JP2007109505A - Transparent conductive base material - Google Patents
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本発明は、基材と反射防止膜と透明導電膜からなる層構造を含む透明導電性基材に関し、特に、透明性及び導電性に優れた、反射防止膜を有する透明導電性基材に関する。 The present invention relates to a transparent conductive substrate including a layer structure composed of a substrate, an antireflection film, and a transparent conductive film, and particularly relates to a transparent conductive substrate having an antireflection film excellent in transparency and conductivity.
スズをドープした酸化インジウム膜（ＩＴＯと称す）やフッ素をドープした酸化スズ膜（ＦＴＯと称す）、アンチモンをドープした酸化スズ膜（ＡＴＯと称す）、アルミニウムをドープした酸化亜鉛膜、インジウムをドープした酸化亜鉛膜はその優れた透明性と導電性を利用して、液晶ディスプレイ、エレクトロルミネッセンスディスプレイ、面発熱体、タッチパネルの電極、太陽電池の電極等に広く使用されている。しかし、ＩＴＯ、ＦＴＯ、ＡＴＯ、酸化亜鉛膜等の透明導電膜は、いずれも屈折率が基板ガラスの屈折率（ソーダライムガラスでは１．５２）に比べて割合高い（１．７〜２．２）ため、透明導電膜と基板ガラスの間の界面での可視光の反射が大きくなり、可視光透過率が低下してしまう。透明導電膜の膜厚を均一に薄くすることにより、可視光の透過率をある程度上昇させることは可能であるが、薄くし過ぎると膜の抵抗値の安定性が悪くなるため、あまり実用的ではない。 Indium oxide film doped with tin (referred to as ITO), tin oxide film doped with fluorine (referred to as FTO), tin oxide film doped with antimony (referred to as ATO), zinc oxide film doped with aluminum, doped with indium Zinc oxide films are widely used for liquid crystal displays, electroluminescence displays, surface heating elements, touch panel electrodes, solar cell electrodes, and the like by utilizing their excellent transparency and conductivity. However, the transparent conductive films such as ITO, FTO, ATO, and zinc oxide film all have a higher refractive index than the refractive index of the substrate glass (1.52 for soda lime glass) (1.7 to 2.2). Therefore, the reflection of visible light at the interface between the transparent conductive film and the substrate glass increases, and the visible light transmittance decreases. Although it is possible to increase the transmittance of visible light to some extent by making the film thickness of the transparent conductive film uniformly thin, if it is too thin, the stability of the film resistance will deteriorate, so it is not very practical. Absent.
導電膜の膜厚を薄くしないで可視光の透過率を上昇させる方法として多層膜化が知られている。多層膜化には、例えば、導電膜とガラス基板の間に高屈折率の膜と低屈折率の膜を新たに設ける方法や、導電膜上に低屈折率の膜を設ける反射防止の理論の応用で達成されることが示されている（非特許文献１参照）。この理論を利用した考案として、特許文献１には、「硝子上に、透明導電膜を真空蒸着で被覆した被覆硝子において、先ず硝子上に導電膜の裏面反射防止膜を被覆し、その上に透明導電膜を被覆したことを特徴とする透過率のすぐれた透明導電膜被覆硝子」が記載されている。また、特許文献１には、酸化スズや酸化インジウムを用いた透明導電膜の屈折率が２．０〜２．１と高いため、屈折率１．５０〜１．５２の通常の硝子に被覆した場合、反射率が上がり、透過率が下がるという現象が起こること、及び硝子と透明導電膜の間に屈折率１．６０〜１．８０の透明膜を設けることによって反射を低下させて透明性を向上させることができることが記載されている。しかし、屈折率１．６０〜１．８０の透明膜の具体的な組成については何ら記載されていない。 Multilayer film formation is known as a method for increasing the visible light transmittance without reducing the thickness of the conductive film. For example, a multilayer film may be formed by a method of newly providing a high refractive index film and a low refractive index film between the conductive film and the glass substrate, or a theory of antireflection by providing a low refractive index film on the conductive film. It has been shown to be achieved by application (see Non-Patent Document 1). As an idea utilizing this theory, Patent Document 1 states that “in a coated glass obtained by coating a transparent conductive film on a glass by vacuum deposition, first, a back-surface antireflection film of the conductive film is coated on the glass, and then on that. “Transparent conductive film-coated glass having excellent transmittance”, characterized in that it is coated with a transparent conductive film. Moreover, since the refractive index of the transparent conductive film using tin oxide and indium oxide is as high as 2.0-2.1 in patent document 1, it coat | covered with normal glass with a refractive index of 1.50-1.52. In this case, the phenomenon that the reflectance increases and the transmittance decreases occurs, and the transparency is reduced by providing a transparent film having a refractive index of 1.60 to 1.80 between the glass and the transparent conductive film. It is described that it can be improved. However, no specific composition of the transparent film having a refractive index of 1.60 to 1.80 is described.
一方、アルミニウムをドープした酸化亜鉛（以下、「アルミドープ酸化亜鉛」という）を透明導電膜として用い得ることは知られているが（特許文献２参照）、それを反射防止膜として用いることは知られていなかった。また、特許文献２の従来技術における「スズを数％ドープした酸化インジウムからなる厚さ５０〜１０００ｎｍの薄膜」との記載から分かるように、ある金属化合物をドープした金属酸化物を透明導電膜として用いる場合、それにドープする金属化合物はドープされる金属酸化物に対してせいぜい１〜３質量％、多くとも５質量％程度であった。 On the other hand, although it is known that zinc oxide doped with aluminum (hereinafter referred to as “aluminum-doped zinc oxide”) can be used as a transparent conductive film (see Patent Document 2), it is known that it can be used as an antireflection film. It was not done. Further, as can be seen from the description of “a thin film having a thickness of 50 to 1000 nm made of indium oxide doped with several percent of tin” in the prior art of Patent Document 2, a metal oxide doped with a certain metal compound is used as a transparent conductive film. When used, the metal compound doped therein was at most about 1 to 3% by mass and at most about 5% by mass with respect to the metal oxide to be doped.
本発明は、上述した従来技術における問題点に鑑みてなされたもので、基材と透明導電膜の間の界面での可視光の反射率が低下し、透明性及び導電性に優れたより実用的な透明導電性基材を提供することを課題とする。 The present invention has been made in view of the above-described problems in the prior art, and the reflectance of visible light at the interface between the base material and the transparent conductive film is reduced, and it is more practical than transparency and conductivity. It is an object to provide a transparent conductive base material.
