JP2015074163A - Transfer film and method for producing transparent conductive laminate - Google Patents
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Abstract
Description
本発明は、透明導電層を形成するための転写フィルム、および、この転写フィルムを用いた透明導電積層体の製造方法に関する。 The present invention relates to a transfer film for forming a transparent conductive layer and a method for producing a transparent conductive laminate using the transfer film.
透明導電性材料は、液晶ディスプレイ、プラズマディスプレイ、有機ＥＬディスプレイ等のディスプレイデバイス、太陽電池、タッチパネルなどの透明電極、ならびに電磁波シールド材などの透明導電膜として極めて有用であるため、幅広く利用されている。 Transparent conductive materials are widely used because they are extremely useful as display devices such as liquid crystal displays, plasma displays, organic EL displays, transparent electrodes such as solar cells and touch panels, and transparent conductive films such as electromagnetic shielding materials. .
従来、透明導電膜は、例えば、インジウム錫酸化物（ＩＴＯ）、酸化インジウム、酸化スズ、酸化亜鉛等の導電性材料を、スパッタリング法、または蒸着法によりガラス板や透明フィルムなど基材上に堆積させることにより形成していた。しかし、スパッタリング法、または蒸着法を用いた透明導電膜の製造は、高額な大型の生産設備を必要とし、少量多品種の生産には適さない。また、このスパッタリング法や蒸着法により形成したＩＴＯなどの金属酸化物の透明導電膜は、フィルムなどの基材の撓みによりクラックが入りやすく、そのため導電性の低下が起こりやすいという問題があった。 Conventionally, a transparent conductive film is formed by depositing a conductive material such as indium tin oxide (ITO), indium oxide, tin oxide, or zinc oxide on a substrate such as a glass plate or a transparent film by sputtering or evaporation. It was formed by letting. However, the production of a transparent conductive film using a sputtering method or a vapor deposition method requires an expensive large-scale production facility, and is not suitable for the production of a small variety of products. In addition, the transparent conductive film of metal oxide such as ITO formed by this sputtering method or vapor deposition method has a problem that it is easy to crack due to bending of a substrate such as a film, so that the conductivity is easily lowered.
一方、低温かつ低コストで成膜可能な透明導電膜の形成方法として、透明フィルムなどの基材にウェットプロセスにより導電性高分子膜を成膜する方法が知られている。導電性高分子などの導電体膜を塗布形成する透明導電性フィルムの製造方法は、製造コストが比較的安く、生産性に優れるという利点がある。また、ウェットプロセスにより塗布形成した導電性高分子などの導電体膜は、膜自体に柔軟性があるため、クラックなどの問題が生じにくい。 On the other hand, as a method of forming a transparent conductive film that can be formed at low temperature and low cost, a method of forming a conductive polymer film on a substrate such as a transparent film by a wet process is known. The method for producing a transparent conductive film in which a conductive film such as a conductive polymer is applied and formed has advantages that the production cost is relatively low and the productivity is excellent. In addition, since a conductive film such as a conductive polymer formed by a wet process is flexible, problems such as cracks hardly occur.
ウェットプロセスにより成膜が可能な透明導電材料としては、導電性高分子膜のほかに、カーボンナノチューブや金属ナノワイヤのような導電性繊維を導電体材料として用いる方法が、提案されている（例えば、特許文献１、特許文献２）。また、特許文献３には、導電体材料としてカーボンナノチューブを含有する導電性繊維層を有する導電層転写シートが提案されている。 As a transparent conductive material that can be formed by a wet process, a method using conductive fibers such as carbon nanotubes and metal nanowires as a conductive material in addition to a conductive polymer film has been proposed (for example, Patent Document 1 and Patent Document 2). Patent Document 3 proposes a conductive layer transfer sheet having a conductive fiber layer containing carbon nanotubes as a conductive material.
しかしながら、特許文献３に開示の導電層転写シートは、透明性が高いものは、その抵抗値が１０８Ω／□程度であり導電性が低く、一方、抵抗値が１０Ω／□程度のものは、全光線透過率が５５％程度であり透明性が低い。すなわち、透明性と導電性の両特性を十分に満たしたものではなく、また、その剥離性や転写性も不十分である。したがって、比較的高抵抗値である帯電防止層等を、被転写体に付与するには適しているが、タッチセンサー等の用途に適した低抵抗値の透明導電層を、被転写体の表面に形成する転写シートとしては、不十分であるという課題がある。 However, the conductive layer transfer sheet disclosed in Patent Document 3 has high transparency, the resistance value is about 10 8 Ω / □, and the conductivity is low, whereas the resistance value is about 10 Ω / □. The total light transmittance is about 55% and the transparency is low. That is, it does not sufficiently satisfy both the characteristics of transparency and conductivity, and its peelability and transferability are insufficient. Therefore, although it is suitable for applying an antistatic layer or the like having a relatively high resistance value to the transfer object, a transparent conductive layer having a low resistance value suitable for applications such as a touch sensor is provided on the surface of the transfer object. There is a problem that the transfer sheet is insufficient.
本発明は、上記課題を解決するもので、低抵抗値、柔軟性、転写性の各特性を満足する透明導電層を有する転写フィルムであり、被転写体の表面に、低抵抗値の透明導電層を形成することができる転写フィルム、およびこの転写フィルムを用いた透明導電積層体の製造方法を提供することを目的とするものである。 The present invention solves the above-described problems, and is a transfer film having a transparent conductive layer that satisfies the properties of low resistance, flexibility, and transferability. It is an object of the present invention to provide a transfer film capable of forming a layer and a method for producing a transparent conductive laminate using the transfer film.
上記目的を達成するために、本発明の転写フィルムは、基材フィルムの一方の面上に、少なくとも、離型層と、金属ナノワイヤと透明高分子樹脂とを含む透明導電層とをこの順に備え、前記離型層は、環状オレフィン系樹脂であることを特徴とする。 In order to achieve the above object, the transfer film of the present invention comprises at least a release layer, a transparent conductive layer containing metal nanowires and a transparent polymer resin in this order on one surface of the base film. The release layer is a cyclic olefin resin.
そして、本発明の透明導電積層体の製造方法は、上記本発明の転写フィルムを用い、前記転写フィルムの透明導電層側を被転写体の表面に接着剤層を介して接着させた後に、基材フィルムを剥離することにより、被転写体表面に透明導電層を形成することを特徴とする。 And the manufacturing method of the transparent conductive laminated body of this invention uses the transfer film of the said invention, and adhere | attaches the transparent conductive layer side of the said transfer film on the surface of a to-be-transferred body through an adhesive layer, A transparent conductive layer is formed on the surface of the transfer object by peeling the material film.
