JP3194851B2 - Transparent conductive film - Google Patents
Transparent conductive filmInfo
- Publication number
- JP3194851B2 JP3194851B2 JP19488395A JP19488395A JP3194851B2 JP 3194851 B2 JP3194851 B2 JP 3194851B2 JP 19488395 A JP19488395 A JP 19488395A JP 19488395 A JP19488395 A JP 19488395A JP 3194851 B2 JP3194851 B2 JP 3194851B2
- Authority
- JP
- Japan
- Prior art keywords
- gas barrier
- layer
- transparent conductive
- barrier layer
- film
- 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.)
- Expired - Fee Related
Links
- 239000010410 layer Substances 0.000 claims description 94
- 230000004888 barrier function Effects 0.000 claims description 48
- 229920006254 polymer film Polymers 0.000 claims description 18
- 239000011253 protective coating Substances 0.000 claims description 12
- 229910052738 indium Inorganic materials 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- 229920001187 thermosetting polymer Polymers 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 229910002064 alloy oxide Inorganic materials 0.000 claims description 6
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 description 42
- 230000001681 protective effect Effects 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 239000004695 Polyether sulfone Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- 229920006393 polyether sulfone Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 229910001128 Sn alloy Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 229910000846 In alloy Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WPUJEWVVTKLMQI-UHFFFAOYSA-N benzene;ethoxyethane Chemical compound CCOCC.C1=CC=CC=C1 WPUJEWVVTKLMQI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 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
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Non-Insulated Conductors (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、フィルム液晶表示
装置に用いられる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 used for a film liquid crystal display.
【０００２】[0002]
【従来の技術】透明導電性フィルムとしては、ポリエス
テルフィルム等の透明高分子フィルム表面に酸化インジ
ウム、酸化錫、あるいは錫、インジウム合金の酸化膜等
の半導体膜や金、銀、パラジウムあるいはそれらの合金
等の金属膜、半導体膜と金属膜を組み合わせて形成され
たもの等が知られている。一方、ガスバリヤー層として
は、高分子フィルム上にＳｉＯ2等を蒸着したもの、あ
るいは、高分子フィルム上に塩化ビニリデン系ポリマー
やビニルアルコール系ポリマーなど相対的にガスバリヤ
ー性のあるポリマーのコーティング層を設けたものが知
られている。例えば、特開平７−４９４８３による高分
子フィルム上にガスバリヤー層として酸化珪素等の絶縁
酸化物を成膜し更に透明電極としてＩｎ、Ｓｎの合金膜
を付与した積層体を用いた液晶表示素子では、工業的設
備で液晶表示素子組立を行った時にガスバリヤー層がロ
ールにより機械的に、あるいは、エッチング液等により
化学的に損傷を受け、液晶表示素子とした時積層フィル
ム本来のガスバリヤー性が喪失してしまい、経時的に表
示欠陥が発生する可能性が大きいことが分かった。さら
に透明導電層、ガスバリヤー層を全く違う材料、設備を
用いて形成する必要があり生産効率が良くないことが分
かった。高分子フィルム液晶表示装置には、ガスバリヤ
ー性、透明導電性を合わせ持つフィルムが必要である
が、これらの機能を有する各層を組み合わせて透明導電
性、ガスバリアー性を付与し、液晶表示装置材料として
必要な耐久性のすべてが十分な透明導電性フィルムは、
いまだ工業的には生産されていない。2. Description of the Related Art As a transparent conductive film, a transparent polymer film such as a polyester film or the like, a semiconductor film such as indium oxide, tin oxide, or an oxide film of tin or indium alloy, gold, silver, palladium or an alloy thereof is used. And the like, and those formed by combining a semiconductor film and a metal film. On the other hand, as the gas barrier layer, SiO 2 or the like is deposited on a polymer film, or a coating layer of a polymer having relatively gas barrier properties such as a vinylidene chloride polymer or a vinyl alcohol polymer on the polymer film. Is known. For example, in a liquid crystal display device using a laminate in which an insulating oxide such as silicon oxide is formed as a gas barrier layer on a polymer film according to JP-A-7-49483, and an alloy film of In and Sn is provided as a transparent electrode. The gas barrier layer is mechanically damaged by a roll when the liquid crystal display element is assembled in industrial equipment, or chemically damaged by an etchant, etc. It has been found that there is a high possibility that display defects occur over time. Further, it was found that it was necessary to form the transparent conductive layer and the gas barrier layer using completely different materials and equipment, resulting in poor production efficiency. A polymer film liquid crystal display device requires a film having both gas barrier properties and transparent conductivity.However, by combining each layer having these functions, transparent conductivity and gas barrier properties are imparted, and a liquid crystal display material is provided. As a transparent conductive film, all of the necessary durability is sufficient,
It is not yet produced industrially.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、かかる現状
に鑑みなされたもので透明性、ガスバリヤー性、耐久性
の優れた透明で導電性を有する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 provide a transparent and conductive film excellent in transparency, gas barrier properties and durability, which has been made in view of the above situation.
