JPH10330916A - Electrically conductive laminated body - Google Patents
Electrically conductive laminated bodyInfo
- Publication number
- JPH10330916A JPH10330916A JP14499697A JP14499697A JPH10330916A JP H10330916 A JPH10330916 A JP H10330916A JP 14499697 A JP14499697 A JP 14499697A JP 14499697 A JP14499697 A JP 14499697A JP H10330916 A JPH10330916 A JP H10330916A
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- Prior art keywords
- film
- conductive
- layer
- conductive laminate
- less
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、構成層としてプラ
スチック基材層とインジウムスズ酸化物（以下「ＩＴ
Ｏ」という）からなる導電層を含んでなる軽量であり、
抵抗性、低カール性、密着性、耐屈曲性、透明性等に優
れた導電性積層体に関する。[0001] The present invention relates to a plastic substrate layer and indium tin oxide (hereinafter referred to as "IT") as constituent layers.
O ").
The present invention relates to a conductive laminate excellent in resistance, low curl, adhesion, bending resistance, transparency and the like.
【０００２】[0002]
【従来の技術】従来、種々の電子部品等においてガラス
基盤にＩＴＯ膜を製膜した導電性積層体が使用されてき
たが、近年、軽量化を図る上で、プラスチック製のフィ
ルムないしはシートを基材とした導電性積層体の開発が
進みつつある。かかる導電性積層体は、フレキシブルＥ
Ｌ（Ｅｌｅｃｔｒｏ Ｌｕｍｉｎｅｓｃｅｎｃｅ）パネ
ルや液晶ディスプレイ、太陽電池等の透明電極、タッチ
パネル、透明スイッチ、メモリ、センサ、静電遮蔽、電
磁シールド、帯電防止等への用途が広がりつつある。2. Description of the Related Art Conventionally, a conductive laminate having an ITO film formed on a glass substrate has been used in various electronic parts and the like. However, in recent years, in order to reduce the weight, a plastic film or sheet has been used. The development of a conductive laminate as a material is progressing. Such a conductive laminate is a flexible E
Applications for L (Electro Luminescence) panels, liquid crystal displays, transparent electrodes such as solar cells, touch panels, transparent switches, memories, sensors, electrostatic shielding, electromagnetic shielding, antistatic, and the like are expanding.
【０００３】[0003]
【発明が解決しようとする課題】従来のＩＴＯ膜をガラ
ス基材上に製膜する場合は、一般に２００℃以上の高温
成で製膜、熱処理することにより低抵抗化が達成され
る。しかしながら、基材ガラスをプラスチックフィルム
に代替することにより、ＩＴＯをより低温で成膜しつ
つ、且つ、低抵抗化を実現させる必要がある。When a conventional ITO film is formed on a glass substrate, the resistance is generally reduced by forming the film at a high temperature of 200 ° C. or higher and performing a heat treatment. However, by substituting the base glass with a plastic film, it is necessary to realize a lower resistance while forming the ITO at a lower temperature.
【０００４】ところが、低温成膜での非結晶性ＩＴＯ膜
では、抵抗値の経時変化が大きい傾向があり、耐久性に
問題がある。また、基材をプラスチックフィルムした場
合には、得られる導電性積層体がカールしやすいなどの
ガラス基板の場合には生じなかった新たな問題もある。
一方、プラスチック基板の特性を活かして湾曲した形状
の製品も考えた場合、新たに耐屈曲性やＩＴＯ膜の基材
に対する密着性等を改良しておくことが望ましい。However, a non-crystalline ITO film formed at a low temperature tends to have a large change in resistance with time, and has a problem in durability. In addition, when the substrate is made of a plastic film, there is a new problem that does not occur in the case of a glass substrate such that the obtained conductive laminate easily curls.
On the other hand, when considering a product having a curved shape utilizing the characteristics of the plastic substrate, it is desirable to newly improve the bending resistance, the adhesion of the ITO film to the base material, and the like.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、上記課題
に鑑み鋭意検討を行った結果、プラスチックを基材とし
てＩＴＯ膜を低温成膜する場合においても、特定の結晶
性のＩＴＯ膜を成膜させた場合においては、低抵抗化が
実現され、且つ、熱、湿度、電気、機械的な力などの外
的な影響を受けても抵抗率の経時変化が小さく、また、
低カール性、耐屈曲性、密着性、透明性等の諸物性も良
好であることを見いだし、本発明に到達した。Means for Solving the Problems The present inventors have conducted intensive studies in view of the above-mentioned problems, and as a result, even when forming an ITO film on a plastic substrate at a low temperature, a specific crystalline ITO film is formed. In the case of forming a film, low resistance is realized, and the temporal change in resistivity is small even under external influences such as heat, humidity, electricity, and mechanical force.
Various physical properties such as low curl property, flex resistance, adhesion, and transparency were also found to be good, and the present invention was reached.
【０００６】即ち、本発明は、表面にインジウムスズ酸
化物からなる導電層を設け、且つ、プラスチック基材を
用いてなる導電性積層体において、導電層が平均粒径２
０ｎｍ以下の結晶性粒子から構成され、その優勢な結晶
配向方位が＜１１１＞、表面粗さＲｍｓが１．５ｎｍ以
下であって、且つ、導電性積層体の体積抵抗率が４×１
０-4Ωｃｍ以下、カール高さが２０ｍｍ以下であること
を特徴とする導電性積層体に存する。That is, according to the present invention, in a conductive laminate having a surface provided with a conductive layer made of indium tin oxide and using a plastic substrate, the conductive layer has an average particle size of 2.
It is composed of crystalline particles of 0 nm or less, the dominant crystal orientation direction is <111>, the surface roughness Rms is 1.5 nm or less, and the volume resistivity of the conductive laminate is 4 × 1.
The present invention provides a conductive laminate characterized by having a curl height of 0-4 Ωcm or less and a curl height of 20 mm or less.