本発明者らは、基材と透明導電膜の間の反射防止膜として、アルミドープ酸化亜鉛からなる膜を用いることにより、基材と透明導電膜の間の界面での可視光の反射率が低下し、透明性及び導電性に優れた透明導電性基材が実際に得られることを見い出し、本発明を完成するに至った。 By using a film made of aluminum-doped zinc oxide as an antireflection film between the substrate and the transparent conductive film, the present inventors have a visible light reflectance at the interface between the substrate and the transparent conductive film. It has been found that a transparent conductive base material having a reduced transparency and conductivity is actually obtained, and the present invention has been completed.
すなわち本発明は、（１）基材、反射防止膜及び透明導電膜が、この順で積層されてなる透明導電性基材であって、前記反射防止膜がアルミドープ酸化亜鉛からなり、かつ原子間力顕微鏡による前記反射防止膜の平均面粗さ（Ｒａ）が１．０ｎｍ以下であることを特徴とする透明導電性基材や、（２）反射防止膜中のアルミニウムの含有率が、反射防止膜中の亜鉛に対して１４０原子％以上であることを特徴とする上記（１）に記載の透明導電性基材や、（３）６６０ｎｍの波長の光を用いて測定した反射防止膜の屈折率が、１．６〜１．９の範囲内であることを特徴とする上記（１）又は（２）に記載の透明導電性基材や、（４）原子間力顕微鏡による反射防止膜の平均面粗さ（Ｒａ）が０．６ｎｍ以下であることを特徴とする上記（１）〜（３）のいずれかに記載の透明導電性基材や、（５）基材が、５５０ｎｍの波長の光の透過率が９０％以上のガラスであることを特徴とする上記（１）〜（４）のいずれかに記載の透明導電性基材や、（６）透明導電膜が、スズドープ酸化インジウム膜であることを特徴とする上記（１）〜（５）のいずれかに記載の透明導電性基材に関する。 That is, the present invention is (1) a transparent conductive substrate in which a substrate, an antireflection film, and a transparent conductive film are laminated in this order, wherein the antireflection film is made of aluminum-doped zinc oxide, and An average surface roughness (Ra) of the antireflection film by an atomic force microscope is 1.0 nm or less, and (2) the content of aluminum in the antireflection film is reflective. The transparent conductive substrate according to (1) above, which is 140 atomic% or more based on zinc in the prevention film, and (3) an antireflection film measured using light having a wavelength of 660 nm The transparent conductive substrate according to the above (1) or (2), wherein the refractive index is in the range of 1.6 to 1.9, and (4) an antireflection film by an atomic force microscope The average surface roughness (Ra) is 0.6 nm or less (1) (1) to (1) above, wherein the transparent conductive substrate according to any one of (3) and (5) the substrate is a glass having a light transmittance of 90% or more at a wavelength of 550 nm. The transparent conductive substrate according to any one of (1) to (5) above, wherein the transparent conductive substrate according to any one of 4) and (6) the transparent conductive film is a tin-doped indium oxide film. Relates to a conductive substrate.
また本発明は、（７）ガラス、反射防止膜、透明導電膜、空気層、透明導電膜が、この順で積層されてなるタッチパネルであって、前記反射防止膜がアルミドープ酸化亜鉛からなり、かつ原子間力顕微鏡による前記反射防止膜の平均面粗さ（Ｒａ）が１．０ｎｍ以下であることを特徴とするタッチパネルに関する。 Further, the present invention is (7) a touch panel in which glass, an antireflection film, a transparent conductive film, an air layer, and a transparent conductive film are laminated in this order, and the antireflection film is made of aluminum-doped zinc oxide, And the average surface roughness (Ra) of the said antireflection film by an atomic force microscope is 1.0 nm or less, It is related with the touchscreen characterized by the above-mentioned.
さらに本発明は、（８）ガラス、反射防止膜、透明導電膜、配向膜、液晶、配向膜、透明導電膜、反射防止膜及びガラスが、この順で積層されてなる液晶パネルであって、前記反射防止膜がアルミドープ酸化亜鉛からなり、かつ原子間力顕微鏡による前記反射防止膜の平均面粗さ（Ｒａ）が１．０ｎｍ以下であることを特徴とする液晶パネルに関する。 Furthermore, the present invention is (8) a liquid crystal panel in which glass, an antireflection film, a transparent conductive film, an alignment film, a liquid crystal, an alignment film, a transparent conductive film, an antireflection film, and glass are laminated in this order, The present invention relates to a liquid crystal panel, wherein the antireflection film is made of aluminum-doped zinc oxide, and an average surface roughness (Ra) of the antireflection film by an atomic force microscope is 1.0 nm or less.
またさらに本発明は、（９）アルミニウムと亜鉛とを含む反射防止膜形成用溶液であって、アルミニウム含有量が亜鉛に対して１０〜７０原子％であることを特徴とする反射防止膜形成液に関する。 Furthermore, the present invention provides (9) an antireflection film-forming solution containing aluminum and zinc, wherein the aluminum content is 10 to 70 atomic% with respect to zinc. About.
本発明の透明導電性基材は、基材と透明導電膜の間に存在する界面での可視光の反射率が低下した結果、透明性及び導電性に優れている。 The transparent conductive substrate of the present invention is excellent in transparency and conductivity as a result of a decrease in visible light reflectance at the interface existing between the substrate and the transparent conductive film.
以下、本発明を実施するための最良の形態について説明する。 Hereinafter, the best mode for carrying out the present invention will be described.
本発明の透明導電性基材は、基材、反射防止膜及び透明導電膜が、この順で積層されてなる透明導電性基材であって、前記反射防止膜がアルミドープ酸化亜鉛からなり、かつ原子間力顕微鏡による前記反射防止膜の平均面粗さが１．０ｎｍ以下であることを特徴とする。このような反射防止膜を用いることにより、基材と透明導電膜との間の界面での可視光の反射率が低下し、透明性及び導電性に優れた透明導電性基材が得られる The transparent conductive substrate of the present invention is a transparent conductive substrate in which a substrate, an antireflection film and a transparent conductive film are laminated in this order, and the antireflection film is made of aluminum-doped zinc oxide, And the average surface roughness of the said antireflection film by an atomic force microscope is 1.0 nm or less. By using such an antireflection film, the reflectance of visible light at the interface between the substrate and the transparent conductive film is reduced, and a transparent conductive substrate excellent in transparency and conductivity is obtained.
