JPH026126A - Transparent conductive laminate - Google Patents
Transparent conductive laminateInfo
- Publication number
- JPH026126A JPH026126A JP63157565A JP15756588A JPH026126A JP H026126 A JPH026126 A JP H026126A JP 63157565 A JP63157565 A JP 63157565A JP 15756588 A JP15756588 A JP 15756588A JP H026126 A JPH026126 A JP H026126A
- Authority
- JP
- Japan
- Prior art keywords
- film
- transparent conductive
- transparent
- haze value
- transparent plastic
- 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
- 239000010409 thin film Substances 0.000 claims abstract description 44
- 229920003023 plastic Polymers 0.000 claims abstract description 28
- 239000002985 plastic film Substances 0.000 claims abstract description 22
- 239000010408 film Substances 0.000 abstract description 32
- 238000010438 heat treatment Methods 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 13
- 239000004033 plastic Substances 0.000 abstract description 8
- -1 polyethylene terephthalate Polymers 0.000 abstract description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 6
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 6
- 238000010030 laminating Methods 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 5
- 229910001887 tin oxide Inorganic materials 0.000 description 5
- KXJGSNRAQWDDJT-UHFFFAOYSA-N 1-acetyl-5-bromo-2h-indol-3-one Chemical compound BrC1=CC=C2N(C(=O)C)CC(=O)C2=C1 KXJGSNRAQWDDJT-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910003437 indium oxide Inorganic materials 0.000 description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- IDCBOTIENDVCBQ-UHFFFAOYSA-N TEPP Chemical compound CCOP(=O)(OCC)OP(=O)(OCC)OCC IDCBOTIENDVCBQ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 229920006300 shrink film Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
この発明はエレクトロルミネッセンス素子やエレクトロ
クロミック素子などを用いた表示装置におけると記各素
子の透明電極として有用な透明導電性積層体に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a transparent conductive laminate useful as a transparent electrode of each element in a display device using electroluminescent elements, electrochromic elements, etc.
エレクトロルミネッセンス素子やエレクトロクロミック
素子などでは、その少なくとも表示側に透明電極を用い
ているが、かかる透明電極として、従来では、透明プラ
スチックフィルムからなる基材フィルム上に酸化インジ
ウム、酸化スズなどの透明導電性薄膜を設けた透明導電
性積層体が多く用いられている。Electroluminescent devices, electrochromic devices, etc. use transparent electrodes at least on the display side. Conventionally, such transparent electrodes are made of transparent conductive materials such as indium oxide or tin oxide on a base film made of a transparent plastic film. Transparent conductive laminates provided with a conductive thin film are often used.
このような透明導電性積層体は、たとえば有機分散型エ
レクトロルミネッセンス素子では、この積層体の透明導
電性薄膜上にリード電極用の銀ペーストと有機分散型発
光体層用材料を順次スクリーン印刷し、各印刷後に所要
の加熱乾燥を経て所定パターンのリード電極および発光
体層を形成し、さらにこの発光体層上に適宜の絶縁層（
誘電体層）を介して背面電極を積層することにより、エ
レクトロルミネッセンス素子を構成させるようにしてい
る。Such a transparent conductive laminate, for example, in an organic dispersion type electroluminescent device, is produced by sequentially screen printing a silver paste for lead electrodes and a material for an organic dispersion type light emitting layer on the transparent conductive thin film of this laminate. After each printing, a predetermined pattern of lead electrodes and a light emitter layer is formed through the required heating and drying process, and an appropriate insulating layer (
An electroluminescent element is constructed by laminating back electrodes via a dielectric layer (dielectric layer).
しかるに、上記従来の透明導電性積層体は、熱的ストレ
スにより収縮する傾向があり、この収縮が前記リード電
極や発光体層を形成する際の加熱乾燥工程などで起こる
結果、スクリーン印刷に微妙なずれをきたし、精密なパ
ターン形成が望まれるエレクトロルミネッセンス素子な
どの表示装置、特に大型の表示装置において表示性能の
低下を招いていた。However, the conventional transparent conductive laminate described above tends to shrink due to thermal stress, and this shrinkage occurs during the heating and drying process when forming the lead electrodes and the luminescent layer, resulting in subtle problems in screen printing. This has caused a misalignment, leading to a decline in display performance in display devices such as electroluminescent devices where precise pattern formation is desired, especially in large display devices.
