JP2017117749A - Transparent conductive film - Google Patents
Transparent conductive film Download PDFInfo
- Publication number
- JP2017117749A JP2017117749A JP2015254982A JP2015254982A JP2017117749A JP 2017117749 A JP2017117749 A JP 2017117749A JP 2015254982 A JP2015254982 A JP 2015254982A JP 2015254982 A JP2015254982 A JP 2015254982A JP 2017117749 A JP2017117749 A JP 2017117749A
- Authority
- JP
- Japan
- Prior art keywords
- resin layer
- conductive film
- transparent
- transparent conductive
- transparent substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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Landscapes
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Abstract
Description
本発明は、透明導電性フィルムに関する。 The present invention relates to a transparent conductive film.
従来、透明導電性フィルムはタッチパネル等の電子機器部品の電極、電子機器の誤作動の原因となる電磁波を遮断する電磁波シールド等に使用されている。透明導電性フィルムは、ＩＴＯなどの金属酸化物層や、金属ナノワイヤ、金属メッシュ等から構成された導電層を形成する方法が提案されている（例えば、特許文献１、２）。このような導電層、特に金属ナノワイヤを含む導電層には、導電層形成材料の保護のため、保護層を形成することが行われている。 Conventionally, transparent conductive films are used for electrodes of electronic device parts such as touch panels, electromagnetic wave shields that block electromagnetic waves that cause malfunction of electronic devices, and the like. For the transparent conductive film, a method of forming a conductive layer composed of a metal oxide layer such as ITO, a metal nanowire, a metal mesh, or the like has been proposed (for example, Patent Documents 1 and 2). In order to protect the conductive layer forming material, a protective layer is formed on such a conductive layer, particularly a conductive layer including metal nanowires.
保護層の表面から導通を得るためには、保護層の厚みを薄くする必要があるが、保護層の厚みを薄くすると、透明導電性フィルムの耐擦傷性が低下したり、信頼性が損なわれたりするという問題がある。一方、保護層の厚みを厚くすると、電気接続用の配線や金属ペーストとの接触抵抗が高くなったり、それらと導通がとれないという問題が生じる。このように、耐擦傷性に優れ、かつ、導電性に優れる透明導電性フィルム（特に、金属ナノワイヤを含む透明導電性フィルム）を実現することは困難である。 In order to obtain conduction from the surface of the protective layer, it is necessary to reduce the thickness of the protective layer. However, reducing the thickness of the protective layer reduces the scratch resistance of the transparent conductive film or impairs the reliability. There is a problem that. On the other hand, when the thickness of the protective layer is increased, there arises a problem that the contact resistance with the wiring for electrical connection or the metal paste is increased or the electrical connection cannot be established. As described above, it is difficult to realize a transparent conductive film (in particular, a transparent conductive film containing metal nanowires) having excellent scratch resistance and excellent conductivity.
本発明は上記の課題を解決するためになされたものであり、その目的とするところは、耐擦傷性および導電性の両方に優れる透明導電性フィルムを提供することにある。 The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a transparent conductive film excellent in both scratch resistance and conductivity.
本発明の導電性フィルムは、透明基材と、透明基材の片面または両面に配置される樹脂層とを備え、透明基材と樹脂層との界面近傍に、金属ナノワイヤを含む導電領域が形成され、該樹脂層が、導電粒子を含み、該導電粒子の少なくとも一部が、該樹脂層の該透明基材側において、金属ナノワイヤと接触し、該導電粒子が、該樹脂層の該透明基材とは反対側において、該樹脂層から突出している。
１つの実施形態においては、上記樹脂層が、前記金属ナノワイヤを覆うようにして形成されている。
１つの実施形態においては、上記導電領域の少なくとも一部が、上記透明基材中に存在する。
１つの実施形態においては、上記導電領域が、上記樹脂層中にのみ存在する。
１つの実施形態においては、上記導電粒子の平均粒径Ｘと、上記樹脂層の厚みＹとが、Ｙ≦Ｘ≦２０Ｙの関係を満たす。
１つの実施形態においては、上記導電粒子の平均一次粒径が５ｎｍ〜１００μｍである。
１つの実施形態においては、上記導電粒子の含有割合が、上記樹脂層を構成するバインダー樹脂１００重量部に対し、０．１重量部〜２０重量部である。
１つの実施形態においては、上記導電粒子が、銀粒子である。
本発明の別の局面に依れば、光学積層体が提供される。この光学積層体は、上記透明導電性フィルムと偏光板とを含む。
The conductive film of the present invention includes a transparent substrate and a resin layer disposed on one or both sides of the transparent substrate, and a conductive region including metal nanowires is formed in the vicinity of the interface between the transparent substrate and the resin layer. The resin layer contains conductive particles, and at least a part of the conductive particles are in contact with the metal nanowires on the transparent substrate side of the resin layer, and the conductive particles are in contact with the transparent group of the resin layer. It protrudes from the resin layer on the side opposite to the material.
In one embodiment, the resin layer is formed so as to cover the metal nanowire.
In one embodiment, at least a part of the conductive region is present in the transparent substrate.
In one embodiment, the conductive region exists only in the resin layer.
In one embodiment, the average particle diameter X of the conductive particles and the thickness Y of the resin layer satisfy the relationship of Y ≦ X ≦ 20Y.
In one embodiment, the average primary particle diameter of the conductive particles is 5 nm to 100 μm.
In one embodiment, the content rate of the said electrically-conductive particle is 0.1 weight part-20 weight part with respect to 100 weight part of binder resin which comprises the said resin layer.
In one embodiment, the conductive particles are silver particles.
According to another aspect of the present invention, an optical laminate is provided. This optical laminate includes the transparent conductive film and a polarizing plate.
本発明によれば、耐擦傷性および導電性の両方に優れる透明導電性フィルムを提供することができる。 According to the present invention, it is possible to provide a transparent conductive film excellent in both scratch resistance and conductivity.
Ａ．透明導電性フィルムの全体構成
図１は、本発明の１つの実施形態による透明導電性フィルムの概略断面図である。透明導電性フィルム１００は、透明基材１０と、透明基材１０の片面または両面（図示例では片面）に配置される樹脂層２０とを備える。透明基材１０と樹脂層２０との界面近傍には、導電領域３０が形成される。導電領域３０は、金属ナノワイヤ１を含む。また、樹脂層２０は、導電粒子２を含む。導電粒子２の少なくとも一部は、樹脂層２０の透明基材１０側において、金属ナノワイヤ１と接触する。一方、樹脂層２０の透明基材１０とは反対側においては、導電粒子２が、樹脂層２０から突出している。なお、樹脂層２０は、金属ナノワイヤ１を保護する保護層として機能し、好ましくは、金属ナノワイヤ１を覆うようにして形成されている。
A. Overall Configuration of Transparent Conductive Film FIG. 1 is a schematic sectional view of a transparent conductive film according to one embodiment of the present invention. The transparent conductive film 100 includes a transparent substrate 10 and a resin layer 20 disposed on one or both surfaces (one surface in the illustrated example) of the transparent substrate 10. A conductive region 30 is formed in the vicinity of the interface between the transparent substrate 10 and the resin layer 20. The conductive region 30 includes the metal nanowire 1. The resin layer 20 includes the conductive particles 2. At least a part of the conductive particles 2 is in contact with the metal nanowire 1 on the transparent substrate 10 side of the resin layer 20. On the other hand, the conductive particles 2 protrude from the resin layer 20 on the opposite side of the resin layer 20 from the transparent substrate 10. The resin layer 20 functions as a protective layer for protecting the metal nanowire 1, and is preferably formed so as to cover the metal nanowire 1.
本発明においては、上記導電粒子と金属ナノワイヤとを接触させ、かつ、導電粒子を樹脂層から突出させることにより、透明導電性フィルムの表面において良好に導通をとることができる。また、接触抵抗を低くすることができる。さらに、樹脂層が金属ナノワイヤを保護し得るところ、本願発明においては、表出する導電粒子を含むことにより、保護層としての樹脂層の厚みを厚くすることができる。その結果、耐擦傷性に優れる透明導電性フィルムを得ることができる。また、金属ナノワイヤの劣化、具体的には、空気中の腐食成分による劣化を防ぐことができ、耐久性に優れ、導電性を経時にわたり維持し得る透明導電性フィルムを得ることができる。保護層としての樹脂層を厚くして耐擦傷性を高めつつも、導電性に優れ、表面からの導通を確保でき、かつ、接触抵抗の低い透明導電性フィルムを実現し得たことは、本発明の成果のひとつである。樹脂層から突出する導電粒子の突出高さＺは、好ましくは１ｎｍ〜１０μｍであり、より好ましくは３ｎｍ〜７μｍである。 In the present invention, electrical conduction can be satisfactorily achieved on the surface of the transparent conductive film by bringing the conductive particles into contact with the metal nanowires and causing the conductive particles to protrude from the resin layer. Further, the contact resistance can be lowered. Furthermore, where the resin layer can protect the metal nanowires, in the present invention, by including the exposed conductive particles, the thickness of the resin layer as the protective layer can be increased. As a result, a transparent conductive film excellent in scratch resistance can be obtained. Moreover, deterioration of metal nanowires, specifically, deterioration due to corrosive components in the air can be prevented, and a transparent conductive film excellent in durability and capable of maintaining conductivity over time can be obtained. The fact that we were able to realize a transparent conductive film with excellent electrical conductivity, electrical conductivity from the surface, and low contact resistance while increasing the scratch resistance by thickening the resin layer as the protective layer. It is one of the achievements of the invention. The protruding height Z of the conductive particles protruding from the resin layer is preferably 1 nm to 10 μm, more preferably 3 nm to 7 μm.
１つの実施形態においては、図１に示すように、導電領域３０の少なくとも一部が、上記透明基材１０中に存在する。より具体的には、導電領域３０に含まれる金属ナノワイヤ１が、樹脂層２０と透明基材１０との界面近傍において、樹脂層２０および透明基材１０の両方に存在する。金属ナノワイヤ１が透明基材１０に含まれるようにすれば、耐擦傷性が顕著に優れる透明導電性フィルムを得ることができる。 In one embodiment, as shown in FIG. 1, at least a part of the conductive region 30 is present in the transparent substrate 10. More specifically, the metal nanowire 1 included in the conductive region 30 exists in both the resin layer 20 and the transparent substrate 10 in the vicinity of the interface between the resin layer 20 and the transparent substrate 10. If the metal nanowire 1 is contained in the transparent base material 10, a transparent conductive film having remarkably excellent scratch resistance can be obtained.
また、図示していないが、導電粒子の少なくとも一部が、透明基材中に存在していてもよい。このようにして導電粒子が存在しいていれば、耐擦傷性が顕著に優れる透明導電性フィルムを得ることができる。 Although not shown, at least a part of the conductive particles may be present in the transparent substrate. If the conductive particles are present in this way, a transparent conductive film having remarkably excellent scratch resistance can be obtained.
図２は、本発明の別の実施形態よる透明導電性フィルムの概略断面図である。透明導電性フィルム２００において、導電領域３０は、樹脂層２０中にのみ存在する。 FIG. 2 is a schematic cross-sectional view of a transparent conductive film according to another embodiment of the present invention. In the transparent conductive film 200, the conductive region 30 exists only in the resin layer 20.
上記導電領域は、例えば、金属ナノワイヤを含む樹脂層形成用組成物を透明基材上に塗工する等の方法により形成させることができる。詳細は後述する。 The conductive region can be formed by, for example, a method of coating a resin layer forming composition containing metal nanowires on a transparent substrate. Details will be described later.
