JPH1044289A - Transparent conductive film for electroluminescent element - Google Patents
Transparent conductive film for electroluminescent elementInfo
- Publication number
- JPH1044289A JPH1044289A JP8219091A JP21909196A JPH1044289A JP H1044289 A JPH1044289 A JP H1044289A JP 8219091 A JP8219091 A JP 8219091A JP 21909196 A JP21909196 A JP 21909196A JP H1044289 A JPH1044289 A JP H1044289A
- Authority
- JP
- Japan
- Prior art keywords
- transparent conductive
- layer
- thickness
- conductive film
- conductive 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.)
- Granted
Links
Landscapes
- Electroluminescent Light Sources (AREA)
- Laminated Bodies (AREA)
- Non-Insulated Conductors (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、エレクトロルミネ
ッセンス（以下、ＥＬという）素子用電極に用いられる
透明導電性フィルム（以下、ＥＬ用透明導電性フィルム
という）に関し、特に発光体層との密着性が良く、ＥＬ
素子として高湿雰囲気下で、連続点灯しても不点灯部の
発生の少ないＥＬ用透明導電性フィルムに関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent conductive film (hereinafter, referred to as "EL transparent conductive film") used for an electrode for an electroluminescence (hereinafter, referred to as "EL") element, and particularly to an adhesive property with a luminescent layer. Good, EL
The present invention relates to a transparent electroconductive film for EL, in which unlit portions are less likely to occur even when continuously lit in a high-humidity atmosphere as an element.
【０００２】[0002]
【従来の技術】従来、ＥＬ素子用透明電極としては、一
般的に、ポリエステルフィルムやポリエーテルスルホン
フィルム等の高分子フィルム表面の片面もしくは両面
に、酸化インジウム、酸化スズあるいはこれらの混合物
からなる透明導電層を真空蒸着法、スパッタリング法、
イオンプレーティング法等の成膜方法により形成したも
のが用いられている。2. Description of the Related Art Conventionally, as a transparent electrode for an EL element, generally, a transparent film made of indium oxide, tin oxide or a mixture thereof is provided on one or both surfaces of a polymer film such as a polyester film or a polyethersulfone film. Vacuum evaporation method, sputtering method,
Those formed by a film forming method such as an ion plating method are used.
【０００３】特に、防湿層のないパッケージレスタイプ
のＥＬ素子は、例えば図１に示したように、透明導電層
上に発光体層、誘電体層、背面電極層を順次積層して作
成されている。従来の防湿層のあるタイプのＥＬに比
べ、製品の厚みを約１／４に薄型化でき、また防湿層の
ヒートシール部がなくなるので小型化できる等の特長が
あり、腕時計や目覚まし時計の文字板照明、小型液晶用
バックライトとして広く利用されている。In particular, a package-less type EL device without a moisture-proof layer is formed by sequentially laminating a light-emitting layer, a dielectric layer, and a back electrode layer on a transparent conductive layer as shown in FIG. I have. Compared to the conventional EL with a moisture-proof layer, the thickness of the product can be reduced to about 1/4 and the heat-sealing part of the moisture-proof layer is eliminated, making it possible to reduce the size. It is widely used as a board illumination and a backlight for small liquid crystals.
【０００４】しかしながら、透明導電層の膜厚が２００
〜４００Åで 表面抵抗が２００〜４００Ω／□である
従来の透明導電性フィルムを使用したパッケージレスタ
イプのＥＬ素子は、高湿雰囲気下でインバーターを用い
て、連続点灯した場合、点状に不点灯部が発生し、発光
輝度が低下して最終的に全面不点灯となる問題を有して
いる。However, the thickness of the transparent conductive layer is 200
A conventional package-less type EL element using a transparent conductive film having a surface resistance of 200 to 400 Ω / □ at a temperature of up to 400 ° C. does not light up in a dot-like manner when continuously lit using an inverter in a high-humidity atmosphere. This causes a problem that the light emission luminance is reduced and the entire surface is finally turned off.
【０００５】また、従来の透明導電性フィルムと発光体
層の密着性が悪いことから、この改善方法として、たと
えば、特開昭６４−４５０８６号公報、特開昭６４−８
１１１２号公報、特開平２−９８４３６号公報などに例
示されているシアノエチルプルランような高誘電率のセ
ルロース系樹脂が透明導電層上に積層されている。しか
しながら、パッケージレスタイプのＥＬは、発光体層に
フッ素系樹脂を含有するため、従来の透明導電性フィル
ムに使用されている高誘電率のセルロース系樹脂では、
発光体層の密着性が悪く、浮きを生じ、不点灯となる問
題を有している。[0005] Further, because of the poor adhesion between the conventional transparent conductive film and the luminous layer, as a method for improving this, for example, JP-A-64-45086 and JP-A-64-8
A cellulose resin having a high dielectric constant, such as cyanoethyl pullulan, which is exemplified in JP-A-1112 and JP-A-2-98436, is laminated on a transparent conductive layer. However, since the packageless type EL contains a fluorine-based resin in the luminous body layer, the high dielectric constant cellulose-based resin used in the conventional transparent conductive film cannot be used.