【０００４】[0004]
【課題を解決するための手段】高分子フィルムの片面に
ガスバリヤー層としてＩｎ、Ｓｎの合金酸化物及び該ガ
スバリヤー層を覆うようにシランカップリング剤を含む
エポキシアクリレート紫外線硬化樹脂の保護コーティン
グ層を順次積層した積層フィルムの少なくとも片側に透
明導電層を有することを特徴とする透明導電性フィルム
であって、さらに、該ガスバリヤー層の膜厚が１００Å
〜５００Åであり、該ガスバリヤー層と該ガスバリヤー
層を覆う保護コーティング層の間にビスフェノールＡ型
のエポキシ熱硬化性樹脂のアンカー層を有する透明導電
性フィルムによって課題を解決することが出来た。層の
構成内容は例えば保護コート層／ガスバリヤー層／高分
子フィルム／透明導電層、保護コート層／エポキシ熱硬
化性樹脂のアンカー層／ガスバリヤー層／高分子フィル
ム／透明導電層、保護コート層／エポキシ熱硬化性樹脂
のアンカー層／ガスバリヤー層／アンカー層／高分子フ
ィルム／アンカー層／透明導電層、透明導電層／保護コ
ート層／ガスバリヤー層／高分子フィルム／透明導電
層、透明導電層／保護コート層／エポキシ熱硬化性樹脂
のアンカー層／ガスバリヤー層／高分子フィルム／透明
導電層、透明導電層／保護コート層／エポキシ熱硬化性
樹脂のアンカー層／ガスバリヤー層／アンカー層／高分
子フィルム／アンカー層／透明導電層等があるが必ずし
もこれらに限定されるわれではない。Means for Solving the Problems A protective coating layer of an epoxy acrylate ultraviolet curable resin containing an alloy oxide of In and Sn as a gas barrier layer and a silane coupling agent so as to cover the gas barrier layer on one surface of a polymer film. Are provided with a transparent conductive layer on at least one side of a laminated film, wherein the gas barrier layer has a thickness of 100 °.
The problem was solved by a transparent conductive film having a bisphenol A type epoxy thermosetting resin anchor layer between the gas barrier layer and the protective coating layer covering the gas barrier layer. The composition of the layers is, for example, protective coat layer / gas barrier layer / polymer film / transparent conductive layer, protective coat layer / anchor layer of epoxy thermosetting resin / gas barrier layer / polymer film / transparent conductive layer, protective coat layer / Anchor layer of epoxy thermosetting resin / gas barrier layer / anchor layer / polymer film / anchor layer / transparent conductive layer, transparent conductive layer / protective coat layer / gas barrier layer / polymer film / transparent conductive layer, transparent conductive Layer / protective coat layer / epoxy thermosetting resin anchor layer / gas barrier layer / polymer film / transparent conductive layer, transparent conductive layer / protective coat layer / epoxy thermosetting resin anchor layer / gas barrier layer / anchor layer / Polymer film / anchor layer / transparent conductive layer, but are not necessarily limited to these.