本発明の反射防止膜は、アルミドープ酸化亜鉛からなり、かつ原子間力顕微鏡（ＡＦＭ）による平均面粗さ（Ｒａ）が１．０ｎｍ以下であることを特徴とする。反射防止膜の平均面粗さが大きくなると、透明導電膜等との接触が悪化することにより、反射防止膜と透明導電膜等との間の導電性が低下する一方、透明導電膜表面での光の反射率も増加して透明性も低下する。本発明における反射防止膜は前述したように極めて優れた平滑性を有しているため、本発明の透明導電性基材においては優れた透明性及び導電性が得られる。平均面粗さとは、基準面（指定面の高さの平均値となるフラット面）から指定面までの偏差の絶対値を平均した値であり、次式で算出される。 The antireflection film of the present invention is made of aluminum-doped zinc oxide and has an average surface roughness (Ra) measured by an atomic force microscope (AFM) of 1.0 nm or less. When the average surface roughness of the antireflection film increases, the contact between the transparent conductive film and the like deteriorates, and the conductivity between the antireflection film and the transparent conductive film decreases. Light reflectivity increases and transparency decreases. Since the antireflection film in the present invention has extremely excellent smoothness as described above, excellent transparency and conductivity can be obtained in the transparent conductive substrate of the present invention. The average surface roughness is a value obtained by averaging the absolute values of deviations from a reference surface (a flat surface that is an average value of heights of designated surfaces) to a designated surface, and is calculated by the following equation.
Ｒａ＝１／Ｓ0∬｜Ｆ（Ｘ，Ｙ）−Ｚ0｜ｄＸｄＹ
ここで、Ｓ0は基準面の面積、Ｚ0は基準面の高さ、Ｆ（Ｘ，Ｙ）は座標（Ｘ，Ｙ）における指定面の高さを表す。Ｒａを算出するために必要な測定値は、例えばNanopics（エスアイアイ・ナノテクノロジー株式会社製）等の原子間力顕微鏡を用いて測定することができる。本発明における平均面粗さの数値は、対象となる膜表面の縦４μｍ×横４μｍの任意の範囲における平均面粗さを意味する。
Ra = 1 / S 0 ∬ | F (X, Y) −Z 0 | dXdY
Here, S 0 represents the area of the reference surface, Z 0 represents the height of the reference surface, and F (X, Y) represents the height of the designated surface at the coordinates (X, Y). The measurement value necessary to calculate Ra can be measured using an atomic force microscope such as Nanopics (manufactured by SII Nanotechnology Inc.). The numerical value of the average surface roughness in the present invention means the average surface roughness in an arbitrary range of 4 μm × 4 μm on the target film surface.
本発明の反射防止膜の平均面粗さは１．０ｎｍ以下であればよいが、０．６ｎｍ以下であることが好ましい。これにより、透明性及び導電性により優れた透明導電性基材を得ることができる。 The average surface roughness of the antireflection film of the present invention may be 1.0 nm or less, but is preferably 0.6 nm or less. Thereby, the transparent conductive base material excellent in transparency and electroconductivity can be obtained.
また、本発明の反射防止膜は、アルミドープ酸化亜鉛からなり、かつ原子間力顕微鏡による前記反射防止膜の平均面粗さが１．０ｎｍ以下である限り、反射膜表面の最大高低差は特に制限されない。反射膜表面の最大高低差は、例えばNanopics（エスアイアイ・ナノテクノロジー株式会社製）等の原子間力顕微鏡を用いて測定することができる。本発明における最大高低差（ｎｍ）とは、対象となる膜表面の縦４μｍ×横４μｍの任意の範囲における最大高低差（ｎｍ）を意味する。 Further, the antireflection film of the present invention is made of aluminum-doped zinc oxide, and the maximum height difference on the surface of the reflection film is particularly limited as long as the average surface roughness of the antireflection film by an atomic force microscope is 1.0 nm or less. Not limited. The maximum height difference on the surface of the reflective film can be measured using an atomic force microscope such as Nanopics (manufactured by SII Nanotechnology Co., Ltd.). The maximum height difference (nm) in the present invention means the maximum height difference (nm) in an arbitrary range of 4 μm × 4 μm on the target film surface.
反射防止膜の平均面粗さが１．０ｎｍ以下である限り、本発明の反射防止膜中の亜鉛に対するアルミニウムの含有量は特に制限されないが、反射防止膜中の亜鉛に対して１４０原子％以上であることが好ましく、１５０原子％以上であることがより好ましく、１５０〜３００原子％の範囲内であることがさらに好ましい。反射防止膜中の亜鉛に対する反射防止膜中のアルミニウムの含有量がこのような範囲内の反射防止膜は、平均面粗さがより低いため、透明性及び導電性により優れた透明導電性基材を得ることができる。 As long as the average surface roughness of the antireflection film is 1.0 nm or less, the content of aluminum with respect to zinc in the antireflection film of the present invention is not particularly limited, but it is 140 atomic% or more with respect to zinc in the antireflection film. It is preferable that it is 150 atomic% or more, and it is still more preferable that it exists in the range of 150-300 atomic%. An antireflection film having an aluminum content in the antireflection film in such a range with respect to zinc in the antireflection film has a lower average surface roughness. Can be obtained.
本発明の反射防止膜は、６６０ｎｍの波長の光を用いて測定した屈折率が通常１．６〜１．９である。後述の実施例に記載された実験結果から分かるように、反射防止膜中の亜鉛に対するアルミニウムの含有量（原子％）が上昇すると、屈折率が低下する傾向があるため、アルミニウムの含有量を調節すること等で望ましい屈折率の反射防止膜を得ることができる。本発明における屈折率は、例えばＳＥ８００（SENTECH社製）等の分光エリプソメーターを用いて測定することができる。 The antireflective film of the present invention usually has a refractive index of 1.6 to 1.9 measured using light having a wavelength of 660 nm. As can be seen from the experimental results described in the examples below, the aluminum content is adjusted because the refractive index tends to decrease as the aluminum content (atomic%) in the antireflection film increases. By doing so, an antireflection film having a desirable refractive index can be obtained. The refractive index in the present invention can be measured using a spectroscopic ellipsometer such as SE800 (manufactured by SENTECH).