There is a problem that the adhesion of the luminous body layer is poor, floating occurs, and the light is not lit.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、上記
のような従来の透明導電性フィルムが有する問題を解消
し、パッケージレスタイプＥＬを高湿雰囲気下でインバ
ーターを用いて、連続点灯しても長時間安定して性能を
保持し、発光体層との密着性に優れたＥＬ用透明導電性
フィルムを提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the conventional transparent conductive film, and to continuously light a packageless type EL using an inverter under a high humidity atmosphere. It is still another object of the present invention to provide a transparent conductive film for EL which stably maintains the performance for a long time and has excellent adhesion to the luminescent layer.
【０００７】[0007]
【課題を解決するための手段】上記の課題を解決するた
めの第一の本発明は、透明高分子フィルムと、その少な
くとも一面上に、酸化スズ（ＳｎＯ2 ）を３〜１５重量
％含有する酸化インジウム（Ｉｎ2 Ｏ3 ）−酸化スズ
（ＳｎＯ2 ）焼結体からなる厚さ５００〜１０００Åの
透明導電層、誘電率１０以上の高誘電率樹脂層を順次積
層してなることを特徴とするＥＬ素子用透明導電性フィ
ルムに関するものである。また第二の本発明は、前記シ
アノアルキル変性フッ素系樹脂層の厚みが０．０５〜
０．５μｍである前記第一の発明のＥＬ素子用透明導電
性フィルムに関するものである。According to a first aspect of the present invention, there is provided a transparent polymer film comprising tin oxide (SnO 2 ) on at least one surface thereof in an amount of 3 to 15% by weight. A transparent conductive layer made of indium oxide (In 2 O 3 ) -tin oxide (SnO 2 ) sintered body having a thickness of 500 to 1000 ° and a high dielectric resin layer having a dielectric constant of 10 or more are sequentially laminated. And a transparent conductive film for an EL element. In the second invention, the thickness of the cyanoalkyl-modified fluorine-based resin layer is 0.05 to
The present invention relates to the transparent conductive film for an EL device of the first invention, which has a thickness of 0.5 μm.
【０００８】また第三の本発明は、前記シアノアルキル
変性フッ素系樹脂層が、ポリフッ化ビニリデン、ポリフ
ッ化ビニル、ポリフッ化ビニリデン−６フッ化プロピレ
ン共重合体、ポリフッ化ビニリデン−６フッ化プロピレ
ン−４フッ化エチレン三元共重合体、４フッ化エチレン
−プロピレン共重合体、ポリ（２，２，２−トリフルオ
ロエチルビニルエーテル）から選ばれた少なくとも１種
のフッ素系樹脂のシアノアルキル変性物からなる前記各
発明のＥＬ素子用透明導電性フィルムに関するものであ
る。さらに本発明は、前記透明導電層が、圧力勾配型放
電によるイオンプレーティング法によって形成されたも
のである前記各発明のＥＬ素子用透明導電性フィルムに
関する。In a third aspect of the present invention, the cyanoalkyl-modified fluororesin layer is made of polyvinylidene fluoride, polyvinyl fluoride, polyvinylidene fluoride-6-propylene copolymer, polyvinylidene fluoride-6-propylene fluoride. From a cyanoalkyl modified product of at least one fluororesin selected from tetrafluoroethylene terpolymer, tetrafluoroethylene-propylene copolymer and poly (2,2,2-trifluoroethyl vinyl ether) And a transparent conductive film for an EL device according to the invention. Furthermore, the present invention relates to the transparent conductive film for an EL element of the above invention, wherein the transparent conductive layer is formed by an ion plating method using a pressure gradient discharge.