本発明の転写フィルムによれば、透明導電層は、金属ナノワイヤと透明高分子樹脂とを含むことで、低抵抗値であるとともに、柔軟性に優れた透明導電層となる。また、離型層は、環状オレフィン系樹脂としたので、上記の透明導電層と組み合わせた場合に、上記透明導電層の剥離が容易となり、転写性に優れた転写フィルムとなる。 According to the transfer film of the present invention, the transparent conductive layer contains a metal nanowire and a transparent polymer resin, so that the transparent conductive layer has a low resistance value and an excellent flexibility. Further, since the release layer is a cyclic olefin resin, when combined with the transparent conductive layer, the transparent conductive layer can be easily peeled off, and a transfer film having excellent transferability can be obtained.
そして、本発明の透明導電積層体の製造方法によれば、上記本発明の転写フィルムを用いるので、例えばタッチセンサー等の用途に適した低抵抗値の透明導電層を、被転写体の表面に、容易かつ生産性良く形成することができ、優れた透明導電積層体の製造方法となる。 According to the method for producing a transparent conductive laminate of the present invention, since the transfer film of the present invention is used, for example, a transparent conductive layer having a low resistance value suitable for uses such as a touch sensor is provided on the surface of the transfer object. Therefore, it can be formed easily and with high productivity, and it becomes an excellent method for producing a transparent conductive laminate.
以下、本発明の転写フィルムについて詳細に説明する。本発明の転写フィルムは、基材フィルムの一方の面上に、少なくとも、離型層と、金属ナノワイヤと透明高分子樹脂とを含む透明導電層とをこの順に備え、前記離型層は、環状オレフィン系樹脂である構成としたものである。本発明の転写フィルムとその製造方法について、以下に、各層毎に順に説明する。 Hereinafter, the transfer film of the present invention will be described in detail. The transfer film of the present invention comprises at least a release layer and a transparent conductive layer containing metal nanowires and a transparent polymer resin in this order on one surface of the base film, and the release layer is annular. The composition is an olefin resin. The transfer film of the present invention and the manufacturing method thereof will be described below in order for each layer.
本発明の転写フィルムの基材フィルムとしては、ポリエステル系樹脂、ポリプロピレン系樹脂、塩化ビニル樹脂、ポリエチレン樹脂、ポリエチレンテレフタレート樹脂、ポリカーボネート樹脂、ナイロン樹脂、ビニロン樹脂、アセテート樹脂、ポリスチレン系樹脂、ポリアミド系樹脂、ポリアクリル系樹脂、ポリ塩化ビニル系樹脂、オレフィン樹脂、環状オレフィン樹脂、などのプラスチックフィルムを使用することができる。中でも、好ましくは、ポリエチレンテレフタレートやポリエチレンナフタレート等の２軸延伸ポリエステル樹脂フィルムである。特に、２軸延伸ポリエチレンテレフタレートフィルムは、耐熱性、機械的強度、平坦性に優れ、比較的安価な点等で好ましい。なお、基材フィルムの厚さとしては、特に制限はなく、例えば、１２〜２５０μｍのものが使用できる。 As the base film of the transfer film of the present invention, polyester resin, polypropylene resin, vinyl chloride resin, polyethylene resin, polyethylene terephthalate resin, polycarbonate resin, nylon resin, vinylon resin, acetate resin, polystyrene resin, polyamide resin Plastic films such as polyacrylic resin, polyvinyl chloride resin, olefin resin, and cyclic olefin resin can be used. Among them, a biaxially stretched polyester resin film such as polyethylene terephthalate or polyethylene naphthalate is preferable. In particular, a biaxially stretched polyethylene terephthalate film is preferable in that it has excellent heat resistance, mechanical strength, and flatness, and is relatively inexpensive. In addition, there is no restriction | limiting in particular as thickness of a base film, For example, the thing of 12-250 micrometers can be used.
また、基材フィルムの表面には、下記の離型層との密着性を向上させるために、予め、コロナ放電処理、プラズマ処理などの表面処理を施してもよく、アンダーコート層等の易接着層を設けてもよい。 In addition, the surface of the base film may be subjected to surface treatment such as corona discharge treatment or plasma treatment in advance in order to improve adhesion with the following release layer, and easy adhesion of the undercoat layer, etc. A layer may be provided.
本発明の転写フィルムの離型層としては、後記の金属ナノワイヤと透明高分子樹脂を含む透明導電層と組み合わせた場合に、優れた剥離性と転写性が得られる効果の観点から、環状オレフィン系樹脂を用いて形成する。具体的には、非極性ノルボルネン系モノマー、より具体的には、非極性ジシクロペンタジエン類、非極性テトラシクロドデセン類から重合される環状オレフィン系樹脂を用いて離型層を形成することにより、後記の透明導電層と組み合わせた場合に、優れた剥離性と転写性が得られる。 As a release layer of the transfer film of the present invention, when combined with a metal nanowire and a transparent conductive layer containing a transparent polymer resin described later, from the viewpoint of the effect of obtaining excellent peelability and transferability, a cyclic olefin type It is formed using a resin. Specifically, by forming a release layer using a non-polar norbornene monomer, more specifically, a cyclic olefin resin polymerized from non-polar dicyclopentadienes and non-polar tetracyclododecenes. When combined with the transparent conductive layer described later, excellent peelability and transferability can be obtained.
離型層の厚さとしては、０．１μｍ未満では十分な効果が得られず、１０μｍを超えると離型層の膜にうねりのような膜厚のばらつきが発生し、後に形成する後記透明導電層の膜厚にばらつきが発生し、抵抗値のばらつきが発生する恐れであるので、０．１μｍ以上１０μｍ以下が好ましい。離型層の形成方法としては、グラビアコート法、バーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法などの塗工法が使用できる。 If the thickness of the release layer is less than 0.1 μm, a sufficient effect cannot be obtained, and if it exceeds 10 μm, the release layer has a film thickness variation such as waviness. It is preferable that the thickness is 0.1 μm or more and 10 μm or less because variations in the film thickness of the layers may occur and resistance values may vary. As a method for forming the release layer, a coating method such as a gravure coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, or a die coating method can be used.
次に、本発明の転写フィルムの透明導電層について、詳細に説明する。透明導電層は、金属ナノワイヤと透明高分子樹脂とを含む層である。この透明導電層を形成する方法としては、例えば、金属ナノワイヤを含む分散液を離型層の上に予め塗布形成した後に、この上に透明高分子樹脂を形成する。 Next, the transparent conductive layer of the transfer film of the present invention will be described in detail. The transparent conductive layer is a layer containing metal nanowires and a transparent polymer resin. As a method for forming this transparent conductive layer, for example, a dispersion liquid containing metal nanowires is previously formed on a release layer, and then a transparent polymer resin is formed thereon.
金属ナノワイヤを含む分散液の金属ナノワイヤに用いられる金属としては、金、銀、銅、アルミ、ニッケル、鉄、ステンレスなどの導電性が高い金属が選ばれる。中でも、銀、銅、鉄などがより好ましい。また、金属ナノワイヤの形状および大きさについては、直径１０〜５００ｎｍ程度の大きさのものが用いられる。より好ましくは２０〜１００ｎｍである。長さは１〜１００μｍであるが、より好ましくは１０〜５０μｍである。 As a metal used for the metal nanowire of the dispersion liquid containing a metal nanowire, a metal having high conductivity such as gold, silver, copper, aluminum, nickel, iron, and stainless steel is selected. Of these, silver, copper, iron and the like are more preferable. Moreover, about the shape and magnitude | size of metal nanowire, the thing of a magnitude | size about 10-500 nm in diameter is used. More preferably, it is 20-100 nm. Although length is 1-100 micrometers, More preferably, it is 10-50 micrometers.