【０００７】[0007]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明の導電性積層体の基材層であるプラスチック原料
としては、フィルム又はシートとして利用されるような
プラスチック原料であれば特に制限はない。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The plastic raw material as the base layer of the conductive laminate of the present invention is not particularly limited as long as it is a plastic raw material used as a film or a sheet.
【０００８】具体的な例としては、エチレン、プロピレ
ン、ブテン等の単独重合体又は共重合体等のポリオレフ
ィン（ＰＯ）系樹脂、環状ポリオレフィン等の非晶質ポ
リオレフィン樹脂（ＡＰＯ）、ポリエチレンテレフタレ
ート（ＰＥＴ）、ポリエチレン−２，６−ナフタレート
（ＰＥＮ）等のポリエステル系樹脂、ナイロン６、ナイ
ロン１２、共重合ナイロン等のポリアミド（ＰＡ）系樹
脂、ポリビニルアルコール（ＰＶＡ）樹脂、エチレン−
ビニルアルコール共重合体（ＥＶＯＨ）等のポリビニル
アルコール系樹脂、ポリイミド（ＰＩ）樹脂、ポリエー
テルイミド（ＰＥＩ）樹脂、ポリサルホン（ＰＳ）樹
脂、ポリエーテルサルホン（ＰＥＳ）樹脂、ポリエーテ
ルエーテルケトン（ＰＥＥＫ）樹脂、ポリカーボネート
（ＰＣ）樹脂、ポリビニルブチラール（ＰＶＢ）樹脂、
ポリアリレート（ＰＡＲ）樹脂、エチレン−四フッ化エ
チレン共重合体（ＥＴＦＥ）、三フッ化塩化エチレン
（ＰＣＴＦＥ）、四フッ化エチレン−六フッ化プロピレ
ン共重合体（ＦＥＰ）、四フッ化エチレン−パーフルオ
ロアルコキシエチレン共重合体（ＰＦＡ）、フッ化ビニ
リデン（ＰＶＤＦ）、フッ化ビニル（ＰＶＦ）、パーフ
ルオロエチレン−パーフロロプロピレン−パーフロロビ
ニルエーテル三元共重合体（ＥＰＥ）等のフッ素系樹
脂、ラジカル反応性不飽和化合物を有するアクリレート
化合物より成る樹脂組成物、このアクリレート化合物と
チオール基を有するメルカプト化合物より成る樹脂組成
物、エポキシアクリレート、ウレタンアクリレート、ポ
リエステルアクリレート、ポリエーテルアクリレート等
のオリゴマーを多官能アクリレートモノマーに溶融せし
めた樹脂組成物等の光硬化性樹脂、及びこれらの混合物
などが挙げられる。Specific examples include polyolefin (PO) resins such as homopolymers or copolymers such as ethylene, propylene and butene, amorphous polyolefin resins (APO) such as cyclic polyolefins, and polyethylene terephthalate (PET). ), Polyester resins such as polyethylene-2,6-naphthalate (PEN), polyamide (PA) resins such as nylon 6, nylon 12, and copolymerized nylon; polyvinyl alcohol (PVA) resins;
Polyvinyl alcohol-based resin such as vinyl alcohol copolymer (EVOH), polyimide (PI) resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin, polyetheretherketone (PEEK) ) Resin, polycarbonate (PC) resin, polyvinyl butyral (PVB) resin,
Polyarylate (PAR) resin, ethylene-tetrafluoroethylene copolymer (ETFE), ethylene trifluoride ethylene chloride (PCTFE), ethylene tetrafluoride-propylene hexafluoride copolymer (FEP), ethylene tetrafluoride Fluororesins such as perfluoroalkoxyethylene copolymer (PFA), vinylidene fluoride (PVDF), vinyl fluoride (PVF), terpolymer of perfluoroethylene-perfluoropropylene-perfluorovinylether (EPE), A resin composition comprising an acrylate compound having a radical-reactive unsaturated compound, a resin composition comprising this acrylate compound and a mercapto compound having a thiol group, and oligomers such as epoxy acrylate, urethane acrylate, polyester acrylate, and polyether acrylate. Chestnut rates monomers photocurable resin in the resin composition or the like brought melt, and the like and mixtures thereof.
【０００９】以上の中では、偏光性、平坦性、耐熱性等
に優れたＡＰＯ、ＰＥＴ、ＰＥＳ、ＰＣ、ＰＡＲが好ま
しく、ＡＰＯの中では環状ポリオレフィンが特に好まし
い。なお、以上のプラスチック原料中には、公知の添加
剤、例えば、帯電防止剤、紫外線吸収剤、可塑剤、滑
剤、フィラー、着色剤等を添加することができる。以上
のようなプラスチック原料を本発明の導電積層体の基材
として用いる場合は、通常、フィルム状ないしはシート
状のものが好ましく、中でも軽量で連続生産に適したフ
ィルム状のものが一般に用いられる。フィルムの厚さ
は、所望の機械強度、可撓性、透明性あるいは用途等に
応じ、適宜選択することができるが、通常５〜５００μ
ｍである。かかるフィルムは、未延伸フィルムでもよい
し延伸フィルムでもよい。また、他のプラスチックフィ
ルムと積層されていてもよい。Among them, APO, PET, PES, PC and PAR which are excellent in polarization property, flatness and heat resistance are preferred, and among APO, cyclic polyolefin is particularly preferred. Known additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, a filler, and a coloring agent can be added to the above-mentioned plastic raw materials. When the above-mentioned plastic raw material is used as the base material of the conductive laminate of the present invention, usually, a film-like or sheet-like material is preferred, and among them, a light-weight film-like material suitable for continuous production is generally used. The thickness of the film can be appropriately selected depending on the desired mechanical strength, flexibility, transparency, application, and the like.
m. Such a film may be an unstretched film or a stretched film. Further, it may be laminated with another plastic film.