【０００９】[0009]
【発明の実施の形態】透明高分子フィルムの材料として
は、耐熱性を有する透明な高分子フィルムであれば特に
制限はなく、１００℃以上においても耐熱性を有するも
のが好ましく、たとえばポリエチレンテレフタレート、
ポリエチレンナフタレート、ポリブチレンテレフタレー
ト、ポリオレフィン、ポリアミド、芳香族ポリアミド、
ポリアミドイミド、ポリエーテルイミド、ポリエーテル
サルフォン、ポリサルフォン、ポリエーテルエーテルケ
トン、ポリアリレート、ポリフェニレンサルファイド、
ポリフェニレンオキサイド、ポリパラバン酸、ポリカー
ボネート、等が例示できる。また透明高分子フィルムの
厚さは、２５〜２５０μｍが好ましく、より好ましくは
５０〜２００μｍである。上記の透明高分子フィルム上
に密着性向上のため、予めコロナ放電処理、表面改質を
行うプラズマ処理やサンドブラストを用いた粗面化処理
等の表面処理、または有機系樹脂による公知のアンカー
コート処理を施してもよい。DESCRIPTION OF THE PREFERRED EMBODIMENTS The material of the transparent polymer film is not particularly limited as long as it is a transparent polymer film having heat resistance. A material having heat resistance even at 100 ° C. or higher is preferable. For example, polyethylene terephthalate,
Polyethylene naphthalate, polybutylene terephthalate, polyolefin, polyamide, aromatic polyamide,
Polyamide imide, polyether imide, polyether sulfone, polysulfone, polyether ether ketone, polyarylate, polyphenylene sulfide,
Examples thereof include polyphenylene oxide, polyparabanic acid, and polycarbonate. Further, the thickness of the transparent polymer film is preferably from 25 to 250 μm, more preferably from 50 to 200 μm. In order to improve adhesion on the transparent polymer film, a surface treatment such as a corona discharge treatment, a plasma treatment for performing surface modification or a surface roughening treatment using sandblasting, or a known anchor coating treatment with an organic resin is performed. May be applied.
【００１０】前記透明高分子フィルムの表面に形成する
透明導電層には、金、銀、銅、酸化インジウム（Ｉｎ2
Ｏ3 ）、酸化スズ（ＳｎＯ2 ）、または酸化インジウム
に３〜１５重量％の酸化スズを含有する焼結体（以下、
ＩＴＯという）を用いることができるが、特に酸化イン
ジウムに３〜１５重量％の酸化スズの焼結体であるＩＴ
Ｏが、本発明に好ましく用いられる。透明導電層の厚さ
は、５００〜１０００Åの範囲が好ましい。厚さが１０
００Åより大であると、耐屈曲性が悪く、ＥＬ加工時に
クラックを生じ、断線し易くなる。一方厚さが５００Å
未満では、高湿雰囲気下で不点灯部が発生し易い。この
ようにして得た透明導電層の表面抵抗は、１５０Ω／□
以下が好ましい。The transparent conductive layer formed on the surface of the transparent polymer film includes gold, silver, copper, indium oxide (In 2
O 3 ), tin oxide (SnO 2 ), or a sintered body containing 3 to 15% by weight of tin oxide in indium oxide (hereinafter referred to as “sintered body”).
In particular, indium oxide is a sintered body of tin oxide of 3 to 15% by weight.
O is preferably used in the present invention. The thickness of the transparent conductive layer is preferably in the range of 500 to 1000 °. Thickness 10
If it is larger than 00 °, the bending resistance is poor, cracks occur during EL processing, and the wires are easily broken. On the other hand, the thickness is 500mm
If it is less than 3, a non-lighting portion is likely to occur in a high humidity atmosphere. The surface resistance of the transparent conductive layer thus obtained was 150 Ω / □.
The following is preferred.
【００１１】透明導電層の形成法としては、真空蒸着
法、スパッタリング法、イオンプレーティング法、ある
いはＣＶＤ法等既知の各種成膜法が上げられる。なかで
もＥＬ素子用の透明導電性フィルムの透明導電層は基材
との密着も重要であることから、陰極と陽極の間に中間
電極を設けて、陰極側の真空度と陽極側の真空度との間
に圧力勾配をもたせて行う圧力勾配型放電方式によるイ
オンプレーティング法は、透明導電層と基材の付着力が
極めて強いのみならず、成膜材料の蒸発量が多く、１０
０〜２００Å／ｓｅｃ程度と、従来の真空蒸着やスパッ
タリング法に比べてイオン化率が高く、大面積での加工
で数十倍〜数百倍の成膜速度が得られるため生産性が高
いし、低温で成膜できるためフィルム面上であっても低
抵抗膜の作成が可能であり、得られる透明導電層が高平
滑度かつ非晶質であって酸エッチング速度が早いなどの
利点があり、好ましい。As a method for forming the transparent conductive layer, various known film forming methods such as a vacuum deposition method, a sputtering method, an ion plating method, and a CVD method can be used. Above all, since the adhesion of the transparent conductive layer of the transparent conductive film for EL elements to the substrate is also important, an intermediate electrode is provided between the cathode and the anode, and the vacuum degree on the cathode side and the vacuum degree on the anode side are provided. The ion plating method by the pressure gradient discharge method in which a pressure gradient is applied between the transparent conductive layer and the substrate is not only extremely strong, but also the evaporation amount of the film forming material is large, and
About 0 to 200 ° / sec, the ionization rate is higher than the conventional vacuum evaporation or sputtering method, and a film formation rate of several tens to several hundred times can be obtained by processing in a large area, so that productivity is high, Since it can be formed at a low temperature, it is possible to form a low-resistance film even on the film surface, and the resulting transparent conductive layer has advantages such as high smoothness and amorphousness and a high acid etching rate, preferable.