分散液の溶媒としては、一般的な溶媒が適用可能であり、水、アルコール系、ケトン系、酢酸エステル系、芳香族系などが使用できる。分散液には、金属ナノワイヤの凝集を防ぐ目的で一般的な分散剤を加えることも可能であり、また、濡れ性、透明高分子樹脂との密着性を考慮してオレフィン系樹脂以外のバインダー樹脂、具体的には、アクリル系、ウレタン系、ポリエステル系、ポリスチレン系、ポリビニルアルコール系、ポリビニルピロリドン系などの樹脂を適宜加えることも可能である。しかし、バインダー樹脂を加え過ぎると導電性が悪くなるため、分散液全量に対して、０．０１〜１重量％程度加えることが好ましい。金属ナノワイヤを含む分散液の塗布形成方法としては、グラビアコート法、バーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法などの塗工法が使用できる。 As a solvent for the dispersion liquid, a general solvent can be applied, and water, alcohols, ketones, acetates, aromatics, and the like can be used. It is possible to add a general dispersant to the dispersion to prevent aggregation of the metal nanowires. In consideration of wettability and adhesion to a transparent polymer resin, binder resins other than olefin resins are also available. Specifically, an acrylic resin, urethane resin, polyester resin, polystyrene resin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, or the like can be added as appropriate. However, if too much binder resin is added, the conductivity will deteriorate, so it is preferable to add about 0.01 to 1% by weight based on the total amount of the dispersion. As a method for coating and forming a dispersion containing metal nanowires, coating methods such as gravure coating, bar coating, knife coating, roll coating, blade coating, and die coating can be used.
そして、本発明の転写フィルムの透明導電層は、金属ナノワイヤの保護、転写後の平滑性付与などを目的として、金属ナノワイヤの上に透明高分子樹脂を形成する。透明高分子樹脂の膜厚は、５０〜１０００ｎｍ程度が好ましく、より好ましくは１００〜３００ｎｍである。膜厚が薄すぎると保護する機能が低下する。膜厚が厚く金属ナノワイヤを完全に覆っても、１０００ｎｍ以下であれば、転写後の透明導電層の導電性には影響を与えないので好ましい。 The transparent conductive layer of the transfer film of the present invention forms a transparent polymer resin on the metal nanowires for the purpose of protecting the metal nanowires and imparting smoothness after transfer. The film thickness of the transparent polymer resin is preferably about 50 to 1000 nm, more preferably 100 to 300 nm. If the film thickness is too thin, the protective function is reduced. Even if the film is thick and completely covers the metal nanowire, it is preferably 1000 nm or less because it does not affect the conductivity of the transparent conductive layer after transfer.
透明高分子樹脂として用いられる樹脂は、透明性が高く、強靭な樹脂であることが望ましく、具体的には、アクリル系、アクリルウレタン系、アクリルエステル系、エポキシ系などの樹脂が用いられる。添加剤として無機粒子などのフィラーを加えることもできる。また、樹脂の硬化には熱または紫外線照射によって硬化できる樹脂が好ましい。透明高分子樹脂の塗布形成方法としてはグラビアコート法、バーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法などの塗工法が使用できる。 The resin used as the transparent polymer resin is preferably a highly transparent and tough resin, and specifically, an acrylic resin, an acrylic urethane resin, an acrylic ester resin, an epoxy resin, or the like is used. A filler such as inorganic particles can also be added as an additive. For curing the resin, a resin that can be cured by heat or ultraviolet irradiation is preferable. As a method for applying and forming the transparent polymer resin, a coating method such as a gravure coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, or a die coating method can be used.
本発明の転写フィルムの透明導電層の特性としては、導電性としてのシート抵抗値は、好ましくは１〜５００Ω／□、より好ましくは１〜１５０Ω／□であることが望ましい。また、透明性としての全光線透過率は、好ましくは７０％以上、特に好ましくは８０％以上であることが望ましい。シート抵抗値および全光線透過率は、金属ナノワイヤ材料の選択および塗布量の制御などにより、適宜調整することが可能である。 As the characteristics of the transparent conductive layer of the transfer film of the present invention, the sheet resistance value as conductivity is preferably 1 to 500Ω / □, more preferably 1 to 150Ω / □. The total light transmittance as transparency is preferably 70% or more, and particularly preferably 80% or more. The sheet resistance value and the total light transmittance can be appropriately adjusted by selecting the metal nanowire material and controlling the coating amount.
そして、本発明の転写フィルムにおいては、被転写体に貼り付けるために、透明導電層の上に、予め接着剤層を備えていても良い。接着剤層は、後述する転写法や成形同時転写法などにより、本発明の転写フィルムを被転写体に接着転写させるための層である。接着剤層を構成する接着剤の材料としては、転写法や成形同時転写法などにより被転写体に転写する際に、転写時の加熱温度により軟化して粘着性を生ずる接着剤が好ましく、アクリル系樹脂、ポリ塩化ビニル系樹脂等の熱可塑性樹脂が好ましい。被転写体の材質がアクリル系樹脂の場合は、アクリル系樹脂接着剤を用いることが好ましい。また、被転写体の材質がフェニレンオキシド・スチレン系樹脂、ポリカーボネート系樹脂、スチレン共重合体系樹脂の場合は、これらの樹脂と親和性のあるアクリル系樹脂接着剤、ポリスチレン系樹脂接着剤、ポリアミド系樹脂接着剤などを選択して使用することが好ましい。接着剤層の厚さは、０．５〜５μｍの範囲が好ましい。 And in the transfer film of this invention, in order to affix on a to-be-transferred body, you may provide the adhesive bond layer previously on the transparent conductive layer. The adhesive layer is a layer for adhesive transfer of the transfer film of the present invention to the transfer target material by a transfer method or a simultaneous molding transfer method described later. As an adhesive material constituting the adhesive layer, an adhesive that is softened by a heating temperature at the time of transfer to transfer to a transfer medium by a transfer method, a simultaneous molding transfer method, or the like is preferable. A thermoplastic resin such as a vinyl resin or a polyvinyl chloride resin is preferred. When the material of the transfer object is an acrylic resin, it is preferable to use an acrylic resin adhesive. In addition, when the material of the material to be transferred is phenylene oxide / styrene resin, polycarbonate resin, styrene copolymer resin, acrylic resin adhesive, polystyrene resin adhesive, polyamide resin having affinity with these resins It is preferable to select and use a resin adhesive or the like. The thickness of the adhesive layer is preferably in the range of 0.5 to 5 μm.