また、上記従来の透明導電性積層体は、そのヘイズ値が
高く、エレクトロルミネッセンス素子などの表示装置で
は視認性の低下をきたし、これがやはり表示性能を低下
させる原因となっていた。In addition, the conventional transparent conductive laminate described above has a high haze value, resulting in a decrease in visibility in display devices such as electroluminescent elements, which also causes a decrease in display performance.
したがって、この発明は、ヘイズ値が低くてかつ上述の
如き加熱による収縮を引き起こしにくい、エレクトロル
ミネッセンス素子やエレクトロクロミック素子などの透
明電極に適用したとき従来のものに比し表示性能にはる
かにすぐれる表示装置を付与しうる透明導電性積層体を
提供することを目的としている。Therefore, when this invention is applied to transparent electrodes such as electroluminescent elements and electrochromic elements, which have a low haze value and do not easily cause shrinkage due to heating as described above, display performance is far superior to that of conventional ones. The object is to provide a transparent conductive laminate that can be provided with a display device.
〔課題を解決するための手段１
この発明者らは、上記の目的を達成するための鋭意検討
の過程において、まず従来の透明導電性積層体のヘイズ
値と加熱による収縮が基材フィルムとして用いる透明プ
ラスチックフィルムに起因する、つまりこのフィルム中
の滑剤などの添加剤成分が光の拡散を招いてフィルム自
体のヘイズ値が高くなり、またこのフィルムが熱収縮を
起こしやすいものであることを知った。[Means for Solving the Problem 1] In the process of intensive study to achieve the above object, the inventors first determined that the haze value and shrinkage due to heating of a conventional transparent conductive laminate were used as a base film. I learned that this is caused by transparent plastic films, that is, additive components such as lubricants in this film cause light diffusion, increasing the haze value of the film itself, and that this film is prone to heat shrinkage. .
そこで、この知見をもとにさらに上記プラスチックフィ
ルムの材料構成やフィルム作製法などの因子につき試行
錯誤的な実験検討を加えた結果、上記プラスチックフィ
ルムとして上述の因子などにて決定される特定のヘイズ
値および熱収縮率を有するものを用いることにより、つ
まりこのフィルムを基材フィルムとしてこの上に透明導
電性薄膜を形成することにより、ヘイズ値が低くてかつ
加熱による収縮を引き起こしにくい、エレクトロルミネ
ッセンス素子やエレクトロクロミック表示素子などの透
明電極として有用な透明導電性積層体が得られるもので
あることを知り、この発明を完成するに至った。Based on this knowledge, we further conducted trial-and-error experimental studies on factors such as the material composition and film manufacturing method of the plastic film, and found that the plastic film has a specific haze determined by the above-mentioned factors. By using a material with a low haze value and heat shrinkage rate, that is, by using this film as a base film and forming a transparent conductive thin film thereon, an electroluminescent element that has a low haze value and does not easily shrink due to heating. The present invention was completed based on the knowledge that a transparent conductive laminate useful as a transparent electrode for electrochromic display devices and the like can be obtained.
すなわち、この発明は、ヘイズ値が１％以下で、かつ１
５０℃、３０分の加熱条件での熱収縮率が０．５％以下
である透明プラスチックフィルムの少なくとも片面に透
明導電性薄膜が形成されてなる透明導電性積層体に係る
ものである。That is, the present invention has a haze value of 1% or less and a haze value of 1% or less.
The present invention relates to a transparent conductive laminate in which a transparent conductive thin film is formed on at least one side of a transparent plastic film having a heat shrinkage rate of 0.5% or less under heating conditions of 50° C. for 30 minutes.
この発明において使用する透明プラスチックフィルムは
、上述のとおり、ヘイズ値が１％以下で、かつ１５０℃
で３０分間加熱したときの熱収縮率が縦横共に０．５％
以下となるものであり、従来の透明導電性積層体に用い
られていた透明プラスチックフィルムのヘイズ値および
上記同様の熱収縮率がそれぞれ約２〜４％および約２〜
５％であったのに較べて、ヘイズ値が低（てかつ加熱に
よる収縮が非常に抑えられたものであることを特徴とし
ている。As mentioned above, the transparent plastic film used in this invention has a haze value of 1% or less and a temperature of 150°C.