【００１２】このような透明導電層の表面上に設けるシ
アノアルキル変性フッ素系樹脂層としては、ＥＬ素子の
発光層バインダーと密着性及び絶縁性がよく、薄層化の
可能な誘電率１０以上のフッ素系樹脂を用いることが好
ましい。誘電率１０未満の場合には、誘電損失が大き
く、消費電力も大きくなり、ＥＬ素子の不点灯部が発生
する。The cyanoalkyl-modified fluororesin layer provided on the surface of such a transparent conductive layer has good adhesion and insulation to the binder of the light-emitting layer of the EL element, and has a dielectric constant of 10 or more which can be thinned. It is preferable to use a fluorine resin. When the dielectric constant is less than 10, the dielectric loss is large, the power consumption is also large, and the non-lighted portion of the EL element occurs.
【００１３】本発明に用いられるシアノアルキル変性フ
ッ素系樹脂層は、炭素数１〜１０のシアノアルキル基で
変性したものであり、変性対象となるフッ素系樹脂とし
ては、ポリフッ化ビニリデン、ポリフッ化ビニル、ポリ
フッ化ビニリデン−６フッ化プロピレン共重合体、ポリ
フッ化ビニリデン−６フッ化プロピレン−４フッ化エチ
レン三元共重合体、４フッ化エチレン−プロピレン共重
合体、ポリ（２，２，２−トリフルオロエチルビニルエ
ーテル）から選ばれた少なくとも１種を用いることが好
ましく、これらは単独または２種類以上を組み合わせて
用いることができる。シアノアルキル変性フッ素系樹脂
層の厚さは、０．０５〜０．５μｍとするのが好まし
い。０．０５μｍ未満の場合には、発光体層との密着性
が向上せず、一方、０．５μｍより厚くなると、透明導
電層と発光層間の絶縁抵抗が高くなるため、ＥＬ素子の
消費電力が高くなり、発光輝度が低下するという悪影響
を及ぼすことがある。The cyanoalkyl-modified fluororesin layer used in the present invention is modified with a cyanoalkyl group having 1 to 10 carbon atoms. The fluororesin to be modified includes polyvinylidene fluoride and polyvinyl fluoride. , Polyvinylidene fluoride-6-propylene copolymer, polyvinylidene fluoride-6-propylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-propylene copolymer, poly (2,2,2- It is preferable to use at least one selected from trifluoroethyl vinyl ether), and these can be used alone or in combination of two or more. The thickness of the cyanoalkyl-modified fluorine-based resin layer is preferably 0.05 to 0.5 μm. When the thickness is less than 0.05 μm, the adhesion to the light emitting layer is not improved, while when the thickness is more than 0.5 μm, the insulation resistance between the transparent conductive layer and the light emitting layer increases, so that the power consumption of the EL element is reduced. And the emission luminance may be reduced.
【００１４】高誘電率樹脂層に用いるシアノアルキル変
性フッ素系樹脂は、アセトン、メチルエチルケトン、ジ
メチルホルムアミド、エチルセロソルブアセテート、ブ
チルセロソルブアセテート、シクロヘキサノンなどの有
機溶剤に溶解して塗工溶液とし、この塗工溶液をロール
コーター、グラビアコーター、バーコーター等により透
明導電層の表面上に塗工し、乾燥する。The cyanoalkyl-modified fluororesin used for the high dielectric constant resin layer is dissolved in an organic solvent such as acetone, methyl ethyl ketone, dimethylformamide, ethyl cellosolve acetate, butyl cellosolve acetate, cyclohexanone to form a coating solution. Is coated on the surface of the transparent conductive layer by a roll coater, a gravure coater, a bar coater or the like, and dried.
【００１５】[0015]
【実施例】以下に実施例を挙げて本発明をより具体的に
説明するが、本発明はこれによって限定されるものでは
ない。 実施例１ 厚さ１２５μｍのポリエチレンテレフタレート基材上に
ＳｎＯ2 を５重量％含むＩＴＯ焼結体を圧力勾配型放電
によるイオンプレーティング法により厚さ５００Åの透
明導電層を形成した。EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. Example 1 An ITO sintered body containing 5% by weight of SnO 2 was formed on a polyethylene terephthalate substrate having a thickness of 125 μm to form a 500 ° thick transparent conductive layer by an ion plating method using a pressure gradient discharge.
