.02 part by mass was mixed to prepare a coating solution. This coating solution was coated on a substrate using a bar coater, heated at 60 ° C. for 1 minute to volatilize and remove the residual solvent in the coating film, and then an integrated light amount of 800 mJ / cm using a 160 W / cm high-pressure mercury lamp. cm²The primer layer was obtained by curing the coating film by irradiating with ultraviolet rays under the conditions described above.
[0161]
Preparation of PET film C with primer layer
After adding 88 parts by mass of acetic acid to a mixed solvent of 720 parts by mass of water and 1080 parts by mass of 2-propanol, 725 parts by mass of 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane and 3-aminopropyltrimethoxysilane are added. 176 parts by mass were sequentially added and stirred for 3 hours, and the film was roll-coated as a coating solution to form a cured resin layer having a dry film thickness of about 2 μm.
[0162]
Preparation of gas barrier layer
A gas barrier layer was formed on the PET film on which the primer layer was formed by the above method. The gas barrier layer was formed by the following method.
[0163]
Production of gas barrier layer 1
A gas barrier layer was formed by subjecting a PET film with a primer layer to atmospheric pressure plasma treatment using the following reaction gas in the same apparatus as that for forming the primer layer A1. The power source used for plasma generation is a high frequency power source JRF-10000 manufactured by JEOL Ltd. and a voltage of 13.56 MHz and 5 W / cm.²Power was supplied.
Inert gas: helium 96.75% by volume
Reactive gas 1: Oxygen 0.50% by volume
Reactive gas 2: Tetraethoxysilane 1.25% by volume
Production of gas barrier layer 2
A gas barrier layer 2 was prepared in the same manner as the gas barrier layer 1 except that the reactive gas had the following composition in the preparation of the gas barrier layer 1.
Inert gas: Helium 98.5% by volume
Reactive gas 1: 0.25% by volume of oxygen
Reactive gas 2: Tetraethoxysilane 1.25% by volume
Production of gas barrier layer 3
In the production of the gas barrier layer 1, at a voltage of 10 kHz and 5 W / cm²A gas barrier layer was produced on a substrate with a primer layer in the same manner as in Yes 1 except that the above power was supplied.
[0164]
Production of gas barrier layer 4
In the production of the gas barrier layer 1, the crest value is 10 kV and the discharge current density is 100 mA / cm as in Example 1 of Japanese Patent Laid-Open No. 2001-74906.²Apply a pulse electric field with a frequency of 6 kHz and 5 W / cm²A gas barrier layer was produced on a substrate with a primer layer in the same manner as in Yes 1 except that the above power was supplied.
[0165]
Method for forming gas barrier layer 5
In the production of the gas barrier layer 1, the input power is 0.1 W / cm.²A gas barrier layer was produced on a substrate with a primer layer in the same manner as in Example 1 except that
[0166]
Method for producing gas barrier layer 6
In the production of the gas barrier layer 1, the input power is 10 W / cm.²A gas barrier layer was produced on the substrate with the primer layer in the same manner as in the production of 1 except for the above.
[0167]
Preparation of gas barrier layer filter
4.000 × 10 4 as a B-doped Si target in a normal magnetron sputtering apparatus^-FourAfter exhausting to Pa, O₂A mixed gas of / Ar = 3: 7 was introduced at 100 sccm, and the pressure was adjusted to 0.1067 Pa. Main roll temperature 25 ° C, input power density 1W / cm²Then, reactive sputtering was performed at a film speed of 1.0 m / min to form a gas barrier layer made of silicon oxide having a thickness of about 30 nm.
[0168]
Production of gas barrier layer
A gas barrier layer was formed under the following conditions using a low pressure plasma CVD apparatus.
Applied power 30 kW
Pressure 66.66Pa
HMDSO (hexamethyldisiloxane) flow rate 1 slm
Oxygen gas flow rate 10 slm
Deposition drum surface temperature (deposition temperature) 100 ° C
The gas flow unit slm is a standard liter per minute.