The heat shrinkage rate when heated for 30 minutes is 0.5% in both length and width.
The haze value of the transparent plastic film used in conventional transparent conductive laminates and the same heat shrinkage rate as above are approximately 2 to 4% and approximately 2 to 2%, respectively.
5%, the haze value is low (and shrinkage due to heating is extremely suppressed).
なお、上記のヘイズ値は、フィルムに可視光を照射した
ときの全透過光に対する拡散透過光の割業株式会社製の
オートマチックデジタルヘーズメータ（ＮＤＨ−２０Ｄ
）を用いて行い、下記の式；にしたがって算出した。こ
のヘイズ値が小さいほどフィルムの透明性にすぐれてい
ることを意味している。The above haze value is measured using an automatic digital haze meter (NDH-20D) manufactured by Wariyo Co., Ltd., which measures the diffusely transmitted light relative to the total transmitted light when the film is irradiated with visible light.
) and calculated according to the following formula; The smaller the haze value, the better the transparency of the film.
また、上記の熱収縮率は、縦横共に５０ｔｔｘの大きさ
に切断した試験フィルムを用いて、加熱試験後に縦横の
寸法を測定し、これと加熱試験前の寸法との差を収縮長
さとして、下記の式；にしたがって縦横の熱収縮率を算
出したものである。この明細書において、縦横の表示を
せず、ただ単に熱収縮率が０．５％以下というときは、
縦方向および横方向共に０．５％以下の熱収縮率である
ことを意味している。In addition, the above heat shrinkage rate is determined by measuring the vertical and horizontal dimensions after the heating test using a test film cut to a size of 50 ttx in both length and width, and taking the difference between this and the dimension before the heating test as the shrinkage length. The longitudinal and lateral thermal shrinkage rates were calculated according to the following formula. In this specification, when the heat shrinkage rate is simply 0.5% or less without indicating the vertical or horizontal direction,
This means that the heat shrinkage rate is 0.5% or less in both the vertical and horizontal directions.
一般に、透明プラスチックフィルムは、プラスチック素
材を押出加工などの公知の各種加工手段でフィルム成形
したのち、延伸加工などの所要の工程を経てつ（られて
いるが、上記のプラスチック素材には種々の目的で滑剤
や触媒、促進剤などの添加剤が添加されることが多い。In general, transparent plastic films are made by forming plastic materials into films using various known processing methods such as extrusion processing, and then going through necessary processes such as stretching processing, but the above plastic materials have various purposes. Additives such as lubricants, catalysts, and accelerators are often added.
この発明の上記透明プラスチックフィルムは、たとえば
上記の添加剤成分のうち、酸化チタンや炭酸カルシウム
の如き滑剤などを極力少なくし、かつこの成形材料を用
いて上記公知の方法で作製された加工フィルム（これは
市販フィルムであってもよい）にさらに特定の熱固定を
施すことにより、得ることができる。The above-mentioned transparent plastic film of the present invention is a processed film ( This can be obtained by further subjecting the film (which may be a commercially available film) to a specific heat setting.
上記の熱固定とは、プラスチック素材の融点に近い温度
まで加熱し、テンションをかけたまま徐冷、つまりゆっ
くりと室温まで冷却するものである。加熱温度はプラス
チック素材により異なるがら一概には決められないが、
一般には１８０〜２２０℃の範囲とするのがよく、最も
代表的なプラスチック素材として知られるポリエチレン
テレフタレートでは特に１９０〜２００℃の範囲が好適
である。加熱時間は通常１〜１０分間程度で充分である
。The heat fixing mentioned above involves heating the plastic material to a temperature close to its melting point and slowly cooling it to room temperature while applying tension. The heating temperature varies depending on the plastic material and cannot be determined unconditionally.
Generally, the temperature range is preferably from 180 to 220°C, and for polyethylene terephthalate, which is known as the most typical plastic material, the temperature range is from 190 to 200°C. A heating time of about 1 to 10 minutes is usually sufficient.
