JP4406237B2 - A method for producing a transparent substrate with a multilayer film having conductivity. - Google Patents
A method for producing a transparent substrate with a multilayer film having conductivity. Download PDFInfo
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Description
本発明は導電性を有する多層膜付透明基板に関する。 The present invention relates to a transparent substrate with a multilayer film having conductivity.
従来より、ガラス板やプラスチック板（プラスチックフィルム）等の透明基板にインジウム錫酸化物（ＩＴＯ）やＳｎＯ2等の透明導電膜を形成して、太陽電池などの光電変換素子の電極や液晶等の表示装置またはタッチパネルの電極、静電防止フィルターや電磁波カットフィルターとして利用するものが知られている。特にタッチパネルとして使用される場合、耐擦傷性（タッチパネルにおいては耐ペン摺動性）に優れた導電性を有する多層膜付透明基板が望まれるようになっている。 Conventionally, a transparent conductive film such as indium tin oxide (ITO) or SnO 2 is formed on a transparent substrate such as a glass plate or a plastic plate (plastic film), and an electrode of a photoelectric conversion element such as a solar cell or a liquid crystal What is used as an electrode of a display device or a touch panel, an antistatic filter or an electromagnetic wave cut filter is known. In particular, when used as a touch panel, a transparent substrate with a multilayer film having conductivity excellent in scratch resistance (pen sliding resistance in a touch panel) has been desired.
このような背景において、基板上にハードコート層を設けるとともに最表面に透明導電膜を形成させることにより、導電性を有する多層膜付透明基板の耐ペン摺動性の向上を図ろうとする技術が知られている（例えば、特許文献１、特許文献２参照）。
しかしながら、上述したような基板上にハードコート層を形成するだけでは現在要望されている耐ペン摺動性を満足することが困難である。また、このような導電性を有する透明基板に電極を形成する場合、電極と最外層との密着性を向上させることが必要となる。
本発明では上記従来技術の問題点に鑑み、耐擦傷性（耐ペン摺動性）及び密着性が高い導電性を有する多層膜付透明基板を提供することを技術課題とする。
However, it is difficult to satisfy the currently required pen slidability simply by forming a hard coat layer on the substrate as described above. Moreover, when forming an electrode on such a transparent substrate having conductivity, it is necessary to improve the adhesion between the electrode and the outermost layer.
In the present invention, in view of the above-mentioned problems of the prior art, it is an object of the present invention to provide a transparent substrate with a multilayer film having high scratch resistance (pen slidability) and high adhesion.
（１） 透明基板上に透明導電体の薄膜を積層する導電性を有する多層膜付透明基板の製造方法において、最外層としてＩＴＯ，ＳｎＯ2，ＩＺＯ，ＩＣＯ，ＡＴＯ，ＦＴＯから選ばれる透明導電体からなる第１導電膜と，該第１導電膜の下層に形成され主成分として酸化亜鉛を含有する透明導電体からなる第２導電膜とからなる導電膜層の全体の膜厚を用途に応じて必要な表面抵抗値が得られるように決定する第１ステップであって，前記第２導電膜の膜厚は前記第１導電膜の膜厚に対して薄い膜厚として決定する第１ステップと、前記透明基板上に反射防止膜用として形成される１層または２層からなる誘電膜層（誘電膜層が１層の場合はSiO 2 を、2層の場合はSiO 2 とZrO 2 とを使用する）の各膜厚を決定する第２ステップであって，前記第１ステップにて決定された前記導電膜層の膜厚及び前記誘電膜層に用いられる誘電体の屈折率を固定値として視野２°，標準光Ｃにおけるクロマティクネス指数ａ*，ｂ*を−２〜＋２の範囲内において９０％以上の視感度透過率が得られるようにメリット関数を使用した最適化アルゴリズムを用いて前記誘電体の膜厚を決定する第２ステップと、前記第１ステップにて決定された前記第１導電膜及び第２導電膜の膜厚，並びに前記第２ステップにて決定された前記誘電体の膜厚となるように真空蒸着方法またはスパッタ方法を用いて前記透明基板上に前記誘電膜層を形成し次いで前記導電膜層を形成させる（なお、前記誘電膜層が２層の場合には、基板側からZrO 2 からなる誘電膜とSiO 2 からなる誘電膜とを順に形成させる）ことを特徴とする。
(1) A transparent conductor selected from ITO, SnO 2 , IZO, ICO, ATO, and FTO as the outermost layer in a method for producing a transparent substrate with a multilayer film having conductivity, in which a thin film of a transparent conductor is laminated on a transparent substrate The total film thickness of the conductive film made of the first conductive film made of and a second conductive film made of a transparent conductor containing zinc oxide as a main component formed under the first conductive film depends on the application. A first step for determining a required surface resistance value, wherein the thickness of the second conductive film is determined to be smaller than the thickness of the first conductive film; the SiO 2 in the case of one layer or two layers dielectric layer (dielectric layer is one layer is formed as anti-reflection film on the transparent substrate, in the case of two layers of SiO 2 and ZrO 2 a second step of determining the respective film thicknesses of the use), the first Thickness of the conductive layer which is determined by step and the field of view 2 ° the refractive index of the dielectric material used in the dielectric layer as a fixed value, the chromaticness indices a in the standard light C *, -2 to the b * In the second step of determining the film thickness of the dielectric using an optimization algorithm using a merit function so that a luminous transmittance of 90% or more is obtained within the range of +2, and determined in the first step The first conductive film and the second conductive film are formed on the transparent substrate using a vacuum deposition method or a sputtering method so as to have a film thickness of the dielectric determined in the second step. Form the dielectric film layer, and then form the conductive film layer. (If the dielectric film layer has two layers, a dielectric film made of ZrO 2 and a dielectric film made of SiO 2 are formed in this order from the substrate side. It is characterized by that) .