さらには、紫外線硬化型樹脂を用いて、被転写体または転写フィルム上に紫外線硬化樹脂を形成し、貼り合わせた後に紫外線を照射し硬化させ転写する方法も用いることができる。この場合は、アクリル系樹脂、アクリルウレタン系樹脂、アクリルエポキシ系樹脂などの紫外線硬化型樹脂を用いることができる。また、粘着剤を用いて、被転写体または転写フィルム上に粘着剤を形成し、貼り合わせ転写する方法も用いることができる。この場合は、アクリル系粘着剤、アクリルゴム系粘着剤など一般的な粘着剤を用いることができる。 Furthermore, an ultraviolet curable resin may be used to form an ultraviolet curable resin on a transfer target or transfer film, and after being bonded, the ultraviolet rays may be irradiated to cure and transfer. In this case, an ultraviolet curable resin such as an acrylic resin, an acrylic urethane resin, or an acrylic epoxy resin can be used. Moreover, the method of forming an adhesive on a to-be-transferred material or a transfer film using an adhesive, and carrying out bonding transfer can also be used. In this case, general adhesives such as an acrylic adhesive and an acrylic rubber adhesive can be used.
続いて、本発明の転写フィルムを用いた本発明の透明導電積層体の製造方法について説明する。 Then, the manufacturing method of the transparent conductive laminated body of this invention using the transfer film of this invention is demonstrated.
本発明の透明導電積層体を製造するための被転写体としては、透明性を有する樹脂材料が望ましい。具体的な樹脂の種類としては、例えば、ポリエチレン、ポリプロピレン等のポリオレフィン系樹脂、ポリスチレン系樹脂、ポリ塩化ビニル系樹脂、ポリ（メタ）アクリレート系樹脂、アクリル系樹脂、ポリアセタール樹脂、ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル樹脂、ポリアミド樹脂、ポリカーボネート樹脂、ポリフェニレンサルファイド樹脂、ポリイミド樹脂等の公知の熱可塑性樹脂がいずれも使用できる。また、被転写体の形状としては、フィルム、シート、板状、および各種形状のものがその用途に応じて使用できる。 As the transfer target for producing the transparent conductive laminate of the present invention, a resin material having transparency is desirable. Specific types of resin include, for example, polyolefin resins such as polyethylene and polypropylene, polystyrene resins, polyvinyl chloride resins, poly (meth) acrylate resins, acrylic resins, polyacetal resins, polyethylene terephthalate, polybutylene. Any known thermoplastic resin such as polyester resin such as terephthalate, polyamide resin, polycarbonate resin, polyphenylene sulfide resin, and polyimide resin can be used. Moreover, as a shape of a to-be-transferred body, the thing of a film, a sheet | seat, plate shape, and various shapes can be used according to the use.
本発明の転写フィルムを用いて、被転写体に透明導電層を転写形成する転写法は、次のようにして行う。まず、被転写体の表面に、転写フィルムの透明導電層上に予め形成した接着剤層を密着させる。次に、シリコンラバーなどの耐熱性弾性体を備えたロール転写機、アップダウン転写機などの転写機を用い、耐熱性弾性体を介して転写フィルムの基材フィルム側から熱および圧力を加える。これにより、接着剤層が被転写体の表面に接着する。そして、被転写体が冷却した後に基材フィルムを剥がすと、接着剤層とともに、透明導電層が被転写体の表面に転写される。以上により、転写工程が完了し、被転写体の表面に透明導電層を形成した透明導電積層体が得られる。 A transfer method for transferring and forming a transparent conductive layer on a transfer target using the transfer film of the present invention is performed as follows. First, an adhesive layer formed in advance on the transparent conductive layer of the transfer film is brought into close contact with the surface of the transfer object. Next, heat and pressure are applied from the base film side of the transfer film through the heat resistant elastic body using a transfer machine such as a roll transfer machine or an up / down transfer machine provided with a heat resistant elastic body such as silicon rubber. As a result, the adhesive layer adheres to the surface of the transfer object. Then, when the substrate film is peeled off after the transferred body is cooled, the transparent conductive layer is transferred onto the surface of the transferred body together with the adhesive layer. As described above, the transfer step is completed, and a transparent conductive laminate having a transparent conductive layer formed on the surface of the transfer target is obtained.
次に、成形同時転写法によって、本発明の透明導電積層体を製造する方法について説明する。本発明の転写フィルムを用いて、被転写体に透明導電層を転写形成する成形同時転写法は、次のようにして行う。まず、可動型と固定型とからなる成形用金型内に、透明導電層上に予め接着剤層を形成した転写フィルムを、基材フィルム側が金型キャビティに面するように金型内に配置する。そして、成形用金型を閉じた後、ゲートから成形樹脂を金型内に射出充填させ、樹脂を固化して被転写体を形成するとともに、その表面に転写フィルムを接着させる。被転写体を冷却した後、成形用金型を開いて被転写体を取り出す。最後に、被転写体から基材フィルムを剥がすと、接着剤層とともに、透明導電層が被転写体の表面に転写形成される。以上により、成形同時転写工程が完了し、被転写体の表面に透明導電層を形成した透明導電積層体が得られる。 Next, a method for producing the transparent conductive laminate of the present invention by the simultaneous molding transfer method will be described. The molding simultaneous transfer method in which the transparent conductive layer is transferred and formed on the transfer object using the transfer film of the present invention is performed as follows. First, a transfer film in which an adhesive layer is previously formed on a transparent conductive layer is placed in a mold that consists of a movable mold and a fixed mold, with the base film facing the mold cavity. To do. Then, after closing the molding die, a molding resin is injected and filled from the gate into the die, and the resin is solidified to form a transfer target, and a transfer film is adhered to the surface. After the transfer body is cooled, the molding die is opened and the transfer body is taken out. Finally, when the substrate film is peeled off from the transfer object, the transparent conductive layer is transferred and formed on the surface of the transfer object together with the adhesive layer. As described above, the molding simultaneous transfer step is completed, and a transparent conductive laminate in which a transparent conductive layer is formed on the surface of the transfer target is obtained.
上記の成形同時転写法によって得られる本発明の製造方法による透明導電積層体は、曲面などの３次元形状の被転写体の表面に、タッチセンサー等の用途に適した低抵抗値の透明導電層を形成することができ、多様な要望に応えられるものとなる。 The transparent conductive laminate obtained by the method of the present invention obtained by the above-mentioned simultaneous molding transfer method has a low resistance transparent conductive layer suitable for applications such as a touch sensor on the surface of a three-dimensional transferred object such as a curved surface. It is possible to meet the various demands.
なお、上記の透明導電積層体の製造方法においては、透明導電層上に予め接着剤層を形成した転写フィルムを用いた場合を例として説明したが、接着剤層は、必ずしも転写フィルムに予め形成する必要はなく、被転写体側に転写時または予め接着剤層を設けても良い。 In the above method for producing a transparent conductive laminate, the case where a transfer film having an adhesive layer previously formed on the transparent conductive layer is used as an example. However, the adhesive layer is not necessarily formed in advance on the transfer film. It is not necessary to perform this, and an adhesive layer may be provided on the transfer target side at the time of transfer or in advance.