この発明に使用可能なプラスチック素材としては、上述
のポリエチレンテレフタレートをはシメとするポリエス
テルのほか、ポリスルホン、ポリエーテルスルホン、ポ
リプロピレン、ポリカーボネート、ポリアミド、ポリイ
ミド、トリアセテートなどが挙げられ、１００℃以上の
耐熱性を有するものが好ましく用いられる。Plastic materials that can be used in this invention include polyester with polyethylene terephthalate as mentioned above, as well as polysulfone, polyethersulfone, polypropylene, polycarbonate, polyamide, polyimide, triacetate, etc. Those having the following are preferably used.
この発明の透明プラスチックフィルムは、ヘイズ値およ
び１５０℃、３０分の加熱条件での熱収縮率が前記要件
を満足する限り、上述とは異なる方法で作製されたもの
であってもよい。フィルムの厚みも特に限定されるもの
ではないが、一般には５０〜２００１ＩＭ程度の厚みを
有しているのが好ましい。The transparent plastic film of the present invention may be produced by a method different from that described above, as long as the haze value and the heat shrinkage rate under heating conditions of 150° C. and 30 minutes satisfy the above requirements. Although the thickness of the film is not particularly limited, it is generally preferred to have a thickness of about 50 to 2001 IM.
この発明において上記の透明プラスチックフィルムから
なる基材フィルムの少なくとも片面に形成される透明導
電性薄膜としては、酸化インジウム、酸化スズ、これら
の混合酸化物、酸化スズと酸化アンチモンとの混合酸化
物などからなる酸化物薄膜、金、銀、銅、白金、パラジ
ウム、アルミニウム、インジウム、スズ、カドミウム、
亜鉛などの金属薄膜、または上記の酸化物薄膜と金属薄
膜とを好ましくはこの順に積層した積層薄膜などが挙げ
られる。これらの中でも、酸化インジウムと酸化スズと
の混合酸化物薄膜上にパラジウム薄膜を積層してなる積
層薄膜が、透明性、導電性およびフィルム基材への密着
性の点で、最も好ましい。In this invention, the transparent conductive thin film formed on at least one side of the base film made of the above transparent plastic film includes indium oxide, tin oxide, mixed oxides thereof, mixed oxides of tin oxide and antimony oxide, etc. Oxide thin film consisting of gold, silver, copper, platinum, palladium, aluminum, indium, tin, cadmium,
Examples include a metal thin film such as zinc, or a laminated thin film in which the above-mentioned oxide thin film and metal thin film are preferably laminated in this order. Among these, a laminated thin film formed by laminating a palladium thin film on a mixed oxide thin film of indium oxide and tin oxide is most preferred in terms of transparency, conductivity, and adhesion to the film base material.
これら各薄膜の形成手段は任意であり、公知の薄膜形成
技術、たとえば真空蒸着法、スパッタリング法、イオン
ブレーティング法などの方法を任意に採用することがで
きる。膜厚としては、酸化物薄膜では通常１００〜１，
０００λ、金属薄膜では通常１０〜２００Ａとするのが
よく、個々の薄膜形成材料に応じて透明性を保有しかつ
薄膜形成後の表面電気抵抗が通常１００〜１，０００Ω
／口の範囲となるように適宜設定される。The means for forming each of these thin films is arbitrary, and any known thin film forming technique, such as a vacuum evaporation method, a sputtering method, an ion blasting method, etc., can be arbitrarily employed. The film thickness for oxide thin films is usually 100 to 1,
000λ, normally 10 to 200A for metal thin films, which maintains transparency and has a surface electrical resistance of usually 100 to 1,000Ω after forming the thin film, depending on the individual thin film forming material.
/mouth range as appropriate.
第１図は、以との構成要素からなるこの発明の透明導電
性積層体の一例を示したもので、図中、１は前記した特
定の透明プラスチックフィルム、２はこのフィルム１の
片面に形成された酸化物薄膜２ａと金属薄膜２ｂとの積
層薄膜からなる透明導電性薄膜である。FIG. 1 shows an example of a transparent conductive laminate of the present invention comprising the following components. In the figure, 1 is the specific transparent plastic film mentioned above, and 2 is formed on one side of this film 1. This is a transparent conductive thin film made of a laminated thin film of an oxide thin film 2a and a metal thin film 2b.