本発明によれば、高い透過率と耐ペン摺動性が得られるとともに、電極と膜との密着性に優れた導電性を有する多層膜付透明基板を得ることができる。
According to the present invention, it is possible to obtain a transparent substrate with a multilayer film having high transmittance and pen sliding resistance, and having conductivity excellent in adhesion between an electrode and a film.
以下、本発明の実施の形態における導電性を有する多層膜付透明基板について、図面を参照しながら説明する。なお、本実施形態では、基板上に反射防止効果をもたせるための薄膜層帯を設けておき、その上に導電性を有する導電膜層を設けた導電性を有する多層膜付透明基板を例にとり、説明する。 Hereinafter, a transparent substrate with a multilayer film having conductivity according to an embodiment of the present invention will be described with reference to the drawings. In this embodiment, a thin film layer band for providing an antireflection effect is provided on the substrate, and a conductive transparent film substrate with a conductive film layer provided thereon is taken as an example. ,explain.
図１は本発明の実施の形態における導電性を有する多層膜付透明基板の積層構成を示す概略図である。
１は透明の基板である。基板１は通常に入手できるものであればよく、屈折率は１．４８以上１．７以下程度のものを使用する。具体的に、基板材料としてはガラス類（屈折率１．４８〜１．７０）、プラスチック類（ポリカーボネイト（屈折率１．５９）、ポリエチレンテレフタレート（屈折率１．６３）等）が用いられ、光学的に透明であれば特に限定されない。また、本実施形態で述べる基板とは板状に限らず、フィルム基板を含むものとしている。
FIG. 1 is a schematic view showing a laminated structure of a transparent substrate with a multilayer film having conductivity in an embodiment of the present invention.
Reference numeral 1 denotes a transparent substrate. The substrate 1 may be any substrate that is normally available and has a refractive index of about 1.48 or more and 1.7 or less. Specifically, glass (refractive index: 1.48 to 1.70), plastics (polycarbonate (refractive index: 1.59), polyethylene terephthalate (refractive index: 1.63), etc.) are used as the substrate material. If it is transparent, it will not be specifically limited. The substrate described in the present embodiment is not limited to a plate shape, and includes a film substrate.
２は基板１上に多層膜の成膜前に事前に形成される薄膜層である。この薄膜層２は、多層膜を成膜する前に基板１にコーティングすることにより、基板１の表面を硬化させ、傷等から保護するためや、基板１と多層膜との間の密着力を上げるために形成される層である（以下、ハードーコート層と記す）。一般的に、ハードコート層２においては、基板１の表面を保護するとともに、基板１と多層膜との間の密着力を上げることが可能なアクリル系ハードコートがよく利用される。 Reference numeral 2 denotes a thin film layer formed in advance on the substrate 1 before the multilayer film is formed. The thin film layer 2 is coated on the substrate 1 before the multilayer film is formed, so that the surface of the substrate 1 is cured and protected from scratches, and the adhesion between the substrate 1 and the multilayer film is increased. It is a layer formed for raising (hereinafter referred to as a hard coat layer). In general, in the hard coat layer 2, an acrylic hard coat that protects the surface of the substrate 1 and can increase the adhesion between the substrate 1 and the multilayer film is often used.
また、基板１にハードコート層２を形成しないで、基板１上に直接多層膜を成膜することも可能であるが、前述したように多層膜の保護や密着力向上のために、基板１上に事前にハードコート処理を行なっておくことが好ましい。また、ハードコートではなく、単に基板１と多層膜との間での密着力向上のために真空蒸着等にて基板上にアンダーコートを行なうこともある。
何れの場合においても、ハードコート（アンダーコート）の膜厚は、光学的な阻害が起こらないように基板の屈折率と同程度の屈折率を有するようにしておくことが好ましい。
Further, it is possible to form a multilayer film directly on the substrate 1 without forming the hard coat layer 2 on the substrate 1, but as described above, in order to protect the multilayer film and improve adhesion, the substrate 1 It is preferable to perform a hard coat treatment in advance. Further, instead of hard coating, an undercoat may be applied on the substrate simply by vacuum deposition or the like in order to improve the adhesion between the substrate 1 and the multilayer film.
In any case, it is preferable that the film thickness of the hard coat (undercoat) has a refractive index comparable to the refractive index of the substrate so that optical inhibition does not occur.