[0169]
A transparent conductive film was formed by the following method on the PET film on which the primer layer and the gas barrier layer were formed by the above method.
[0170]
Method for forming transparent conductive film
A transparent conductive film was formed on a PET film with a primer layer and a gas barrier layer to form a transparent conductive film laminate. The method for forming the transparent conductive film was as follows.
[0171]
Method for forming transparent conductive film 11
A transparent conductive film laminate was produced on a substrate with a primer and gas barrier layer using a gas having the following composition as a reaction gas. The power source used for plasma generation is a high frequency power source JRF-10000 manufactured by JEOL Ltd. and a frequency of 13.56 MHz and 5 W / cm.²Power was supplied.
Inert gas: Helium 98.5% by volume
Reactive gas 1: 0.25% by volume of oxygen
Reactive gas 2: Tris (2,4-pentanedionato) indium 1.2% by volume
Reactive gas 3: Dibutyltin diacetate 0.05% by volume
Method for forming transparent conductive film 12
In the production of the transparent conductive film 11, a voltage of 10 kHz and 5 W / cm²A transparent conductive film laminate was prepared on a substrate with a primer and gas barrier layer in the same manner as in 11 except that the above power was supplied.
[0172]
Method for forming transparent conductive film 13
In the production of the transparent conductive film 11, the crest value is 10 kV and the discharge current density is 100 mA / cm in the same manner as in Example 1 of JP-A-2001-74906.²Apply a pulse electric field with a frequency of 6 kHz and 5 W / cm²A transparent conductive film laminate was prepared on a substrate with a primer and gas barrier layer in the same manner as in 11 except that the above power was supplied.
[0173]
Method for forming transparent conductive film 14
In the production of the transparent conductive film 11, the input power is 0.1 W / cm.²A transparent conductive film laminate was produced on a substrate with a primer and gas barrier layer in the same manner as in the production of 11 except that.
[0174]
Method for producing transparent conductive film 15
In the production of the transparent conductive film 11, the input power is 10 W / cm.²A transparent conductive film laminate was produced on a substrate with a primer and gas barrier layer in the same manner as in the production of 11 except that.
[0175]
Method for forming transparent conductive film 2
A primer and gas barrier layer-coated PET base material is mounted on a DC magnetron sputtering apparatus, and the inside of the vacuum chamber is 1.3332 × 10^-3The pressure was reduced to Pa or lower. A sputtering target having a composition of indium oxide: tin oxide 95: 5 was used. Thereafter, a mixed gas of argon gas and oxygen gas is used (Ar: O₂= 1000: 3) is 1 × 10^-3It introduced until it became Pa, and formed the transparent conductive film laminated body with the sputter | spatter output 100W and the substrate temperature of 100 degreeC.
[0176]
Method for forming transparent conductive film 3
A transparent conductive film laminate was prepared in the same manner as the transparent conductive film 11 except that the transparent conductive layer was prepared by dip coating organic ITO paste New Flow Coat EC-L manufactured by Kyoto Elex Co., Ltd.
[0177]
The above-described primer layer, gas barrier layer, and transparent conductive film were combined as shown in Table 3 to prepare 27 transparent conductive film laminates.
[0178]
Evaluation of the obtained transparent conductive film laminated body was performed by the method mentioned above. The gas barrier property evaluation method is described below.
[0179]
<Gas barrier properties>
The oxygen permeability was used as an indicator of gas barrier properties. The oxygen permeability was measured for a polymer film in which a primer layer and a gas barrier layer were laminated before laminating a transparent conductive layer. The measurement was performed in an environment of 40 ° C. and 90% RH using an Oxytran 2/20 model manufactured by MOCON.
[0180]
[Table 3]

[0181]
From Table 3, it can be seen that the transparent conductive film laminate of the present invention is excellent in gas barrier properties, transmittance, resistivity, flexibility, and deterioration test.
[0182]
【The invention's effect】
  Manufacturing method for producing a high-performance transparent conductive film having high transparency, electrical conductivity, and adhesion to a substrate with high productivity and low environmental load according to the present invention.The lawCould be provided.