上記導電領域の厚さは、好ましくは１０ｎｍ〜２０μｍである。導電領域の少なくとも一部が、上記透明基材中に存在する場合、透明基材における導電領域の厚みは、好ましくは１ｎｍ〜１９μｍであり、より好ましくは２ｎｍ〜１５μｍである。また、導電領域の少なくとも一部が、上記透明基材中に存在する場合、樹脂層における導電領域の厚みは、好ましくは１ｎｍ〜１９μｍであり、より好ましくは２ｎｍ〜１５μｍである。本明細書において、導電領域とは、上記のとおり、金属ナノワイヤが含まれる領域を意味し、したがって、導電領域の厚さとは、厚み方向において金属ナノワイヤが存在する領域の最上部と最下部に挟まれた領域の厚さを意味する。上記導電領域は、例えばフィルムをエポキシ樹脂にて包埋処理後ウルトラマイクロトームで切削することで断面を形成し、走査型電子顕微鏡を使用して観察することが可能である。 The thickness of the conductive region is preferably 10 nm to 20 μm. When at least a part of the conductive region is present in the transparent base material, the thickness of the conductive region in the transparent base material is preferably 1 nm to 19 μm, more preferably 2 nm to 15 μm. Moreover, when at least one part of an electroconductive area | region exists in the said transparent base material, the thickness of the electroconductive area | region in a resin layer becomes like this. Preferably it is 1 nm-19 micrometers, More preferably, it is 2 nm-15 micrometers. In this specification, the conductive region means a region including metal nanowires as described above, and thus the thickness of the conductive region is sandwiched between the uppermost part and the lowermost part of the region where the metal nanowires exist in the thickness direction. Means the thickness of the defined area. The conductive region can be observed using, for example, a scanning electron microscope by forming a cross section by cutting the film with an epoxy resin and then cutting with an ultramicrotome.
本発明の透明導電性フィルムの表面抵抗値は、好ましくは０．１Ω／□〜１０００Ω／□であり、より好ましくは０．５Ω／□〜３００Ω／□であり、特に好ましくは１Ω／□〜２００Ω／□である。 The surface resistance value of the transparent conductive film of the present invention is preferably 0.1Ω / □ to 1000Ω / □, more preferably 0.5Ω / □ to 300Ω / □, and particularly preferably 1Ω / □ to 200Ω. / □.
本発明の透明導電性フィルムのヘイズ値は、好ましくは２０％以下であり、より好ましくは１０％以下であり、さらに好ましくは０．１％〜５％である。 The haze value of the transparent conductive film of the present invention is preferably 20% or less, more preferably 10% or less, and further preferably 0.1% to 5%.
本発明の透明導電性フィルムの全光線透過率は、好ましくは３０％以上であり、より好ましくは３５％以上であり、特に好ましくは４０％以上である。 The total light transmittance of the transparent conductive film of the present invention is preferably 30% or more, more preferably 35% or more, and particularly preferably 40% or more.
Ｂ．樹脂層
上記樹脂層は、バインダー樹脂と、導電粒子とを含む。また、上記樹脂層は、導電領域の少なくとも一部を含む。したがって、上記樹脂層は、金属ナノワイヤを含む。
B. Resin Layer The resin layer includes a binder resin and conductive particles. The resin layer includes at least a part of the conductive region. Therefore, the resin layer includes metal nanowires.
上記のとおり、樹脂層が、金属ナノワイヤを覆うようにして形成されていることが好ましい。より具体的には、上記樹脂層は、導電領域を含む層（すなわち、金属ナノワイヤを含む層；図１および図２における層２１）と、金属ナノワイヤを実質的に含まない層（図１および図２における層２２）とから構成されていることが好ましい。金属ナノワイヤを実質的に含まない層は、樹脂層の透明基材とは反対側に形成される。金属ナノワイヤを実質的に含まない層を形成することにより、金属ナノワイヤを有効に保護することができ、耐擦傷性に優れる透明導電性フィルムを得ることができる。上記のような多層構成の樹脂層は、例えば、金属ナノワイヤを含む樹脂層形成用組成物を塗工した後に、金属ナノワイヤを含まない樹脂層形成用組成物を塗工して形成することができる。詳細は、後述する。なお、本明細書において、「金属ナノワイヤを実質的に含まない層」とは、金属ナノワイヤの含有割合が、樹脂層を構成するバインダー樹脂１００重量部に対して、０．１重量部未満である層のことを意味する。 As described above, the resin layer is preferably formed so as to cover the metal nanowires. More specifically, the resin layer includes a layer including a conductive region (that is, a layer including metal nanowires; a layer 21 in FIGS. 1 and 2) and a layer substantially free from metal nanowires (FIGS. 1 and 2). 2). The layer substantially free of metal nanowires is formed on the opposite side of the resin layer from the transparent substrate. By forming a layer substantially free of metal nanowires, the metal nanowires can be effectively protected, and a transparent conductive film excellent in scratch resistance can be obtained. The resin layer having a multilayer structure as described above can be formed, for example, by applying a resin layer forming composition containing metal nanowires and then applying a resin layer forming composition not containing metal nanowires. . Details will be described later. In the present specification, the “layer substantially free of metal nanowires” means that the content of metal nanowires is less than 0.1 parts by weight with respect to 100 parts by weight of the binder resin constituting the resin layer. It means a layer.
上記樹脂層の厚みＹは、好ましくは０．１５μｍ〜５μｍであり、より好ましくは０．１５μｍ〜３μｍであり、さらに好ましくは０．１５μｍ〜２μｍである。なお、本明細書において、樹脂層の厚みＹとは、図１に示すように、樹脂層の一方の平坦面から他方の平坦面までの距離であり、言い換えれば、導電粒子の突出部を除外したと仮定した場合の樹脂層の厚みを意味する。本発明においては、導電粒子により導通を確保することができるため、樹脂層を比較的厚くすることができる。その結果、耐擦傷性および耐久性に優れる透明導電性フィルムを得ることができる。 The thickness Y of the resin layer is preferably 0.15 μm to 5 μm, more preferably 0.15 μm to 3 μm, and still more preferably 0.15 μm to 2 μm. In this specification, the thickness Y of the resin layer is a distance from one flat surface of the resin layer to the other flat surface, as shown in FIG. 1, in other words, excluding protruding portions of the conductive particles. This means the thickness of the resin layer when it is assumed. In the present invention, since conduction can be ensured by the conductive particles, the resin layer can be made relatively thick. As a result, a transparent conductive film excellent in scratch resistance and durability can be obtained.
樹脂層における、上記金属ナノワイヤを実質的に含まない層の厚みは、好ましくは０．１０μｍ〜４．５０μｍであり、より好ましくは０．２０μｍ〜３．００μｍである。このような範囲であれば、耐擦傷性に優れる透明導電性フィルムを得ることができる。 The thickness of the resin layer that does not substantially contain the metal nanowire is preferably 0.10 μm to 4.50 μm, and more preferably 0.20 μm to 3.00 μm. If it is such a range, the transparent conductive film which is excellent in abrasion resistance can be obtained.
上記樹脂層の全光線透過率は、好ましくは８５％以上であり、より好ましくは９０％以上であり、さらに好ましくは９５％以上である。 The total light transmittance of the resin layer is preferably 85% or more, more preferably 90% or more, and further preferably 95% or more.
Ｂ−１．バインダー樹脂
上記バインダー樹脂としては、任意の適切な樹脂が用いられ得る。該樹脂としては、例えば、アクリル系樹脂；ポリエチレンテレフタレート等のポリエステル系樹脂；ポリスチレン、ポリビニルトルエン、ポリビニルキシレン、ポリイミド、ポリアミド、ポリアミドイミド等の芳香族系樹脂；ポリウレタン系樹脂；エポキシ系樹脂；ポリオレフィン系樹脂；アクリロニトリル−ブタジエン−スチレン共重合体（ＡＢＳ）；セルロース；シリコン系樹脂；ポリ塩化ビニル；ポリアセテート；ポリノルボルネン；合成ゴム；フッ素系樹脂等が挙げられる。
B-1. Binder resin Any appropriate resin may be used as the binder resin. Examples of the resin include acrylic resins; polyester resins such as polyethylene terephthalate; aromatic resins such as polystyrene, polyvinyltoluene, polyvinylxylene, polyimide, polyamide, and polyamideimide; polyurethane resins; epoxy resins; Resin; Acrylonitrile-butadiene-styrene copolymer (ABS); Cellulose; Silicon resin; Polyvinyl chloride; Polyacetate; Polynorbornene; Synthetic rubber;
１つの実施形態においては、上記バインダー樹脂として、硬化性樹脂が用いられる。該硬化性樹脂は多官能モノマーを含むモノマー組成物から得られ得る。多官能モノマーとしては、例えば、トリシクロデカンジメタノールジアクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリメチロールプロパントリアクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジメチロールプロパントテトラアクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、１，６−ヘキサンジオール（メタ）アクリレート、１，９−ノナンジオールジアクリレート、１,１０−デカンジオール（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジアクリレート、イソシアヌル酸トリ（メタ）アクリレート、エトキシ化グリセリントリアクリレート、エトキシ化ペンタエリスリトールテトラアクリレート等が挙げられる。多官能モノマーは、単独で用いてもよく、複数を組み合わせて用いてもよい。 In one embodiment, a curable resin is used as the binder resin. The curable resin can be obtained from a monomer composition containing a polyfunctional monomer. Examples of the polyfunctional monomer include tricyclodecane dimethanol diacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol tetra (meth) acrylate, and dimethylolpropanthate. Tetraacrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol (meth) acrylate, 1,9-nonanediol diacrylate, 1,10-decanediol (meth) acrylate, polyethylene glycol di (meth) acrylate , Polypropylene glycol di (meth) acrylate, dipropylene glycol diacrylate, isocyanuric acid tri (meth) acrylate, ethoxylated glycerin Examples include triacrylate and ethoxylated pentaerythritol tetraacrylate. A polyfunctional monomer may be used independently and may be used in combination of multiple.
上記モノマー組成物は、単官能モノマーをさらに含んでいてもよい。上記モノマー組成物が単官能モノマーを含む場合、単官能モノマーの含有割合は、モノマー組成物中のモノマー１００重量部に対して、好ましくは４０重量部以下であり、より好ましくは２０重量部以下である。 The monomer composition may further contain a monofunctional monomer. When the monomer composition contains a monofunctional monomer, the content ratio of the monofunctional monomer is preferably 40 parts by weight or less, more preferably 20 parts by weight or less with respect to 100 parts by weight of the monomer in the monomer composition. is there.
上記単官能モノマーとしては、例えば、エトキシ化ｏ−フェニルフェノール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、２−エチルヘキシルアクリレート、ラウリルアクリレート、イソオクチルアクリレート、イソステアリルアクリレート、シクロヘキシルアクリレート、イソホロニルアクリレート、ベンジルアクリレート、２−ヒドロキシ−３−フェノキシアクリレート、アクリロイルモルホリン、２−ヒドロキシエチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、ヒドロキシエチルアクリルアミド等が挙げられる。１つの実施形態においては、上記単官能モノマーとして、水酸基を有するモノマーが用いられる。 Examples of the monofunctional monomer include ethoxylated o-phenylphenol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-ethylhexyl acrylate, lauryl acrylate, isooctyl acrylate, and isostearyl. Examples include acrylate, cyclohexyl acrylate, isophoronyl acrylate, benzyl acrylate, 2-hydroxy-3-phenoxy acrylate, acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and hydroxyethyl acrylamide. . In one embodiment, a monomer having a hydroxyl group is used as the monofunctional monomer.
Ｂ−２．導電粒子
上記樹脂層中での導電粒子は、単粒子として存在していてもよく、凝集体として存在していてもよい。また、単粒子と凝集体とが混在していてもよい。
B-2. Conductive particles The conductive particles in the resin layer may exist as single particles or may exist as aggregates. Single particles and aggregates may be mixed.