本発明における反射防止膜の膜厚は特に制限されず、透明導電膜の膜厚に合わせて適宜選択することができるが、例えば３０〜５００ｎｍ、好ましくは３０〜３００ｎｍとすることができる。本発明における膜厚は、例えばＳＥ８００（SENTECH社製）等の分光エリプソメーターを用いて測定することができる。 The film thickness of the antireflection film in the present invention is not particularly limited and can be appropriately selected according to the film thickness of the transparent conductive film, and can be, for example, 30 to 500 nm, preferably 30 to 300 nm. The film thickness in the present invention can be measured using a spectroscopic ellipsometer such as SE800 (manufactured by SENTECH).
本発明の反射防止膜の製造方法は、アルミドープ酸化亜鉛からなり、かつ原子間力顕微鏡による前記反射防止膜の平均面粗さ（Ｒａ）が１．０ｎｍ以下の膜を形成し得る方法である限り特に制限されない。例えば、アルミドープ酸化亜鉛膜が得られる限り、用いるアルミニウム化合物や亜鉛化合物の種類は特に制限されず、アルミニウム化合物又は亜鉛化合物のいずれかを２種以上用いてもよいし、アルミニウム化合物及び亜鉛化合物をそれぞれ２種以上用いてもよい。 The method for producing an antireflection film of the present invention is a method that can form a film made of aluminum-doped zinc oxide and having an average surface roughness (Ra) of 1.0 nm or less by an atomic force microscope. There are no particular restrictions. For example, as long as an aluminum-doped zinc oxide film is obtained, the kind of aluminum compound or zinc compound to be used is not particularly limited, and two or more kinds of aluminum compounds or zinc compounds may be used, or an aluminum compound and a zinc compound may be used. Two or more of each may be used.
本発明の反射防止膜の製造方法として、具体的には、例えばスパッター法、電子ビーム蒸着法、イオンプレーティング法、化学気相成膜法（ＣＶＤ法）、パイロゾル法等の一般的な成膜方法を用いることができる。スパッター法によれば、例えば亜鉛とアルミニウムとの混合物を酸素ガス存在下で焼結させたもの等をターゲットとして用いることにより、アルミドープ酸化亜鉛からなる反射防止膜を成膜することができる。また、電子ビーム法やイオンプレーテイング法によれば、例えば亜鉛とアルミニウムとの混合物を酸素ガス存在下で焼結させたもの等を蒸発物質として用いることにより、アルミドープ酸化亜鉛からなる反射防止膜を成膜することができる。また、化学気相成膜法やパイロゾル法によれば、例えば亜鉛とアルミニウムを含有する有機溶媒溶液（反射防止膜形成液）等を蒸発物として用いることにより、アルミドープ酸化亜鉛からなる反射防止膜を成膜することができる。なお、用いる亜鉛に対するアルミニウムの量を増加させると、得られる反射防止膜の平均面粗さが低下する傾向がある。このような傾向を利用すれば、例示した上記方法を用いた場合はもちろんのこと他の成膜方法を用いた場合であっても、用いる亜鉛に対するアルミニウムの量や、成膜時の温度、膜厚等を適宜調節することにより、平均面粗さが１．０ｎｍ以下の本発明の反射防止膜が容易に得られる。例えばパイロゾル法の場合、例えば、亜鉛に対して１０〜７０原子％、好ましくは４０〜７０原子％のアルミニウムを含む有機溶媒溶液を蒸発物とし、成膜温度を３００〜５５０℃の範囲内で適宜調節して成膜することにより、平均面粗さが１．０ｎｍ以下の好適な反射防止膜が得られる。 Specific examples of the method for producing the antireflection film of the present invention include general film formation such as sputtering, electron beam evaporation, ion plating, chemical vapor deposition (CVD), and pyrosol. The method can be used. According to the sputtering method, for example, an antireflection film made of aluminum-doped zinc oxide can be formed by using a target obtained by sintering a mixture of zinc and aluminum in the presence of oxygen gas. Further, according to the electron beam method or the ion plating method, for example, an antireflective film made of aluminum-doped zinc oxide is used by using a mixture of zinc and aluminum sintered in the presence of oxygen gas as an evaporating substance. Can be formed. Further, according to the chemical vapor deposition method or the pyrosol method, for example, an organic solvent solution containing zinc and aluminum (antireflection film forming liquid) or the like is used as an evaporant, so that the antireflection film made of aluminum-doped zinc oxide is used. Can be formed. In addition, when the quantity of aluminum with respect to the zinc to be used is increased, the average surface roughness of the obtained antireflection film tends to decrease. By utilizing such a tendency, the amount of aluminum with respect to zinc used, the temperature at the time of film formation, the film even when other film formation methods are used as well as when the above-described method is used. By appropriately adjusting the thickness and the like, the antireflection film of the present invention having an average surface roughness of 1.0 nm or less can be easily obtained. For example, in the case of the pyrosol method, for example, an organic solvent solution containing 10 to 70 atomic%, preferably 40 to 70 atomic% of aluminum with respect to zinc is used as an evaporate, and the film forming temperature is appropriately set within a range of 300 to 550 ° C. By adjusting the film formation, a suitable antireflection film having an average surface roughness of 1.0 nm or less can be obtained.
化学気相成膜法（ＣＶＤ法）、パイロゾル法等で用いる蒸発物中の有機溶媒溶液としては、アルミドープ酸化亜鉛が成膜を妨げない限り特に制限はないが、アセトン、アセチルアセトン、メチルイソブチルケトン、ジエチルケトン等のケトン系溶媒、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール等のアルコール系溶媒、アセト酢酸メチル、アセト酢酸エチル、マロン酸ジメチル、マロン酸ジエチル、酢酸エチル、酢酸ブチル等のエステル系溶媒、メチルセルソルブ、テトラヒドロフラン等のエーテル系溶媒、ベンゼン、トルエン、キシレン等の芳香族炭化水素類、ヘキサン、ヘプタン、オクタン、シクロヘキサン等の脂肪族炭化水素類等を例示することができ、中でもβ−ジケトン類化合物を特に特に好ましく例示することができる。 The organic solvent solution in the evaporant used in chemical vapor deposition (CVD), pyrosol method, etc. is not particularly limited as long as aluminum-doped zinc oxide does not interfere with film formation, but acetone, acetylacetone, methyl isobutyl ketone , Ketone solvents such as diethyl ketone, alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol, ester solvents such as methyl acetoacetate, ethyl acetoacetate, dimethyl malonate, diethyl malonate, ethyl acetate, butyl acetate , Ether solvents such as methyl cellosolve and tetrahydrofuran, aromatic hydrocarbons such as benzene, toluene and xylene, and aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane. Particularly preferred examples of diketone compounds It can be.