３は反射防止効果をもたせるためにハードコート層２上に形成される反射防止膜層（誘電膜層）である。本実施形態における誘電膜層３は、基板の屈折率より低い屈折率をもつ透明誘電体から形成される。誘電体層として用いられる透明誘電体は、使用する基板１に応じて適宜選択されるが、基板１の屈折率よりも低い屈折率が必要なため、基板１の最高屈折率１．７０より低くする必要がある。また同時に、安価に入手可能でかつ安定した成膜が確認されているものが好ましいため、それらを考慮して屈折率が屈折率１．３５以上１．６０以下程度の範囲のものが使用される。具体的には、誘電膜層３の主成分にはＳｉＯ2（屈折率１．４６）やＭｇＦ2（屈折率１．３８）が挙げられる。また、誘電膜層３の光学的膜厚（以下、単に膜厚と記す）は、１０ｎｍ以上６００ｎｍ以下が好ましく、より好ましくは５０ｎｍ以上５５０ｎｍ以下である。膜厚がこれ以上薄くても厚くても、反射防止効果が得られにくい。なお、本実施形態では誘電膜層を１層のみとしているがこれに限るものではない、屈折率の異なる透明誘電体層を順に積層させることによって反射防止効果を得るようにしてもよい。 Reference numeral 3 denotes an antireflection film layer (dielectric film layer) formed on the hard coat layer 2 in order to have an antireflection effect. The dielectric film layer 3 in this embodiment is formed of a transparent dielectric having a refractive index lower than that of the substrate. The transparent dielectric used as the dielectric layer is appropriately selected according to the substrate 1 to be used. However, since a refractive index lower than the refractive index of the substrate 1 is required, it is lower than the maximum refractive index 1.70 of the substrate 1. There is a need to. At the same time, it is preferable that the film is available at a low cost and has been confirmed to have a stable film formation. Therefore, a film having a refractive index in the range of about 1.35 to 1.60 is used in consideration of them. . Specifically, the main component of the dielectric film layer 3 includes SiO 2 (refractive index 1.46) and MgF 2 (refractive index 1.38). Further, the optical film thickness (hereinafter simply referred to as film thickness) of the dielectric film layer 3 is preferably 10 nm or more and 600 nm or less, and more preferably 50 nm or more and 550 nm or less. Even if the film thickness is thinner or thicker than this, it is difficult to obtain the antireflection effect. In this embodiment, only one dielectric film layer is used. However, the present invention is not limited to this. An antireflection effect may be obtained by sequentially laminating transparent dielectric layers having different refractive indexes.
４は誘電膜層３上に積層され、導電性を有する第２導電膜層である。第２導電膜層４の透明導電体には、酸化亜鉛、ＡＺＯ（アルミニウムドープ酸化亜鉛）やＧＺＯ（ガリウムドープ酸化亜鉛）等の酸化亜鉛を主成分とする材料を用いることができる。５は第２導電膜層４上に積層され、最表面となる導電性を有する第１導電膜層である。第１導電膜層５の透明導電体にはＩＴＯ（スズドープ酸化インジウム）、ＳｎＯ2（酸化スズ）、ＩＺＯ（亜鉛ドープ酸化インジウム）、ＩＣＯ（セリウムドープ酸化インジウム）、ＡＴＯ（アンチモンドープ酸化スズ）、ＦＴＯ（フッ素ドープ酸化スズ）等の酸化亜鉛を主成分としない透明かつ導電性を有する材料が挙げられる。
このように、ＩＴＯ等からなる第１導電膜層５の直下に酸化亜鉛を主成分とする第２導電膜層４を形成することにより、従来の導電性を有する多層膜付透明基板に比べ、耐ペン摺動性の性能が格段に向上する。また、このような構成を有する多層膜付透明基板に対して図２に示すように第１導電膜層５の上に電極６を形成した場合、導電膜層と電極との密着性が向上する。
Thus, by forming the second
また、このような構成を有する多層膜付透明基板における表面抵抗値は、第１導電膜層５と第２導電膜層４とを合わせた膜厚により表面抵抗値が決定される。したがって、表面抵抗値を低抵抗値に設定する場合には、一方の膜厚或いは両方の膜厚を厚くすればよい。また、表面抵抗値を高抵抗値に設定する場合には一方の膜厚或いは両方の膜厚を薄くすればよい。なお、第１導電膜層５にＩＴＯ等の抵抗率が良い（低い）材料を用いた場合、第２導電膜層４の膜厚の増減に対して、第１導電膜層５の膜厚を増減させる方が、表面抵抗値の値が大きく変動する。このため、所望する表面抵抗値を得るために主として第１導電膜層５の膜厚を増減させることにより、導電膜層全体の膜厚を薄くさせることができるため、透過率の向上が期待できる。
Further, the surface resistance value in the transparent substrate with a multilayer film having such a configuration is determined by the film thickness of the first conductive film layer 5 and the second
また、表面抵抗値は使用目的に応じて適宜決定すれば良いが、電気光学素子用、光電変換素子用、液晶用、タッチパネル用等に用いるのであれば、好ましくは表面抵抗値が１００Ω／□以上５０００Ω／□以下であり、より好ましくは１００Ω／□以上１０００Ω／□以下である。また、表面抵抗値と対応する第１導電膜層５と第２導電膜層４との合計の膜厚は１０ｎｍ以上１０００ｎｍ以下が好ましく、より好ましくは１５ｎｍ以上１００ｎｍ以下である。
Further, the surface resistance value may be appropriately determined according to the purpose of use, but when used for an electro-optical element, a photoelectric conversion element, a liquid crystal, a touch panel, etc., the surface resistance value is preferably 100Ω / □ or more. It is 5000Ω / □ or less, more preferably 100Ω / □ or more and 1000Ω / □ or less. The total film thickness of the first conductive film layer 5 and the second
また、各層の最適な膜厚は以下の方法により決定される。
初めに、用途に応じて必要な表面抵抗値が得られるような導電膜層（ここでは第１導電膜層５及び第２導電膜層４）の膜厚を決定させておく。次に誘電膜層３に使用する材料の屈折率を固定値とし、最適化アルゴリズムを用いながら誘電膜層３の膜厚を変化させていく。このような手法により、視野２°、標準光ＣにおけるＬ*ａ*ｂ*表色系のクロマティクネス指数ａ*、ｂ*を−２〜＋２の範囲以内としつつ、このようなクロマティクネス指数ａ*、ｂ*の範囲内において最も高い透過率若しくは最も低い反射率が得られるような誘電体層膜厚を求める。最適化アルゴリズムは例えば、Adaptive Random SearchやModified Gardient、Monte Carilo method、Simurated Annealing等、メリット関数を使用した様々な最適化手法を基に与えられる。
Moreover, the optimal film thickness of each layer is determined by the following method.