上記導電粒子の平均粒径Ｘと、樹脂層の厚みＹとは、Ｙ≦Ｘ≦２０Ｙの関係を満たすことが好ましく、Ｙ≦Ｘ≦１５Ｙの関係を満たすことがより好ましく、Ｙ≦Ｘ≦１０Ｙの関係を満たすことがさらに好ましい。１つの実施形態においては、Ｙ≦Ｘとすることで該導電粒子の一部が、樹脂層から突出し、導通に寄与することができ、より高い導通性を確保できる。一方、Ｘ≦２０Ｙとすることにより、樹脂層中、導電粒子が良好に保持される。なお、本明細書において、単に「平均粒径」という場合、該「平均粒径」は、単粒子として存在する導電粒子の平均粒径（一次粒径）および凝集体として存在する導電粒子の該凝集体の平均粒径（二次粒径）の両方を含む概念である。平均粒径および凝集体を構成する導電粒子の平均一次粒径（後述）は、顕微鏡（例えば、光学顕微鏡、走査型電子顕微鏡または透過型電子顕微鏡）により樹脂層表面あるいは断面像から無作為に抽出した１００個の粒子を観察して測定された粒径のメジアン径（５０％径；数基準）である。 The average particle diameter X of the conductive particles and the thickness Y of the resin layer preferably satisfy the relationship of Y ≦ X ≦ 20Y, more preferably satisfy the relationship of Y ≦ X ≦ 15Y, and Y ≦ X ≦ 10Y It is more preferable to satisfy this relationship. In one embodiment, by setting Y ≦ X, a part of the conductive particles protrudes from the resin layer, can contribute to conduction, and higher conductivity can be secured. On the other hand, by setting X ≦ 20Y, the conductive particles are favorably retained in the resin layer. In the present specification, when simply referred to as “average particle diameter”, the “average particle diameter” means the average particle diameter (primary particle diameter) of conductive particles existing as single particles and the conductive particles existing as aggregates. It is a concept that includes both the average particle size (secondary particle size) of the aggregate. The average particle diameter and the average primary particle diameter of the conductive particles constituting the aggregate (described later) are randomly extracted from the resin layer surface or cross-sectional image with a microscope (for example, an optical microscope, a scanning electron microscope, or a transmission electron microscope). The median diameter (50% diameter; number basis) of the particle diameter measured by observing 100 particles.
上記樹脂層中に存在する導電粒子の平均一次粒径は、好ましくは５ｎｍ〜１００μｍであり、より好ましくは１０ｎｍ〜５０μｍであり、さらに好ましくは２０ｎｍ〜１０μｍである。このような範囲であれば、導通に優れる樹脂層を形成することができる。また、導電粒子の平均一次粒径を１０μｍ以下とすることにより、耐擦傷性により優れる透明導電性フィルムを得ることができる。 The average primary particle size of the conductive particles present in the resin layer is preferably 5 nm to 100 μm, more preferably 10 nm to 50 μm, and further preferably 20 nm to 10 μm. If it is such a range, the resin layer excellent in conduction | electrical_connection can be formed. Moreover, the transparent conductive film which is excellent by abrasion resistance can be obtained by making the average primary particle diameter of electroconductive particle into 10 micrometers or less.
上記導電粒子の含有割合は、上記バインダー樹脂１００重量部に対して、好ましくは０．１重量部〜２０重量部であり、より好ましくは０．２重量部〜１０重量部である。このような範囲であれば、導通と耐擦傷性との両方に優れる透明導電性フィルムを得ることができる。また、透明性に優れる透明導電性フィルムを得ることができる。 The content ratio of the conductive particles is preferably 0.1 parts by weight to 20 parts by weight, and more preferably 0.2 parts by weight to 10 parts by weight with respect to 100 parts by weight of the binder resin. If it is such a range, the transparent conductive film which is excellent in both conduction | electrical_connection and abrasion resistance can be obtained. Moreover, the transparent conductive film excellent in transparency can be obtained.
上記導電粒子は金属粒子が好ましい。金属粒子を構成する金属としては、導電性金属である限り、任意の適切な金属が用いられ得る。上記金属粒子を構成する金属としては、例えば、銀、金、銅、ニッケル、パラジウム等が挙げられる。また、これらの金属にメッキ処理（例えば、金メッキ処理）を行った材料を用いてもよい。なかでも好ましくは、導電性の観点から、銀、銅、パラジウムまたは金であり、より好ましくは銀である。 The conductive particles are preferably metal particles. Any appropriate metal can be used as the metal constituting the metal particle as long as it is a conductive metal. As a metal which comprises the said metal particle, silver, gold | metal | money, copper, nickel, palladium etc. are mentioned, for example. Moreover, you may use the material which performed the plating process (for example, gold plating process) to these metals. Among these, silver, copper, palladium or gold is preferable from the viewpoint of conductivity, and silver is more preferable.
Ｂ−３．金属ナノワイヤ
金属ナノワイヤとは、材質が金属であり、形状が針状または糸状であり、径がナノメートルサイズの導電性物質をいう。金属ナノワイヤは直線状であってもよく、曲線状であってもよい。金属ナノワイヤを用いれば、金属ナノワイヤが網の目状となることにより、少量の金属ナノワイヤであっても良好な電気伝導経路を形成することができ、電気抵抗の小さい透明導電性フィルムを得ることができる。さらに、金属ナノワイヤが網の目状となることにより、網の目の隙間に開口部を形成して、光透過率の高い透明導電性フィルムを得ることができる。
B-3. Metal nanowire The metal nanowire is a conductive material having a metal material, a needle shape or a thread shape, and a diameter of nanometer. The metal nanowire may be linear or curved. If metal nanowires are used, the metal nanowires can form a network, so that even with a small amount of metal nanowires, a good electrical conduction path can be formed, and a transparent conductive film with low electrical resistance can be obtained. it can. Furthermore, when the metal nanowire has a mesh shape, an opening is formed in the mesh space, and a transparent conductive film having high light transmittance can be obtained.
上記金属ナノワイヤの太さｄと長さＬとの比（アスペクト比：Ｌ／ｄ）は、好ましくは１０〜１００，０００であり、より好ましくは５０〜１００，０００であり、特に好ましくは１００〜１０，０００である。このようにアスペクト比の大きい金属ナノワイヤを用いれば、金属ナノワイヤが良好に交差して、少量の金属ナノワイヤにより高い導電性を発現させることができる。その結果、光透過率の高い透明導電性フィルムを得ることができる。なお、本明細書において、「金属ナノワイヤの太さ」とは、金属ナノワイヤの断面が円状である場合はその直径を意味し、楕円状である場合はその短径を意味し、多角形である場合は最も長い対角線を意味する。金属ナノワイヤの太さおよび長さは、走査型電子顕微鏡または透過型電子顕微鏡によって確認することができる。 The ratio (aspect ratio: L / d) between the thickness d and the length L of the metal nanowire is preferably 10 to 100,000, more preferably 50 to 100,000, and particularly preferably 100 to 100. 10,000. If metal nanowires having a large aspect ratio are used in this way, the metal nanowires can cross well and high conductivity can be expressed by a small amount of metal nanowires. As a result, a transparent conductive film having a high light transmittance can be obtained. In the present specification, the “thickness of the metal nanowire” means the diameter when the cross section of the metal nanowire is circular, and the short diameter when the cross section of the metal nanowire is elliptical. In some cases it means the longest diagonal. The thickness and length of the metal nanowire can be confirmed by a scanning electron microscope or a transmission electron microscope.
上記金属ナノワイヤの太さは、好ましくは５００ｎｍ未満であり、より好ましくは２００ｎｍ未満であり、特に好ましくは１０ｎｍ〜１００ｎｍであり、最も好ましくは１０ｎｍ〜５０ｎｍである。このような範囲であれば、光透過率の高い樹脂層を形成することができる。 The thickness of the metal nanowire is preferably less than 500 nm, more preferably less than 200 nm, particularly preferably 10 nm to 100 nm, and most preferably 10 nm to 50 nm. Within such a range, a resin layer having a high light transmittance can be formed.
上記金属ナノワイヤの長さは、好ましくは１μｍ〜１０００μｍであり、より好ましくは１０μｍ〜５００μｍであり、特に好ましくは１０μｍ〜１００μｍである。このような範囲であれば、導電性の高い透明導電性フィルムを得ることができる。 The length of the metal nanowire is preferably 1 μm to 1000 μm, more preferably 10 μm to 500 μm, and particularly preferably 10 μm to 100 μm. If it is such a range, a highly conductive transparent conductive film can be obtained.
上記金属ナノワイヤを構成する金属としては、導電性金属である限り、任意の適切な金属が用いられ得る。上記金属ナノワイヤを構成する金属としては、例えば、銀、金、銅、ニッケル等が挙げられる。また、これらの金属にメッキ処理（例えば、金メッキ処理）を行った材料を用いてもよい。なかでも好ましくは、導電性の観点から、銀、銅または金であり、より好ましくは銀である。 Any appropriate metal can be used as the metal constituting the metal nanowire as long as it is a conductive metal. As a metal which comprises the said metal nanowire, silver, gold | metal | money, copper, nickel etc. are mentioned, for example. Moreover, you may use the material which performed the plating process (for example, gold plating process) to these metals. Among these, silver, copper, or gold is preferable from the viewpoint of conductivity, and silver is more preferable.
上記金属ナノワイヤの製造方法としては、任意の適切な方法が採用され得る。例えば溶液中で硝酸銀を還元する方法、前駆体表面にプローブの先端部から印可電圧又は電流を作用させ、プローブ先端部で金属ナノワイヤを引き出し、該金属ナノワイヤを連続的に形成する方法等が挙げられる。溶液中で硝酸銀を還元する方法においては、エチレングリコール等のポリオール、およびポリビニルピロリドンの存在下で、硝酸銀等の銀塩の液相還元することにより、銀ナノワイヤが合成され得る。均一サイズの銀ナノワイヤは、例えば、Ｘｉａ， Ｙ．ｅｔａｌ．， Ｃｈｅｍ．Ｍａｔｅｒ．（２００２）、１４、４７３６−４７４５、Ｘｉａ， Ｙ．ｅｔａｌ．， Ｎａｎｏ ｌｅｔｔｅｒｓ（２００３）３（７）、９５５−９６０に記載される方法に準じて、大量生産が可能である。 Any appropriate method can be adopted as a method for producing the metal nanowire. For example, a method of reducing silver nitrate in a solution, a method in which an applied voltage or current is applied to the precursor surface from the tip of the probe, a metal nanowire is drawn out at the probe tip, and the metal nanowire is continuously formed, etc. . In the method of reducing silver nitrate in a solution, silver nanowires can be synthesized by liquid phase reduction of a silver salt such as silver nitrate in the presence of a polyol such as ethylene glycol and polyvinylpyrrolidone. Uniformly sized silver nanowires are described in, for example, Xia, Y. et al. etal. Chem. Mater. (2002), 14, 4736-4745, Xia, Y. et al. etal. , Nano letters (2003) 3 (7), 955-960, mass production is possible.
上記樹脂層における導電領域中の金属ナノワイヤの含有割合は、導電領域を含む層を構成するバインダー樹脂１００重量部に対して、好ましくは０．１重量部以上であり、より好ましくは０．１重量部〜５０重量部であり、さらに好ましくは０．１重量部〜３０重量部である。このような範囲であれば、導電性および光透過性に優れる透明導電性フィルムを得ることができる。 The content ratio of the metal nanowires in the conductive region in the resin layer is preferably 0.1 parts by weight or more, more preferably 0.1 parts by weight with respect to 100 parts by weight of the binder resin constituting the layer including the conductive region. Part to 50 parts by weight, more preferably 0.1 part to 30 parts by weight. If it is such a range, the transparent conductive film excellent in electroconductivity and light transmittance can be obtained.