本発明の基材は、５５０ｎｍの波長の光の透過率が７０％以上であれば特に制限はなく、任意の材質、形状、付加的構成をとることができる。具体的な材質は特に制限されないが、アルカリガラス、石英ガラス等のガラス、ポリカーボネート、ポリエチレンテレフタレート、ポリアリレート等のポリエステル、ポリエーテルスルホン系樹脂、アモルファスポリオレフィン、ポリスチレン、アクリル樹脂等を例示することができ、中でもガラスを好ましく例示することができる。これらの材質は、最終的に用いる製品の用途に応じて最適なものを適宜選択することができる。また、形状についても、板状、フィルム状、シート状等、最終的に用いる製品の用途に応じて最適なものを適宜選択することができる。付加的構成として、例えば本発明の反射防止膜以外の反射防止膜を、本発明の反射防止膜と反対側の基材表面にさらに有していてもよいし、また、基材中から基材成分の移行を抑制する処理が施されていてもよい。 The base material of the present invention is not particularly limited as long as the transmittance of light having a wavelength of 550 nm is 70% or more, and can have any material, shape, and additional configuration. Specific materials are not particularly limited, and examples thereof include glass such as alkali glass and quartz glass, polyester such as polycarbonate, polyethylene terephthalate, and polyarylate, polyethersulfone resin, amorphous polyolefin, polystyrene, and acrylic resin. Of these, glass is preferable. These materials can be appropriately selected according to the intended use of the final product. In addition, as for the shape, a plate shape, a film shape, a sheet shape, or the like can be appropriately selected according to the intended use of the final product. As an additional configuration, for example, an antireflection film other than the antireflection film of the present invention may further be provided on the surface of the substrate opposite to the antireflection film of the present invention. The process which suppresses a transfer of a component may be performed.
本発明における透明導電膜として、具体的には、スズドープ酸化インジウム膜（ＩＴＯ膜）、フッ素ドープ酸化スズ膜（ＦＴＯ膜）、アンチモンドープ酸化亜鉛膜及びインジウムドープ酸化亜鉛膜等を好ましく例示することができる。これらの透明導電膜を成膜する方法として、例えば、上述したようなスパッター法、電子ビーム蒸着法、イオンプレーティング法、化学気相成膜法（ＣＶＤ法）、パイロゾル法等の一般的な成膜方法を用いることができる。 Specific examples of the transparent conductive film in the present invention are preferably a tin-doped indium oxide film (ITO film), a fluorine-doped tin oxide film (FTO film), an antimony-doped zinc oxide film, an indium-doped zinc oxide film, and the like. it can. As a method for forming these transparent conductive films, for example, the general methods such as the sputtering method, the electron beam evaporation method, the ion plating method, the chemical vapor deposition method (CVD method), and the pyrosol method as described above are used. A membrane method can be used.
本発明の透明導電性基材は、本発明の基材、反射防止膜及び透明導電膜のみをこの順で有していてもよいが、本発明の透明導電性基材の透明性及び導電性を損なわない限り、基材、反射防止膜及び透明導電膜以外に任意の構成を有していてもよい。そのような構成として、例えば、反射防止膜と反対側の透明導電膜表面にさらに１層又は２層以上のコーティング層を有していてもよいし、反射防止膜と透明導電膜の間にさらに１層又は２層以上の中間層を有していてもよいし、基材と反射防止膜の間にさらに１層又は２層以上の中間層を有していてもよいし、反射防止膜と反対側の基材表面にさらに１層又は２層以上のコーティング層を有していてもよい。これらのコーティング層、中間層は、その組成、厚さ、機能、用途には一切制限はない。コーティング層、中間層の具体例としては、反射防止膜、カラーフィルター、配向膜、液晶膜等が挙げられる。また、本発明の透明導電性基材はいずれかの部分に１層又は２層以上の空気層を有していてもよい。また、本発明の透明導電性基材は、本発明の基材、反射防止膜及び透明導電膜をこの順でそれぞれ１層ずつ有していればよいが、本発明の基材、反射防止膜及び透明導電膜のいずれか１つ又は２つ以上を２層以上有していてもよい。例えば、本発明の基材、反射防止膜及び透明導電膜を、基材、反射防止膜、透明導電膜、反射防止膜の順で有するものや、透明導電膜、反射防止膜、基材、反射防止膜、透明導電膜の順で有するものも、本発明の透明導電性基材に含まれる。 The transparent conductive base material of the present invention may have only the base material of the present invention, the antireflection film and the transparent conductive film in this order, but the transparency and conductivity of the transparent conductive base material of the present invention. As long as the above is not impaired, the substrate may have any configuration other than the base material, the antireflection film and the transparent conductive film. As such a configuration, for example, one or two or more coating layers may be further provided on the surface of the transparent conductive film opposite to the antireflection film, and further between the antireflection film and the transparent conductive film. One or two or more intermediate layers may be included, and one or two or more intermediate layers may be further provided between the substrate and the antireflection film. One or two or more coating layers may be further provided on the opposite substrate surface. These coating layers and intermediate layers are not limited at all in their composition, thickness, function and application. Specific examples of the coating layer and the intermediate layer include an antireflection film, a color filter, an alignment film, and a liquid crystal film. In addition, the transparent conductive substrate of the present invention may have one layer or two or more air layers in any part. Further, the transparent conductive substrate of the present invention may have one layer each of the substrate of the present invention, the antireflection film and the transparent conductive film in this order. And two or more layers of any one or two or more of the transparent conductive films. For example, the substrate, the antireflection film and the transparent conductive film of the present invention having the substrate, the antireflection film, the transparent conductive film and the antireflection film in this order, the transparent conductive film, the antireflection film, the substrate and the reflection What has in order of a prevention film and a transparent conductive film is also contained in the transparent conductive base material of this invention.