First, the film thicknesses of the conductive film layers (here, the first conductive film layer 5 and the second conductive film layer 4) that can obtain a necessary surface resistance value in accordance with the application are determined. Next, the refractive index of the material used for the dielectric film layer 3 is set to a fixed value, and the film thickness of the dielectric film layer 3 is changed using an optimization algorithm. By such a method, the chromaticness index a is set such that the chromaticness index a * and b * of the L * a * b * color system in the field of view 2 ° and the standard light C is within the range of −2 to +2. The dielectric layer thickness is determined so as to obtain the highest transmittance or the lowest reflectance within the range of * and b *. The optimization algorithm is given based on various optimization methods using merit functions such as Adaptive Random Search, Modified Gardient, Monte Carilo method, and Simulated Rated Annealing.
上記で示した各薄膜層（導電膜層、誘電膜層）を基板１上に形成する方法としては、物理的気層成長方法（ＰＶＤ）では真空蒸着方法やスパッタ方法、イオンプレーティング方法等が挙げられる。また、化学的気層成長方法（ＣＶＤ）ではめっき方法や化学的気層成長方法等が挙げられる。これらの成膜方法は、本実施の形態としてすべて使用可能であるが、成膜に際して高温を伴うような方法では熱によるプラスチック基板の変形等が考えられるため、プラスチック基板での多層膜の成膜は高熱を必要としない真空蒸着方法やスパッタ方法が好適に用いられる。 As a method of forming each thin film layer (conductive film layer, dielectric film layer) on the substrate 1, the physical vapor deposition method (PVD) includes a vacuum deposition method, a sputtering method, an ion plating method, and the like. Can be mentioned. In addition, examples of the chemical vapor deposition method (CVD) include a plating method and a chemical vapor deposition method. Any of these film forming methods can be used as this embodiment mode. However, since a method involving a high temperature during film formation may cause deformation of the plastic substrate due to heat, the multilayer film is formed on the plastic substrate. A vacuum deposition method or sputtering method that does not require high heat is preferably used.
なお、前述の実施形態では1層からなる反射防止層帯の上に導電膜層を２層積層するものとしているが、これに限るものではない。例えば、導電性を有する多層膜付透明基板の透過率（反射率）を考慮する必要がなければ、このような反射防止層帯を設けなくとも良い。また、反射防止層帯を形成する場合であっても前述したように１層に限るものではなく、所望する透過率（反射率）が得られるような多層構造（例えば2層〜６層等）を形成すればよい。 In the above-described embodiment, the two conductive film layers are laminated on the antireflection belt made of one layer. However, the present invention is not limited to this. For example, if it is not necessary to consider the transmittance (reflectance) of a transparent substrate with a multilayer film having conductivity, such an antireflection layer band may not be provided. Further, even when the antireflection layer is formed, it is not limited to one layer as described above, but a multilayer structure (for example, two to six layers) that can obtain a desired transmittance (reflectance). May be formed.
以下に実施例、及び比較例を挙げる。
＜実施例１＞
ハードコート付きポリカーボネイト基板（屈折率１．５９）を用意し、真空蒸着法により、誘電膜層を基板上に形成した。第１誘電膜層としては、オプトロン社製ＳｉＯ2顆粒を使用し、アンダーコート層であるハードコート上にＳｉＯ2を主成分とする薄膜層を形成した。このときの誘電膜層の膜厚は６０ｎｍとした。
次に住友金属鉱山（株）製ＡＺＯターゲットを使用し、第２導電膜層として誘電膜層上にＡＺＯの薄膜層をスパッタ法により形成した。このときの第２導電膜層の膜厚は５ｎｍとした。また、最表面となる第１導電膜層としては、真空治金（株）製ＩＴＯターゲットを使用し、第１導電膜層としてＩＴＯを主成分とする薄膜層をスパッタ法により形成した。このときの第１導電膜層の膜厚は２５ｎｍとした。
Examples and comparative examples are given below.
<Example 1>
A hard-coated polycarbonate substrate (refractive index: 1.59) was prepared, and a dielectric film layer was formed on the substrate by vacuum deposition. As the first dielectric film layer, SiO 2 granules made by Optron were used, and a thin film layer mainly composed of SiO 2 was formed on the hard coat as the undercoat layer. The thickness of the dielectric film layer at this time was 60 nm.
Next, an AZO target manufactured by Sumitomo Metal Mining Co., Ltd. was used, and a thin film layer of AZO was formed as a second conductive film layer on the dielectric film layer by sputtering. The thickness of the second conductive film layer at this time was 5 nm. In addition, as the first conductive film layer serving as the outermost surface, an ITO target manufactured by Vacuum Metallurgical Co., Ltd. was used, and a thin film layer mainly composed of ITO was formed as a first conductive film layer by a sputtering method. The film thickness of the first conductive film layer at this time was 25 nm.