Ｂ−４．樹脂層の形成方法
上記樹脂層は、例えば、上記透明基材上に、樹脂層用組成物を塗工して形成され得る。１つの実施形態においては、樹脂層用組成物は、バインダー樹脂、金属ナノワイヤおよび導電粒子を含む。
B-4. Method for Forming Resin Layer The resin layer can be formed, for example, by applying a resin layer composition on the transparent substrate. In one embodiment, the resin layer composition includes a binder resin, metal nanowires, and conductive particles.
別の実施形態においては、金属ナノワイヤと導電粒子とを含む樹脂層形成用組成物（ＮＰ）を塗工（塗布、ならびに、乾燥および／または硬化処理）した後、バインダー樹脂を含む樹脂層形成用組成物（Ｒ）を塗工して、樹脂層が形成され得る。この時、金属ナノワイヤと導電粒子とを含む樹脂層形成用組成物（ＮＰ）にも、バインダー樹脂、または分散安定性を向上させ得る任意の適切な樹脂等を含有させてよい。バインダー樹脂を含む樹脂層形成用組成物（Ｒ）は金属ナノワイヤを含まないことが好ましい。このような方法によれば、導電領域を含む層（すなわち、金属ナノワイヤを含む層；図１および図２における層２１）と、金属ナノワイヤを実質的に含まない層（図１および図２における層２２）とから構成される樹脂層を良好に形成させることができる。 In another embodiment, a resin layer forming composition (NP) containing metal nanowires and conductive particles is applied (applied and dried and / or cured) and then a resin layer containing a binder resin is formed. A resin layer may be formed by applying the composition (R). At this time, the resin layer forming composition (NP) including the metal nanowires and the conductive particles may also contain a binder resin or any appropriate resin that can improve dispersion stability. The resin layer forming composition (R) containing a binder resin preferably does not contain metal nanowires. According to such a method, a layer including a conductive region (ie, a layer including metal nanowires; layer 21 in FIGS. 1 and 2) and a layer substantially free of metal nanowires (layers in FIGS. 1 and 2). 22) can be formed satisfactorily.
さらに別の実施形態においては、金属ナノワイヤを含む樹脂層形成用組成物（Ｎ）を塗工（塗布、ならびに、乾燥および／または硬化処理）した後、バインダー樹脂と導電粒子とを含む樹脂層形成用組成物（ＲＰ）を塗工して、樹脂層が形成され得る。この時、金属ナノワイヤを含む樹脂層形成用組成物（Ｎ）にも、バインダー樹脂、または分散安定性を向上させ得る任意の適切な樹脂等を含有させてよい。この実施形態においては、金属ナノワイヤを含む樹脂層形成用組成物（Ｎ）を塗工した後、バインダー樹脂と導電粒子とを含む樹脂層形成用組成物（ＲＰ）を塗工する前に、バインダー樹脂を含む樹脂層形成用組成物（Ｒ）を塗工してもよい。このとき、バインダー樹脂を含む樹脂層形成用組成物（Ｒ）は金属ナノワイヤを含まないことが好ましい。このような方法によれば、導電領域を含む層（すなわち、金属ナノワイヤを含む層；図１および図２における層２１）と、金属ナノワイヤを実質的に含まない層（図１および図２における層２２）とから構成される樹脂層を良好に形成させることができる。 In yet another embodiment, the resin layer forming composition (N) containing metal nanowires is applied (applied and dried and / or cured), and then a resin layer containing a binder resin and conductive particles is formed. The resin layer can be formed by applying the composition (RP). At this time, the resin layer forming composition (N) containing metal nanowires may also contain a binder resin or any appropriate resin that can improve dispersion stability. In this embodiment, after applying the resin layer forming composition (N) containing metal nanowires, before applying the resin layer forming composition (RP) containing a binder resin and conductive particles, the binder A resin layer forming composition (R) containing a resin may be applied. At this time, it is preferable that the resin layer forming composition (R) containing the binder resin does not contain metal nanowires. According to such a method, a layer including a conductive region (ie, a layer including metal nanowires; layer 21 in FIGS. 1 and 2) and a layer substantially free of metal nanowires (layers in FIGS. 1 and 2). 22) can be formed satisfactorily.
好ましくは、上記樹脂層形成用組成物（ＮＰ、Ｎ、ＲＰ、Ｒ）は、任意の適切な溶媒に金属ナノワイヤおよび／または導電粒子を分散させて得られる分散液である。該溶媒としては、水、アルコール系溶媒、ケトン系溶媒、エーテル系溶媒、炭化水素系溶媒、芳香族系溶媒等が挙げられる。 Preferably, the resin layer forming composition (NP, N, RP, R) is a dispersion obtained by dispersing metal nanowires and / or conductive particles in any appropriate solvent. Examples of the solvent include water, alcohol solvents, ketone solvents, ether solvents, hydrocarbon solvents, aromatic solvents and the like.
１つの実施形態においては、上記溶媒として、透明基材に浸透し得る溶媒が用いられる。このような溶媒としては、例えば、２−メチルテトラヒドロフラン、塩化炭化水素、フッ化炭化水素、ケトン、パラフィン、アセトアルデヒド、酢酸、無水酢酸、アセトン、アセトニトリル、アルキン、オレフィン、アニリン、ベンゼン、ベンゾニトリル、ベンジルアルコール、ベンジルエーテル、ブタノール、ブタノン、酢酸ブチル、ブチルエーテル、ギ酸ブチル、ブチルアルデヒド、酪酸、ブチロニトリル、二硫化炭素、四塩化炭素、クロロベンゼン、クロロブタン、クロロホルム、脂環式炭化水素、シクロヘキサン、シクロヘキサノール、シクロヘキサノン、シクロペンタノン、シクロペンチルメチルエーテル、ジアセトンアルコール、ジクロロエタン、ジクロロメタン、炭酸ジエチル、ジエチルエーテル、ジエチレングリコール、ジグリム、ジ−イソプロピルアミン、ジメトキシエタン、ジメチルアミン、ジメチルブタン、ジメチルエーテル、ジメチルホルムアミド、ジメチルスルホキシド、ジオキサン、ドデカフルオロ−１−ヘプタノール、エタノール、酢酸エチル、エチルエーテル、ギ酸エチル、プロピオン酸エチル、二酸化エチレン、エチレングリコール、ホルムアミド、ギ酸、グリセリン、ヘプタン、ヘキサフルオロイソプロパノール、ヘキサメチルホスホルアミド、ヘキサメチルリン酸トリアミド、ヘキサン、ヘキサノン、過酸化水素、次亜塩素酸塩、ｉ−酢酸ブチル、ｉ−ブチルアルコール、ｉ−ギ酸ブチル、ｉ−ブチルアミン、ｉ−オクタン、ｉ−酢酸プロピル、ｉ−プロピルエーテル、イソプロパノール、イソプロピルアミン、ケトンペルオキシド、メタノールおよび塩化カルシウム溶液、メタノール、メトキシエタノール、酢酸メチル、メチルエチルケトン（またはＭＥＫ）、ギ酸メチル、ｎ−酪酸メチル、メチルｎ−プロピルケトン、メチルｔ−ブチルエーテル、塩化メチレン、メチレン、メチルヘキサン、メチルペンタン、鉱油、ｍ−キシレン、ｎ−ブタノール、ｎ−デカン、ｎ−ヘキサン、ニトロベンゼン、ニトロエタン、ニトロメタン、ニトロプロパン、２−Ｎ−メチル−２−ピロリジノン、ｎ−プロパノール、オクタフルオロ−１−ペンタノール、オクタン、ペンタン、ペンタノン、石油エーテル、フェノール、プロパノール、プロピオンアルデヒド、プロピオン酸、プロピオニトリル、酢酸プロピル、プロピルエーテル、ギ酸プロピル、プロピルアミン、ｐ−キシレン、ピリジン、ピロリジン、ｔ−ブタノール、ｔ−ブチルアルコール、ｔ−ブチルメチルエーテル、テトラクロロエタン、テトラフルオロプロパノール、テトラヒドロフラン、テトラヒドロナフタレン、トルエン、トリエチルアミン、トリフルオロ酢酸、トリフルオロエタノール、トリフルオロプロパノール、トリメチルブタン、トリメチルヘキサン、トリメチルペンタン、バレロニトリル、キシレン、キシレノール等が挙げられる。これらの溶媒は、単独で、または２種以上組み合わせて用いてもよい。金属ナノワイヤを含む樹脂層形成用組成物（ＮＰ、Ｎ）が透明基材に浸透し得る溶媒を含んでいれば、導電領域の少なくとも一部が透明基材中に存在している、透明導電性フィルム（図１に示す透明導電性フィルム）を得ることができる。 In one embodiment, a solvent that can permeate the transparent substrate is used as the solvent. Examples of such solvents include 2-methyltetrahydrofuran, chlorohydrocarbon, fluorinated hydrocarbon, ketone, paraffin, acetaldehyde, acetic acid, acetic anhydride, acetone, acetonitrile, alkyne, olefin, aniline, benzene, benzonitrile, and benzyl. Alcohol, benzyl ether, butanol, butanone, butyl acetate, butyl ether, butyl formate, butyraldehyde, butyric acid, butyronitrile, carbon disulfide, carbon tetrachloride, chlorobenzene, chlorobutane, chloroform, alicyclic hydrocarbons, cyclohexane, cyclohexanol, cyclohexanone , Cyclopentanone, cyclopentyl methyl ether, diacetone alcohol, dichloroethane, dichloromethane, diethyl carbonate, diethyl ether, diethylene glycol, di Rim, di-isopropylamine, dimethoxyethane, dimethylamine, dimethylbutane, dimethyl ether, dimethylformamide, dimethyl sulfoxide, dioxane, dodecafluoro-1-heptanol, ethanol, ethyl acetate, ethyl ether, ethyl formate, ethyl propionate, ethylene dioxide , Ethylene glycol, formamide, formic acid, glycerin, heptane, hexafluoroisopropanol, hexamethylphosphoramide, hexamethylphosphoric triamide, hexane, hexanone, hydrogen peroxide, hypochlorite, i-butyl acetate, i-butyl Alcohol, i-butyl formate, i-butylamine, i-octane, i-propyl acetate, i-propyl ether, isopropanol, isopropylamine, ketone peroxide, meta And calcium chloride solution, methanol, methoxyethanol, methyl acetate, methyl ethyl ketone (or MEK), methyl formate, n-methyl butyrate, methyl n-propyl ketone, methyl t-butyl ether, methylene chloride, methylene, methyl hexane, methyl pentane Mineral oil, m-xylene, n-butanol, n-decane, n-hexane, nitrobenzene, nitroethane, nitromethane, nitropropane, 2-N-methyl-2-pyrrolidinone, n-propanol, octafluoro-1-pentanol, Octane, pentane, pentanone, petroleum ether, phenol, propanol, propionaldehyde, propionic acid, propionitrile, propyl acetate, propyl ether, propyl formate, propylamine, p-xylene, pyridine, Pyrrolidine, t-butanol, t-butyl alcohol, t-butyl methyl ether, tetrachloroethane, tetrafluoropropanol, tetrahydrofuran, tetrahydronaphthalene, toluene, triethylamine, trifluoroacetic acid, trifluoroethanol, trifluoropropanol, trimethylbutane, trimethylhexane , Trimethylpentane, valeronitrile, xylene, xylenol and the like. These solvents may be used alone or in combination of two or more. If the resin layer forming composition (NP, N) containing metal nanowires contains a solvent that can penetrate into the transparent substrate, at least a part of the conductive region is present in the transparent substrate. A film (transparent conductive film shown in FIG. 1) can be obtained.