【０００５】本発明で用いる透明の高分子フィルムとし
てはポリエステルフィルム、ポリエーテルイミドフィル
ム、ポリアリレートフィルム、ポリエーテルサルフォン
フィルム等があげられる。本発明で用いられる透明な高
分子フィルムの全光線透過率は少なくとも４０％以上、
好ましくは８０％以上が望ましい。本発明に用いる透明
な高分子フィルムはガスバリヤー層、透明導電層の形成
に先立ち各層及び高分子フィルム相互の密着力を高める
ために脱ガス処理、コロナ放電処理、火炎処理等の表面
処理やエポキシアクリル系の公知のアンカーコートが施
されていてもよい。The transparent polymer film used in the present invention includes a polyester film, a polyetherimide film, a polyarylate film, a polyether sulfone film and the like. The total light transmittance of the transparent polymer film used in the present invention is at least 40% or more,
Preferably, it is 80% or more. Prior to the formation of the gas barrier layer and the transparent conductive layer, the transparent polymer film used in the present invention has a surface treatment such as a degassing treatment, a corona discharge treatment, a flame treatment or an epoxy to enhance the adhesion between the respective layers and the polymer film. A known acrylic anchor coat may be applied.
【０００６】本発明でいうガスバリヤー層は、Ｉｎ、Ｓ
ｎの合金酸化物であって、Ｉｎ、Ｓｎの合金、あるい
は、Ｉｎ、Ｓｎの合金の酸化物を公知のＥＢ蒸着、イオ
ンプレーティング、あるいは、プレーナーマグネトロン
スパッタリングにより形成することができるが、鋭意検
討することにより密度９５％以上のＩｎ、Ｓｎの合金酸
化物ターゲットを用いてプレナーマグネトロンスパッタ
リングにより厚み１００Å〜５００Åで形成したガスバ
リヤー層は生産性がＩｎ、Ｓｎ合金ターゲットに比べ
１．５倍以上、透明性は全光線透過率で８５％以上と優
れ、かつ酸素ガス透過率が１ｃｃ／ｍ2・ｄａｙ・ａｔ
ｍ以下と良好であることを見いだした。該ガスバリヤー
層の厚みは、１００Å〜３００Åがより好ましい。１０
０Å以下では該ガスバリヤー層が完全な連続構造となっ
ておらず温度変化での積層フィルムの伸び縮みでガスバ
リヤー層が破壊されてしまう確率が大きくなる。ガスバ
リヤー層の厚みが５００Å以上では、着色によるの透明
性の低下、ガスバリヤー層の内部応力に起因するクラッ
クの発生によるガスバリヤー性の低下が起こり好ましく
ない。さらに言えば、ガスバリヤー性を高めるために
は、ガスバリヤー層の厚みが内部応力に起因するクラッ
クが発生しない２５０Å程度が好ましい。In the present invention, the gas barrier layer is composed of In, S
An alloy oxide of n, an alloy of In and Sn, or an oxide of an alloy of In and Sn can be formed by known EB deposition, ion plating, or planar magnetron sputtering, but has been studied diligently. As a result, the gas barrier layer formed at a thickness of 100 to 500 ° by planar magnetron sputtering using an alloy oxide target of In and Sn having a density of 95% or more has a productivity of 1.5 times or more as compared with the In and Sn alloy targets. The transparency is as excellent as 85% or more in total light transmittance, and the oxygen gas transmittance is 1 cc / m 2 · day · at.
m or less and found to be good. The thickness of the gas barrier layer is more preferably 100 ° to 300 °. 10
When the temperature is 0 ° or less, the gas barrier layer does not have a completely continuous structure, and the probability that the gas barrier layer is broken due to expansion and contraction of the laminated film due to a temperature change increases. If the thickness of the gas barrier layer is 500 ° or more, the transparency due to coloring decreases and the gas barrier property decreases due to the generation of cracks due to the internal stress of the gas barrier layer, which is not preferable. Furthermore, in order to enhance the gas barrier property, the thickness of the gas barrier layer is preferably about 250 ° at which cracks due to internal stress do not occur.