また、被転写体の表面に透明導電層を形成した上記の透明導電積層体に、さらに、透明導電層の上に透明導電性の金属酸化物膜を形成することが好ましい。金属酸化物膜を積層することにより、金属ナノワイヤだけでは不均一である微小領域で導電性を均一化することが可能となり、微小領域でのより安定した導電性が得られる。これにより、具体的には、透明導電層をパターニングした場合でも良好な導電性が得られ、結果として、幅３０μｍのような狭配線の導体パターンを形成することが可能となる。 Moreover, it is preferable that a transparent conductive metal oxide film is further formed on the transparent conductive layer in the transparent conductive laminate in which the transparent conductive layer is formed on the surface of the transfer target. By laminating the metal oxide film, it is possible to make the conductivity uniform in a minute region that is not uniform only by the metal nanowires, and more stable conductivity in the minute region can be obtained. Thus, specifically, good conductivity can be obtained even when the transparent conductive layer is patterned, and as a result, a narrow wiring conductor pattern having a width of 30 μm can be formed.
上記の透明導電性の金属酸化物膜としては、インジウムスズ酸化物（ＩＴＯ）、酸化インジウム（Ｉｎ２Ｏ３）、酸化スズ（ＳｎＯ２）、酸化亜鉛（ＺｎＯ）、アルミニウム亜鉛酸化物（ＡＺＯ）、ガリウム亜鉛酸化物（ＧＺＯ）、インジウム亜鉛酸化物（ＩＺＯ）等の金属酸化物半導体の蒸着膜またはスパッタ膜などを用いることができる。 As the transparent conductive metal oxide film, indium tin oxide (ITO), indium oxide (In 2 O 3 ), tin oxide (SnO 2 ), zinc oxide (ZnO), aluminum zinc oxide (AZO) Alternatively, a deposited film or a sputtered film of a metal oxide semiconductor such as gallium zinc oxide (GZO) or indium zinc oxide (IZO) can be used.
上記の透明導電性の金属酸化物膜の膜厚は、１０〜５００ｎｍが好ましい。透明性と導電性、および膜厚均一性を考慮した場合、２０〜２００ｎｍがより好ましい。 The thickness of the transparent conductive metal oxide film is preferably 10 to 500 nm. In consideration of transparency, conductivity, and film thickness uniformity, 20 to 200 nm is more preferable.
以下に、本発明の転写フィルムおよび透明導電積層体の製造方法について、実施例に基づき具体的に説明する。ただし、本発明は実施例に限定されるものではない。 Below, the manufacturing method of the transfer film of this invention and a transparent conductive laminated body is demonstrated concretely based on an Example. However, the present invention is not limited to the examples.
本実施例においては、本発明の範囲外の比較例も含めて、試料Ｎｏ．１〜９の９種類の転写フィルム、およびこれを用いた透明導電積層体を作製して、これらを評価した。試料Ｎｏ．１〜９の９種類の転写フィルムは、離型層を形成するために用いた離型樹脂組成物が異なるのみである。 In this example, the sample No. including the comparative example outside the scope of the present invention was used. Nine types of transfer films 1 to 9 and transparent conductive laminates using the same were prepared and evaluated. Sample No. The nine types of transfer films 1 to 9 differ only in the release resin composition used to form the release layer.
次に、試料Ｎｏ．１〜９の９種類の転写フィルム、およびこれを用いた透明導電積層体の作製方法について、具体的に説明する。まず、基材フィルムとして、厚さ３８μｍのポリエチレンテレフタレート（ＰＥＴ）フィルム準備した。 Next, sample No. 9 types of transfer films 1 to 9 and a method for producing a transparent conductive laminate using the transfer films will be specifically described. First, a 38 μm-thick polyethylene terephthalate (PET) film was prepared as a base film.
また、試料Ｎｏ．１〜９の９種類の転写フィルムの透明導電層を形成するための金属ナノワイヤ分散液としては、銀ナノワイヤ分散液（直径５０ｎｍ、長さ２０μｍ、水系溶媒）を用いた。また、透明高分子樹脂としては、ジペンタエリスリトールヘキサアクリレート（新中村化学工業株式会社製、Ａ−ＤＰＨ）をトルエンとＭＥＫで５ｗｔ％に希釈し、イルガキュア１８４（チバ・ジャパン株式会社製）をモノマー比で５ｗｔ％添加して調整した塗料を用いた。 Sample No. As the metal nanowire dispersion liquid for forming the transparent conductive layers of nine kinds of transfer films 1 to 9, a silver nanowire dispersion liquid (diameter 50 nm, length 20 μm, aqueous solvent) was used. As the transparent polymer resin, dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-DPH) is diluted with toluene and MEK to 5 wt%, and Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) is used as a monomer. A paint prepared by adding 5 wt% in a ratio was used.
はじめに、試料Ｎｏ．１の転写フィルムは、以下のようにして作製した。まず、離型層を形成するための離型樹脂組成物を作製した。試料Ｎｏ．１の転写フィルムの離型樹脂組成物として、環状オレフィン樹脂であるゼオネックス３３０Ｒ（日本ゼオン株式会社製、固形分量１００ｗｔ％）５重量部に、トルエン５０重量部、キシレン３０重量部、メチルシクロヘキサン１５重量部の溶剤を加えて離型樹脂組成物を調製した。 First, sample no. The transfer film 1 was prepared as follows. First, a release resin composition for forming a release layer was prepared. Sample No. As a release resin composition of 1 transfer film, 50 parts by weight of toluene, 30 parts by weight of xylene, and 15 parts by weight of methylcyclohexane are added to 5 parts by weight of ZEONEX 330R (manufactured by ZEON Corporation, solid content 100 wt%) which is a cyclic olefin resin. Part of the solvent was added to prepare a release resin composition.
次に、この離型樹脂組成物を用い、基材フィルムとして準備した厚さ３８μｍのポリエチレンテレフタレート（ＰＥＴ）フィルム上に、離型樹脂組成物を乾燥後の厚さが５００ｎｍとなるよう塗工し、１２０℃で１分乾燥させ、離型層を形成した。 Next, using this release resin composition, a release resin composition was applied on a polyethylene terephthalate (PET) film having a thickness of 38 μm prepared as a base film so that the thickness after drying was 500 nm. , And dried at 120 ° C. for 1 minute to form a release layer.
続いて、この離型層の上に、上記で準備した銀ナノワイヤ分散液を用い、塗布量１０ｇ／ｍ２になるように塗工し、１２０℃で３０秒間乾燥させて、銀ナノワイヤの膜を形成した。次に、上記で調整し準備した透明高分子樹脂を含有する塗料を、乾燥後の厚さが１５０ｎｍになるように塗工し、８０℃で１分間乾燥させて、１０００ｍＪ／ｃｍ２の紫外線量を照射し、硬化させて透明高分子樹脂を形成して、透明導電層を得た。 Subsequently, on the release layer, the silver nanowire dispersion liquid prepared above was applied so that the coating amount was 10 g / m 2 and dried at 120 ° C. for 30 seconds to form a silver nanowire film. Formed. Next, the coating material containing the transparent polymer resin prepared and prepared as described above was applied so that the thickness after drying was 150 nm, dried at 80 ° C. for 1 minute, and an ultraviolet ray amount of 1000 mJ / cm 2 . And cured to form a transparent polymer resin to obtain a transparent conductive layer.