このようにして得られた導電性を有する多層膜付透明基板の視感度透過率を測定した。測定装置は朝日分光社製 視感度透過率計ＭＯＤＥＬ３０４を用いた。得られた視感透過率は９０．３％であった。また、表面抵抗値は５００Ω／□であった。
次に、物理膜厚１８８μｍのＩＴＯ付のＰＥＴ（ポリエチレンテレフタレート）フィルムのＩＴＯ形成面側と作成した多層膜付透明基板の膜形成面側とを張り合わせた後、耐ペン摺動性評価を行った。耐ペン摺動性評価は、張り合わせたＰＥＴフィルムのＩＴＯ電極面の裏面より、ポリアセタール製のペン（先端形状は、０．８mmR）に２５０ｇの荷重を掛け、往復１０万回の摺動試験を行うことにより評価した。往復１０万回の摺動試験を行っても、目視にて多層膜付基板上に白濁が見られなければ○、白濁が生じていれば×とした。
The visibility transmittance of the thus obtained transparent substrate with a multilayer film having electrical conductivity was measured. As a measuring apparatus, Asahi Spectroscopic Visibility Transmittance Model MODEL304 was used. The luminous transmittance obtained was 90.3%. The surface resistance value was 500Ω / □.
Next, after sticking the ITO forming surface side of the PET (polyethylene terephthalate) film with ITO having a physical film thickness of 188 μm and the film forming surface side of the prepared transparent substrate with a multilayer film, pen sliding resistance was evaluated. . The pen sliding resistance evaluation is performed by applying a load of 250 g to a polyacetal pen (tip shape: 0.8 mmR) from the back surface of the ITO electrode surface of the laminated PET film, and performing a sliding test of 100,000 round trips. It was evaluated by. Even if a sliding test was performed 100,000 times in a reciprocating manner, it was evaluated as “◯” if no white turbidity was observed on the multilayer film-coated substrate, and “X” if white turbidity occurred.
また、得られた導電性を有する多層膜付透明基板の表面に電極を形成し、電極の密着性について評価を行った。電極の形成は第１導電膜層の表面に銀ペーストを塗布し、温度９０°にて３０分加熱することによって形成した。電極の形成後、多層膜付透明基板を温度６０℃、湿度９５％の雰囲気中に１２時間置いた後、カッターを用いて電極に１ｍｍ間隔でマス目を１００個作り、セロハン粘着テープによる剥離試験（クロスカットテープ試験）を３回行い残ったマス目の数を調べた。マス目が全て残っていれば（一つも剥がれていなければ）○とし、マス目が一つでも剥がれていれば×とした。また、２°の視野で標準光Ｃにおけるクロマティクネス指数ａ*、ｂ*を測定した。測定装置は島津製作所製ＵＶ-2400ＰＣを用いた。このときのクロマティクネス指数ａ*は-0.25、ｂ*は1.40であった。
以上の結果を表１に示す。
Moreover, the electrode was formed in the surface of the obtained transparent substrate with a multilayer film which has electroconductivity, and the adhesiveness of the electrode was evaluated. The electrode was formed by applying a silver paste to the surface of the first conductive film layer and heating at a temperature of 90 ° for 30 minutes. After the electrode is formed, the transparent substrate with a multilayer film is placed in an atmosphere of 60 ° C. and 95% humidity for 12 hours, and then 100 squares are made on the electrode at 1 mm intervals using a cutter, and a peel test using a cellophane adhesive tape. (Cross cut tape test) was performed three times to check the number of remaining squares. If all the squares remain (if none of them are peeled off), it is marked as ◯, and if even one square is peeled off, it is marked as x. Further, the chromaticness index a * and b * in the standard light C was measured with a visual field of 2 °. As a measuring device, UV-2400PC manufactured by Shimadzu Corporation was used. At this time, the chromaticness index a * was −0.25, and b * was 1.40.
The results are shown in Table 1.
＜実施例２＞
実施例２では、第２導電膜層をＡＺＯからＧＺＯに変えた以外は、すべて実施例１と同じ条件にて導電性を有する多層膜付透明基板を得た。なお、第２導電膜層に用いたＧＺＯは、住友金属鉱山（株）製ＧＺＯターゲットを使用してスパッタ法により形成した。得られた導電性を有する多層膜付透明基板の視感度透過率は、９０．４％であった。また、表面抵抗値は５００Ω／□であった。
また、実施例１と同様に摺動試験及び密着性の評価を行った。また、クロマティクネス指数ａ*は-0.23、ｂ*は1.30であった。その結果を表１に示す。
<Example 2>
In Example 2, a transparent substrate with a multilayer film having conductivity was obtained under the same conditions as in Example 1 except that the second conductive film layer was changed from AZO to GZO. The GZO used for the second conductive film layer was formed by sputtering using a GZO target manufactured by Sumitomo Metal Mining Co., Ltd. The visibility transmittance of the obtained transparent substrate with a multilayer film having electrical conductivity was 90.4%. The surface resistance value was 500Ω / □.
Further, the sliding test and the adhesion evaluation were performed in the same manner as in Example 1. The chromaticness index a * was −0.23 and b * was 1.30. The results are shown in Table 1.