【０００７】本発明に使用されるガスバリヤー層を覆う
保護コーティング層としては、エポキシアクリレートプ
レポリマーにシランカップリング剤を添加したものを紫
外線硬化させたものが上げられる。該保護コーティング
層は、透明でかつガスバリヤー層に対して密着力があ
り、かつ透明導電層形成時に電極膜膜質を損なうような
ガスの発生がないことをみいだした。シランカップリン
グ剤の添加量は、０．５〜１．０重量％が望ましい。シ
ランカップリング剤としては、例えば信越化学（株）製
のＫＢＭ−５０３、ＫＢＭ−８０３，日本ユニカー
（株）製のＡ−１８７が用いられるが、特にエポキシ
基、アミノ基、メルカプトン基を有するものが好まし
い。エポキシアクリレートプレポリマーは、融点が５０
℃以上のものが好ましく、昭和高分子（株）製のＶＲ−
６０があげられる。保護コーティング層とガスバリヤー
層との密着力を上げ、信頼性をより高めるためにガスバ
リヤー層と保護コーティング層の間に、例えば旭電化
（株）製のＥＸＰ−４９−１０等ビスフェノールＡ型の
エポキシ熱硬化性樹脂をアンカー剤として塗布すること
で効果があることが見いだせた。即ち、本発明による積
層フィルムは、透明導電性フィルムを用いてＬＣＤを作
製する際に必要なＮａＯＨ溶液浸せき処理、ＨＣｌ浸せ
き処理により欠陥が生じ、ガスバリヤー性が損なわれる
問題をガスバリヤー層に必要な耐久性が付与可能な該保
護コーティングを施すことにより克服することができ
た。尚、上記の透明導電層の形成法としては、従来から
公知の真空蒸着法、イオンプレーティング法、スパッタ
法等の物理的堆積法が適用できる。[0007] As the protective coating layer covering the gas barrier layer used in the present invention, there can be mentioned a layer obtained by adding a silane coupling agent to an epoxy acrylate prepolymer and curing it by ultraviolet rays. The present inventors have found that the protective coating layer is transparent, has an adhesive force to the gas barrier layer, and does not generate gas that impairs the quality of the electrode film when the transparent conductive layer is formed. The addition amount of the silane coupling agent is desirably 0.5 to 1.0% by weight. As the silane coupling agent, for example, KBM-503 and KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd., and A-187 manufactured by Nippon Unicar Co., Ltd. are used. In particular, they have an epoxy group, an amino group, and a mercapton group. Are preferred. Epoxy acrylate prepolymer has a melting point of 50
° C or higher is preferable, and VR-
60. In order to increase the adhesion between the protective coating layer and the gas barrier layer and further enhance the reliability, a bisphenol A type such as EXP-49-10 manufactured by Asahi Denka Co., Ltd. is provided between the gas barrier layer and the protective coating layer. It was found that application of an epoxy thermosetting resin as an anchoring agent was effective. That is, the laminated film according to the present invention requires the gas barrier layer to have a problem that defects occur due to NaOH solution immersion treatment and HCl immersion treatment required when producing an LCD using a transparent conductive film and gas barrier properties are impaired. This could be overcome by applying the protective coating, which can provide excellent durability. As a method of forming the transparent conductive layer, a conventionally known physical vapor deposition method such as a vacuum deposition method, an ion plating method, and a sputtering method can be applied.
【０００８】[0008]
《実施例１》高分子フィルムに厚さ１００μｍのポリエ
ーテルスルフォンフィルムを用い、そのフィルムの片側
に透明導電層、反対側にガスバリヤー層を設けるにおい
て、透明導電層とポリエーテルスルフォンフィルム及び
ガスバリヤー層とポリエーテルスルフォンフィルムとの
密着力を向上させるために、アンカー層を分子量約１０
４０、融点５５℃のエポキシアクリレートプレポリマー
（昭和高分子（株）製ＶＲ−６０）１００重量部、ジエ
チレングリコール２００重量部、酢酸エチル１００重量
部、ベンゼンエチルエーテル２重量部、シランカップリ
ング剤（信越化学（株）製ＫＢＭ−５０３）１重量部を
５０℃にて撹はん溶解して均一な溶液をディップ法によ
り両面に塗布し、８０℃で１０分間加熱した後紫外線を
照射して形成した。その後ガスバリヤー層としてバルク
に対する相対重量密度９５％以上のＩｎ、Ｓｎ（ＳｎＯ
2 １０ｗｔ％）の合金酸化物ターゲットを用いたプレ
ーナーマグネトロンスパッタリングにより厚み２００
Å、比抵抗５×１０-4Ω・ｃｍのＩｎ、Ｓｎの合金酸化
膜を形成した。さらに、保護コート層とガスバリヤー層
の密着力を向上させるアンカー層をビスフェノールＡ型