次に、この透明導電層の上に、接着剤としてアクリル系樹脂を乾燥後３μｍの厚さになるように塗工し、１２０℃で１分間乾燥させて、接着剤層を形成した。以上により、試料Ｎｏ．１の転写フィルムを得た。 Next, on this transparent conductive layer, an acrylic resin as an adhesive was applied to a thickness of 3 μm after drying, and dried at 120 ° C. for 1 minute to form an adhesive layer. As described above, the sample No. 1 transfer film was obtained.
そして、試料Ｎｏ．１の転写フィルムの接着剤層側を、厚さ２ｍｍアクリル板に当接し、ロール転写機を用いて、２００℃、１．２ｍ／分、１０ｋｇ／ｃｍ２の条件で加熱加圧し、冷却した後、基材フィルムを剥離した。以上により、アクリル板の表面に透明導電層を転写して形成し、試料Ｎｏ．１の転写フィルムを用いた透明導電積層体を作製した。 And sample no. After the adhesive layer side of transfer film 1 was brought into contact with an acrylic plate having a thickness of 2 mm, and heated and pressurized under the conditions of 200 ° C., 1.2 m / min, 10 kg / cm 2 using a roll transfer machine, and cooled. The base film was peeled off. As described above, the transparent conductive layer was transferred and formed on the surface of the acrylic plate. A transparent conductive laminate using the transfer film 1 was prepared.
試料Ｎｏ．２の転写フィルムは、離型層を形成するための離型樹脂組成物として、ゼオネックス３３０Ｒに代えて、環状オレフィン樹脂であるゼオネックス４８０Ｒ（日本ゼオン株式会社製、固形分量１００ｗｔ％）を用いた以外は、試料Ｎｏ．１の転写フィルムと全く同様にして作製した。また、同様に、試料Ｎｏ．２の転写フィルムを用いた透明導電積層体を作製した。 Sample No. 2 transfer film, except that Zeonex 480R (made by Nippon Zeon Co., Ltd., solid content: 100 wt%), which is a cyclic olefin resin, was used instead of Zeonex 330R as a release resin composition for forming a release layer. Sample No. 1 was produced in the same manner as the transfer film No. 1. Similarly, Sample No. A transparent conductive laminate using the transfer film 2 was prepared.
試料Ｎｏ．３の転写フィルムは、離型層を形成するための離型樹脂組成物として、ゼオネックス３３０Ｒに代えて、環状オレフィン樹脂であるアートンＦ４５２０（ＪＳＲ株式会社製、固形分量１００ｗｔ％）を用いた以外は、試料Ｎｏ．１の転写フィルムと全く同様にして作製した。また、同様に、試料Ｎｏ．３の転写フィルムを用いた透明導電積層体を作製した。 Sample No. The transfer film of No. 3 was used except that AEONON F4520 (manufactured by JSR Corporation, solid content: 100 wt%), which is a cyclic olefin resin, was used instead of ZEONEX 330R as a release resin composition for forming a release layer. Sample No. 1 was produced in the same manner as the transfer film No. 1. Similarly, Sample No. A transparent conductive laminate using the transfer film 3 was prepared.
試料Ｎｏ．４の転写フィルムは、離型層を形成するための離型樹脂組成物として、ゼオネックス３３０Ｒに代えて、環状オレフィン樹脂であるアートンＤ４５４０（ＪＳＲ株式会社製、固形分量１００ｗｔ％）用いた以外は、試料Ｎｏ．１の転写フィルムと全く同様にして作製した。また、同様に、試料Ｎｏ．４の転写フィルムを用いた透明導電積層体を作製した。 Sample No. The transfer film No. 4 was used as a release resin composition for forming a release layer, except that Arton D4540 (manufactured by JSR Corporation, solid content: 100 wt%), which is a cyclic olefin resin, was used instead of Zeonex 330R. Sample No. 1 was produced in the same manner as the transfer film No. 1. Similarly, Sample No. A transparent conductive laminate using the transfer film No. 4 was prepared.
試料Ｎｏ．５の転写フィルムは、離型層を形成するための離型樹脂組成物として、ゼオネックス３３０Ｒに代えて、環状オレフィン樹脂であるアペルＡＰＬ５０１４ＤＰ（三井化学株式会社製、固形分量１００ｗｔ％）を用いた以外は、試料Ｎｏ．１の転写フィルムと全く同様にして作製した。また、同様に、試料Ｎｏ．５の転写フィルムを用いた透明導電積層体を作製した。 Sample No. The transfer film of No. 5 was replaced with ZEONEX 330R as a release resin composition for forming a release layer, except that Apel APL5014DP (made by Mitsui Chemicals, solid content: 100 wt%), which is a cyclic olefin resin, was used. Sample No. 1 was produced in the same manner as the transfer film No. 1. Similarly, Sample No. A transparent conductive laminate using the transfer film No. 5 was prepared.
試料Ｎｏ．６の転写フィルムは、離型層を形成するための離型樹脂組成物として、アクリル系樹脂（固形分量１００ｗｔ％）５重量部に対し、トルエン３０重量部、メチルエチルケトン５０重量部、シクロヘキサノン１５重量部、フッ素系添加剤（固形分量１００ｗｔ％）０．００５重量部を添加した組成とした離型樹脂組成物を用いた。これ以外は、試料Ｎｏ．１の転写フィルムと全く同様にして、試料Ｎｏ．６の転写フィルムを作製した。また、同様に、試料Ｎｏ．６の転写フィルムを用いた透明導電積層体を作製した。 Sample No. 6 is a release resin composition for forming a release layer. To 5 parts by weight of an acrylic resin (solid content: 100 wt%), 30 parts by weight of toluene, 50 parts by weight of methyl ethyl ketone, and 15 parts by weight of cyclohexanone. A release resin composition having a composition to which 0.005 part by weight of a fluorine-based additive (solid content: 100 wt%) was added was used. Other than this, sample no. In the same manner as in the transfer film of Sample No. 1, 6 transfer film was produced. Similarly, Sample No. A transparent conductive laminate using the transfer film No. 6 was prepared.
試料Ｎｏ．７の転写フィルムは、離型層を形成するための離型樹脂組成物として、アクリル系樹脂（固形分量１００ｗｔ％）５重量部に代えて樹脂を、アクリル系樹脂（固形分量１００ｗｔ％）２．５重量部およびメラミン系樹脂（固形分量１００ｗｔ％）２．５重量部とした離型樹脂組成物を用いた以外は、試料Ｎｏ．６の転写フィルムと全く同様にして作製した。また、同様に、試料Ｎｏ．７の転写フィルムを用いた透明導電積層体を作製した。 Sample No. 7 is a release resin composition for forming a release layer. Instead of 5 parts by weight of an acrylic resin (solid content: 100 wt%), an acrylic resin (solid content: 100 wt%) is used. Sample No. 5 was used except that a release resin composition having 5 parts by weight and 2.5 parts by weight of melamine-based resin (solid content: 100 wt%) was used. 6 was produced in the same manner as the transfer film No. 6. Similarly, Sample No. A transparent conductive laminate using the transfer film of No. 7 was produced.