＜実施例３＞
実施例３では、第２導電膜層をＡＺＯからＺｎＯに変えた以外は、すべて実施例１と同じ条件にて導電性を有する多層膜付透明基板を得た。なお、第２導電膜層に用いたＺｎＯは、三和研磨工業（株）製ＺｎＯタブレットを使用して真空蒸着方法により形成した。得られた導電性を有する多層膜付透明基板の視感度透過率は、９０．３％であった。また、表面抵抗値は５００Ω／□であった。
また、実施例１と同様に摺動試験及び密着性の評価を行った。また、クロマティクネス指数ａ*は-0.24、ｂ*は1.35であった。その結果を表１に示す。
<Example 3>
In Example 3, a transparent substrate with a multilayer film having conductivity was obtained under the same conditions as in Example 1 except that the second conductive film layer was changed from AZO to ZnO. In addition, ZnO used for the 2nd electrically conductive film layer was formed with the vacuum evaporation method using the Sanwa Abrasive Industry Co., Ltd. ZnO tablet. The visibility transmittance | permeability of the obtained transparent substrate with a multilayer film which has electroconductivity was 90.3%. The surface resistance value was 500Ω / □.
Further, the sliding test and the adhesion evaluation were performed in the same manner as in Example 1. The chromaticness index a * was −0.24 and b * was 1.35. The results are shown in Table 1.
＜比較例１＞
比較例１では、第２導電膜層をＡＺＯからＩＴＯに変えた以外は、すべて実施例１と同じ条件にて導電性を有する多層膜付透明基板を得た。得られた導電性を有する多層膜付透明基板の視感度透過率は、９０．２％であった。また、表面抵抗値は５００Ω／□であった。
また、実施例１と同様に摺動試験及び密着性の評価を行った。また、クロマティクネス指数ａ*は-0.28、ｂ*は1.31であった。その結果を表１に示す。
<Comparative Example 1>
In Comparative Example 1, a transparent substrate with a multilayer film having conductivity was obtained under the same conditions as in Example 1 except that the second conductive film layer was changed from AZO to ITO. The visibility transmittance of the obtained transparent substrate with a multilayer film having electrical conductivity was 90.2%. The surface resistance value was 500Ω / □.
Further, the sliding test and the adhesion evaluation were performed in the same manner as in Example 1. The chromaticness index a * was −0.28 and b * was 1.31. The results are shown in Table 1.
＜比較例２＞
比較例２では、第１導電膜層をＡＺＯ（膜厚5ｎｍ）、第２導電膜層をＩＴＯ（膜厚２５ｎｍ）に変えた以外は、すべて実施例１と同じ条件にて導電性を有する多層膜付透明基板を得た。得られた導電性を有する多層膜付透明基板の視感度透過率は、９０．４％であった。また、表面抵抗値は５００Ω／□であった。
また、実施例１と同様に摺動試験及び密着性の評価を行った。また、クロマティクネス指数ａ*は-0.22、ｂ*は1.31であった。その結果を表１に示す。
<Comparative example 2>
In Comparative Example 2, a multilayer having conductivity under the same conditions as in Example 1 except that the first conductive film layer was changed to AZO (film thickness 5 nm) and the second conductive film layer was changed to ITO (film thickness 25 nm). A transparent substrate with a film was obtained. The visibility transmittance of the obtained transparent substrate with a multilayer film having electrical conductivity was 90.4%. The surface resistance value was 500Ω / □.
Further, the sliding test and the adhesion evaluation were performed in the same manner as in Example 1. The chromaticness index a * was −0.22 and b * was 1.31. The results are shown in Table 1.
＜結果＞
表１に示すように、実施例１〜３の導電性を有する多層膜付透明基板においては、何れも視感度透過率が９０％以上と高透過率を示すとともに、クロマティクネス指数は-1.5〜1.5の範囲内にあり、無色に近い透過光が得られていることが示された。また、ペン摺動による白濁も無く、高い耐ペン摺動性を有することが確認された。また、剥離試験による電極の剥がれも無く、密着性も良好であった。なお、比較例２の導電性を有する多層膜付透明基板においては摺動試験は良好であったものの、剥離試験においては電極の剥がれが生じてしまい、密着性が悪い結果となった。
<Result>
As shown in Table 1, in the transparent substrates with a multilayer film having conductivity of Examples 1 to 3, all showed a high transmittance of 90% or more, and a chromaticness index was -1.5 to It was in the range of 1.5, and it was shown that transmitted light almost colorless was obtained. Moreover, it was confirmed that there was no cloudiness by pen sliding and it had high pen sliding resistance. Moreover, there was no peeling of the electrode by a peeling test, and the adhesiveness was also good. In addition, although the sliding test was favorable in the transparent substrate with a multilayer film having conductivity of Comparative Example 2, the peeling of the electrode occurred in the peeling test, resulting in poor adhesion.
次に、反射防止層帯を１層ではなく、２層とした例を以下に挙げる。
＜実施例４＞
実施例４では、基板側から順にＺｒＯ2からなる誘電層（第１層）を膜厚５５nm、ＳｉＯ2からなる誘電層（第２層）を膜厚１００nm積層して反射防止層帯とし、さらにこの上にＡＺＯからなる導電層（第２導電層）を５nm、ＩＴＯからなる導電層（第１導電層）を２５nm積層することにより、導電性を有する多層膜付透明基板を得た。得られた導電性を有する多層膜付透明基板の視感度透過率は、９１．２％であった。また、表面抵抗値は５００Ω／□であった。
また、実施例１と同様に摺動試験及び密着性の評価を行った。また、クロマティクネス指数ａ*は-0.99、ｂ*は0.07であった。その結果を表２に示す。
Next, an example in which the antireflection layer band is not one layer but two layers will be described below.