第２図は、上記第１図の透明導電性積層体をエレクトロ
ルミネッセンス素子の透明電極として応用した例を示し
たものである。すなわち、透明プラスチックフィルム１
と透明導電性薄膜２とからなる透明導電性積層体３の上
記薄膜２上にリード電極用の銀ペーストと有機分散型発
光体層用材料を順次スクリーン印刷し、各印刷後に所要
の加熱乾燥を経て所定パターンのリード電極４および発
光体層５を形成し、さらにこの発光体層５上に絶縁層（
誘電体層）６を介して背面電極７を積層することにより
、エレクトロルミネッセンス素子を構成させるようにし
たものである。FIG. 2 shows an example in which the transparent conductive laminate shown in FIG. 1 is applied as a transparent electrode of an electroluminescent device. That is, transparent plastic film 1
A silver paste for a lead electrode and a material for an organic dispersed light emitter layer are sequentially screen printed on the thin film 2 of the transparent conductive laminate 3 consisting of a transparent conductive thin film 3 and a transparent conductive thin film 2, and the required heat drying is carried out after each printing. After that, a lead electrode 4 and a light emitter layer 5 are formed in a predetermined pattern, and an insulating layer (
By stacking a back electrode 7 via a dielectric layer 6, an electroluminescent element is constructed.
このように構成されるエレクトロルミネッセンス素子に
おいては、用いる透明導電性積層体３がその透明プラス
チックフィルム１の低熱収縮性（こ起因して加熱による
収縮を引き起こしにくいものであるために、リード電極
４や発光体層５などのスクリーン印刷にほとんどずれが
みられず、かつ上記フィルムのヘイズ値が低くて視認性
の悪化もないことから、この素子を表示装置に組み込ん
だとき非常にすぐれた表示性能が得られる。In the electroluminescent device constructed in this way, the transparent conductive laminate 3 used has a low heat shrinkage of the transparent plastic film 1 (which makes it difficult to cause shrinkage due to heating), so the lead electrodes 4 and There is almost no deviation in the screen printing of the luminescent layer 5, etc., and the haze value of the film is low, so there is no deterioration in visibility, so when this element is incorporated into a display device, it has excellent display performance. can get.
〔発明の効果１
以上のように、この発明によれば、ヘイズ値が低くてか
つ加熱による収縮を引き起こしにくい、エレクトロルミ
ネッセンス素子やエレクトロクロミック素子などの透明
電極に適用したとき従来のものに比しはるかに表示性能
にすぐれる表示装置を付与しうる透明導電性積層体を提
供することができる。[Effect of the invention 1 As described above, according to the present invention, when applied to transparent electrodes such as electroluminescent elements and electrochromic elements, which have a low haze value and are difficult to cause shrinkage due to heating, compared to conventional ones. It is possible to provide a transparent conductive laminate that can provide a display device with far superior display performance.
［実施例］
つぎに、この発明の実施例を記載してより具体的に説明
する。[Examples] Next, examples of the present invention will be described and explained more specifically.
実施例
厚さ７５／”のポリエチレンテレフタレートフィルム〔
帝人■製のテトロンフィルム、０タイプ；ヘイズ値０．
３％〕を用い、このフィルムを２００℃で３分間加熱し
たのち、テンションをかけたまま徐冷した。得られたフ
ィルムは、１５０℃、３０分の加熱条件での熱収縮率が
縦方向で０．４％、横方向で０．１％であった。Example: Polyethylene terephthalate film with a thickness of 75 mm
Tetoron film manufactured by Teijin ■, type 0; haze value 0.
3%], the film was heated at 200° C. for 3 minutes, and then slowly cooled under tension. The resulting film had a heat shrinkage rate of 0.4% in the longitudinal direction and 0.1% in the transverse direction under heating conditions of 150° C. for 30 minutes.