試料Ｎｏ．８の転写フィルムは、離型層を形成するための離型樹脂組成物として、アクリル系樹脂（固形分量１００ｗｔ％）５重量部に代えて樹脂を、シリコーン系樹脂（固形分量１００ｗｔ％）５重量部とした離型樹脂組成物を用いた以外は、試料Ｎｏ．６の転写フィルムと全く同様にして作製した。また、同様に、試料Ｎｏ．８の転写フィルムを用いた透明導電積層体を作製した。 Sample No. The transfer film of No. 8 is a release resin composition for forming a release layer. Instead of 5 parts by weight of an acrylic resin (solid content: 100 wt%), the resin is replaced with a silicone resin (solid content: 100 wt%) of 5 wt. Sample No. except that the release resin composition as the part was used. 6 was produced in the same manner as the transfer film No. 6. Similarly, Sample No. A transparent conductive laminate using the transfer film of No. 8 was produced.
試料Ｎｏ．９の転写フィルムは、離型層を形成するための離型樹脂組成物として、アクリル系樹脂（固形分量１００ｗｔ％）５重量部に代えて樹脂を、ワックス系樹脂（固形分量１００ｗｔ％）５重量部とした離型樹脂組成物を用いた以外は、試料Ｎｏ．６の転写フィルムと全く同様にして作製した。また、同様に、試料Ｎｏ．９の転写フィルムを用いた透明導電積層体を作製した。 Sample No. 9 is a release resin composition for forming a release layer. Instead of 5 parts by weight of an acrylic resin (solid content 100 wt%), a resin is used as a wax resin (solid content 100 wt%) 5 wt. Sample No. except that the release resin composition as the part was used. 6 was produced in the same manner as the transfer film No. 6. Similarly, Sample No. A transparent conductive laminate using the transfer film of No. 9 was produced.
以上により得られた試料Ｎｏ．１〜９の９種類の転写フィルム、およびこれらを用いた透明導電積層体について、評価した。評価としては、接着剤層形成前の転写フィルムの透明導電層のシート抵抗値Ｒ０、転写後の透明導電積層体のシート抵抗値Ｒを測定し、Ｒ／Ｒ０から転写前後のシート抵抗変化率を求めた。なお、本発明の転写フィルムにおいては、転写前後のシート抵抗変化率が１．１未満であるものを得ることを目標とし、この目標に達しない試料を、本発明の範囲外のものとした。また、転写後の透明導電積層体の全光線透過率を評価した。評価結果を、転写フィルムの離型樹脂組成物の内容とともに、（表１）に示す。 Sample No. obtained as described above was obtained. Nine types of transfer films 1 to 9 and transparent conductive laminates using these were evaluated. For evaluation, the sheet resistance value R 0 of the transparent conductive layer of the transfer film before forming the adhesive layer and the sheet resistance value R of the transparent conductive laminate after transfer were measured, and the sheet resistance change before and after transfer from R / R 0. The rate was determined. In the transfer film of the present invention, the objective was to obtain a sheet resistance change rate before and after transfer of less than 1.1, and samples that did not reach this target were out of the scope of the present invention. Moreover, the total light transmittance of the transparent conductive laminated body after transfer was evaluated. An evaluation result is shown in (Table 1) with the content of the mold release resin composition of a transfer film.
なお、それぞれの評価は、次のようにして行った。シート抵抗値は、（株）三菱化学アナリテック製表面抵抗測定器ＭＣＰ−Ｔ６１０を用いて、ＪＩＳ Ｋ７１９４に準じて、四端子法により測定した。電圧端子間距離は５ｍｍとした。 In addition, each evaluation was performed as follows. The sheet resistance value was measured by a four-terminal method according to JIS K7194 using a surface resistance measuring device MCP-T610 manufactured by Mitsubishi Chemical Analytech. The distance between the voltage terminals was 5 mm.
また、全光線透過率は、日本電色工業（株）製ＮＤＨ−４０００を用い、ＪＩＳ Ｋ７３６１−１に準じて、入射光強度に対する透過光強度の割合を全光線透過率として測定した。透明導電層側を入射光側として測定した。 Further, the total light transmittance was measured by using NDH-4000 manufactured by Nippon Denshoku Industries Co., Ltd., and the ratio of the transmitted light intensity to the incident light intensity was measured as the total light transmittance according to JIS K7361-1. The transparent conductive layer side was measured as the incident light side.
（表１）の評価結果に示したように、試料Ｎｏ．１〜５の転写フィルムは、いずれも、シート抵抗値が５０Ω／□であり、極めて低抵抗値であった。また、試料Ｎｏ．１〜５の転写フィルムを用いて作製した透明導電積層体は、いずれも、転写前後のシート抵抗変化率が１．１未満であり極めて小さく、剥離性および転写性が優れていることが確認できた。そして、試料Ｎｏ．１〜５の転写フィルムを用いて作製した透明導電積層体は、いずれも、全光線透過率が８８％であり、透明性が高く低抵抗値の透明導電層を、被転写体の表面に有する積層体が得られた。 As shown in the evaluation results of (Table 1), sample No. All of the transfer films 1 to 5 had a sheet resistance value of 50Ω / □ and an extremely low resistance value. Sample No. It can be confirmed that all of the transparent conductive laminates produced using the transfer films 1 to 5 have an extremely small sheet resistance change rate before and after transfer of less than 1.1, and are excellent in peelability and transferability. It was. And sample no. Each of the transparent conductive laminates produced using the transfer films 1 to 5 has a total light transmittance of 88%, and has a transparent conductive layer with high transparency and low resistance on the surface of the transfer target. A laminate was obtained.
一方、試料Ｎｏ．６〜９の転写フィルムは、いずれも、試料Ｎｏ．１〜５の転写フィルムに比較してシート抵抗値が大であった。また、試料Ｎｏ．６〜９の転写フィルムを用いて作成した透明導電性積層体は、シート抵抗値が大きすぎたため測定することができなかった。これは、試料Ｎｏ．６〜９の転写フィルムは、いずれも、剥離性、転写性が悪く、透明導電層が十分に転写できていないためである。また、試料Ｎｏ．６および試料Ｎｏ．７の転写フィルムを用いて作成した透明導電性積層体は、全光線透過率が９１％であることから判断しても、剥離性、転写性が悪く、透明導電層が転写できていないことが分かった。 On the other hand, sample No. As for the transfer films of 6-9, all are sample No.2. The sheet resistance value was large as compared with the transfer films of 1 to 5. Sample No. The transparent conductive laminate produced using the transfer films of 6 to 9 could not be measured because the sheet resistance value was too large. This is the sample No. This is because all of the transfer films 6 to 9 have poor peelability and transferability, and the transparent conductive layer cannot be transferred sufficiently. Sample No. 6 and sample no. The transparent conductive laminate produced using the transfer film of No. 7 has poor peelability and transferability even when judged from the total light transmittance of 91%, and the transparent conductive layer cannot be transferred. I understood.