【００１６】次いで、下記のシアノエチル化ポリフッ化
ビニリデンー６フッ化プロピレン共重合体（誘電率１
９）からなる塗工液を、膜厚０．０５μｍとなるように
透明導電層の表面上にグラビアロールコーターにて塗工
し、１００℃で２分間乾燥して高誘電率樹脂層を形成し
た。 （高誘電率樹脂層用塗工液） シアノエチル化ポリフッ化ビニリデン−６フッ化 プロピレン共重合体 ５重量部 エチルセロソルブアセテート ９５重量部Next, the following cyanoethylated polyvinylidene fluoride-propylene hexafluoride copolymer (dielectric constant: 1)
The coating liquid comprising 9) was applied on the surface of the transparent conductive layer by a gravure roll coater so as to have a thickness of 0.05 μm, and dried at 100 ° C. for 2 minutes to form a high dielectric constant resin layer. . (Coating liquid for high dielectric constant resin layer) 5 parts by weight of cyanoethylated polyvinylidene fluoride-6-fluoropropylene copolymer 95 parts by weight of ethyl cellosolve acetate
【００１７】このようにして得られたＥＬ用透明導電性
フィルムのＩＴＯ膜厚、表面抵抗、高誘電率樹脂層の厚
さ、耐屈曲性を第１表に示した。また、耐屈曲性につい
ては、１０ｍｍφの丸棒に１ｃｍ巾×６ｃｍ長のＥＬ用
透明導電性フィルムのＩＴＯ膜面を上にして荷重１００
ｇを掛け、９０度曲げを１０回繰り返し、その試験前後
の表面抵抗変化の倍率で表した。Table 1 shows the ITO film thickness, surface resistance, thickness of the high dielectric constant resin layer, and flex resistance of the thus obtained transparent conductive film for EL. Regarding the bending resistance, a load of 100 mm was applied to a 10 mmφ round bar with the ITO film surface of the transparent conductive film for EL having a width of 1 cm and a length of 6 cm facing upward.
g, and 90-degree bending was repeated 10 times, and represented by the magnification of the change in surface resistance before and after the test.
【００１８】次いで、下記の発光体層用塗工液を、膜厚
３０μｍとなるように透明導電層の表面上にスクリーン
印刷し、１２０℃で３０分間乾燥し、発光体層を形成し
た。 （発光体層用塗工液） ポリフッ化ビニリデン−６フッ化プロピレン共重合体 １５重量部 硫化亜鉛 ４５重量部 エチルセロソルブアセテート ６０重量部Next, the following luminescent layer coating solution was screen-printed on the surface of the transparent conductive layer to a thickness of 30 μm and dried at 120 ° C. for 30 minutes to form a luminescent layer. (Coating solution for luminous body layer) Polyvinylidene fluoride-6-fluoropropylene copolymer 15 parts by weight Zinc sulfide 45 parts by weight Ethyl cellosolve acetate 60 parts by weight
【００１９】さらに、下記の誘電体層用塗工液を、膜厚
２０μｍとなるように発光体層の表面上にスクリーン印
刷し、１２０℃で３０分間乾燥し、誘電体層を形成し
た。 （誘電体層用塗工液） ポリフッ化ビニリデン−６フッ化プロピレン共重合体 １５重量部 チタン酸バリウム ４５重量部 エチルセロソルブアセテート ６０重量部Further, the following coating solution for a dielectric layer was screen-printed on the surface of the luminescent layer so as to have a thickness of 20 μm, and dried at 120 ° C. for 30 minutes to form a dielectric layer. (Coating liquid for dielectric layer) Polyvinylidene fluoride-6-fluoropropylene copolymer 15 parts by weight Barium titanate 45 parts by weight Ethyl cellosolve acetate 60 parts by weight
【００２０】さらに、前記のように形成した誘電体層の
上に、カーボンペースト（日本アチソン社製、商標：Ｅ
ｌｅｃｔｒｏｄａｇ ５０５ＳＳ）を厚さ１０μｍとな
るようにスクリーン印刷し、１２０℃で６０分間乾燥し
て、背面電極層を形成した。Further, on the dielectric layer formed as described above, a carbon paste (trade name: E, manufactured by Acheson Japan Co., Ltd.)
Electrodag 505SS) was screen-printed to a thickness of 10 μm and dried at 120 ° C. for 60 minutes to form a back electrode layer.
【００２１】このようにして作製した２ｃｍ×５ｃｍサ
イズのパッケージレスＥＬを３個作製し、４０℃、９０
％ＲＨの雰囲気下、１００Ｖ，４００Ｈｚの交流電源
で、４８時間点灯させ、発光面に０．５ｍｍ以上の不点
灯部の個数を数え、不点灯部の発生状況を評価した。不
点灯部が全く発生していないものを〇、不点灯部が１〜
５個未満のものを△、不点灯部が５個以上のものを×と
した。Three 2 cm × 5 cm packageless ELs manufactured as described above were manufactured,
The lamp was lit for 48 hours with an AC power supply of 100 V and 400 Hz in an atmosphere of% RH, and the number of unlit portions having a size of 0.5 mm or more on the light emitting surface was counted to evaluate the occurrence of unlit portions. If no non-lighting part is generated,
Those with less than 5 were rated as Δ, and those with 5 or more unlit portions were rated as x.