つぎに、スパッタ装置の基板側に上記の低熱収縮フィル
ムを基材フィルムとして取り付け、スパッタ電極上にイ
ンジウム９０重量％とスズ１０重量％とからなる合金タ
ーゲットを装着し、１×１Ｏ−３Ｐａまで真空引きを行
ったうえで、アルゴンガスを１００ＣＣ／分、酸素ガス
を１５ＣＣ／分流入させて、装置内を４Ｘ１０ Ｐａ
に保った。この状態で上記のスパッタ電極に直流電圧４
００Ｖを印加してグロー放電させ、３０秒間スパッタリ
ングを行うことにより、つまり反応性マグネトロシスバ
ッタリングを行うことにより、低収縮フィルムの片面に
酸化インジウムと酸化スズとの混合酸化物からなる厚さ
が２０ＯＡの酸化物薄膜を形成した。Next, the above-mentioned low heat shrink film was attached to the substrate side of the sputtering device as a base film, an alloy target consisting of 90% by weight of indium and 10% by weight of tin was mounted on the sputtering electrode, and a vacuum was applied to 1×1O-3Pa. After pulling the air, argon gas was introduced at 100 cc/min and oxygen gas was introduced at 15 cc/min.
I kept it. In this state, the above sputtering electrode is applied with a DC voltage of 4
By applying 00V to generate a glow discharge and performing sputtering for 30 seconds, that is, by performing reactive magnetrosis sputtering, a thickness of a mixed oxide of indium oxide and tin oxide is formed on one side of the low shrinkage film. An oxide thin film of 20 OA was formed.
ついで、上記のスパッタ装置をそのまま用いて、ターゲ
ットをパラジウムに変え、かつアルゴンガスのみを流入
させるようにした以外は、上記と同様にして３秒間スパ
ッタリングを行うことにより、酸化物薄膜上に厚さが２
ＯＡのパラジウム薄膜からなる金属薄膜を形成した。Next, using the above sputtering apparatus as is, sputtering was performed for 3 seconds in the same manner as above, except that the target was changed to palladium and only argon gas was introduced, thereby forming a thin film on the oxide thin film. is 2
A metal thin film consisting of an OA palladium thin film was formed.
このようにして得られたポリエチレンテレフタレートか
らなる透明プラスチックフィルムとこの上の上記酸化物
薄膜および上記金属薄膜からなる透明導電性薄膜とで構
成された第１図に示す構造の透明導電性積層体は、その
表面電気抵抗が３００Ω／口、５５０ｎｍでの光透過率
が８２９６、ヘイズ値が０，８％であり、また１５０℃
、３０分の加熱条件での熱収縮率が縦方向で０．４％、
横方向で０．１％であった。A transparent conductive laminate having the structure shown in FIG. 1 is composed of a transparent plastic film made of polyethylene terephthalate obtained in this way, and a transparent conductive thin film made of the above-mentioned oxide thin film and the above-mentioned metal thin film thereon. , its surface electrical resistance is 300 Ω/hole, its light transmittance at 550 nm is 8296, its haze value is 0.8%, and its temperature is 150°C.
, Thermal shrinkage rate is 0.4% in the longitudinal direction under heating conditions of 30 minutes,
It was 0.1% in the lateral direction.
つぎに、この透明導電性積層体を用いて以下の方法でエ
レクトロルミネッセンス素子を作製した。Next, an electroluminescent device was produced using this transparent conductive laminate in the following manner.
まず、上記積層体の透明導電性薄膜上に銀ペーストをス
クリーン印刷し、１５０℃で３０分間加熱乾燥して厚さ
４０μのリード電極を形成した。ついで、上記薄膜上に
バインダとしてのシアノエチルセルロースのアセトン溶
液にけい光体粉末を分散させてなる液をスクリーン印刷
し、６０℃で１２０分間加熱したのち、１５０℃に昇温
しで２分間加熱し、厚さが６０μの発光体層を形成した
。First, a silver paste was screen printed on the transparent conductive thin film of the above laminate and dried by heating at 150° C. for 30 minutes to form a lead electrode with a thickness of 40 μm. Next, a solution prepared by dispersing phosphor powder in an acetone solution of cyanoethylcellulose as a binder was screen printed on the thin film, heated at 60°C for 120 minutes, and then raised to 150°C for 2 minutes. , a phosphor layer having a thickness of 60 μm was formed.