[Brief description of the drawings]
FIG. 1 is a schematic view showing an example of a plasma discharge treatment vessel installed in a plasma discharge treatment apparatus used in a production method of the present invention.
FIG. 2 is a schematic view showing an example of a plasma discharge treatment vessel installed in a plasma discharge treatment apparatus used in the production method of the present invention.
FIGS. 3A and 3B are schematic views showing an example of a cylindrical roll electrode used in the plasma discharge treatment according to the present invention.
FIGS. 4A and 4B are schematic views showing an example of a fixed cylindrical electrode used in the plasma discharge treatment according to the present invention.
FIGS. 5A and 5B are schematic views showing an example of a fixed prismatic electrode used in the plasma discharge treatment according to the present invention.
FIG. 6 is a conceptual diagram showing an example of a plasma discharge treatment apparatus used in the transparent conductive film forming method of the present invention.
[Explanation of symbols]
25, 25c, 25C Roll electrode
26, 26c, 26C, 36, 36c, 36C Electrode
25a, 25A, 26a, 26A, 36a, 36A Conductive base material such as metal
25b, 26b, 36b Ceramic coated dielectric
25B, 26B, 36B Lining dielectric
31 Plasma discharge treatment vessel
41 Power supply
51 Gas generator
52 Air supply port
53 Exhaust vent
60 Electrode cooling unit
61 Original winding base material
65, 66 Nip roller
64, 67 Guide rollers

Claims (21)

In a method for producing a transparent conductive film laminate in which a primer layer and a transparent conductive layer are laminated on a transparent substrate, a high frequency voltage of a continuous sine wave having a frequency of 150 kHz or more under atmospheric pressure or pressure near atmospheric pressure. In addition, an electric field discharged by supplying electric power of 1 to 50 W / cm ² is applied to the discharge space when forming the primer layer and the transparent conductive layer, and at least one kind of inert gas and at least one kind The primer layer is formed on the transparent substrate by introducing a mixed gas composed of the above organometallic compound and at least one kind of reactive gas into a discharge space to form a plasma state and exposing the transparent substrate. Furthermore, at least one kind of inert gas, at least one kind of organometallic compound, and at least one kind or more under atmospheric pressure or pressure near atmospheric pressure. The transparent conductive layer is formed on the primer layer by introducing a mixed gas composed of the reactive gas in the discharge space to a plasma state and exposing the substrate on which the primer layer is formed on the transparent substrate. The manufacturing method of the transparent conductive film laminated body characterized by these. In a method for producing a transparent conductive film laminate in which a primer layer, a gas barrier layer, and a transparent conductive layer are laminated on a transparent substrate, a continuous sine wave having a frequency of 150 kHz or more under atmospheric pressure or pressure near atmospheric pressure . At least one kind of inertness is applied to the discharge space when the primer layer, the gas barrier layer and the transparent conductive layer are formed by applying an electric field discharged by supplying a power of 1 to 50 W / cm ² at a high frequency voltage. A gas, a mixed gas composed of at least one or more kinds of organometallic compounds and at least one kind of reactive gas is introduced into a discharge space to form a plasma state, and the transparent substrate is exposed to the plasma on the transparent substrate. The primer layer is formed, and at least one kind of inert gas and at least one kind of organometalation under atmospheric pressure or pressure near atmospheric pressure. By introducing a mixed gas composed of a compound and at least one kind of reactive gas into the discharge space to be in a plasma state and exposing the substrate on which the primer layer is formed on the transparent substrate, the primer layer is exposed to the primer layer. A gas mixture is formed by forming a gas barrier layer and then comprising at least one or more inert gases, at least one or more organometallic compounds, and at least one or more reactive gases at or near atmospheric pressure. The transparent conductive layer is formed on the gas barrier layer by exposing the base material in which the primer layer and the gas barrier layer are formed on the transparent base material by introducing into the discharge space into a plasma state. Manufacturing method of electrically conductive film laminated body.   The gas barrier layer is an inorganic compound containing at least one element selected from the group consisting of magnesium, silicon, zirconium, titanium, tungsten, tantalum, aluminum, zinc, indium, chromium, vanadium, niobium, and tin. Manufacturing method of transparent conductive film laminate. The method for producing a transparent conductive film laminate according to any one of claims 1 to 3, wherein the primer layer is a film of the following general formula (1).