１つの実施形態においては、ポリエステル系樹脂（好ましくはポリエチレンテレフタレート）を含む透明基材を用い、かつ、上記樹脂層形成用組成物（ＮＰ、Ｎ、ＲＰ、Ｒ）の分散液に用いる溶媒として、アセトン、ジメチルスルホキシド、ジエチレングリコールモノエチルエーテルアセタート、プロピレングリコール１−モノメチル２−アセタート、酢酸２−エトキシエチルアセタート、または、これらの溶媒１種以上からなる混合溶媒を用いる。 In one embodiment, a transparent substrate containing a polyester-based resin (preferably polyethylene terephthalate) is used, and as a solvent used in the dispersion of the resin layer forming composition (NP, N, RP, R), Acetone, dimethyl sulfoxide, diethylene glycol monoethyl ether acetate, propylene glycol 1-monomethyl 2-acetate, acetic acid 2-ethoxyethyl acetate, or a mixed solvent composed of one or more of these solvents is used.
上記金属ナノワイヤを含む樹脂層形成用組成物（ＮＰ、Ｎ）中の金属ナノワイヤの分散濃度は、好ましくは０．０１重量％〜５重量％である。このような範囲であれば、導電性および光透過性に優れる樹脂層を形成することができる。 The dispersion concentration of the metal nanowires in the resin layer forming composition (NP, N) containing the metal nanowires is preferably 0.01% by weight to 5% by weight. If it is such a range, the resin layer excellent in electroconductivity and light transmittance can be formed.
上記導電粒子を含む樹脂層形成用組成物（ＮＰ、ＲＰ）中の導電粒子の分散濃度は、好ましくは０．００１重量％〜５重量％である。このような範囲であれば、導電性および光透過性に優れる樹脂層を形成することができる。 The dispersion concentration of the conductive particles in the resin layer forming composition (NP, RP) containing the conductive particles is preferably 0.001 wt% to 5 wt%. If it is such a range, the resin layer excellent in electroconductivity and light transmittance can be formed.
上記樹脂層形成用組成物は、目的に応じて任意の適切な添加剤をさらに含有し得る。上記添加剤としては、例えば、金属ナノワイヤおよび／または導電粒子の腐食を防止する腐食防止材、金属ナノワイヤの凝集を防止する界面活性剤等が挙げられる。また、樹脂層形成用組成物は、可塑剤、熱安定剤、光安定剤、滑剤、抗酸化剤、紫外線吸収剤、難燃剤、着色剤、帯電防止剤、相溶化剤、架橋剤、増粘剤、無機粒子、界面活性剤、および分散剤等の添加剤を含み得る。使用される添加剤の種類、数および量は、目的に応じて適切に設定され得る。 The composition for resin layer formation may further contain any appropriate additive depending on the purpose. Examples of the additive include a corrosion inhibitor for preventing corrosion of metal nanowires and / or conductive particles, and a surfactant for preventing aggregation of metal nanowires. In addition, the resin layer forming composition includes a plasticizer, a heat stabilizer, a light stabilizer, a lubricant, an antioxidant, an ultraviolet absorber, a flame retardant, a colorant, an antistatic agent, a compatibilizer, a crosslinking agent, and a thickening agent. Additives such as agents, inorganic particles, surfactants, and dispersants may be included. The type, number and amount of additives used can be appropriately set according to the purpose.
上記樹脂層形成用組成物の塗布方法としては、任意の適切な方法が採用され得る。塗布方法としては、例えば、スプレーコート、バーコート、ロールコート、ダイコート、インクジェットコート、スクリーンコート、ディップコート、凸版印刷法、凹版印刷法、グラビア印刷法等が挙げられる。塗布層の乾燥方法としては、任意の適切な乾燥方法（例えば、自然乾燥、送風乾燥、加熱乾燥）が採用され得る。例えば、加熱乾燥の場合には、乾燥温度は代表的には８０℃〜１５０℃であり、乾燥時間は代表的には１〜２０分である。また、バインダー樹脂を含む樹脂層形成用組成物（例えば、樹脂層形成用組成物（Ｒ、ＲＰ、ＲＮ））を塗工した後、塗工層に硬化処理（例えば、加熱処理、紫外線照射処理）を施してもよい。 Any appropriate method can be adopted as a method for applying the resin layer forming composition. Examples of the coating method include spray coating, bar coating, roll coating, die coating, inkjet coating, screen coating, dip coating, letterpress printing method, intaglio printing method, and gravure printing method. Any appropriate drying method (for example, natural drying, air drying, heat drying) can be adopted as a method for drying the coating layer. For example, in the case of heat drying, the drying temperature is typically 80 ° C. to 150 ° C., and the drying time is typically 1 to 20 minutes. Moreover, after coating the resin layer forming composition (for example, resin layer forming composition (R, RP, RN)) containing the binder resin, the coating layer is cured (for example, heat treatment, ultraviolet irradiation treatment). ) May be applied.
Ｃ．透明基材
上記透明基材を構成する材料は、任意の適切な材料が用いられ得る。具体的には、例えば、フィルムやプラスチックス基材などの高分子基材が好ましく用いられる。透明基材の平滑性および樹脂層形成用組成物に対する濡れ性に優れ、また、ロールによる連続生産により生産性を大幅に向上させ得るからである。
C. Transparent substrate Any appropriate material can be used as the material constituting the transparent substrate . Specifically, for example, a polymer substrate such as a film or a plastics substrate is preferably used. It is because it is excellent in the smoothness of a transparent base material, and the wettability with respect to the composition for resin layer formation, and productivity can be improved significantly by the continuous production by a roll.
上記透明基材を構成する材料は、代表的には熱可塑性樹脂を主成分とする高分子フィルムである。熱可塑性樹脂としては、例えば、ポリエステル系樹脂；ポリノルボルネン等のシクロオレフィン系樹脂；アクリル系樹脂；ポリカーボネート樹脂；セルロース系樹脂等が挙げられる。なかでも好ましくは、ポリエステル系樹脂、シクロオレフィン系樹脂またはアクリル系樹脂である。これらの樹脂は、透明性、機械的強度、熱安定性、水分遮蔽性などに優れる。上記熱可塑性樹脂は、単独で、または２種以上組み合わせて用いてもよい。また、偏光板に用いられるような光学フィルム、例えば、低位相差基材、高位相差基材、位相差板、輝度向上フィルム等を基材として用いることも可能である。 The material constituting the transparent substrate is typically a polymer film containing a thermoplastic resin as a main component. Examples of the thermoplastic resin include polyester resins; cycloolefin resins such as polynorbornene; acrylic resins; polycarbonate resins; and cellulose resins. Of these, polyester resins, cycloolefin resins, and acrylic resins are preferable. These resins are excellent in transparency, mechanical strength, thermal stability, moisture shielding properties and the like. You may use the said thermoplastic resin individually or in combination of 2 or more types. In addition, an optical film used for a polarizing plate, for example, a low retardation substrate, a high retardation substrate, a retardation plate, a brightness enhancement film, or the like can be used as the substrate.
上記透明基材の厚みは、好ましくは５μｍ〜２００μｍであり、より好ましくは１０μｍ〜１５０μｍである。 The thickness of the transparent substrate is preferably 5 μm to 200 μm, more preferably 10 μm to 150 μm.
上記透明基材の全光線透過率は、好ましくは３０％以上であり、より好ましくは３５％以上であり、さらに好ましくは４０％以上である。 The total light transmittance of the transparent substrate is preferably 30% or more, more preferably 35% or more, and further preferably 40% or more.
Ｄ．光学積層体
１つの実施形態においては、上記透明導電性フィルムと偏光板とを積層して得られる光学積層体が提供される。透明導電性フィルムと偏光板とは、任意の適切な接着剤または粘着剤を介して、貼り合わせられ得る。上記偏光板としては、任意の適切な偏光板が用いられ得る。当該光学積層体はタッチセンサー特性あるいは電磁波シールド特性を備える偏光要素として好適に用いられ得、例えば、液晶表示装置の液晶セルの視認側偏光板あるいは背面側偏光板として用いられる。
D. In one embodiment of the optical laminate, an optical laminate obtained by laminating the transparent conductive film and the polarizing plate is provided. The transparent conductive film and the polarizing plate can be bonded together via any appropriate adhesive or pressure-sensitive adhesive. Any appropriate polarizing plate can be used as the polarizing plate. The optical layered body can be suitably used as a polarizing element having touch sensor characteristics or electromagnetic wave shielding characteristics, and is used, for example, as a viewing side polarizing plate or a back side polarizing plate of a liquid crystal cell of a liquid crystal display device.
以下、実施例により本発明を具体的に説明するが、本発明はこれら実施例になんら限定されるものではない。実施例における評価方法は以下のとおりである。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples at all. The evaluation methods in the examples are as follows.
（１）表面抵抗値
表面抵抗値は、ナプソン株式会社製の非接触表面抵抗計 商品名「ＥＣ−８０」を用いて、渦電流法により測定した。測定温度は２３℃とした。
(1) Surface Resistance Value The surface resistance value was measured by an eddy current method using a non-contact surface resistance meter trade name “EC-80” manufactured by Napson Corporation. The measurement temperature was 23 ° C.
（２）接触抵抗値
樹脂層上に、所定の間隔（５ｍｍ、１５ｍｍおよび３５ｍｍ）で銀ペーストのライン（長さ２０ｍｍ×幅１ｍｍ）を塗布し、２点間の抵抗値を三和電気計器社製の商品名「デジタルマルチメータＣＤ８００ａ」を用いて計測した。２点間の距離と抵抗値との相関から線形式を得、切片を２で除した値を透明導電性フィルムの接触抵抗値とした。
(2) Contact resistance value A silver paste line (length 20 mm x width 1 mm) is applied to the resin layer at predetermined intervals (5 mm, 15 mm, and 35 mm), and the resistance value between the two points is calculated by Sanwa Denki Keiki Co., Ltd. Measurement was performed using a product name “Digital Multimeter CD800a”. A linear form was obtained from the correlation between the distance between the two points and the resistance value, and the value obtained by dividing the intercept by 2 was defined as the contact resistance value of the transparent conductive film.
（３）耐擦傷性
スチールウール＃００００を使用し、半径２５ｍｍのプローブを荷重３００ｇで長さ１０ｃｍ×１０往復させる条件にて、透明導電性フィルムの樹脂層の耐擦傷性を評価した。中心部（２５ｍｍ×２５ｍｍ）において目視にて確認されたキズが１０本以下の場合を〇、１０本を超えた場合を×とした。
(3) Scratch resistance Using steel wool # 0000, the scratch resistance of the resin layer of the transparent conductive film was evaluated under the condition that a probe with a radius of 25 mm was reciprocated 10 cm × 10 times with a load of 300 g. A case where the number of scratches visually confirmed in the central portion (25 mm × 25 mm) was 10 or less was marked as “O”, and a case where it exceeded 10 was marked as “X”.
（４）金属ナノワイヤ、導電粒子のサイズ測定
オリンパス社製の光学顕微鏡「ＢＸ−５１」、日立ハイテクノロジーズ社製の走査型電子顕微鏡「Ｓ−４８００」および日立ハイテクノロジーズ社製の電界放出形透過電子顕微鏡「ＨＦ−２０００」を用いて測定した。平均粒径は、該顕微鏡により樹脂層表面あるいは断面において無作為に抽出した１００個の粒子を観察して測定された粒径のメジアン径（５０％径；数基準）とした。
(4) Size measurement of metal nanowires and conductive particles Olympus optical microscope “BX-51”, Hitachi High-Technologies scanning electron microscope “S-4800” and Hitachi High-Technologies field emission transmission electrons Measurement was performed using a microscope “HF-2000”. The average particle diameter was defined as the median diameter (50% diameter; several standards) of the particle diameter measured by observing 100 particles randomly extracted on the resin layer surface or cross section with the microscope.