本実施例２においては、上記実施例１で作製した透明導電積層体に、さらに、透明導電層の上に透明導電性の金属酸化物膜を形成して透明導電積層体を作製し、これらを評価した。 In this Example 2, a transparent conductive laminate is produced by forming a transparent conductive metal oxide film on the transparent conductive layer on the transparent conductive laminate produced in Example 1 above. evaluated.
はじめに、試料Ｎｏ．１１の透明導電積層体は、上記実施例１で作製した試料Ｎｏ．１の透明導電積層体に、さらに、透明導電性の金属酸化物膜として、酸化インジウムを膜厚が２０ｎｍになるようにスパッタリングして形成し、透明導電積層体を作製した。 First, sample no. The transparent conductive laminate of No. 11 is the sample No. 1 prepared in Example 1 above. 1 was formed by sputtering indium oxide so that the film thickness was 20 nm as a transparent conductive metal oxide film, thereby producing a transparent conductive laminate.
試料Ｎｏ．１２の透明導電積層体は、上記実施例１で作製した試料Ｎｏ．２の透明導電積層体に、さらに、透明導電性の金属酸化物膜として、酸化インジウムを膜厚が２０ｎｍになるようにスパッタリングして形成し、透明導電積層体を作製した。 Sample No. The transparent conductive laminate of No. 12 was manufactured using Sample No. 1 prepared in Example 1 above. The transparent conductive laminate of No. 2 was further formed by sputtering indium oxide as a transparent conductive metal oxide film so as to have a film thickness of 20 nm, thereby producing a transparent conductive laminate.
試料Ｎｏ．１３の透明導電積層体は、透明導電性の金属酸化物膜を形成せず、上記実施例１で作製した試料Ｎｏ．１の透明導電積層体をそのまま用いた。 Sample No. The transparent conductive laminate of No. 13 does not form a transparent conductive metal oxide film, but the sample No. 13 prepared in Example 1 above. 1 transparent conductive laminate was used as it was.
以上により準備した試料Ｎｏ．１１〜１３の３種類の透明導電積層体について、評価した。評価としては、酸化インジウムを積層した後の透明導電積層体のシート抵抗値Ｒ１を測定した。さらに評価として、レーザーエッチング法により、透明導電層をエッチングして、ライン幅３０μｍ、長さ５０ｍｍの細線導体パターンを形成し、この細線導体パターンの導電性を評価した。導電性の評価は、細線導体パターンの抵抗値をデジタルマルチメータで測定して、１ＭΩ未満の導通性が取れるものを○とし、１ＭΩ以上で導通性がないものを×とした。評価結果を、（表２）に示す。 Sample No. prepared as described above. Three types of transparent conductive laminates 11 to 13 were evaluated. The evaluation was measured sheet resistance value R 1 of the transparent conductive laminate after the laminating indium oxide. Further, as an evaluation, the transparent conductive layer was etched by a laser etching method to form a fine line conductor pattern having a line width of 30 μm and a length of 50 mm, and the conductivity of the fine line conductor pattern was evaluated. For the evaluation of electrical conductivity, the resistance value of the thin wire conductor pattern was measured with a digital multimeter, and the case where the electrical conductivity was less than 1 MΩ could be taken as “◯”, and the case where the electrical conductivity was 1 MΩ or higher and there was no electrical conductivity was rated as “X”. The evaluation results are shown in (Table 2).
なお、レーザーエッチング法によるエッチングは、波長１０６４ｎｍ、周波数５０Ｈｚのファイバーレーザーを用いて、２．０Ｗの出力でエッチングを行った。 Note that the etching by the laser etching method was performed using a fiber laser having a wavelength of 1064 nm and a frequency of 50 Hz with an output of 2.0 W.
（表２）の評価結果に示したように、試料Ｎｏ．１１、および１２の透明導電積層体は、いずれも、透明導電層の上に金属酸化物膜を形成しているので、レーザーエッチングにより形成した細線導体パターンでも導通が確保できた。一方、透明導電層の上に金属酸化物膜を形成していない試料Ｎｏ．１３の透明導電積層体は、細線導体パターンでは導通が得られなかった。 As shown in the evaluation results of (Table 2), sample No. In each of the transparent conductive laminates 11 and 12, the metal oxide film was formed on the transparent conductive layer, so that conduction was ensured even with the fine wire conductor pattern formed by laser etching. On the other hand, Sample No. in which no metal oxide film was formed on the transparent conductive layer. As for the transparent conductive laminate of No. 13, conduction was not obtained with the fine conductor pattern.
以上のように、被転写体の表面に透明導電層を形成した上記の透明導電積層体に、さらに、透明導電層の上に透明導電性の金属酸化物膜を形成することにより、金属ナノワイヤだけでは不均一である微小領域で導電性を均一化することが可能となり、微小領域でのより安定した導電性が得られる。これにより、透明導電層をパターニングした場合でも良好な導電性が得られ、細線導体パターンの形成が可能となる。 As described above, by forming a transparent conductive metal oxide film on the transparent conductive layer on the transparent conductive layered body in which the transparent conductive layer is formed on the surface of the transfer object, only the metal nanowires are formed. Then, it becomes possible to make the conductivity uniform in a minute region which is not uniform, and more stable conductivity can be obtained in the minute region. Thereby, even when the transparent conductive layer is patterned, good conductivity is obtained, and a thin conductor pattern can be formed.
本発明に係る転写フィルム、およびこの転写フィルムを用いた透明導電積層体の製造方法は、低抵抗値、柔軟性、転写性の各特性を満足する透明導電層を有する転写フィルムであり、比較的簡易に、被転写体の表面に低抵抗値の透明導電層を形成することができ、例えば、タッチセンサー等の用途に適した透明導電層を形成する方法として、特に有用である。
The transfer film according to the present invention and the method for producing a transparent conductive laminate using the transfer film are transfer films having a transparent conductive layer that satisfies the properties of low resistance, flexibility, and transferability, A transparent conductive layer having a low resistance value can be easily formed on the surface of the transfer object, and is particularly useful as a method for forming a transparent conductive layer suitable for applications such as a touch sensor.
Claims (4)
Using the transfer film according to claim 1, the transparent conductive layer side of the transfer film is bonded to the surface of the transfer target body via an adhesive layer, and then the base film is peeled off, whereby the surface of the transfer target is transferred. A conductive pattern is formed by forming a transparent conductive layer, further forming a transparent conductive metal oxide film on the transparent conductive layer, and then removing a part of the transparent conductive layer and the metal oxide film. A process for producing a transparent conductive laminate, characterized in that is formed.
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