なお、上記のけい光体粉末としては硫化亜鉛を主成分と
する粉末を用い、この粉末とシアノエチルセルロースと
の重量配合比は８４：１６とした。As the phosphor powder, a powder containing zinc sulfide as a main component was used, and the weight mixing ratio of this powder and cyanoethyl cellulose was 84:16.
しかるのち、上記の発光体層上に上記と同じシアノエチ
ルセルロースのアセトン溶液にチタン酸バリウム粉末を
分散させたものを塗布した。なお、チタン酸バリウム粉
末とシアノエチルセルロースとの重量配合比は１：１と
した。その後、６０℃で１２０分間加熱して大部分のア
セトンを除去したうえで、厚さ２００μのアルミニウム
箔を載置し、このアルミニウム箔と一体に１５０℃に昇
温しで２分間加熱することにより、厚さが４０７”の絶
縁層を形成するとともに、この絶縁層上に背面電極とし
てのアルミニウム箔を密着一体化させた第２図に示す構
造のエレクトロルミネッセンス素子を得た。Thereafter, a solution prepared by dispersing barium titanate powder in the same acetone solution of cyanoethylcellulose as above was applied onto the above luminescent layer. Note that the weight mixing ratio of barium titanate powder and cyanoethyl cellulose was 1:1. After that, most of the acetone was removed by heating at 60°C for 120 minutes, and then a 200μ thick aluminum foil was placed on it, and the temperature was raised to 150°C together with this aluminum foil for 2 minutes. An electroluminescent element having the structure shown in FIG. 2 was obtained in which an insulating layer with a thickness of 407'' was formed and an aluminum foil as a back electrode was closely integrated on this insulating layer.
この素子は、加熱工程での透明導電性積層体の熱収縮が
小さいため、リード電極や発光体層の印刷ずれが０．１
％以下に抑えられており、また表示側（透明電極側）の
透明性の低下もみられず、これを組み込んだ表示装置は
すぐれた表示性能を発揮するものであることが確認され
た。This element has a small thermal shrinkage of the transparent conductive laminate during the heating process, so the printing misalignment of the lead electrodes and light emitting layer is 0.1.
% or less, and no deterioration in transparency on the display side (transparent electrode side) was observed, confirming that the display device incorporating this exhibits excellent display performance.
比較例
厚さ７５／’Ｉのポリエチレンテレフタレートフイルム
［奇人■製のテトロンフィルム、Ｓタイプ；ヘイズ値２
％］をそのまま、つまり２００℃、３分の熱固定処理を
施さないで用いた以外は、実施例と全く同様にして第１
図に示す構造の透明導電性積層体を得た。Comparative Example Polyethylene terephthalate film with a thickness of 75/'I [Tetron film manufactured by Kijin ■, S type; haze value 2
%] was used as it was, that is, without heat setting at 200°C for 3 minutes, in the same manner as in Example 1.
A transparent conductive laminate having the structure shown in the figure was obtained.
なお、上記基材フィルムの１５０℃、３０分の加熱条件
での熱収縮率は縦方向で３％、横方向で１．５％であっ
た。また、得られた積層体の表面電気抵抗は３００Ω／
口、５５０ｎｍでの光透過率は８０％、ヘイズ値は２．
２％であり、さらに１５０℃、３０分の加熱条件での熱
収縮率は縦方向で２゜８％、横方向で１，４％であった
。The heat shrinkage rate of the base film under heating conditions of 150° C. for 30 minutes was 3% in the longitudinal direction and 1.5% in the transverse direction. In addition, the surface electrical resistance of the obtained laminate was 300Ω/
The light transmittance at 550 nm is 80%, and the haze value is 2.
Furthermore, the heat shrinkage rate under heating conditions of 150° C. for 30 minutes was 2.8% in the longitudinal direction and 1.4% in the transverse direction.
つぎに、この透明導電性積層体を用いて実施例と同様に
してエレクトロルミネッセンス素子を作製したところ、
リード電極や発光体層の印刷ずれが２％と大きく、かつ
表示側の透明性が大きく損なわれており、これを組み込
んだ表示装置は実施例のものに比し表示性能に著しく劣
っていた。Next, an electroluminescent device was produced using this transparent conductive laminate in the same manner as in the example.
The printing misalignment of the lead electrodes and the light emitter layer was as large as 2%, and the transparency on the display side was greatly impaired, and the display device incorporating this was significantly inferior in display performance compared to the example.