本発明の基材、反射防止膜及び透明導電膜以外に任意の構成を有している本発明の透明導電性基材として、例えば、タッチパネル、液晶パネルが挙げられる。本発明のタッチパネルは、ガラス、反射防止膜、透明導電膜、空気層、透明導電膜が、この順で積層されてなるタッチパネルであって、前記反射防止膜がアルミドープ酸化亜鉛からなり、かつ原子間力顕微鏡による前記反射防止膜の平均面粗さ（Ｒａ）が１．０ｎｍ以下である限り特に制限されない。本発明のタッチパネルは、透明性及び導電性に優れている。本発明のタッチパネルにおける反射防止膜及び透明導電膜については上述したものと同様である。 Examples of the transparent conductive substrate of the present invention having any configuration other than the substrate, antireflection film and transparent conductive film of the present invention include a touch panel and a liquid crystal panel. The touch panel of the present invention is a touch panel in which glass, an antireflection film, a transparent conductive film, an air layer, and a transparent conductive film are laminated in this order, and the antireflection film is made of aluminum-doped zinc oxide and is an atom. There is no particular limitation as long as the average surface roughness (Ra) of the antireflection film by an atomic force microscope is 1.0 nm or less. The touch panel of the present invention is excellent in transparency and conductivity. The antireflection film and the transparent conductive film in the touch panel of the present invention are the same as those described above.
本発明のタッチパネルにおけるガラスは、５５０ｎｍの波長の光の透過率が７０％以上であれば特に制限はなく、アルカリガラス、石英ガラス等のいずれの種類のガラスも含まれる。本発明のタッチパネルに用いるガラスにおける、５５０ｎｍの波長の光の透過率は７０％以上であれば特に制限はないが、８０％以上であることが好ましく、９０％以上であることがより好ましく、９５％以上であることがさらに好ましく、９８％以上であることが最も好ましい。 The glass in the touch panel of the present invention is not particularly limited as long as the transmittance of light having a wavelength of 550 nm is 70% or more, and includes any kind of glass such as alkali glass and quartz glass. The transmittance of light having a wavelength of 550 nm in the glass used in the touch panel of the present invention is not particularly limited as long as it is 70% or more, but is preferably 80% or more, more preferably 90% or more, and 95 % Or more is more preferable, and 98% or more is most preferable.
本発明のタッチパネルは、上述のガラス、反射防止膜、透明導電膜、空気層、透明導電膜が、この順で積層されている限り、他に任意の構成を有していてもよい。例えば、ガラス、反射防止膜、透明導電膜、空気層、透明導電膜に加えて、それより上にフィルム層及び／又はハードコート膜等を有していてもよい。 The touch panel of the present invention may have any other configuration as long as the glass, the antireflection film, the transparent conductive film, the air layer, and the transparent conductive film are laminated in this order. For example, in addition to glass, an antireflection film, a transparent conductive film, an air layer, and a transparent conductive film, a film layer and / or a hard coat film may be provided thereon.
本発明の液晶パネルは、ガラス、反射防止膜、透明導電膜、配向膜、液晶、配向膜、透明導電膜、反射防止膜及びガラスが、この順で積層されてなる液晶パネルであって、前記反射防止膜がアルミドープ酸化亜鉛からなり、かつ原子間力顕微鏡による前記反射防止膜の平均面粗さ（Ｒａ）が１．０ｎｍ以下である限り特に制限されない。本発明の液晶パネルにおける反射防止膜及び透明導電膜については上述したものと同様である。なお、ガラス、反射防止膜、透明導電膜、配向膜、液晶、配向膜、透明導電膜及びガラスが、この順で積層されてなる液晶パネルや、ガラス、透明導電膜、配向膜、液晶、配向膜、透明導電膜、反射防止膜及びガラスが、この順で積層されてなる液晶パネルも、本発明の液晶パネルに便宜上含まれる。 The liquid crystal panel of the present invention is a liquid crystal panel in which glass, antireflection film, transparent conductive film, alignment film, liquid crystal, alignment film, transparent conductive film, antireflection film and glass are laminated in this order, There is no particular limitation as long as the antireflection film is made of aluminum-doped zinc oxide and the average surface roughness (Ra) of the antireflection film by an atomic force microscope is 1.0 nm or less. The antireflection film and the transparent conductive film in the liquid crystal panel of the present invention are the same as those described above. Glass, antireflection film, transparent conductive film, alignment film, liquid crystal, alignment film, transparent conductive film and glass are laminated in this order, glass, transparent conductive film, alignment film, liquid crystal, alignment A liquid crystal panel in which a film, a transparent conductive film, an antireflection film, and glass are laminated in this order is also included for convenience in the liquid crystal panel of the present invention.
本発明の液晶パネルにおけるガラスは、５５０ｎｍの波長の光の透過率が７０％以上であれば特に制限はなく、アルカリガラス、石英ガラス等のいずれの種類のガラスも含まれる。本発明の液晶パネルに用いるガラスにおける、５５０ｎｍの波長の光の透過率は７０％以上であれば特に制限はないが、８０％以上であることが好ましく、９０％以上であることがより好ましく、９５％以上であることがさらに好ましく、９８％以上であることが最も好ましい。 The glass in the liquid crystal panel of the present invention is not particularly limited as long as the transmittance of light having a wavelength of 550 nm is 70% or more, and includes any kind of glass such as alkali glass and quartz glass. The transmittance of light having a wavelength of 550 nm in the glass used for the liquid crystal panel of the present invention is not particularly limited as long as it is 70% or more, but is preferably 80% or more, more preferably 90% or more, It is more preferably 95% or more, and most preferably 98% or more.
本発明の液晶パネルの液晶における、５５０ｎｍの波長の光の透過率は特に制限されない。本発明における液晶の種類は特に制限されないが、ＳＴＮ、ＴＦＴ等を具体的に挙げることができる。 The transmittance of light having a wavelength of 550 nm in the liquid crystal of the liquid crystal panel of the present invention is not particularly limited. The kind of the liquid crystal in the present invention is not particularly limited, but specific examples include STN, TFT, and the like.
本発明の液晶パネルは、例えば、カラーフィルタ等、他に任意の構成を有していてもよい。 The liquid crystal panel of the present invention may have any other configuration such as a color filter, for example.
本発明の基材、反射防止膜及び透明導電膜における、５５０ｎｍの波長の光の透過率はそれぞれ７０％以上である限り、有色（有色透明）であってもよい。また、本発明の基材、反射防止膜及び透明導電膜は、５５０ｎｍの波長の光の透過率が７０％以上の部分を少なくとも一部にそれぞれ有している限り、該透過率が７０％未満の部分を有していてもよい。 In the base material, antireflection film and transparent conductive film of the present invention, the transmittance of light having a wavelength of 550 nm may be colored (colored and transparent) as long as it is 70% or more. In addition, the base material, antireflection film and transparent conductive film of the present invention have a transmittance of less than 70% as long as the transmittance of light having a wavelength of 550 nm has at least a part of 70% or more. It may have a part.