（５）金属ナノワイヤ及び導電粒子の厚み方向断面における位置の解析と樹脂層の厚み測定
エポキシ樹脂にて包埋処理後ウルトラマイクロトームで切削することで断面を形成し、日立ハイテクノロジーズ社製の走査型電子顕微鏡「Ｓ−４８００」を使用して、金属ナノワイヤ及び金属性粒子の厚み方向における位置を特定し、また、樹脂層の厚みを測定した。
(5) Analysis of position in cross section in the thickness direction of metal nanowire and conductive particles and measurement of resin layer thickness Cross section is formed by embedding with epoxy resin and cutting with ultra microtome, and scanning made by Hitachi High-Technologies Corporation Using a scanning electron microscope “S-4800”, the positions of the metal nanowires and the metallic particles in the thickness direction were specified, and the thickness of the resin layer was measured.
（６）耐久性試験
６５℃／９０％ＲＨ環境下で５００時間経過した後の表面抵抗値を上記の方法で測定し、耐久試験後表面抵抗値とした。初期表面抵抗値との差を表面抵抗値変化とした。
(6) Durability test The surface resistance value after lapse of 500 hours in a 65 ° C./90% RH environment was measured by the above method to obtain a surface resistance value after the durability test. The difference from the initial surface resistance value was defined as a change in surface resistance value.
＜製造例１＞銀ナノワイヤの合成および銀ナノワイヤ分散液（樹脂層形成用組成物（Ｎ））の調製
硝酸銀１．５ｇ、形態調整剤としてのポリビニルピロリドンＫ−９０(ナカライテスク社製、平均分子量：３６０,０００）５．８ｇ、食塩（ＮａＣｌ）０．０４ｇ及びエチレングリコール（１８０ｍｌ）を、環流器及び攪拌機が付いたフラスコに添加し、攪拌しつつ溶解した後、温度をエチレングリコールの沸点近傍である１７０℃まで昇温し、６０分間反応させた。反応終了後、室温下で放置して冷却した。次いで、上記のようにして得られた銀ナノワイヤを含む反応混合物に、該反応混合物の体積が５倍になるまでアセトンを加えた後、該反応混合物を遠心分離した（２０００ｒｐｍ、２０分）。この作業を数回繰返し、銀ナノワイヤを得た。得られた銀ナノワイヤは、直径が１０ｎｍ〜６０ｎｍであり、長さは１μｍ〜５０μｍであった。なお、銀ナノワイヤのサイズは、日立ハイテクノロジーズ社製の走査型電子顕微鏡「Ｓ−４８００」を用い、該顕微鏡により無作為に抽出した３０個の金属ナノワイヤを観察して長さおよび直径を測定した。純水中に、該銀ナノワイヤ（濃度：０．２重量％）、およびペンタエチレングリコールモノドデシルエーテル（濃度：０．１重量％）を分散させ、銀ナノワイヤ分散液を調製した。
<Production Example 1> Synthesis of silver nanowire and preparation of silver nanowire dispersion (resin layer-forming composition (N)) 1.5 g of silver nitrate, polyvinylpyrrolidone K-90 (manufactured by Nacalai Tesque, average molecular weight) as a form modifier : 360,000) 5.8 g, sodium chloride (NaCl) 0.04 g and ethylene glycol (180 ml) were added to a flask equipped with a circulator and a stirrer, dissolved while stirring, and the temperature was close to the boiling point of ethylene glycol. The temperature was raised to 170 ° C. and reacted for 60 minutes. After completion of the reaction, it was allowed to cool at room temperature. Next, acetone was added to the reaction mixture containing silver nanowires obtained as described above until the volume of the reaction mixture became 5 times, and then the reaction mixture was centrifuged (2000 rpm, 20 minutes). This operation was repeated several times to obtain silver nanowires. The obtained silver nanowires had a diameter of 10 nm to 60 nm and a length of 1 μm to 50 μm. The size of the silver nanowires was measured using a scanning electron microscope “S-4800” manufactured by Hitachi High-Technologies Corporation, and the length and diameter were measured by observing 30 metal nanowires randomly extracted by the microscope. . The silver nanowire (concentration: 0.2% by weight) and pentaethylene glycol monododecyl ether (concentration: 0.1% by weight) were dispersed in pure water to prepare a silver nanowire dispersion.
＜製造例２＞樹脂層形成用組成物（Ｒ）の調製
ペンタエリスリトールトリアクリレート（ＰＥＴＡ）（大阪有機化学工業社製、商品名「ビスコート＃３００」）３．６重量部、オルガノシリカゾル（日産化学工業社製、商品名「ＭＥＫ−ＡＣ−２１４０Ｚ」、濃度４０％）２．７重量部、光重合開始剤（ＢＡＳＦ社製、商品名「イルガキュア９０７」）０．２重量部をシクロペンタノン９３重量部で希釈して、固形分濃度５重量％の樹脂層形成用組成物（Ｒ）を得た。
<Production Example 2> Preparation of Resin Layer Forming Composition (R) Pentaerythritol triacrylate (PETA) (trade name “Biscoat # 300” manufactured by Osaka Organic Chemical Industry Co., Ltd.) 3.6 parts by weight, organosilica sol (Nissan Chemical) 2.7 parts by weight of trade name “MEK-AC-2140Z” (concentration 40%) manufactured by Kogyo Co., Ltd. and 0.2 parts by weight of photopolymerization initiator (trade name “Irgacure 907” manufactured by BASF AG) were added to cyclopentanone 93. The resin layer forming composition (R) having a solid content concentration of 5% by weight was obtained by dilution with parts by weight.
＜製造例３＞バインダー樹脂と導電粒子とを含む樹脂層形成用組成物（ＲＰ−Ｉ）の調製
ペンタエリスリトールトリアクリレート（ＰＥＴＡ）（大阪有機化学工業社製、商品名「ビスコート＃３００」）３．６重量部、オルガノシリカゾル（日産化学工業社製、商品名「ＭＥＫ−ＡＣ−２１４０Ｚ」、濃度４０％）２．７重量部、光重合開始剤（ＢＡＳＦ社製、商品名「イルガキュア９０７」）０．２重量部、平均粒径が１．３μｍの１重量％銀粒子（三井金属鉱業株式会社製、商品名「ＳＰＮ０５Ｓ」）シクロペンタノン溶液１０重量部をシクロペンタノン８３重量部で希釈して、導電粒子を含む樹脂層形成用組成物（ＲＰ−Ｉ）（固形分濃度６重量％）を得た。
<Production Example 3> Preparation of Resin Layer Forming Composition (RP-I) Containing Binder Resin and Conductive Particles Pentaerythritol triacrylate (PETA) (trade name “Biscoat # 300” manufactured by Osaka Organic Chemical Industry Co., Ltd.) 3 .6 parts by weight, organosilica sol (manufactured by Nissan Chemical Industries, trade name “MEK-AC-2140Z”, concentration 40%) 2.7 parts by weight, photopolymerization initiator (manufactured by BASF, trade name “Irgacure 907”) 0.2 parts by weight, 1% by weight silver particles having an average particle size of 1.3 μm (Mitsui Metal Mining Co., Ltd., trade name “SPN05S”) 10 parts by weight of cyclopentanone solution was diluted with 83 parts by weight of cyclopentanone. Thus, a resin layer forming composition (RP-I) (solid content concentration 6 wt%) containing conductive particles was obtained.
＜製造例４＞バインダー樹脂と導電粒子とを含む樹脂層形成用組成物（ＲＰ−ＩＩ）の調製
平均粒径が１．３μｍの銀粒子（三井金属鉱業株式会社製、商品名「ＳＰＮ０５Ｓ」）に代えて、平均粒径が５．１μｍの銀粒子（株式会社徳力本店製、商品名「ＡＧＦ−５Ｓ」）を用いたこと以外は、製造例３と同様にして樹脂層形成用組成物（ＰＰ−ＩＩ）を得た。
<Production Example 4> Preparation of Resin Layer Forming Composition (RP-II) Containing Binder Resin and Conductive Particles Silver particles having an average particle diameter of 1.3 μm (trade name “SPN05S” manufactured by Mitsui Kinzoku Mining Co., Ltd.) Instead of using silver particles having an average particle size of 5.1 μm (trade name “AGF-5S” manufactured by Tokuru Honten Co., Ltd.), a resin layer forming composition ( PP-II) was obtained.
＜製造例５＞バインダー樹脂と導電粒子とを含む樹脂層形成用組成物（ＲＰ−ＩＩＩ）の調製
平均粒径が１．３μｍの銀粒子（三井金属鉱業株式会社製、商品名「ＳＰＮ０５Ｓ」）に代えて、平均粒径が１．１μｍの銀メッキ銅粒子（三井金属工業株式会社製、商品名「１１００Ｙ」）を用いたこと以外は、製造例３と同様にして樹脂層形成用組成物（ＰＰ−ＩＩＩ）を得た。
<Production Example 5> Preparation of resin layer forming composition (RP-III) containing binder resin and conductive particles Silver particles having an average particle diameter of 1.3 μm (trade name “SPN05S” manufactured by Mitsui Mining & Smelting Co., Ltd.) Instead of using silver-plated copper particles having an average particle diameter of 1.1 μm (trade name “1100Y” manufactured by Mitsui Kinzoku Kogyo Co., Ltd.), a resin layer forming composition was produced in the same manner as in Production Example 3. (PP-III) was obtained.
＜製造例６＞バインダー樹脂と導電粒子とを含む樹脂層形成用組成物（ＲＰ−ＩＶ）の調製
平均粒径が１．３μｍの銀粒子（三井金属鉱業株式会社製、商品名「ＳＰＮ０５Ｓ」）に代えて、平均粒径が１．５μｍのパラジウム粒子(田中貴金属工業株式会社製、商品名「ＡＹ−４０６」)を用いたこと以外は、製造例３と同様にして樹脂層形成用組成物（ＰＰ−ＩＶ）を得た。
<Production Example 6> Preparation of Resin Layer Forming Composition (RP-IV) Containing Binder Resin and Conductive Particles Silver particles having an average particle size of 1.3 μm (trade name “SPN05S” manufactured by Mitsui Kinzoku Mining Co., Ltd.) Instead of using palladium particles having an average particle diameter of 1.5 μm (trade name “AY-406”, manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.), a resin layer forming composition was prepared in the same manner as in Production Example 3. (PP-IV) was obtained.
＜実施例１＞
透明基材としてＰＥＴ基材（三菱樹脂株式会社製、商品名「Ｔ６０２」、厚み：５０μｍ）を用いた。この透明基材上にバーコーター（第一理科社製、製品名「バーコーター Ｎｏ．１５」）を用いて製造例１で調整した銀ナノワイヤ分散液（樹脂層形成用組成物（Ｎ））を塗布し、１２０℃の送風乾燥機内で２分間乾燥させ金属ナノワイヤを含む層を形成した。
上記金属ナノワイヤを含む層上に、製造例２で調整した樹脂層形成用組成物（Ｒ）をＷｅｔ膜厚２μｍでスロットダイにて塗布し、８０℃の送風乾燥機内で２分間乾燥させた。次いで、酸素濃度１００ｐｐｍ環境とした紫外光照射装置（Ｆｕｓｉｏｎ ＵＶ Ｓｙｓｔｅｍｓ社製）で積算照度２１０ｍＪ／ｃｍ２の紫外光を照射して上記樹脂層形成用組成物（Ｒ）を硬化させた。
さらに、樹脂層形成用組成物（Ｒ）から形成された層に製造例３で調整した樹脂層形成用組成物（ＲＰ−Ｉ）をＷｅｔ膜厚６μｍでスロットダイにて塗布し、８０℃の送風乾燥機内で２分間乾燥させた。次いで、酸素濃度１００ｐｐｍ環境とした紫外光照射装置（Ｆｕｓｉｏｎ ＵＶ Ｓｙｓｔｅｍｓ社製）で積算照度２１０ｍＪ／ｃｍ２の紫外光を照射して樹脂層形成用組成物（ＲＰ−Ｉ）を硬化させ、透明導電性フィルムを得た。
この透明導電性フィルムにおいて、樹脂層の厚みは０．３μｍであり、金属ナノワイヤを含む導電領域は樹脂層に形成され、導電粒子は樹脂層に存在し、かつ樹脂層表面から突出していた（突出部高さ：１．０μｍ）。また、この透明導電性フィルムの初期接触抵抗値は０．９Ω、初期表面抵抗値は４８．２Ω／□、耐久試験後表面抵抗値は４９．６Ω／□、表面抵抗値変化は１．４Ω／□であった。耐擦傷性は○であった。
<Example 1>
A PET substrate (manufactured by Mitsubishi Plastics, trade name “T602”, thickness: 50 μm) was used as the transparent substrate. The silver nanowire dispersion liquid (resin layer forming composition (N)) prepared in Production Example 1 using a bar coater (product name “Bar Coater No. 15” manufactured by Daiichi Kagaku Co., Ltd.) on the transparent substrate. It was applied and dried for 2 minutes in a blast dryer at 120 ° C. to form a layer containing metal nanowires.