【００１０】更に、該フィルムには、コロナ放電処理、
火炎処理、プラズマ処理、グロー放電処理、粗面化処
理、薬品処理等の従来公知の方法による表面処理や、薄
膜とフィルムとの密着性を向上させるためにアンカーコ
ート処理などを行うこともできる。本発明の導電性積層
体は、上記プラスチック層を基材層とし、表明層に導電
層としてインジウムスズ酸化物（ＩＴＯ）を用いる。Ｉ
ＴＯは酸化インジウムと酸化スズの混合酸化物であり、
通常、酸化インジウムを９９〜９０重量％、酸化スズを
１〜１０重量％を含むものが、導電性、透明性の面から
望ましい。Further, the film is subjected to a corona discharge treatment,
A surface treatment by a conventionally known method such as a flame treatment, a plasma treatment, a glow discharge treatment, a surface roughening treatment, and a chemical treatment, and an anchor coat treatment for improving the adhesion between the thin film and the film can also be performed. The conductive laminate of the present invention uses the above-mentioned plastic layer as a base material layer, and uses indium tin oxide (ITO) as a conductive layer for the assertion layer. I
TO is a mixed oxide of indium oxide and tin oxide,
In general, those containing 99 to 90% by weight of indium oxide and 1 to 10% by weight of tin oxide are preferable from the viewpoint of conductivity and transparency.
【００１１】以下、本発明の導電性積層体におけるＩＴ
Ｏ膜導電層の物性について説明する。ＩＴＯ膜の膜厚は
特に制限はないが、結晶性、透明性、可撓性、生産効
率、コスト等から考え合わせると、通常１０〜５００ｎ
ｍ、好ましくは５０〜２００ｎｍである。一般に膜厚が
厚くなるほど膜の結晶性が高まるが、透明性や可撓性は
低下する傾向がある。また、膜厚は膜の各部分より均一
であることが望ましい。Hereinafter, the IT in the conductive laminate of the present invention will be described.
The physical properties of the O film conductive layer will be described. The thickness of the ITO film is not particularly limited, but is generally 10 to 500 n in consideration of crystallinity, transparency, flexibility, production efficiency, cost, and the like.
m, preferably 50 to 200 nm. Generally, as the film thickness increases, the crystallinity of the film increases, but transparency and flexibility tend to decrease. Further, it is desirable that the film thickness is more uniform than each part of the film.
【００１２】ＩＴＯ膜はＩＴＯの粒子の集合体として構
成されるが、そのＩＴＯ粒子は結晶性粒子であって、そ
の平均粒径は２０ｎｍ以下、好ましくは１５ｎｍ以下で
ある。また、粒子形状、粒径分布のが揃っている方が望
ましい。粒径が２０ｎｍより大きくなると、電気抵抗が
大きくなる傾向があるので好ましくない。ＩＴＯ粒子が
小さいほど粒子が密に充填されやすくなり、また、膜表
面もなめらかとなり、抵抗が小さくなるものと推定され
る。なお、ここで言う平均晶粒径とは、ＩＴＯ膜の表面
を垂直方向から電界放射型２次電子顕微鏡で観察したと
きのＩＴＯ膜表面の多角形状粒子の対角線距離あるいは
円形状粒子の直径の平均値を意味する。また、ＩＴＯ成
膜時の基板温度や後工程の熱処理によって、それらの粒
子が一つの領域内で集合した形態であるドメイン構造を
採る場合もある。このドメイン構造径は、通常１００〜
１０００ｎｍである。The ITO film is formed as an aggregate of ITO particles. The ITO particles are crystalline particles and have an average particle size of 20 nm or less, preferably 15 nm or less. Further, it is desirable that the particle shape and the particle size distribution are uniform. If the particle size is larger than 20 nm, the electric resistance tends to increase, which is not preferable. It is presumed that the smaller the ITO particles, the easier the particles are to be densely packed, the smoother the film surface, and the lower the resistance. Here, the average crystal grain size means a diagonal distance of polygonal particles on the surface of the ITO film or an average of diameters of circular particles when the surface of the ITO film is observed from a vertical direction with a field emission secondary electron microscope. Mean value. In addition, a domain structure in which the particles are aggregated in one region may be adopted by a substrate temperature during ITO film formation or a heat treatment in a later step. This domain structure diameter is usually 100 to
1000 nm.
【００１３】また、本発明のＩＴＯ膜の表明粗さＲｍｓ
（自乗平均平方根値）は１．５ｎｍ以下、好ましくは
１．０ｎｍ以下である。この表面粗さＲｍｓは原子間力
顕微鏡を用いて１μｍ角を測定し、得られたＩＴＯ膜表
面の３次元像に対して傾斜補正処理を行い、粗さ解析に
より求める。この表面粗さＲｍｓが１．５ｎｍより大き
くなると抵抗も顕著に大きくなるので好ましくない。Further, the surface roughness Rms of the ITO film of the present invention is described.
(Root mean square value) is 1.5 nm or less, preferably 1.0 nm or less. The surface roughness Rms is obtained by measuring a 1 μm square using an atomic force microscope, performing a tilt correction process on the obtained three-dimensional image of the ITO film surface, and performing a roughness analysis. If the surface roughness Rms is larger than 1.5 nm, the resistance is also undesirably increased.
【００１４】更に、ＩＴＯ膜には、一般に結晶性のもの
と非結晶性のものと両方が存在するが、本発明でのＩＴ
Ｏ膜は結晶性のもの、結晶性のものでも特定の構造を有
するものを使用する。その結晶構造は、薄膜Ｘ線回折で
酸化インジウム成分に由来する結晶ピークの検出により
判別する。結晶性のＩＴＯ膜では、薄膜Ｘ線回折におい
て、主に酸化インジウムの（２２２）面、（４００）
面、（４４０）面、（６２２）面等のピークが検出され
るが、そのうち（２２２）面と（４００）面のピーク強
度比の大きさにより、優勢な結晶配向方向が判明する。
具体的には、（４００）面の結晶ピーク強度Ｉ（４０
０）に対する（２２２）面の結晶ピーク強度Ｉ（２２
２）の比Ｉ（４００）／Ｉ（２２２）が０．３３未満で
ある場合を優勢な結晶配向方位が＜１１１＞であると言
い、逆に０．３３以上である場合を優勢な結晶配向方位
が＜１００＞であると言う。この０．３３は酸化インジ
ウムのランダム配向している場合のＡＳＴＭ値である。
そして、本発明でのＩＴＯ膜の優勢な結晶配向方向は＜
１１１＞であり、好ましくは、前記のピーク強度比が
０．２５以下、即ち、＜１１１＞配向性がより強いもの
である。Further, there are generally both a crystalline film and an amorphous film in the ITO film.