本発明における反射防止膜は、従来から用いられてきたスズドープ酸化インジウム膜（ＩＴＯ膜）、フッ素ドープ酸化スズ膜（ＦＴＯ膜）、アンチモンドープ酸化亜鉛膜及びインジウムドープ酸化亜鉛膜等の透明導電膜より上及び／又は下に積層することにより、好適に用いることができる。得られた本発明の透明導電性基材は、透明性及び導電性に優れているため、光学素子やタッチパネル、液晶パネル等の、透明性及び導電性を必要とする用途に好適に用いることができる。
また、本発明の反射防止膜中の亜鉛に対するアルミニウムの含有量（原子％）を適宜調節することにより、上記のＩＴＯ膜等以外の透明導電膜を用いる場合であっても、優れた透明性及び導電性を発揮する透明導電性基材を得ることができる。
The antireflection film in the present invention is a conventional conductive film such as a tin-doped indium oxide film (ITO film), a fluorine-doped tin oxide film (FTO film), an antimony-doped zinc oxide film, and an indium-doped zinc oxide film. It can be suitably used by laminating on the top and / or bottom. Since the obtained transparent conductive substrate of the present invention is excellent in transparency and conductivity, it can be suitably used for applications requiring transparency and conductivity, such as optical elements, touch panels, and liquid crystal panels. it can.
Moreover, even if it is a case where transparent conductive films other than said ITO film | membrane etc. are used by adjusting suitably aluminum content (atomic%) with respect to zinc in the antireflection film of this invention, excellent transparency and A transparent conductive substrate that exhibits conductivity can be obtained.
以下、実施例により本発明をより具体的に説明するが、本発明の技術的範囲はこれらの例示に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the technical scope of this invention is not limited to these illustrations.
（実施例１）基材−反射防止膜（アルミニウム５０原子％、４００℃で成膜）
０．２モル／Ｌのジンクアセチルアセトネートを含むアセチルアセトン溶液を用意した。該溶液中の亜鉛に対してアルミニウムが５０原子％になるように、アルミニウムアセチルアセトネートを該溶液に加えて反射防止膜形成液を調製した。
次に、無アルカリガラス（ＯＡ−１０）のガラス基板（３００×３００×０．５mm）を用意した。４００℃に加熱したコンベアー炉の中にこのガラス基板をベルトコンベアーで投入し、該ガラス基板を４００℃に加熱した。霧滴状にした前記反射防止膜形成液を、空気をキャリアガスとしてコンベアー炉の中に吹き込み、ガラス基板の表面に接触させて熱分解させることにより、膜厚４６ｎｍのアルミドープ酸化亜鉛膜（実施例１）を該ガラス基板上に形成させた。
(Example 1) Base material-antireflection film (aluminum 50 atom%, film formation at 400 ° C)
An acetylacetone solution containing 0.2 mol / L of zinc acetylacetonate was prepared. Aluminum acetylacetonate was added to the solution so that aluminum was 50 atomic% with respect to zinc in the solution to prepare an antireflection film forming solution.
Next, a non-alkali glass (OA-10) glass substrate (300 × 300 × 0.5 mm) was prepared. This glass substrate was put into a conveyor furnace heated to 400 ° C. by a belt conveyor, and the glass substrate was heated to 400 ° C. The anti-reflective film forming liquid in the form of mist is blown into a conveyor furnace using air as a carrier gas and brought into contact with the surface of the glass substrate to cause thermal decomposition, whereby an aluminum-doped zinc oxide film having a thickness of 46 nm (implemented) Example 1) was formed on the glass substrate.
（実施例２）基材−反射防止膜（アルミニウム５０原子％、４５０℃で成膜）
ガラス基板を加熱する温度を４００℃ではなく４５０℃としたこと以外は、実施例１と同様の操作を行い、アルミドープ酸化亜鉛膜（実施例２）を得た。
(Example 2) Base material-antireflection film (aluminum 50 atom%, film formation at 450 ° C.)
Except that the temperature for heating the glass substrate was changed to 450 ° C. instead of 400 ° C., the same operation as in Example 1 was performed to obtain an aluminum-doped zinc oxide film (Example 2).
（比較例１）基材−反射防止膜（アルミニウム５０原子％、５００℃で成膜）
ガラス基板を加熱する温度を４００℃ではなく５００℃としたこと以外は、実施例１と同様の操作を行い、アルミドープ酸化亜鉛膜（比較例１）を得た。
(Comparative example 1) Base material-Antireflection film (aluminum 50 atom%, formed at 500 ° C.)
Except that the temperature for heating the glass substrate was changed to 500 ° C. instead of 400 ° C., the same operation as in Example 1 was performed to obtain an aluminum-doped zinc oxide film (Comparative Example 1).
実施例１、実施例２及び比較例１のアルミドープ酸化亜鉛膜の平均面粗さＲａ及び最大高低差ＲＰ−Ｖを、原子間力顕微鏡（Nanopics：エスアイアイ・ナノテクノロジー株式会社製）を用いてそれぞれ測定した。この結果を表１に示す。また、実施例１、実施例２及び比較例１のアルミドープ酸化亜鉛膜中の亜鉛に対するアルミニウム含有量〔原子（ＡＴ）％〕を、ＥＳＣＡ Ｑ２０００（アルバック・ファイ社製）を用いてそれぞれ測定した。この結果を表１に示す。 The average surface roughness Ra and the maximum height difference RP-V of the aluminum-doped zinc oxide films of Example 1, Example 2 and Comparative Example 1 were measured using an atomic force microscope (Nanopics: manufactured by SII Nano Technology Co., Ltd.). Measured respectively. The results are shown in Table 1. Further, the aluminum content [atomic (AT)%] relative to zinc in the aluminum-doped zinc oxide films of Example 1, Example 2 and Comparative Example 1 was measured using ESCA Q2000 (manufactured by ULVAC-PHI). . The results are shown in Table 1.
表１の結果から、反射防止膜中のアルミニウムの含有量が増加するにつれて、平均面粗さＲａ及び最大高低差ＲＰ−Ｖの数値がそれぞれ減少する傾向が見られた。 From the results of Table 1, there was a tendency that the average surface roughness Ra and the numerical value of the maximum height difference RP-V decreased as the aluminum content in the antireflection film increased.