【００２２】また、ＪＩＳ−Ｋ５４００の碁盤目テープ
法により、透明導電層と発光体層の密着性を評価した。
はがれが全くないものを〇、はがれの面積が３５％未満
のものを△、はがれの面積が３５％以上のものを×とし
た。Further, the adhesion between the transparent conductive layer and the light emitting layer was evaluated by a grid tape method of JIS-K5400.
A sample with no peeling was rated as Δ, a sample with a peeling area of less than 35% was rated as Δ, and a sample with a peeling area of 35% or more was rated as ×.
【００２３】実施例２ 実施例１のポリエチレンテレフタレート基材上に透明導
電層の膜厚を９００ÅとしてＥＬ用透明導電性フィルム
を作製し、これを用いてＥＬ素子を実施例１と同様に作
製し、評価した。Example 2 A transparent conductive film for EL was prepared on the polyethylene terephthalate substrate of Example 1 with a transparent conductive layer having a thickness of 900 °, and an EL element was prepared in the same manner as in Example 1 using this. ,evaluated.
【００２４】実施例３ 実施例１の高誘電率樹脂層の塗工厚さを０．５μｍとす
る以外、実施例１と同様にＥＬ素子を作製し、評価し
た。Example 3 An EL element was prepared and evaluated in the same manner as in Example 1 except that the coating thickness of the high dielectric constant resin layer in Example 1 was changed to 0.5 μm.
【００２５】実施例４ 実施例１のポリエチレンテレフタレート基材上に透明導
電層の膜厚を９００Åとし、また高誘電率樹脂層の塗工
厚さを０．５μｍとする以外、実施例１と同様にＥＬ素
子を作製し、評価した。Example 4 Same as Example 1 except that the thickness of the transparent conductive layer was 900 ° on the polyethylene terephthalate substrate of Example 1, and the coating thickness of the high dielectric constant resin layer was 0.5 μm. An EL device was prepared and evaluated.
【００２６】比較例１ 実施例１のポリエチレンテレフタレート基材上にＳｎＯ
2 を２０重量％含むＩＴＯ燒結体とした以外、実施例１
と同様にＥＬ素子を作製し、評価した。Comparative Example 1 On the polyethylene terephthalate substrate of Example 1,
Except that the ITO sintered body containing 2 20% by weight, Example 1
An EL element was prepared and evaluated in the same manner as described above.
【００２７】比較例２ 誘電率６のポリエステル樹脂からなる下記塗工液を膜厚
０. ０５μｍとなるように、透明導電層の表面上にグラ
ビアロールコーターにて塗工し、１００℃で２分間乾燥
して、誘電体層を形成した以外は、実施例１と同様にＥ
Ｌ素子を作製し、評価した。 （誘電体層用塗工液） ポリエステル樹脂 ５重量部 トルエン／メチルエチルケトン＝１／１ ９５重量部Comparative Example 2 The following coating solution comprising a polyester resin having a dielectric constant of 6 was coated on the surface of the transparent conductive layer with a gravure roll coater so as to have a thickness of 0.05 μm, and then was applied at 100 ° C. for 2 minutes. Except for drying to form a dielectric layer, E was the same as in Example 1.
An L element was prepared and evaluated. (Coating solution for dielectric layer) Polyester resin 5 parts by weight Toluene / methyl ethyl ketone = 1/1 95 parts by weight
【００２８】比較例３ 実施例１のポリエチレンテレフタレート基材上に透明導
電層の膜厚を３００ÅとしてＥＬ用透明導電性フィルム
を作製し、これを用いてＥＬ素子を実施例１と同様に作
製し、評価した。Comparative Example 3 A transparent conductive film for EL was prepared on the polyethylene terephthalate substrate of Example 1 with a transparent conductive layer having a thickness of 300 °, and an EL element was prepared in the same manner as in Example 1 using this. ,evaluated.
【００２９】比較例４ 実施例１のポリエチレンテレフタレート基材上に透明導
電層の膜厚を３００Åとし、および高誘電率樹脂層の塗
工厚みを１．０μｍとする以外、実施例１と同様にＥＬ
素子を作製し、評価した。Comparative Example 4 The procedure of Example 1 was repeated, except that the thickness of the transparent conductive layer was 300 mm on the polyethylene terephthalate substrate of Example 1 and the coating thickness of the high dielectric constant resin layer was 1.0 μm. EL
A device was manufactured and evaluated.
【００３０】比較例５ 実施例１のポリエチレンテレフタレート基材上に透明導
電層の膜厚を１１００ÅとしてＥＬ用透明導電性フィル
ムを作製し、これを用いてＥＬ素子を実施例１と同様に
作製し、評価した。Comparative Example 5 A transparent conductive film for EL was prepared on the polyethylene terephthalate substrate of Example 1 with a transparent conductive layer having a thickness of 1100 °, and an EL element was prepared in the same manner as in Example 1 using this. ,evaluated.