As the O film, a crystalline one or a crystalline one having a specific structure is used. The crystal structure is determined by detecting a crystal peak derived from an indium oxide component by thin-film X-ray diffraction. In a crystalline ITO film, in the thin film X-ray diffraction, the (222) plane and the (400) plane of indium oxide are mainly used.
The peaks of the (440) plane, the (622) plane, etc. are detected, and the predominant crystal orientation direction is determined by the magnitude of the peak intensity ratio between the (222) plane and the (400) plane.
Specifically, the (400) plane crystal peak intensity I (40
0) to the (222) plane crystal peak intensity I (22)
When the ratio I (400) / I (222) of 2) is less than 0.33, the predominant crystal orientation is <111>, and when it is 0.33 or more, the predominant crystal orientation. Say the orientation is <100>. This 0.33 is an ASTM value when indium oxide is randomly oriented.
And the predominant crystal orientation direction of the ITO film in the present invention is <
111>, preferably, the peak intensity ratio is 0.25 or less, that is, the <111> orientation is stronger.
【００１５】なお、ＩＴＯ膜の電気的性質は、不純物、
結晶構造学上の酸素欠陥や格子欠陥、結晶粒界などの種
々の要因が影響すると考えられており、本発明の導電性
積層体においては上記の結晶構造のものを用いている
が、他の結晶構造を有するＩＴＯ膜や非結晶性のＩＴＯ
膜が導電膜として常に不適当であるとは判断できるもの
ではない。The electrical properties of the ITO film include impurities,
It is thought that various factors such as oxygen defects and lattice defects on the crystal structure, crystal grain boundaries and the like are affected, and in the conductive laminate of the present invention, those having the above crystal structure are used. ITO film with crystalline structure or amorphous ITO
It cannot be determined that the film is always inappropriate as a conductive film.
【００１６】以上のような本発明の導電性積層体の表面
に存するＩＴＯ膜は、本発明で規定する物性要件を満た
すものであれば、成膜方法などは特に制限はないが、通
常、成膜方法としては、真空蒸着、イオンプレーティン
グ、スパッタリング、化学気相成膜法（ＣＶＤ）等の方
法が採用される。また、成膜は、酸素ガスや水蒸気、不
活性ガス等のガス存在下で実施してもよい。あるいは、
ＩＴＯ膜の低抵抗化のため、大気中又は真空中で、プラ
スチック基材の変形が生じない程度の条件下で熱処理を
行ってよい。The ITO film present on the surface of the conductive laminate of the present invention as described above is not particularly limited as long as it satisfies the physical properties defined by the present invention. As a film method, methods such as vacuum deposition, ion plating, sputtering, and chemical vapor deposition (CVD) are employed. The film formation may be performed in the presence of a gas such as oxygen gas, water vapor, or an inert gas. Or,
In order to reduce the resistance of the ITO film, heat treatment may be performed in the air or in a vacuum under such a condition that the plastic substrate is not deformed.
【００１７】本発明の導電性積層体は、基本的には、以
上のプラスチック基材層とＩＴＯ膜からなる導電層の２
層から構成されるが、導電性積層体の性能の安定性ない
し耐久性向上のために、プラスチック基材層と導電層と
の間に、いわゆる接着層やガスバリア層の役割を有する
中間層層を介在させてもよい。かかるた中間層として好
ましいものとして、紫外線又は電子線硬化樹脂層があ
る。この紫外線又は電子線硬化樹脂層は、一般にハード
コートと呼ばれる塗膜であり、公知のプレポリマー及び
若しくはモノマーを混合し、塗布、硬化させた膜であ
る。例えば、ポリエステル、又はポリエーテル、又はウ
レタン、又はエポキシ系のアクリレート又はメタクリレ
ートのモノマー及びオリゴマーの単独物或いは混合物が
挙げられる。具体的には、トリメチロールプロパントリ
アクリレート、トリメチロールプロパントリメタクリレ
ート、ペンタエリスリトールアクリレート、ペンタエリ
スリトールトリメタクリレート、ペンタエリスリトール
テトラアクリレート、ペンタエリスリトールテトラメタ
クリレート、ジペンタエリスリトールヘキサアクリレー
ト、ジペンタエリスリトールヘキサメタクリレート、イ
ソアミルアクリレート、エトキシジエチレングリコール
アクリレート、メトキシジエチレングリコールアクリレ
ート、Ｎ−ビニルピロリドンなど、１個以上の炭素−炭
素２重結合を有する単官能及び多官能のアクリルモノマ
ー、メタクリルモノマー、ビニルモノマー類などであ
る。また、必要に応じて、シランカップリング剤等の接
着性改良剤、重合開始剤、希釈剤等を添加してもよい。
コート方法としては、公知のグラビアコート、リバース
ロールコート、キスロールコート、スピンコートなどが
実施される。硬化後の層厚さは、通常２〜２０μｍで、
厚さむらがなく表面平坦性が良好であるものが好まし
い。The conductive laminate of the present invention basically comprises two layers of the above-mentioned plastic substrate layer and the conductive layer composed of an ITO film.