エポキシ熱硬化製樹脂（旭電化（株）製ＥＰＸ−４９−
１０）を同量の酢酸メチルで希釈してバーコーターにて
コーティングした後８０℃で２時間硬化させて形成し
た。その上に保護コート層を分子量約１０４０、融点５
５℃のエポキシアクリレートプレポリマー（昭和高分子
（株）製ＶＲ−６０）１００重量部、ジエチレングリコ
ール２００重量部、酢酸エチル１００重量部、ベンゼン
エチルエーテル２重量部、シランカップリング剤（信越
化学（株）製ＫＢＭ−５０３）１重量部を５０℃にて撹
はん溶解した均一な溶液をバーコーターにより塗布し８
０℃で１０分間加熱した。その後、透明導電層とポリエ
ーテルスルフォンの密着力を向上させるためにすでに形
成済みのアンカー層の上に、リアクティブマグネトロン
スパッタ装置により厚さ３００ÅのＩｎ，Ｓｎの合金酸
化物膜を形成し透明導電層とした。このようにして作製
した透明導電性フィルムにおいて、透明導電層を形成す
る前の状態で濃度１規定、液温３０℃のＨＣｌに５分間
浸せきする前後で酸素ガスバリヤー性を測定したところ
処理前後ともに０．３ｃｃ／ｍ2・ｄａｙ・ａｔｍであ
り、十分なガスバリアー性を示した。Example 1 A 100 μm-thick polyethersulfone film was used as a polymer film, and a transparent conductive layer was provided on one side of the film and a gas barrier layer was provided on the other side. In order to improve the adhesion between the layer and the polyethersulfone film, the anchor layer has a molecular weight of about 10
40 parts by weight of epoxy acrylate prepolymer having a melting point of 55 ° C. (VR-60 manufactured by Showa Polymer Co., Ltd.), 200 parts by weight of diethylene glycol, 100 parts by weight of ethyl acetate, 2 parts by weight of benzene ethyl ether, a silane coupling agent (Shin-Etsu) One part by weight of KBM-503 manufactured by Chemical Co., Ltd.) was stirred and dissolved at 50 ° C., and a uniform solution was applied on both sides by a dipping method, heated at 80 ° C. for 10 minutes, and then irradiated with ultraviolet rays to form a solution. . Thereafter, as a gas barrier layer, In, Sn (SnO) having a relative weight density of 95% or more to the bulk
2 10 wt%) by planar magnetron sputtering using an alloy oxide target of 200 wt.
Å, an alloy oxide film of In and Sn having a specific resistance of 5 × 10 −4 Ω · cm was formed. Further, the anchor layer for improving the adhesion between the protective coating layer and the gas barrier layer is made of a bisphenol A type epoxy thermosetting resin (EPX-49- manufactured by Asahi Denka Co., Ltd.).
10) was diluted with the same amount of methyl acetate, coated with a bar coater, and cured at 80 ° C. for 2 hours. A protective coat layer having a molecular weight of about 1040 and a melting point of 5
100 parts by weight of an epoxy acrylate prepolymer (VR-60 manufactured by Showa Polymer Co., Ltd.) at 5 ° C., 200 parts by weight of diethylene glycol, 100 parts by weight of ethyl acetate, 2 parts by weight of benzene ethyl ether, a silane coupling agent (Shin-Etsu Chemical Co., Ltd. ) Manufactured KBM-503) 1 part by weight of a uniform solution obtained by stirring and dissolving at 50 ° C was applied by a bar coater.
Heat at 0 ° C. for 10 minutes. Thereafter, to improve the adhesion between the transparent conductive layer and the polyethersulfone, a 300 mm thick In, Sn alloy oxide film is formed on the already formed anchor layer by a reactive magnetron sputtering apparatus to form a transparent conductive layer. Layers. In the transparent conductive film thus prepared, before the transparent conductive layer was formed, the oxygen gas barrier property was measured before and after immersion in HCl at a concentration of 1N and a liquid temperature of 30 ° C. for 5 minutes. 0.3 cc / m 2 · day · atm, indicating a sufficient gas barrier property.