On the layer containing the metal nanowire, the resin layer forming composition (R) prepared in Production Example 2 was applied with a slot die having a wet film thickness of 2 μm, and dried for 2 minutes in an air blow dryer at 80 ° C. Subsequently, the resin layer forming composition (R) was cured by irradiating with ultraviolet light having an integrated illuminance of 210 mJ / cm 2 with an ultraviolet light irradiation apparatus (Fusion UV Systems) having an oxygen concentration of 100 ppm.
Further, the resin layer forming composition (RP-I) prepared in Production Example 3 was applied to the layer formed from the resin layer forming composition (R) with a slot die with a wet film thickness of 6 μm, It was dried for 2 minutes in an air dryer. Next, the resin layer forming composition (RP-I) is cured by irradiating ultraviolet light with an integrated illuminance of 210 mJ / cm 2 with an ultraviolet light irradiation device (Fusion UV Systems) having an oxygen concentration of 100 ppm, and transparent conductive A characteristic film was obtained.
In this transparent conductive film, the thickness of the resin layer was 0.3 μm, the conductive region including the metal nanowire was formed in the resin layer, the conductive particles were present in the resin layer, and protruded from the surface of the resin layer (protrusion) Part height: 1.0 μm). The transparent conductive film had an initial contact resistance value of 0.9Ω, an initial surface resistance value of 48.2Ω / □, a surface resistance value after an endurance test of 49.6Ω / □, and a change in surface resistance value of 1.4Ω / □. It was □. The scratch resistance was ○.
＜実施例２＞
製造例１で調整した銀ナノワイヤ分散液に、ジエチレングリコールモノエチルエーテルアセタートを添加して銀ナノワイヤ分散液（銀ナノワイヤの濃度：１．０重量％）を調製し、これを樹脂層形成用組成物（Ｎ）として、実施例１で用いた透明基材上に塗布し、１２０℃の送風乾燥機内で２分間乾燥させ金属ナノワイヤを含む層を形成した。
上記金属ナノワイヤを含む層上に、製造例２で調整した樹脂層形成用組成物（Ｒ）をＷｅｔ膜厚２μｍでスロットダイにて塗布し、８０℃の送風乾燥機内で２分間乾燥させた。次いで、酸素濃度１００ｐｐｍ環境とした紫外光照射装置（Ｆｕｓｉｏｎ ＵＶ Ｓｙｓｔｅｍｓ社製）で積算照度２１０ｍＪ／ｃｍ２の紫外光を照射して上記樹脂層形成用組成物（Ｒ）を硬化させた。
樹脂層形成用組成物（Ｒ）を硬化させて得られた層上に、製造例３で調整したバインダー樹脂と導電粒子とを含む樹脂層形成用組成物（ＲＰ−Ｉ）をＷｅｔ膜厚６μｍでスロットダイにて塗布し、８０℃の送風乾燥機内で２分間乾燥させた。次いで、酸素濃度１００ｐｐｍ環境とした紫外光照射装置（Ｆｕｓｉｏｎ ＵＶ Ｓｙｓｔｅｍｓ社製）で積算照度２１０ｍＪ／ｃｍ２の紫外光を照射して上記樹脂層形成用組成物（ＲＰ−Ｉ）を硬化させ、透明導電性フィルムを得た。
この透明導電性フィルムにおいて、樹脂層の膜厚は０．３μｍであり、金属ナノワイヤを含む導電領域は樹脂層および透明基材に形成され、透明基材中の導電領域の厚みは、０．１２μｍであった。また、導電粒子は樹脂層に存在し、かつ樹脂層表面から突出していた（突出部高さ：０．８μｍ）。また、この透明導電性フィルムの初期接触抵抗値は１．４Ω、初期表面抵抗値は４７．１Ω／□、耐久試験後表面抵抗値は４７．５Ω／□、表面抵抗値変化は０．４Ω／□であった。耐擦傷性は○であった。
<Example 2>
Diethylene glycol monoethyl ether acetate is added to the silver nanowire dispersion liquid prepared in Production Example 1 to prepare a silver nanowire dispersion liquid (concentration of silver nanowire: 1.0% by weight), and this is a resin layer forming composition. As (N), it apply | coated on the transparent base material used in Example 1, and it dried for 2 minutes within 120 degreeC ventilation drying machine, and formed the layer containing a metal nanowire.
On the layer containing the metal nanowire, the resin layer forming composition (R) prepared in Production Example 2 was applied with a slot die having a wet film thickness of 2 μm, and dried for 2 minutes in an air blow dryer at 80 ° C. Subsequently, the resin layer forming composition (R) was cured by irradiating with ultraviolet light having an integrated illuminance of 210 mJ / cm 2 with an ultraviolet light irradiation apparatus (Fusion UV Systems) having an oxygen concentration of 100 ppm.
On the layer obtained by curing the resin layer forming composition (R), the resin layer forming composition (RP-I) containing the binder resin and conductive particles prepared in Production Example 3 is used. Then, it was applied with a slot die and dried in an air blow dryer at 80 ° C. for 2 minutes. Next, the resin layer forming composition (RP-I) is cured by irradiating ultraviolet light with an integrated illuminance of 210 mJ / cm 2 with an ultraviolet light irradiation apparatus (Fusion UV Systems) with an oxygen concentration of 100 ppm. A conductive film was obtained.
In this transparent conductive film, the thickness of the resin layer is 0.3 μm, the conductive region including the metal nanowire is formed on the resin layer and the transparent substrate, and the thickness of the conductive region in the transparent substrate is 0.12 μm. Met. In addition, the conductive particles were present in the resin layer and protruded from the surface of the resin layer (projection height: 0.8 μm). Further, this transparent conductive film had an initial contact resistance value of 1.4Ω, an initial surface resistance value of 47.1Ω / □, a surface resistance value after an endurance test of 47.5Ω / □, and a change in surface resistance value of 0.4Ω / □. It was □. The scratch resistance was ○.
＜実施例３＞
実施例２で用いた銀ナノワイヤ分散液に銀粒子（三井金属鉱業株式会社製、商品名「ＳＰＮ０５Ｓ」、平均粒径：１．３μｍ、濃度：０．０２重量％）を分散させて、樹脂層形成用組成物（ＮＰ）を調製した。
実施例１で用いた透明基材上に、樹脂層形成用組成物（ＮＰ）を塗布し、１２０℃の送風乾燥機内で２分間乾燥させ金属ナノワイヤおよび導電粒子（銀粒子）を含む層を形成した。
金属ナノワイヤおよび導電粒子（銀粒子）を含む層上に、製造例２で調整した樹脂層形成用組成物（Ｒ）をＷｅｔ膜厚２μｍでスロットダイにて塗布し、８０℃の送風乾燥機内で２分間乾燥させた。次いで、酸素濃度１００ｐｐｍ環境とした紫外光照射装置（Ｆｕｓｉｏｎ ＵＶ Ｓｙｓｔｅｍｓ社製）で積算照度２１０ｍＪ／ｃｍ２の紫外光を照射して上記樹脂層形成用組成物（Ｒ）を硬化させた。
樹脂層形成用組成物（Ｒ）を硬化させて得られた層上に、製造例２で調製した樹脂層形成用組成物（Ｒ）をＷｅｔ膜厚６μｍでスロットダイにて塗布し、８０℃の送風乾燥機内で２分間乾燥させた。次いで、酸素濃度１００ｐｐｍ環境とした紫外光照射装置（Ｆｕｓｉｏｎ ＵＶ Ｓｙｓｔｅｍｓ社製）で積算照度２１０ｍＪ／ｃｍ２の紫外光を照射して樹脂層形成用組成物（Ｒ）を硬化させ、透明導電性フィルムを得た。
この透明導電性フィルムにおいて、樹脂層の膜厚は０．３μｍであり、金属ナノワイヤを含む導電領域は樹脂層および透明基材に形成され、透明基材中の導電領域の厚みは、０．１１μｍであった。また、導電粒子はその一部が透明基材に侵入し、かつ、樹脂層表面から突出していた（突出部高さ：０．９μｍ）。また、この透明導電性フィルムの初期接触抵抗値は３．１Ω、初期表面抵抗値は４９．２Ω／□、耐久試験後表面抵抗値は５０．０Ω／□、表面抵抗値変化は０．８Ω／□であった。耐擦傷性は○であった。
<Example 3>
Silver particles (Mitsui Metal Mining Co., Ltd., trade name “SPN05S”, average particle size: 1.3 μm, concentration: 0.02 wt%) are dispersed in the silver nanowire dispersion liquid used in Example 2 to obtain a resin layer. A forming composition (NP) was prepared.
A resin layer forming composition (NP) is applied on the transparent substrate used in Example 1, and dried for 2 minutes in an air dryer at 120 ° C. to form a layer containing metal nanowires and conductive particles (silver particles). did.
On the layer containing the metal nanowires and the conductive particles (silver particles), the resin layer forming composition (R) prepared in Production Example 2 was applied with a slot die with a wet film thickness of 2 μm, and in an air blow dryer at 80 ° C. Dry for 2 minutes. Subsequently, the resin layer forming composition (R) was cured by irradiating with ultraviolet light having an integrated illuminance of 210 mJ / cm 2 with an ultraviolet light irradiation apparatus (Fusion UV Systems) having an oxygen concentration of 100 ppm.
On the layer obtained by curing the resin layer-forming composition (R), the resin layer-forming composition (R) prepared in Production Example 2 was applied with a slot die at a wet film thickness of 6 μm, and 80 ° C. For 2 minutes. Next, the resin layer forming composition (R) is cured by irradiating ultraviolet light with an integrated illuminance of 210 mJ / cm 2 with an ultraviolet light irradiation device (Fusion UV Systems) with an oxygen concentration of 100 ppm, and a transparent conductive film Got.
In this transparent conductive film, the thickness of the resin layer is 0.3 μm, the conductive region including the metal nanowire is formed on the resin layer and the transparent substrate, and the thickness of the conductive region in the transparent substrate is 0.11 μm. Met. Part of the conductive particles penetrated the transparent substrate and protruded from the resin layer surface (projection height: 0.9 μm). Further, this transparent conductive film had an initial contact resistance value of 3.1Ω, an initial surface resistance value of 49.2Ω / □, a surface resistance value after an endurance test of 50.0Ω / □, and a change in surface resistance value of 0.8Ω / □. It was □. The scratch resistance was ○.