Although it is composed of layers, in order to improve the stability or durability of the performance of the conductive laminate, an intermediate layer having a role of a so-called adhesive layer or gas barrier layer is provided between the plastic base layer and the conductive layer. It may be interposed. Preferred as such an intermediate layer is an ultraviolet or electron beam curable resin layer. The ultraviolet or electron beam curable resin layer is a coating film generally called a hard coat, and is a film obtained by mixing a known prepolymer and / or monomer, and applying and curing the mixture. For example, polyesters, polyethers, urethanes, or epoxy-based acrylate or methacrylate monomers and oligomers may be used alone or as a mixture. Specifically, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol acrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, isoamyl acrylate And monofunctional and polyfunctional acrylic monomers, methacrylic monomers, and vinyl monomers having one or more carbon-carbon double bonds, such as ethoxydiethylene glycol acrylate, methoxydiethylene glycol acrylate, and N-vinylpyrrolidone. If necessary, an adhesion improver such as a silane coupling agent, a polymerization initiator, a diluent, and the like may be added.
As a coating method, a known gravure coat, reverse roll coat, kiss roll coat, spin coat, or the like is performed. The layer thickness after curing is usually 2 to 20 μm,
It is preferable that the material has no thickness unevenness and good surface flatness.
【００１８】また、中間層として、ガスバリア性に優れ
た、インジウムスズ酸化物以外の無機酸化物膜を用いる
ことも好ましい。この場合の無機酸化物としては、金
属、非金属、亜金属の酸化物があり、具体例としては、
酸化アルミニウム、酸化亜鉛、酸化アンチモン、酸化イ
ンジウム、酸化カルシウム、酸化カドミウム、酸化銀、
酸化金、酸化クロム、珪素酸化物、酸化コバルト、酸化
ジルコニウム、酸化スズ、酸化チタン、酸化鉄、酸化
銅、酸化ニッケル、酸化白金、酸化パラジウム、酸化ビ
スマス、酸化マグネシウム、酸化マンガン、酸化モリブ
デン、酸化バナジウム、酸化バリウム等が挙げられる。
以上では、珪素酸化物、酸化アルミニウムは、安価であ
り、且つ、ガスバリア性と透明性も特に優れているので
好ましい。なお、以上の無機酸化物には、微量の金属、
非金属、亜金属単体やそれらの水酸化物、また、可撓性
を向上させるために、炭素又はフッ素成分が適宜が含ま
れていてもよい。以上の無機酸化物薄膜を形成させる方
法は、前記のＩＴＯ膜を形成させる方法と同様に真空蒸
着、イオンプレーテイング、スパッタリング等である。
以上の無機酸化物薄膜の厚さは、通常５〜５００ｎｍで
あり、厚さむらがなく、表面平坦性が良好であるものが
好ましい。It is also preferable to use an inorganic oxide film other than indium tin oxide, which is excellent in gas barrier properties, as the intermediate layer. Inorganic oxides in this case include metal, non-metal, and sub-metal oxides.
Aluminum oxide, zinc oxide, antimony oxide, indium oxide, calcium oxide, cadmium oxide, silver oxide,
Gold oxide, chromium oxide, silicon oxide, cobalt oxide, zirconium oxide, tin oxide, titanium oxide, iron oxide, copper oxide, nickel oxide, platinum oxide, palladium oxide, bismuth oxide, magnesium oxide, manganese oxide, molybdenum oxide, oxidation Vanadium, barium oxide and the like can be mentioned.
Above, silicon oxide and aluminum oxide are preferable because they are inexpensive and have particularly excellent gas barrier properties and transparency. Note that the above inorganic oxides include a trace amount of metal,
A non-metal, a sub-metal, a hydroxide thereof, and a carbon or fluorine component may be appropriately contained in order to improve flexibility. The method for forming the above-mentioned inorganic oxide thin film includes vacuum deposition, ion plating, sputtering and the like, as in the above-described method for forming the ITO film.
The thickness of the above-mentioned inorganic oxide thin film is usually from 5 to 500 nm, and it is preferable that the thickness is not uneven and the surface flatness is good.
【００１９】以上のような本発明の導電性積層体は低抵
抗性であり、ＪＩＳ Ｋ７１９７のの四探針四端子法に
て測定した体積抵抗率が４×１０-4Ωｃｍ以下、好まし
くは３×１０-4Ωｃｍ以下である。また、導電性積層体
ののカール高さは２０ｍｍ以下、好ましくは１０ｍｍ以
下である。ここに、カール高さとは、１２０ｍｍ角の大
きさの積層体を水平平坦な場所に荷重をかけず自然に置
いた場合のフィルムを置いた面からフィルムの最大高さ
までの距離である。カール高さは導電性積層体の各層の
性質や密着状態に依存して決まってくると推定される
が、カール高さが上記の値を超えるような場合は導電性
積層体の耐屈曲性や密着性が低下するので好ましくな
い。The conductive laminate of the present invention as described above has a low resistance, and has a volume resistivity of 4 × 10 −4 Ωcm or less, preferably 3 × 10 −4 Ωcm, as measured by a four-probe four-terminal method of JIS K7197. × 10 −4 Ωcm or less. The curl height of the conductive laminate is 20 mm or less, preferably 10 mm or less. Here, the curl height is the distance from the surface on which the film is placed to the maximum height of the film when the laminate having a size of 120 mm square is naturally placed on a horizontally flat place without applying a load. The curl height is estimated to be determined depending on the properties and adhesion of each layer of the conductive laminate, but if the curl height exceeds the above value, the flex resistance of the conductive laminate and It is not preferable because the adhesion is reduced.
【００２０】更に、本発明の導電性積層体では透明性に
優れたものであり、波長５５０ｎｍにおける光線透過率
が通常８５％以上である。この導電性積層体の用途とし
ては、高透明性が要求される場合が多く、かかる場合は
光線透過率が高いほど望ましい。Further, the conductive laminate of the present invention has excellent transparency, and the light transmittance at a wavelength of 550 nm is usually 85% or more. In many cases, the transparency of the conductive laminate is required to be high. In such a case, a higher light transmittance is more desirable.