【０００９】《比較例１》保護コーティング層、保護コ
ーティング層のアンカー層を省略した以外は実施例１と
同様にして作った透明導電性フィルムにおいて、電極形
成前の状態での酸素ガスバリヤー性が２．５ｃｃ／ｍ2
・ｄａｙ・ａｔｍであったが、濃度１規定、液温３０℃
のＨＣｌに５分間浸せきした後測定したところ１００ｃ
ｃ／ｍ2・ｄａｙ・ａｔｍと劣化していることが確認さ
れた。[0009] "Comparative Example 1" protective coating layer, the transparent conductive film except for omitting the anchor layer made in the same manner as in Example 1 of the protective coating layer, oxygen gas barrier property at the front electrode formation conditions 2.5cc / m 2
・ Day ・ atm, concentration 1N, liquid temperature 30 ℃
Was immersed in HCl for 5 minutes and measured.
It was confirmed that c / m 2 · day · atm was deteriorated.
【００１０】[0010]
【発明の効果】本発明により、透明性、ガスバリヤー
性、耐久性の優れた透明導電性フィルムを提供すること
が可能となった。According to the present invention, it has become possible to provide a transparent conductive film having excellent transparency, gas barrier properties and durability.
Claims (3)
としてＩｎ、Ｓｎの合金酸化物及び該ガスバリヤー層を
覆うようにシランカップリング剤を含むエポキシアクリ
レート紫外線硬化樹脂の保護コーティング層を順次積層
した積層フィルムの少なくとも片側に透明導電層を有す
ることを特徴とする透明導電性フィルム。1. A protective coating layer of an epoxy acrylate ultraviolet curable resin containing a silane coupling agent and a silane coupling agent is sequentially laminated on one surface of a polymer film as a gas barrier layer so as to cover an alloy oxide of In and Sn and the gas barrier layer. A transparent conductive film having a transparent conductive layer on at least one side of a laminated film.
０Åであることを特徴とする特許請求の範囲請求項１の
透明導電性フィルム。2. The gas barrier layer has a thickness of 100 to 50.
The transparent conductive film according to claim 1, wherein the angle is 0 °.
覆う保護コーティング層の間にビスフェノールＡ型のエ
ポキシ熱硬化性樹脂のアンカー層を有することを特徴と
する特許請求の範囲請求項１又は請求項２の透明導電性
フィルム。3. The method according to claim 1, further comprising an anchor layer of a bisphenol A type epoxy thermosetting resin between the gas barrier layer and a protective coating layer covering the gas barrier layer. Item 7. The transparent conductive film according to Item 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19488395A JP3194851B2 (en) | 1995-07-31 | 1995-07-31 | Transparent conductive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19488395A JP3194851B2 (en) | 1995-07-31 | 1995-07-31 | Transparent conductive film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0939151A JPH0939151A (en) | 1997-02-10 |
| JP3194851B2 true JP3194851B2 (en) | 2001-08-06 |
Family
ID=16331914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19488395A Expired - Fee Related JP3194851B2 (en) | 1995-07-31 | 1995-07-31 | Transparent conductive film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3194851B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3403882B2 (en) * | 1995-12-25 | 2003-05-06 | 帝人株式会社 | Transparent conductive film |
| JPH10296898A (en) * | 1997-04-28 | 1998-11-10 | Sumitomo Bakelite Co Ltd | Antistatic film |
| JPH10329254A (en) * | 1997-05-30 | 1998-12-15 | Sumitomo Bakelite Co Ltd | Laminated film and liquid crystal display device |
| JP2000285752A (en) * | 1999-03-30 | 2000-10-13 | Hoya Corp | Transparent electrode and forming method therefor |
| JP4827293B2 (en) * | 2000-11-24 | 2011-11-30 | 株式会社きもと | Protective film for inorganic thin film |
| JP6796460B2 (en) * | 2016-11-14 | 2020-12-09 | 日東電工株式会社 | Transparent conductive film and touch panel |
-
1995
- 1995-07-31 JP JP19488395A patent/JP3194851B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0939151A (en) | 1997-02-10 |
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