【００３１】比較例６ 誘電率１９のシアノエチルプルラン樹脂からなる下記塗
工液を膜厚０．０５μｍとなるように、透明導電層の表
面上にグラビアロールコーターにて塗工し、１００℃で
２分間乾燥して、高誘電体層を形成した以外は、実施例
１と同様にＥＬ素子を作製し、評価した。 （高誘電体層用塗工液） シアノエチルプルラン樹脂 ５重量部 メチルエチルケトン／ジメチルフォルムアミド＝３／２ ９５重量部Comparative Example 6 The following coating solution comprising a cyanoethyl pullulan resin having a dielectric constant of 19 was coated on the surface of the transparent conductive layer with a gravure roll coater so as to have a thickness of 0.05 μm. An EL element was prepared and evaluated in the same manner as in Example 1 except that the high-dielectric layer was formed after drying for minutes. (Coating solution for high dielectric layer) Cyanoethyl pullulan resin 5 parts by weight Methyl ethyl ketone / dimethylformamide = 3/2 95 parts by weight
【００３２】[0032]
【表１】 [Table 1]
【００３３】第１表の結果からも明らかなように、実施
例１〜４のＥＬ用透明導電性フィルムは、耐屈曲性が良
好であり、不点灯部が発生せず、発光体層の密着性が良
好であり、発光輝度も高い。一方、比較例１は、表面抵
抗が、２３０Ω／□以上と高くなり、ＥＬ素子の発光体
面に不点灯部が３箇所発生した。また、比較例２は、Ｅ
Ｌ素子の発光面に不点灯部は、発生しないが、誘電損失
が大きくなり、発光輝度が５８. ６ｃｄ／ｍ2 と低くな
った。比較例３〜４は、ＥＬ素子の発光体面に不点灯が
５箇所以上発生し、発光輝度が低い。比較例５は、屈曲
した場合の表面抵抗変化が大きく、ＥＬ加工後点灯した
場合、断線による不点灯部が見られた。比較例６は、Ｅ
Ｌ用透明導電性フィルムと発光体層との密着性が悪く、
浮きを生じ、連続点灯ができなくなった。以上詳しく説
明した通り、本発明によってＥＬ用透明導電性フィルム
と発光体層との密着性が良好であり、しかもＥＬ素子の
発光体面に不点灯箇所が発生しないことが確認された。As is clear from the results shown in Table 1, the transparent electroconductive films for EL of Examples 1 to 4 have good bending resistance, do not generate unlit portions, and adhere to the luminescent layer. And the emission luminance is high. On the other hand, in Comparative Example 1, the surface resistance was as high as 230 Ω / □ or more, and three non-lighting portions occurred on the luminous body surface of the EL element. Further, Comparative Example 2
No non-lighting portion was generated on the light emitting surface of the L element, but the dielectric loss was large and the light emission luminance was low at 58.6 cd / m 2 . In Comparative Examples 3 and 4, non-lighting occurred at five or more places on the luminous body surface of the EL element, and the light emission luminance was low. Comparative Example 5 showed a large change in surface resistance when bent, and when turned on after EL processing, an unlit portion due to disconnection was observed. Comparative Example 6
Poor adhesion between the transparent conductive film for L and the luminescent layer,
Floating occurred and continuous lighting was not possible. As described above in detail, it has been confirmed that the present invention has good adhesiveness between the transparent electroconductive film for EL and the luminescent layer, and that no unlit portion is generated on the luminescent surface of the EL element.
【００３４】[0034]
【発明の効果】本発明のＥＬ用透明導電性フィルムは、
特に、ＥＬ用電極として使用した場合、透明導電層上の
高誘電率樹脂層により、発光体層との密着力を高めるこ
とができ、かつ、高湿度雰囲気下で、ＥＬ素子を連続点
灯しても、ＥＬ素子の発光体面に不点灯箇所が発生しな
い耐久性の格段に優れたＥＬを得ることができる。The transparent conductive film for EL of the present invention comprises:
In particular, when used as an electrode for EL, the high dielectric constant resin layer on the transparent conductive layer can enhance the adhesion to the light emitting layer, and can continuously light the EL element in a high humidity atmosphere. Also, it is possible to obtain an EL having extremely excellent durability in which no unlighted portion is generated on the light emitting body surface of the EL element.
【図１】パッケージレスＥＬ素子の断面図である。FIG. 1 is a sectional view of a packageless EL device.