General formula (1) MO _x (R) _y
(In the formula, M represents at least one metal selected from silicon, zirconium, titanium, tungsten, tantalum, aluminum, zinc, indium, chromium, vanadium, niobium, and tin, and R represents an alkyl group having 1 to 8 carbon atoms. X represents 1.50 to 1.99, and y represents 0.02 to 1.00.)   M of general formula (1) is silicon, The manufacturing method of the transparent conductive film laminated body of any one of Claims 1-4 characterized by the above-mentioned. The organometallic compound introduced into the discharge space to form the transparent conductive film is an organometallic compound represented by the following general formula (2) or general formula (3): The manufacturing method of the transparent conductive film laminated body of any one of these.

(In the formula, M is at least one selected from indium, tin and zinc, R ₁ and R ₂ each independently represents a fluoroalkyl group containing at least one fluorine having 1 to 10 carbon atoms, and n Represents an integer of 1 to 2)   A mixed gas containing at least one kind of inert gas is introduced into the discharge space for forming a primer layer or a transparent conductive film, and the inert gas contains argon or helium. The manufacturing method of the transparent conductive film laminated body of any one of these. The mixed gas containing at least one kind of inert gas is introduced into the discharge space forming the gas barrier layer, and the inert gas contains argon or helium. The manufacturing method of the transparent conductive film laminated body of description. The method for producing a transparent conductive film laminate according to any one of claims 1 to 8 , wherein the high-frequency voltage is less than 150 MHz . The method for producing a transparent conductive film laminate according to claim 9, wherein the high frequency voltage, characterized in der Rukoto than 200kHz. The method according to claim 9 or 10 transparent conductive film laminate, wherein the high-frequency voltage is on 800k Hz or more. Electric power is 1.2 W / cm < ² > or more , The manufacturing method of the transparent conductive film laminated body of any one of Claims 1-8 characterized by the above-mentioned. The process according to claim 1 second transparent conductive film laminate, wherein the power is 50 W / cm ² or less. The method of claim 12 or 13 transparent conductive film laminate, wherein the power is ² hereinafter 20 W / cm. The method for producing a transparent conductive film laminate according to any one of claims 8 to 14 , wherein at least one of the electrodes is coated with a dielectric . The method for producing a transparent conductive film laminate according to claim 1 5 in which the dielectric constant of the dielectric is characterized in that an inorganic material of 6 to 45. The surface roughness Rmax of an electrode is 10 micrometers or less , The manufacturing method of the transparent conductive film laminated body of Claim 15 or 16 characterized by the above-mentioned. The transparent conductive thin film mainly includes at least one selected from indium oxide, tin oxide, zinc oxide, F-doped tin oxide, Al-doped zinc oxide, Sb-doped tin oxide, ITO, and an In ₂ O ₃ —ZnO-based amorphous transparent conductive film. the method for producing a transparent conductive film laminate of any one of claims 1 to 17, characterized in that the components. The transparent conductive film is an ITO film, any one of claims 1 to 18, wherein the ITO film is in the range of 100 / 0.1 to 100/15 in an In / Sn atomic ratio Manufacturing method of transparent conductive film laminate. After forming the primer layer if there is no gas barrier layer on a transparent substrate, the claims if they have a gas barrier layer and forming a transparent conductive film without after forming the gas barrier layer, winding 1 The manufacturing method of the transparent conductive film laminated body of any one of -19 . 21. The method for producing a transparent conductive film laminate according to claim 1, wherein the carbon content of the transparent conductive film is in the range of 0 to 5.0 atomic concentration .

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