【００２１】[0021]
【実施例】以下、本発明を実施例により更に詳細に説明
するが、本発明はその要旨を越えない限り以下の例に限
定されるものではない。なお、以下の例において、導電
性積層体の評価及び測定を次の方法で行った。 ＜導電層の厚さ（ｎｍ）＞積層体の断面を透過型電子顕
微鏡（日立製作所製Ｈ−６００型）で観察し積層体の導
電層の厚さを測定した。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention. In the following examples, the evaluation and measurement of the conductive laminate were performed by the following methods. <Thickness of conductive layer (nm)> The cross section of the laminate was observed with a transmission electron microscope (H-600, manufactured by Hitachi, Ltd.), and the thickness of the conductive layer of the laminate was measured.
【００２２】＜導電層の結晶性及びその結晶配向方位＞
薄膜Ｘ線回折装置（リガク製ＲＩＮＴＩ５００型）を用
い、管球Ｃｕ（ＣｕＫα１線）、管電圧５０ｋＶ、管電
流２００ｍＡ、広角ゴニオメータ、サンプリング角度
０．０５０゜、走査速度３．０゜／分、走査軸２θ、固
定角度１．０゜、回転速度１２０回／分の条件で測定
し、結晶ピークの有無からＩＴＯ膜の結晶性を、また、
ピーク強度比Ｉ（４００）／Ｉ（２２２）から主要結晶
配向方位を調べた。この測定条件の場合、（４００）面
の結晶ピークは２θ＝３０．５゜付近、（２２２）面の
結晶ピークは２θ＝３５．４゜付近に検出される。<Crystallinity of Conductive Layer and its Crystal Orientation>
Using a thin-film X-ray diffractometer (Rigti RINTI500 type), tube Cu (CuKα1 line), tube voltage 50 kV, tube current 200 mA, wide-angle goniometer, sampling angle 0.050 °, scanning speed 3.0 ° / min, scanning Measured under the conditions of axis 2θ, fixed angle 1.0 °, and rotation speed 120 times / min, the crystallinity of the ITO film was determined based on the presence or absence of a crystal peak.
The main crystal orientation direction was examined from the peak intensity ratio I (400) / I (222). Under this measurement condition, the crystal peak of the (400) plane is detected near 2θ = 30.5 °, and the crystal peak of the (222) plane is detected near 2θ = 35.4 °.
【００２３】＜導電層の結晶粒径＞電界放射型２次電子
顕微鏡（日立製作所製Ｓ−９００型）を用い、傾斜なし
の無蒸着の条件下でＩＴＯ膜表面を観察し、その１０万
倍像から、多角形状または円形状である粒子形状の対角
線距離或いは直径を測定した。 ＜導電層の表面粗さ＞原子間力顕微鏡（セイコー電子工
業製ＳＰＩ３７００型）を用い、共振モード、測定面積
１μｍ角、走査速度１Ｈｚ、５１２×５１２分割の条件
で測定し、装置付属ソフトで自動傾斜処理を行い、同じ
く装置付属ソフトで粗さ解析し、表面粗さＲｍｓを求め
た。<Crystal Grain Size of Conductive Layer> Using a field emission secondary electron microscope (S-900, manufactured by Hitachi, Ltd.), the surface of the ITO film was observed under conditions of non-evaporation without inclination, and 100,000 times the size of the ITO film. From the images, the diagonal distance or the diameter of the polygonal or circular particle shape was measured. <Surface Roughness of Conductive Layer> Using an atomic force microscope (SPI3700, manufactured by Seiko Instruments Inc.), the measurement is performed under the conditions of resonance mode, measurement area of 1 μm square, scanning speed of 1 Hz, and 512 × 512 divisions, and is automatically performed by software attached to the apparatus. A tilt treatment was performed, and a roughness analysis was similarly performed using software attached to the apparatus to determine a surface roughness Rms.
【００２４】＜導電性積層体の体積抵抗率＞８０×５０
ｍｍの大きさの積層体について、抵抗率計（三菱化学製
ＬＯＲＥＳＴＡ−ＳＰ型）で測定した。 ＜導電性積層体のカール高さ＞１２０ｍｍ角の大きさの
積層体を、水平平坦な場所に荷重をかけず自然に置き、
積層体を置いた面から積層体の最大高さまでの距離を物
差しで計測した。<Volume resistivity of conductive laminate> 80 × 50
The laminate having a size of mm was measured with a resistivity meter (model LORESTA-SP manufactured by Mitsubishi Chemical Corporation). <Curl height of conductive laminate> A laminate having a size of 120 mm square is naturally placed on a horizontal flat place without applying a load,
The distance from the surface on which the laminate was placed to the maximum height of the laminate was measured with a ruler.
【００２５】＜導電性積層体の耐屈曲性＞ＩＴＯ膜を内
側にした場合と外側にした場合の２通りとも、１０×１
００ｍｍ大きさの導電性フィルムを、φ１５ｍｍの丸棒
に沿って１８０゜曲げ３０秒保持した後、体積抵抗率を
測定し、曲げる前の体積抵抗率との変化率が１．５以下
である条件を２通りとも満たした場合を○、そうでない
場合を×とした。 ＜導電性積層体の密着性＞１０×３０ｍｍの大きさの導
電性フィルムを、水温２５℃の３％水酸化ナトリウム水
溶液に１０分浸漬させた後、水洗、乾燥し、セロハンテ
ープをＩＴＯ膜に貼って剥がしても、ＩＴＯ膜が下地に
すべて残っている条件を満たした場合を○、そうでない
場合を×とした。。<Bending Resistance of Conductive Laminate> Both the case where the ITO film is inside and the case where the ITO film is outside are 10 × 1.
After holding a conductive film having a size of 00 mm along a φ15 mm round bar at 180 ° bending for 30 seconds, the volume resistivity was measured, and the rate of change from the volume resistivity before bending was 1.5 or less. Was satisfied when both were satisfied, and x was determined when not. <Adhesion of Conductive Laminated Body> A conductive film having a size of 10 × 30 mm was immersed in a 3% aqueous solution of sodium hydroxide at a water temperature of 25 ° C. for 10 minutes, washed with water and dried, and a cellophane tape was applied to the ITO film. Even when the ITO film was adhered and peeled, the condition was satisfied when the condition that all of the ITO film remained on the underlayer was satisfied. .