第１図はこの発明の透明導電性積層体の一例を示す断面
図、第２図は上記積層体を用いて作製したエレクトロル
ミネッセンス素子の構成例を示す断面図である。
１・・・透明プラスチックフィルム、２ （２ａ、２ｂ
）・・・透明導電性薄膜、３・・・透明導電性積層体特
許出願人 日東電気工業株式会社FIG. 1 is a cross-sectional view showing an example of a transparent conductive laminate of the present invention, and FIG. 2 is a cross-sectional view showing an example of the structure of an electroluminescent device manufactured using the above-mentioned laminate. 1...Transparent plastic film, 2 (2a, 2b
)...Transparent conductive thin film, 3...Transparent conductive laminate patent applicant Nitto Electric Industry Co., Ltd.
Claims (1)
加熱条件での熱収縮率が０．５％以下である透明プラス
チックフィルムの少なくとも片面に透明導電性薄膜が形
成されてなる透明導電性積層体。(1) A transparent plastic film with a transparent conductive thin film formed on at least one side of a transparent plastic film having a haze value of 1% or less and a heat shrinkage rate of 0.5% or less when heated at 150°C for 30 minutes. Conductive laminate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63157565A JP2545116B2 (en) | 1988-06-25 | 1988-06-25 | Transparent conductive laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63157565A JP2545116B2 (en) | 1988-06-25 | 1988-06-25 | Transparent conductive laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH026126A true JPH026126A (en) | 1990-01-10 |
| JP2545116B2 JP2545116B2 (en) | 1996-10-16 |
Family
ID=15652462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63157565A Expired - Lifetime JP2545116B2 (en) | 1988-06-25 | 1988-06-25 | Transparent conductive laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2545116B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5145746A (en) * | 1990-10-26 | 1992-09-08 | Diafoil Company, Ltd. | Laminating material for safety glass |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5874324A (en) * | 1981-10-30 | 1983-05-04 | Toray Ind Inc | Heat treatment of polyester film |
| JPS59158015A (en) * | 1983-02-28 | 1984-09-07 | 住友ベークライト株式会社 | Transparent conductive film |
| JPS60229009A (en) * | 1984-04-27 | 1985-11-14 | Sumitomo Bakelite Co Ltd | Transparent conductive film for liquid crystal electrode |
| JPS61255847A (en) * | 1985-05-09 | 1986-11-13 | コニカ株式会社 | Manufacture of transparent conductive film |
| JPS6218254A (en) * | 1985-07-16 | 1987-01-27 | 日東電工株式会社 | Laminate |
| JPS62140828A (en) * | 1985-12-13 | 1987-06-24 | Diafoil Co Ltd | Polyester film for transparent electrically conductive film |
| JPS632129A (en) * | 1986-06-20 | 1988-01-07 | Dainippon Printing Co Ltd | Protection film for optical information recording medium |
-
1988
- 1988-06-25 JP JP63157565A patent/JP2545116B2/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5874324A (en) * | 1981-10-30 | 1983-05-04 | Toray Ind Inc | Heat treatment of polyester film |
| JPS59158015A (en) * | 1983-02-28 | 1984-09-07 | 住友ベークライト株式会社 | Transparent conductive film |
| JPS60229009A (en) * | 1984-04-27 | 1985-11-14 | Sumitomo Bakelite Co Ltd | Transparent conductive film for liquid crystal electrode |
| JPS61255847A (en) * | 1985-05-09 | 1986-11-13 | コニカ株式会社 | Manufacture of transparent conductive film |
| JPS6218254A (en) * | 1985-07-16 | 1987-01-27 | 日東電工株式会社 | Laminate |
| JPS62140828A (en) * | 1985-12-13 | 1987-06-24 | Diafoil Co Ltd | Polyester film for transparent electrically conductive film |
| JPS632129A (en) * | 1986-06-20 | 1988-01-07 | Dainippon Printing Co Ltd | Protection film for optical information recording medium |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5145746A (en) * | 1990-10-26 | 1992-09-08 | Diafoil Company, Ltd. | Laminating material for safety glass |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2545116B2 (en) | 1996-10-16 |
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