また、実施例１、実施例２及び比較例１のアルミドープ酸化亜鉛膜の屈折率及び膜厚を、分光エリプソメーター（ＳＥ８００：SENTECH社製）を用いてそれぞれ測定した。その結果を表２に示す。 Moreover, the refractive index and film thickness of the aluminum dope zinc oxide film of Example 1, Example 2 and Comparative Example 1 were measured using a spectroscopic ellipsometer (SE800: manufactured by SENTECH). The results are shown in Table 2.
表２の結果から、本発明の反射防止膜の屈折率は、１．６〜１．９の範囲内であった。 From the results in Table 2, the refractive index of the antireflection film of the present invention was in the range of 1.6 to 1.9.
（実施例３）基材−反射防止膜（４００℃で成膜）−透明導電膜（ＩＴＯ膜）
インジウムアセチルアセトナート（Ｉｎ（ＡｃＡｃ）３）をアセチルアセトンにモル濃度で０．２ｍｏｌ／Ｌになるように溶解して黄色透明溶液を得た。この溶液にＳｎ／Ｉｎ＝５質量％となるようにジ−ｎ−ブチルスズジアセテートを加えてＩＴＯ膜形成液を調製した。
このＩＴＯ膜形成液を用いてパイロゾル法により、ＩＴＯ膜形成液の霧化による化学的熱分解量を調整しながら、実施例１の反射防止膜上にＩＴＯ膜を形成し、透明性導電性基材（実施例３）を得た。
(Example 3) Base material-Antireflection film (formed at 400 ° C.)-Transparent conductive film (ITO film)
Indium acetylacetonate (In (AcAc) 3 ) was dissolved in acetylacetone at a molar concentration of 0.2 mol / L to obtain a yellow transparent solution. Di-n-butyltin diacetate was added to this solution so that Sn / In = 5% by mass to prepare an ITO film forming solution.
Using this ITO film forming liquid, an ITO film is formed on the antireflection film of Example 1 while adjusting the amount of chemical thermal decomposition by atomization of the ITO film forming liquid by a pyrosol method. A material (Example 3) was obtained.
（実施例４）基材−反射防止膜（４５０℃で成膜）−透明導電膜（ＩＴＯ膜）
実施例１の反射防止膜の代わりに、実施例２の反射防止膜を用いたこと以外は実施例３と同様の操作を行い、透明導電性基材（実施例４）を得た。
(Example 4) Substrate-Antireflection film (deposited at 450 ° C)-Transparent conductive film (ITO film)
A transparent conductive substrate (Example 4) was obtained in the same manner as in Example 3 except that the antireflection film of Example 2 was used instead of the antireflection film of Example 1.
（比較例２）基材−反射防止膜（５００℃で成膜）−透明導電膜（ＩＴＯ膜）
実施例１の反射防止膜の代わりに、比較例１の反射防止膜を用いたこと以外は実施例３と同様の操作を行い、透明導電性基材（比較例２）を得た。
(Comparative example 2) Base material-Antireflection film (deposited at 500 ° C)-Transparent conductive film (ITO film)
A transparent conductive substrate (Comparative Example 2) was obtained in the same manner as in Example 3 except that the antireflection film of Comparative Example 1 was used instead of the antireflective film of Example 1.
実施例３、実施例４及び比較例２の透明導電性基材のシート抵抗値（Ω/□）を測定した結果を表３に示す。 Table 3 shows the results of measuring the sheet resistance values (Ω / □) of the transparent conductive substrates of Example 3, Example 4, and Comparative Example 2.
表３の結果から、本発明の反射防止膜（実施例３及び４）を用いた場合は、平均面粗さが１．０より大きい反射防止膜（比較例２）を用いた場合に比べて、シート抵抗値が低く、導電性に優れていることが分かる。また、平均面粗さがより小さい実施例３の透明導電性基材の方が、実施例４の透明導電性基材に比べてシート抵抗値が低いことから、反射防止膜を有する透明導電性基材においては、反射防止膜の平均面粗さが小さいほど、導電性により優れた透明導電性基材が得られることが示された。
From the results of Table 3, when the antireflection film of the present invention (Examples 3 and 4) is used, the average surface roughness is larger than 1.0 when compared with the case of using the antireflection film (Comparative Example 2). It can be seen that the sheet resistance is low and the conductivity is excellent. Further, since the transparent conductive substrate of Example 3 having a smaller average surface roughness has a lower sheet resistance value than the transparent conductive substrate of Example 4, the transparent conductive substrate having an antireflection film is used. In the base material, it was shown that the transparent conductive base material excellent in electroconductivity is obtained, so that the average surface roughness of an antireflection film is small.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| WO2013100031A1 (en) * | 2011-12-27 | 2013-07-04 | 積水化学工業株式会社 | Light transmissive conductive film and capacitance-type touch panel using same |
| JP5651106B2 (en) * | 2009-03-30 | 2015-01-07 | リンテック株式会社 | Transparent conductive film |
| WO2016092902A1 (en) * | 2014-12-09 | 2016-06-16 | リンテック株式会社 | Transparent conductive film and method for producing transparent conductive film |
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| JPH09221340A (en) * | 1996-02-09 | 1997-08-26 | Nippon Sheet Glass Co Ltd | Substrate with transparent conductive film |
| JP2002015623A (en) * | 2000-04-27 | 2002-01-18 | Mitsui Chemicals Inc | Transparent electrode |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH09221340A (en) * | 1996-02-09 | 1997-08-26 | Nippon Sheet Glass Co Ltd | Substrate with transparent conductive film |
| JP2002015623A (en) * | 2000-04-27 | 2002-01-18 | Mitsui Chemicals Inc | Transparent electrode |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| JP5651106B2 (en) * | 2009-03-30 | 2015-01-07 | リンテック株式会社 | Transparent conductive film |
| WO2013100031A1 (en) * | 2011-12-27 | 2013-07-04 | 積水化学工業株式会社 | Light transmissive conductive film and capacitance-type touch panel using same |
| WO2016092902A1 (en) * | 2014-12-09 | 2016-06-16 | リンテック株式会社 | Transparent conductive film and method for producing transparent conductive film |
| JPWO2016092902A1 (en) * | 2014-12-09 | 2017-09-21 | リンテック株式会社 | Transparent conductive film and method for producing transparent conductive film |
| TWI676185B (en) * | 2014-12-09 | 2019-11-01 | 日商琳得科股份有限公司 | Transparent conductive film and its producing method thereof |
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