【００２６】＜導電性積層体の透明性＞自記分光光度計
（日立製作所製Ｕ−３４１０型）を用い測定し、波長５
５０ｎｍにおける光線透過率を求めた。 実施例１ 環状ポリオレフィンフィルム（日本合成ゴム製、アート
ン、厚さ１００μｍ）の片面に、厚さ３５ｎｍのＳｉＯ
x膜を蒸着させ、その上に厚さ５μｍの紫外線硬化樹脂
層を形成させ、またその上に厚さ１２０ｎｍのＩＴＯ膜
を成膜して、抵抗率、カール性、耐屈曲性、密着性、透
明性とも良好な導電性フィルムを得た。<Transparency of Conductive Laminate> Measured using a self-recording spectrophotometer (U-3410, manufactured by Hitachi, Ltd.) and having a wavelength of 5
The light transmittance at 50 nm was determined. Example 1 A 35 nm-thick SiO2 film was formed on one surface of a cyclic polyolefin film (manufactured by Nippon Synthetic Rubber Co., Arton, 100 μm thick).
x film is deposited, and a 5 μm thick ultraviolet curable resin layer is formed thereon, and an ITO film having a thickness of 120 nm is formed thereon, and the resistivity, curl property, bending resistance, adhesion, A conductive film having good transparency was obtained.
【００２７】ＳｉＯx膜の蒸着は、蒸着材料としてＳｉ
Ｏ（住友シチックス製）を用い、高周波誘導加熱源（日
本真空技術製）で、圧力２×１０-5Ｔｏｒｒ条件下で行
った。紫外線硬化樹脂層は、三菱レイヨン製ダイヤビー
ムＵＲ−６５２１を１００重量部と東レダウコーニング
シリコーン製ＳＺ６０３０を１０重量部の割合で配合し
た塗布液をリバースロール方式で塗布し、紫外線硬化装
置（オーク社製）を用い、メタルハライドランプ、積算
光量５００ｍＪ／ｃｍ2の条件で硬化させた。The SiO x film is deposited by using Si as a deposition material.
Using O (manufactured by Sumitomo Citix), a high-frequency induction heating source (manufactured by Nippon Vacuum Technology) was used under a pressure of 2 × 10 −5 Torr. The ultraviolet-curing resin layer is coated by a reverse roll method with a coating solution containing 100 parts by weight of Mitsubishi Rayon Diamond Beam UR-6521 and 10 parts by weight of Toray Dow Corning Silicone SZ6030. Using a metal halide lamp and an integrated light quantity of 500 mJ / cm 2 .
【００２８】ＩＴＯ膜の成膜は、蒸着材料としてＩｎ2
Ｏ3−ＳｎＯ2（５重量部）焼結体を用い、プラズマガン
装置（中外炉工業製）で、ベース真空度１×１０-5Ｔｏ
ｒｒ、成膜真空度５×１０-4Ｔｏｒｒ、Ａｒ流量３０ｓ
ｃｃｍ、Ｏ2流量１００ｓｃｃｍ、基板温度１５０℃、
成膜速度３ｎｍ／秒、ガン出力５５Ｖ、１５０Ａ、膜厚
１２０ｎｍの条件下で行った。得られた導電性フィルム
の評価結果を表ー１に示す。The ITO film is formed by depositing In 2 as an evaporation material.
O 3 -SnO 2 (5 parts by weight) sintered body was used, and a plasma gun device (manufactured by Chugai Furnace Industry) was used. The base vacuum degree was 1 × 10 −5 To.
rr, film formation vacuum degree 5 × 10 −4 Torr, Ar flow rate 30 s
ccm, O 2 flow rate 100 sccm, substrate temperature 150 ° C.,
The film formation rate was 3 nm / sec, the gun output was 55 V, the current was 150 A, and the film thickness was 120 nm. Table 1 shows the evaluation results of the obtained conductive films.
【００２９】比較例１ 実施例１において、ＩＴＯ成膜条件の成膜温度を１００
℃に代えた他は、同様な方法で導電性フィルムを得た。
評価結果を表ー１に示す。この導電性フィルムは優勢な
結晶配向方位が＜１００＞であり、抵抗率、密着性が不
良であった。 実施例２ 比較例１と同様にＩＴＯ成膜した後、大気下、１５０
℃、１時間の条件で熱処理を行い、導電性フィルムを得
た。評価結果を表ー１に示す。Comparative Example 1 In Example 1, the film forming temperature under the ITO film forming condition was set to 100
A conductive film was obtained in the same manner except that the temperature was changed to ° C.
The evaluation results are shown in Table-1. This conductive film had a predominant crystal orientation direction of <100>, and was poor in resistivity and adhesion. Example 2 After forming an ITO film in the same manner as in Comparative Example 1, 150
Heat treatment was performed at 1 ° C. for 1 hour to obtain a conductive film. The evaluation results are shown in Table-1.
【００３０】比較例２ 実施例１において、紫外線硬化樹脂層の塗布液成分及び
配合を、大日精化製セイカビームＥＸＦ−０１Ｂを１０
０重量部、東レダウコーニングシリコーン製ＳＺ６０３
０を１０重量部に代えた他は、同様な方法で導電性フィ
ルムを得た。評価結果を表ー１に示す。この導電性フィ
ルムはカール性、耐屈曲性、密着性が不良であった。COMPARATIVE EXAMPLE 2 In Example 1, the composition and the composition of the coating liquid for the ultraviolet curable resin layer were changed to 10 by Seika Beam EXF-01B manufactured by Dainichi Seika.