<Example 4>
In Example 4, a dielectric layer (first layer) made of ZrO 2 and a dielectric layer (second layer) made of SiO 2 with a thickness of 55 nm and 100 nm are laminated in order from the substrate side to form an antireflection layer, A conductive layer (second conductive layer) made of AZO was laminated thereon with a thickness of 5 nm, and a conductive layer made of ITO (first conductive layer) was laminated with a thickness of 25 nm, thereby obtaining a transparent substrate with a multilayer film having conductivity. The visibility transmittance of the obtained transparent substrate with a multilayer film having electrical conductivity was 91.2%. The surface resistance value was 500Ω / □.
Further, the sliding test and the adhesion evaluation were performed in the same manner as in Example 1. The chromaticness index a * was −0.99, and b * was 0.07. The results are shown in Table 2.
＜実施例５＞
実施例５では、第２導電層をＧＺＯとした以外は、すべて実施例４と同じ条件にて導電性を有する多層膜付透明基板を得た。得られた導電性を有する多層膜付透明基板の視感度透過率は、９１．１％であった。また、表面抵抗値は５００Ω／□であった。
また、実施例１と同様に摺動試験及び密着性の評価を行った。また、クロマティクネス指数ａ*は-0.91、ｂ*は0.13であった。その結果を表２に示す。
<Example 5>
In Example 5, a transparent substrate with a multilayer film having conductivity was obtained under the same conditions as in Example 4 except that the second conductive layer was GZO. The visibility transmittance of the obtained transparent substrate with a multilayer film having electrical conductivity was 91.1%. The surface resistance value was 500Ω / □.
Further, the sliding test and the adhesion evaluation were performed in the same manner as in Example 1. The chromaticness index a * was −0.91 and b * was 0.13. The results are shown in Table 2.
＜実施例６＞
実施例６では、第２導電層をＺｎＯとした以外は、すべて実施例４と同じ条件にて導電性を有する多層膜付透明基板を得た。得られた導電性を有する多層膜付透明基板の視感度透過率は、９１．０％であった。また、表面抵抗値は５００Ω／□であった。
また、実施例１と同様に摺動試験及び密着性の評価を行った。また、クロマティクネス指数ａ*は-1.11、ｂ*は0.53であった。その結果を表２に示す。
<Example 6>
In Example 6, a transparent substrate with a multilayer film having conductivity was obtained under the same conditions as in Example 4 except that the second conductive layer was ZnO. The visibility transmittance | permeability of the obtained transparent substrate with a multilayer film which has electroconductivity was 91.0%. The surface resistance value was 500Ω / □.
Further, the sliding test and the adhesion evaluation were performed in the same manner as in Example 1. The chromaticness index a * was −1.11 and b * was 0.53. The results are shown in Table 2.
＜比較例３＞
比較例３では、第２導電層をＩＴＯとした以外は、すべて実施例４と同じ条件にて導電性を有する多層膜付透明基板を得た。得られた導電性を有する多層膜付透明基板の視感度透過率は、９１．２％であった。また、表面抵抗値は５００Ω／□であった。
また、実施例１と同様に摺動試験及び密着性の評価を行った。また、クロマティクネス指数ａ*は-1.03、ｂ*は0.23であった。その結果を表２に示す。
<Comparative Example 3>
In Comparative Example 3, a transparent substrate with a multilayer film having conductivity was obtained under the same conditions as in Example 4 except that the second conductive layer was ITO. The visibility transmittance of the obtained transparent substrate with a multilayer film having electrical conductivity was 91.2%. The surface resistance value was 500Ω / □.
Further, the sliding test and the adhesion evaluation were performed in the same manner as in Example 1. The chromaticness index a * was -1.03, and b * was 0.23. The results are shown in Table 2.
＜比較例４＞
比較例４では、第１導電膜層をＡＺＯ（膜厚5ｎｍ）、第２導電膜層をＩＴＯ（膜厚２５ｎｍ）に変えた以外は、すべて実施例４と同じ条件にて導電性を有する多層膜付透明基板を得た。得られた導電性を有する多層膜付透明基板の視感度透過率は、９１．２％であった。また、表面抵抗値は５００Ω／□であった。
また、実施例１と同様に摺動試験及び密着性の評価を行った。また、クロマティクネス指数ａ*は-1.03、ｂ*は0.15であった。その結果を表２に示す。
<Comparative example 4>
In Comparative Example 4, a multilayer having conductivity under the same conditions as in Example 4 except that the first conductive film layer was changed to AZO (film thickness 5 nm) and the second conductive film layer was changed to ITO (film thickness 25 nm). A transparent substrate with a film was obtained. The visibility transmittance of the obtained transparent substrate with a multilayer film having electrical conductivity was 91.2%. The surface resistance value was 500Ω / □.
Further, the sliding test and the adhesion evaluation were performed in the same manner as in Example 1. The chromaticness index a * was -1.03, and b * was 0.15. The results are shown in Table 2.