＜実施例４＞
製造例３で調整した樹脂層形成用組成物（ＲＰ−Ｉ）のＷｅｔを膜厚２０μｍとしたこと以外は、実施例１と同様にして、透明導電性フィルムを得た。
この透明導電性フィルムにおいて、樹脂層の膜厚は１．０μｍであり、金属ナノワイヤを含む導電領域は樹脂層に形成され、導電粒子は樹脂層に存在し、かつ樹脂層表面から突出していた（突出部高さ：０．２μｍ）。また、この透明導電性フィルムの初期接触抵抗値は４．５Ω、初期表面抵抗値は４９．５Ω／□、耐久試験後表面抵抗値は４９．８Ω／□、表面抵抗値変化は０．３Ω／□であった。耐擦傷性は○であった。
<Example 4>
A transparent conductive film was obtained in the same manner as in Example 1 except that the resin layer forming composition (RP-I) prepared in Production Example 3 had a wet thickness of 20 μm.
In this transparent conductive film, the thickness of the resin layer was 1.0 μm, the conductive region including the metal nanowires was formed in the resin layer, the conductive particles were present in the resin layer, and protruded from the surface of the resin layer ( Projection height: 0.2 μm). Further, this transparent conductive film had an initial contact resistance value of 4.5Ω, an initial surface resistance value of 49.5Ω / □, a surface resistance value after endurance test of 49.8Ω / □, and a change in surface resistance value of 0.3Ω / □. It was □. The scratch resistance was ○.
＜実施例５＞
製造例３で調製した樹脂層形成用組成物（ＲＰ−Ｉ）に代えて、製造例４で調製した樹脂層形成用組成物（ＲＰ−ＩＩ）を用いたこと以外は、実施例１と同様にして透明導電性フィルムを得た。
この透明導電性フィルムにおいて、樹脂層の膜厚は０．３μｍであり、金属ナノワイヤを含む導電領域は樹脂層に形成され、導電粒子は樹脂層に存在し、かつ樹脂層表面から突出していた（突出部高さ：４．５μｍ）。また、この透明導電性フィルムの初期接触抵抗値は０．８Ω、初期表面抵抗値は４６．８Ω／□、耐久試験後表面抵抗値は４８．５Ω／□、表面抵抗値変化は１．７Ω／□であった。耐擦傷性は○であった。
<Example 5>
The same as Example 1 except that the resin layer forming composition (RP-II) prepared in Production Example 4 was used instead of the resin layer forming composition (RP-I) prepared in Production Example 3. Thus, a transparent conductive film was obtained.
In this transparent conductive film, the thickness of the resin layer was 0.3 μm, the conductive region including the metal nanowires was formed in the resin layer, the conductive particles were present in the resin layer, and protruded from the resin layer surface ( Projection height: 4.5 μm). The transparent conductive film had an initial contact resistance value of 0.8Ω, an initial surface resistance value of 46.8Ω / □, a surface resistance value after an endurance test of 48.5Ω / □, and a change in surface resistance value of 1.7Ω / □. It was □. The scratch resistance was ○.
＜実施例６＞
製造例３で調製した樹脂層形成用組成物（ＲＰ−Ｉ）に代えて、製造例５で調製した樹脂層形成用組成物（ＲＰ−ＩＩＩ）を用いたこと以外は、実施例１と同様にして透明導電性フィルムを得た。
この透明導電性フィルムにおいて、樹脂層の膜厚は０．３μｍであり、金属ナノワイヤを含む導電領域は樹脂層に形成され、導電粒子は樹脂層に存在し、かつ樹脂層表面から突出していた（突出部高さ：０．６μｍ）。また、この透明導電性フィルムの初期接触抵抗値は３．２Ω、初期表面抵抗値は５１．２Ω／□、耐久試験後表面抵抗値は５１．７Ω／□、表面抵抗値変化は０．５Ω／□であった。耐擦傷性は○であった。
<Example 6>
The same as Example 1 except that the resin layer forming composition (RP-III) prepared in Production Example 5 was used instead of the resin layer forming composition (RP-I) prepared in Production Example 3. Thus, a transparent conductive film was obtained.
In this transparent conductive film, the thickness of the resin layer was 0.3 μm, the conductive region including the metal nanowires was formed in the resin layer, the conductive particles were present in the resin layer, and protruded from the resin layer surface ( Projection height: 0.6 μm). The transparent conductive film had an initial contact resistance value of 3.2Ω, an initial surface resistance value of 51.2Ω / □, a surface resistance value after endurance test of 51.7Ω / □, and a change in surface resistance value of 0.5Ω / □. It was □. The scratch resistance was ○.
＜実施例７＞
製造例３で調製した樹脂層形成用組成物（ＲＰ−Ｉ）に代えて、製造例６で調製した樹脂層形成用組成物（ＲＰ−ＩＶ）を用いたこと以外は、実施例１と同様にして透明導電性フィルムを得た。
この透明導電性フィルムにおいて、樹脂層の膜厚は０．３μｍであり、金属ナノワイヤを含む導電領域は樹脂層に形成され、導電粒子は樹脂層に存在し、かつ樹脂層表面から突出していた。また、導電粒子は樹脂層に存在し、かつ樹脂層表面から突出していた（突出部高さ：１．１μｍ）。また、この透明導電性フィルムの初期接触抵抗値は１．２Ω、初期表面抵抗値は４９．３Ω／□、耐久試験後表面抵抗値は４９．７Ω／□、表面抵抗値変化は０．４Ω／□であった。耐擦傷性は○であった。
<Example 7>
The same as Example 1 except that the resin layer forming composition (RP-IV) prepared in Production Example 6 was used instead of the resin layer forming composition (RP-I) prepared in Production Example 3. Thus, a transparent conductive film was obtained.
In this transparent conductive film, the thickness of the resin layer was 0.3 μm, the conductive region including the metal nanowires was formed in the resin layer, the conductive particles were present in the resin layer, and protruded from the surface of the resin layer. The conductive particles were present in the resin layer and protruded from the resin layer surface (projection height: 1.1 μm). The transparent conductive film had an initial contact resistance value of 1.2Ω, an initial surface resistance value of 49.3Ω / □, a surface resistance value after an endurance test of 49.7Ω / □, and a change in surface resistance value of 0.4Ω / □. It was □. The scratch resistance was ○.
＜比較例１＞
透明基材としてＰＥＴ基材（三菱樹脂株式会社製、商品名「Ｔ６０２」、厚み：５０μｍ）を用いた。この透明基材上にバーコーター（第一理科社製、製品名「バーコーター Ｎｏ．１５」）を用いて、実施例２で用いた銀ナノワイヤ分散液を塗布し、１２０℃の送風乾燥機内で２分間乾燥させて透明導電性フィルムを得た。この透明導電性フィルムにおいて、金属ナノワイヤは、透明基材に０．１１μｍの厚みで侵入するとともに、その一部が表出していた。また、この透明導電性フィルムの初期接触抵抗値は１．０Ω、初期表面抵抗値は５０．１Ω／□、耐久試験後表面抵抗値は７０．３Ω／□、表面抵抗値変化は２０．２Ω／□であった。耐擦傷性は×であった。
<Comparative Example 1>
A PET substrate (manufactured by Mitsubishi Plastics, trade name “T602”, thickness: 50 μm) was used as the transparent substrate. On this transparent base material, the silver nanowire dispersion liquid used in Example 2 was applied using a bar coater (product name “Bar Coater No. 15”, manufactured by Daiichi Science Co., Ltd.), A transparent conductive film was obtained by drying for 2 minutes. In this transparent conductive film, the metal nanowire penetrated into the transparent base material with a thickness of 0.11 μm, and a part thereof was exposed. The transparent conductive film had an initial contact resistance value of 1.0Ω, an initial surface resistance value of 50.1Ω / □, a surface resistance value after an endurance test of 70.3Ω / □, and a change in surface resistance value of 20.2Ω / □. It was □. The scratch resistance was x.
＜比較例２＞
製造例３で調整したバインダー樹脂と導電粒子とを含む樹脂層形成用組成物（ＲＰ−Ｉ）に代えて、製造例２で調整した樹脂層形成用組成物（Ｒ）を用いたこと以外は、実施例２と同様にして、透明導電性フィルムを得た。
この透明導電性フィルムにおいて、樹脂層の膜厚は０．３μｍであり、金属ナノワイヤを含む導電領域は樹脂層および透明基材に形成され、透明基材中の導電領域の厚みは、０．１３μｍであった。この透明導電性フィルムの初期接触抵抗値は測定できなかった。初期表面抵抗値は４９．３Ω／□、耐久試験後表面抵抗値は４９．７Ω／□、表面抵抗値変化は０．４Ω／□であった。耐擦傷性は○であった。
<Comparative example 2>
Except that the resin layer forming composition (R) prepared in Production Example 2 was used instead of the resin layer forming composition (RP-I) containing the binder resin and conductive particles prepared in Production Example 3. In the same manner as in Example 2, a transparent conductive film was obtained.
In this transparent conductive film, the thickness of the resin layer is 0.3 μm, the conductive region including the metal nanowire is formed on the resin layer and the transparent substrate, and the thickness of the conductive region in the transparent substrate is 0.13 μm. Met. The initial contact resistance value of this transparent conductive film could not be measured. The initial surface resistance value was 49.3 Ω / □, the surface resistance value after the durability test was 49.7 Ω / □, and the change in surface resistance value was 0.4 Ω / □. The scratch resistance was ○.
本発明の透明導電性フィルムは、表示素子等の電子機器に用いられ得る。 The transparent conductive film of the present invention can be used in electronic devices such as display elements.
１０ 透明基材
２０ 樹脂層
３０ 導電領域
１００、２００ 透明導電性フィルム
DESCRIPTION OF SYMBOLS 10 Transparent base material 20 Resin layer 30 Conductive area 100, 200 Transparent conductive film
Claims (9)
透明基材と樹脂層との界面近傍に、金属ナノワイヤを含む導電領域が形成され、
該樹脂層が、導電粒子を含み、
該導電粒子の少なくとも一部が、該樹脂層の該透明基材側において、金属ナノワイヤと接触し、
該導電粒子が、該樹脂層の該透明基材とは反対側において、該樹脂層から突出している、
透明導電性フィルム。 A transparent substrate and a resin layer disposed on one or both sides of the transparent substrate;
In the vicinity of the interface between the transparent substrate and the resin layer, a conductive region including metal nanowires is formed,
The resin layer includes conductive particles,
At least a part of the conductive particles are in contact with the metal nanowires on the transparent substrate side of the resin layer,
The conductive particles protrude from the resin layer on the opposite side of the resin layer from the transparent substrate.
Transparent conductive film.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2010015487A (en) * | 2008-07-07 | 2010-01-21 | Citizen Electronics Co Ltd | Transparent electrode, method for forming the electrode, and display device using the method |
| JP2014102962A (en) * | 2012-11-20 | 2014-06-05 | Toray Ind Inc | Conductive laminate, patterned conductive laminate, its manufacturing method and touch panel using them |
| JP2015040316A (en) * | 2013-08-20 | 2015-03-02 | デクセリアルズ株式会社 | Nanoparticle carrying metal nanowire, dispersion, transparent conductive film and production method thereof, as well as touch panel |
| JP2015081843A (en) * | 2013-10-23 | 2015-04-27 | 大日本印刷株式会社 | Conductive material for biosensor and biosensor |
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| JP2010015487A (en) * | 2008-07-07 | 2010-01-21 | Citizen Electronics Co Ltd | Transparent electrode, method for forming the electrode, and display device using the method |
| JP2014102962A (en) * | 2012-11-20 | 2014-06-05 | Toray Ind Inc | Conductive laminate, patterned conductive laminate, its manufacturing method and touch panel using them |
| JP2015040316A (en) * | 2013-08-20 | 2015-03-02 | デクセリアルズ株式会社 | Nanoparticle carrying metal nanowire, dispersion, transparent conductive film and production method thereof, as well as touch panel |
| JP2015081843A (en) * | 2013-10-23 | 2015-04-27 | 大日本印刷株式会社 | Conductive material for biosensor and biosensor |
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