１．背面電極層 ２．誘電体層 ３．発光体層 ４．透明導電層 ５．基材 ６．高誘電率樹脂層 ７．ＥＬ用透明導電性フィルム 1. Back electrode layer 2. 2. dielectric layer Luminous body layer 4. Transparent conductive layer 5. Substrate 6. 6. High dielectric constant resin layer Transparent conductive film for EL
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０５Ｂ 33/28 Ｈ０５Ｂ 33/28 Continued on the front page (51) Int.Cl. 6 Identification number Reference number in the agency FI Technical display location H05B 33/28 H05B 33/28
Claims (4)
一面上に、酸化スズ（ＳｎＯ2 ）を３〜１５重量％含有
する酸化インジウム（Ｉｎ2 Ｏ3 ）−酸化スズ（ＳｎＯ
2 ）焼結体からなる厚み５００〜１０００Åの透明導電
層、誘電率１０以上のシアノアルキル変性フッ素系樹脂
層を順次積層してなることを特徴とするエレクトロルミ
ネッセンス素子用透明導電性フィルム。1. A transparent polymer film and indium oxide (In 2 O 3 ) -tin oxide (SnO 2 ) containing tin oxide (SnO 2 ) in an amount of 3 to 15% by weight on at least one surface thereof.
2 ) A transparent conductive film for an electroluminescent element, which is formed by sequentially laminating a transparent conductive layer of a sintered body having a thickness of 500 to 1000 ° and a cyanoalkyl-modified fluororesin layer having a dielectric constant of 10 or more.
の厚みが０．０５〜０．５μｍである請求項１記載のエ
レクトロルミネッセンス素子用透明導電性フィルム。2. The transparent conductive film for an electroluminescent device according to claim 1, wherein the thickness of the cyanoalkyl-modified fluororesin layer is 0.05 to 0.5 μm.
が、ポリフッ化ビニリデン、ポリフッ化ビニル、ポリフ
ッ化ビニリデン−６フッ化プロピレン共重合体、ポリフ
ッ化ビニリデン−６フッ化プロピレン−４フッ化エチレ
ン三元共重合体、４フッ化エチレン−プロピレン共重合
体、ポリ（２，２，２−トリフルオロエチルビニルエー
テル）から選ばれた少なくとも１種のフッ素系樹脂のシ
アノアルキル変性物からなる請求項１又は２記載のエレ
クトロルミネッセンス素子用透明導電性フィルム。3. The cyanoalkyl-modified fluorine-based resin layer is formed of polyvinylidene fluoride, polyvinyl fluoride, polyvinylidene fluoride-6-propylene copolymer, polyvinylidene fluoride-6-propylene / 4-fluoroethylene ternary. 3. A cyanoalkyl modified product of at least one fluorine-based resin selected from a copolymer, a tetrafluoroethylene-propylene copolymer, and poly (2,2,2-trifluoroethyl vinyl ether). The transparent conductive film for an electroluminescent element according to the above.
るイオンプレーティング法によって形成されたものであ
る請求項１〜３のいずれか１項記載のエレクトロルミネ
ッセンス素子用透明導電性フィルム。4. The transparent conductive film for an electroluminescent device according to claim 1, wherein the transparent conductive layer is formed by an ion plating method using a pressure gradient discharge.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21909196A JP3341277B2 (en) | 1996-08-02 | 1996-08-02 | Transparent conductive film for electroluminescence device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21909196A JP3341277B2 (en) | 1996-08-02 | 1996-08-02 | Transparent conductive film for electroluminescence device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1044289A true JPH1044289A (en) | 1998-02-17 |
| JP3341277B2 JP3341277B2 (en) | 2002-11-05 |
Family
ID=16730122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21909196A Expired - Fee Related JP3341277B2 (en) | 1996-08-02 | 1996-08-02 | Transparent conductive film for electroluminescence device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3341277B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003509817A (en) * | 1999-09-03 | 2003-03-11 | スリーエム イノベイティブ プロパティズ カンパニー | Large area organic electronic device having conductive polymer buffer layer and method of manufacturing the same |
| WO2005122651A1 (en) * | 2004-06-07 | 2005-12-22 | Matsushita Electric Industrial Co., Ltd. | Light-emitting device and display |
| WO2006019019A1 (en) * | 2004-08-17 | 2006-02-23 | Toray Industries, Inc. | Composite transparent conductive substrate for touch panel and touch panel |
-
1996
- 1996-08-02 JP JP21909196A patent/JP3341277B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003509817A (en) * | 1999-09-03 | 2003-03-11 | スリーエム イノベイティブ プロパティズ カンパニー | Large area organic electronic device having conductive polymer buffer layer and method of manufacturing the same |
| WO2005122651A1 (en) * | 2004-06-07 | 2005-12-22 | Matsushita Electric Industrial Co., Ltd. | Light-emitting device and display |
| WO2006019019A1 (en) * | 2004-08-17 | 2006-02-23 | Toray Industries, Inc. | Composite transparent conductive substrate for touch panel and touch panel |
| JPWO2006019019A1 (en) * | 2004-08-17 | 2008-05-08 | 東レ株式会社 | Composite transparent conductive substrate for touch panel and touch panel |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3341277B2 (en) | 2002-11-05 |
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