＜結果＞
表２に示すように、実施例４〜６の導電性を有する多層膜付透明基板においては、透過率及びクロマティクネス指数ともに実施例１〜３よりも良い結果が得られた。また、ペン摺動による白濁も無く、高い耐ペン摺動性を有することが確認された。また、剥離試験による電極の剥がれも無く、密着性も良好であった。なお、比較例４の導電性を有する多層膜付透明基板においては摺動試験は良好であったものの、剥離試験においては電極の剥がれが生じてしまい、密着性が悪い結果となった。
<Result>
As shown in Table 2, in the transparent substrate with a multilayer film having conductivity of Examples 4 to 6, both the transmittance and the chromaticness index were better than those of Examples 1 to 3. Moreover, it was confirmed that there was no cloudiness by pen sliding and it had high pen sliding resistance. Moreover, there was no peeling of the electrode by a peeling test, and the adhesiveness was also good. In addition, although the sliding test was favorable in the transparent substrate with a multilayer film having the conductivity of Comparative Example 4, in the peeling test, the electrode peeled off, resulting in poor adhesion.
１ 透明基板
２ 薄膜層
３ 誘電膜層
４ 第２導電膜層
５ 第１導電膜層
DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Thin film layer 3
Claims (1)
最外層としてＩＴＯ，ＳｎＯ2，ＩＺＯ，ＩＣＯ，ＡＴＯ，ＦＴＯから選ばれる透明導電体からなる第１導電膜と，該第１導電膜の下層に形成され主成分として酸化亜鉛を含有する透明導電体からなる第２導電膜とからなる導電膜層の全体の膜厚を用途に応じて必要な表面抵抗値が得られるように決定する第１ステップであって，前記第２導電膜の膜厚は前記第１導電膜の膜厚に対して薄い膜厚として決定する第１ステップと、前記透明基板上に反射防止膜用として形成される１層または２層からなる誘電膜層（誘電膜層が１層の場合はSiO 2 を、2層の場合はSiO 2 とZrO 2 とを使用する）の各膜厚を決定する第２ステップであって，前記第１ステップにて決定された前記導電膜層の膜厚及び前記誘電膜層に用いられる誘電体の屈折率を固定値として視野２°，標準光Ｃにおけるクロマティクネス指数ａ*，ｂ*を−２〜＋２の範囲内において９０％以上の視感度透過率が得られるようにメリット関数を使用した最適化アルゴリズムを用いて前記誘電体の膜厚を決定する第２ステップと、前記第１ステップにて決定された前記第１導電膜及び第２導電膜の膜厚，並びに前記第２ステップにて決定された前記誘電体の膜厚となるように真空蒸着方法またはスパッタ方法を用いて前記透明基板上に前記誘電膜層を形成し次いで前記導電膜層を形成させる（なお、前記誘電膜層が２層の場合には、基板側からZrO 2 からなる誘電膜とSiO 2 からなる誘電膜とを順に形成させる）ことを特徴とする導電性を有する多層膜付透明基板の製造方法。 In the method for producing a transparent substrate with a multilayer film having conductivity, a thin film of a transparent conductor is laminated on a transparent substrate,
A first conductive film made of a transparent conductor selected from ITO, SnO 2 , IZO, ICO, ATO, and FTO as an outermost layer, and a transparent conductor containing zinc oxide as a main component formed under the first conductive film A first step of determining the entire film thickness of the conductive film layer made of the second conductive film so as to obtain a necessary surface resistance value according to the application, wherein the film thickness of the second conductive film is A first step of determining a thin film thickness with respect to the film thickness of the first conductive film, and a dielectric film layer (dielectric film layer having one or two layers) formed on the transparent substrate for an antireflection film. In the second step of determining the film thickness of SiO 2 for one layer and SiO 2 and ZrO 2 for two layers ) , the conductive film determined in the first step The film thickness of the layer and the refractive index of the dielectric used for the dielectric film layer are fixed values. Using an optimization algorithm using a merit function so that a luminosity transmittance of 90% or more can be obtained when the chromaticness index a * , b * in the field of view 2 ° and the standard light C is within the range of −2 to +2. A second step of determining a film thickness of the dielectric; a film thickness of the first conductive film and the second conductive film determined in the first step; and a thickness of the dielectric determined in the second step. The dielectric film layer is formed on the transparent substrate using a vacuum deposition method or a sputtering method so as to have a film thickness, and then the conductive film layer is formed (in the case where the dielectric film layer has two layers, A dielectric film made of ZrO 2 and a dielectric film made of SiO 2 are formed in this order from the substrate side ) .
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| WO2006109586A1 (en) * | 2005-04-06 | 2006-10-19 | Sharp Kabushiki Kaisha | Substrate with conductive layer, display unit and process for producing substrate with conductive layer |
| JP2007163995A (en) * | 2005-12-15 | 2007-06-28 | Geomatec Co Ltd | Substrate with transparent conductive film and manufacturing method thereof |
| JP4967529B2 (en) * | 2006-08-23 | 2012-07-04 | 凸版印刷株式会社 | Transparent conductive laminate |
| JP2009238416A (en) * | 2008-03-26 | 2009-10-15 | Toppan Printing Co Ltd | Substrate with transparent conductive film and its manufacturing method |
| JPWO2010004937A1 (en) * | 2008-07-09 | 2012-01-05 | 株式会社アルバック | Touch panel manufacturing method and film forming apparatus |
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| JP5794013B2 (en) | 2011-07-22 | 2015-10-14 | セイコーエプソン株式会社 | Electro-optical device and electronic apparatus |
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