0 parts by weight, SZ603 made by Toray Dow Corning Silicone
A conductive film was obtained in the same manner except that 0 was changed to 10 parts by weight. The evaluation results are shown in Table-1. This conductive film was poor in curl properties, bending resistance, and adhesion.
【００３１】比較例３ 実施例１において、ＩＴＯ成膜をスパッタ装置で、ベー
ス真空度１×１０−５Ｔｏｒｒ、成膜真空度５×１０−
４Ｔｏｒｒ、Ａｒ流量２５０ｓｃｃｍ、Ｏ2流量５０ｓ
ｃｃｍ、基板温度１５０℃、成膜速度０．２ｎｍ／秒、
膜厚１２０ｎｍの条件下で行った他は、同様にして導電
性フィルムを得た。評価結果を表ー１に示す。この導電
性フィルムは優優勢な結晶配向方位は＜１１１＞ではあ
るが、結晶粒径、表面粗さは大きく、抵抗率、カール
性、密着性が不良であった。Comparative Example 3 In Example 1, the ITO film was formed by a sputtering apparatus using a base vacuum of 1 × 10 −5 Torr and a film forming vacuum of 5 × 10 −5.
4 Torr, Ar flow rate 250 sccm, O 2 flow rate 50 s
ccm, substrate temperature 150 ° C., film formation rate 0.2 nm / sec,
A conductive film was obtained in the same manner as above except that the film thickness was 120 nm. The evaluation results are shown in Table-1. Although this conductive film had a predominant crystal orientation direction of <111>, the crystal grain size and surface roughness were large, and the resistivity, curl properties, and adhesion were poor.
【００３２】比較例４ 比較例３において、ＩＴＯ成膜時の基板温度を１００℃
に変えた他は、同様な方法で導電性フィルムを得た。評
価結果を表ー１に示す。この導電性フィルムのＩＴＯ膜
は非晶性であり、抵抗率、カール性、密着性が不良であ
った。Comparative Example 4 In Comparative Example 3, the substrate temperature at the time of forming the ITO film was 100 ° C.
A conductive film was obtained in the same manner except that the above-mentioned method was used. The evaluation results are shown in Table-1. The ITO film of this conductive film was amorphous, and had poor resistivity, curl, and adhesion.
【００３３】[0033]
【表１】 上記表−１においてＡ〜Ｈ欄は以下を意味する。 Ａ：ＩＴＯ膜の優勢な結晶配向方位 Ｂ：ＩＴＯ膜の結晶粒径（ｎｍ） Ｃ：ＩＴＯ膜の表面粗さ（ｎｍ） Ｄ：導電性積層体の体積抵抗率（Ωｃｍ） Ｅ：導電性積層体のカール高さ（ｍｍ） Ｆ：導電性積層体の耐屈曲性 Ｇ：導電性積層体の密着性 Ｈ：導電性積層体の透明性（％）[Table 1] In Table 1 above, columns A to H mean the following. A: Dominant crystal orientation of ITO film B: Crystal grain size of ITO film (nm) C: Surface roughness of ITO film (nm) D: Volume resistivity of conductive laminate (Ωcm) E: Conductive laminate Curl height of body (mm) F: Flex resistance of conductive laminate G: Adhesion of conductive laminate H: Transparency of conductive laminate (%)
【００３４】[0034]
【発明の効果】本発明によれば、軽量であり、低抵抗
性、低カール性、耐屈曲性、密着性等に優れた導電性積
層体が提供できる。According to the present invention, it is possible to provide a conductive laminate which is lightweight and excellent in low resistance, low curl, bending resistance, adhesion and the like.
Claims (6)
電層を設け、且つ、プラスチック基材を用いてなる導電
性積層体において、導電層が平均粒径２０ｎｍ以下の結
晶性粒子から構成され、その優勢な結晶配向方位が＜１
１１＞、表面粗さＲｍｓが１．５ｎｍ以下であって、且
つ、導電性積層体の体積抵抗率が４×１０-4Ωｃｍ以
下、カール高さが２０ｍｍ以下であることを特徴とする
導電性積層体。1. A conductive laminate comprising an indium tin oxide provided on a surface thereof and using a plastic substrate, wherein the conductive layer is made of crystalline particles having an average particle size of 20 nm or less. Dominant crystal orientation <1
11>, a conductive laminate having a surface roughness Rms of 1.5 nm or less, a volume resistivity of the conductive laminate of 4 × 10 −4 Ωcm or less, and a curl height of 20 mm or less. Laminate.
外線又は電子線硬化樹脂層を介在してなることを特徴と
する請求項１の導電性積層体。2. The conductive laminate according to claim 1, wherein an ultraviolet or electron beam curable resin layer is interposed between the plastic substrate layer and the conductive layer.
スバリア性無機酸化物層を介在してなることを特徴とす
る請求項１又は２の導電性積層体。3. The conductive laminate according to claim 1, wherein a gas barrier inorganic oxide layer is interposed between the plastic base material layer and the conductive layer.
ンであることを特徴とする請求項１ないし３のいずれか
の導電性積層体。4. The conductive laminate according to claim 1, wherein the plastic substrate layer is a cyclic polyolefin.
粒子から構成されることを特徴とする請求項１ないし４
のいずれかの導電性積層体。5. The conductive layer is made of crystalline particles having an average particle diameter of 15 nm or less.
The conductive laminate of any one of the above.
５％以上であることを特徴とする請求項１ないし５のい
ずれかの導電性積層体。6. A light transmittance at a wavelength of 550 nm of 8
The conductive laminate according to any one of claims 1 to 5, wherein the content is 5% or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14499697A JPH10330916A (en) | 1997-06-03 | 1997-06-03 | Electrically conductive laminated body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14499697A JPH10330916A (en) | 1997-06-03 | 1997-06-03 | Electrically conductive laminated body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10330916A true JPH10330916A (en) | 1998-12-15 |
Family
ID=15375053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14499697A Pending JPH10330916A (en) | 1997-06-03 | 1997-06-03 | Electrically conductive laminated body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10330916A (en) |
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