JP6083463B2 - Conductive laminate, bubble or crack occurrence reducing sheet, and bubble or crack occurrence reducing method - Google Patents
Conductive laminate, bubble or crack occurrence reducing sheet, and bubble or crack occurrence reducing method Download PDFInfo
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- JP6083463B2 JP6083463B2 JP2015227342A JP2015227342A JP6083463B2 JP 6083463 B2 JP6083463 B2 JP 6083463B2 JP 2015227342 A JP2015227342 A JP 2015227342A JP 2015227342 A JP2015227342 A JP 2015227342A JP 6083463 B2 JP6083463 B2 JP 6083463B2
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- film
- meth
- inorganic oxide
- acrylate
- bubble
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- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 46
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Images
Description
本発明は、無機酸化物透明導電層を有する導電性導電体に関する。また本発明は、導電性導電体に発生する気泡や亀裂を低減するシートと、導電性導電体における気泡や亀裂の発生を低減する方法にも関する。 The present invention relates to a conductive conductor having an inorganic oxide transparent conductive layer. The present invention also relates to a sheet for reducing bubbles and cracks generated in a conductive conductor and a method for reducing the occurrence of bubbles and cracks in the conductive conductor.
フラットパネルディスプレイ、タッチパネル、電磁波シールド材等においては、可視光透過性を有しつつ導電性を有する透明導電層が備えられている。透明導電層としては、錫ドープ酸化インジウム（以下ＩＴＯという）層が広く用いられており、最近ではインジウム（Ｉｎ）、ガリウム（Ｇａ）、亜鉛（Ｚｎ）、酸素（Ｏ）からなる酸化物半導体（以下ＩＧＺＯという）層の採用も提案されている（非特許文献１参照）。 In a flat panel display, a touch panel, an electromagnetic shielding material, and the like, a transparent conductive layer having conductivity while having visible light permeability is provided. As the transparent conductive layer, a tin-doped indium oxide (hereinafter referred to as ITO) layer is widely used, and recently an oxide semiconductor (indium (In), gallium (Ga), zinc (Zn), oxygen (O)) ( The use of a layer (hereinafter referred to as IGZO) has also been proposed (see Non-Patent Document 1).
これらの無機酸化物透明導電層を有する導電性導電体は、粘着シートを介して光学部材などの他の部材と貼り合わせて使用されるのが一般的である。例えば、液晶パネル、前面板、反射防止体といった光学部材と組み合わせて使用される。これらと組み合わせた導電性導電体は、様々な製品として用いられている。その用途や使用態様は多岐にわたっており、過酷な条件下で長期間使用されることもある。このため、導電性導電体は多様な使用態様に置かれた場合であっても、問題なく長期間にわたって継続使用することが可能であることが要求されている。 The conductive conductor having these inorganic oxide transparent conductive layers is generally used by being bonded to another member such as an optical member via an adhesive sheet. For example, it is used in combination with optical members such as a liquid crystal panel, a front plate, and an antireflection body. Conductive conductors combined with these are used as various products. There are various uses and modes of use, and they may be used for a long time under harsh conditions. For this reason, even when the conductive conductor is placed in various usage modes, it is required that the conductive conductor can be continuously used for a long time without any problem.
しかしながら、導電性導電体を用いた製品を屋外や高湿度下などの過酷な条件下で長期間使用すると、導電性導電体に起因した発泡や亀裂が発生することが本発明者らの検討により明らかになった。このような発泡や亀裂は、透明性や表示性能の低下に繋がり、製品の性能低下の一因となる。そこで本発明者らは、このような従来技術の課題を解決するために、無機酸化物導電層を有する導電性導電体における気泡や亀裂の発生を低減することを目的として検討を進めた。 However, when the product using the conductive conductor is used for a long time under harsh conditions such as outdoors or under high humidity, foaming and cracking due to the conductive conductor may occur. It was revealed. Such foaming or cracking leads to a decrease in transparency and display performance, and contributes to a decrease in product performance. In order to solve such problems of the prior art, the present inventors have made studies for the purpose of reducing the occurrence of bubbles and cracks in a conductive conductor having an inorganic oxide conductive layer.
上記の課題を解決するために鋭意検討を行なった結果、本発明者らは、特定の条件を満たすシートを貼り合わせることにより、導電性導電体における気泡や亀裂の発生を効果的に低減できることを見出して、本発明を完成するに至った。すなわち、課題を解決する手段として、以下の本発明を提供するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that the occurrence of bubbles and cracks in the conductive conductor can be effectively reduced by laminating sheets satisfying specific conditions. As a result, the present invention has been completed. That is, the following present invention has been provided as means for solving the problems.
［１］ 無機酸化物透明導電層、透明フィルム状基材、紫外線吸収剤と粘着剤を含有する機能層を順に積層体した構造を有する導電性積層体。
［２］ 前記透明フィルム状基材が複数の層の積層体であることを特徴とする［１］に記載の導電性積層体。
［３］ 前記透明フィルム状基材の機能層側表面が架橋重合体を含む層であることを特徴とする［１］または［２］に記載の導電性積層体。
［４］ 前記架橋重合体を含む層がアクリル系樹脂を含む層であって、厚みが０．５〜２０μｍであることを特徴とする［３］に記載の導電性積層体。
［５］ 前記透明フィルム状基材の機能層側表面が多官能アクリレートの架橋重合体を含む層であることを特徴とする［１］〜［４］のいずれか１項に記載の導電性積層体。
［６］ 前記無機酸化物透明導電層がＩＴＯ層またはＩＧＺＯ層であることを特徴とする［１］〜［５］のいずれか１項に記載の導電性積層体。
［７］ 前記粘着剤が有機溶剤を用いた溶液重合法で重合させた粘着剤であることを特徴とする［１］〜［６］のいずれか１項に記載の導電性積層体。
［８］ 前記粘着剤が活性エネルギー線硬化型の粘着剤であることを特徴とする［１］〜［６］のいずれか１項に記載の導電性積層体。
［９］ 前記機能層の波長３８０ｎｍの紫外線透過率が５％未満であることを特徴とする［１］〜［８］のいずれか１項に記載の導電性積層体。
［１０］ 前記紫外線吸収剤が２３℃で油状または液状である化合物を少なくとも１種含有し、かつ前記機能層の固形分１００質量部に対して０．５〜８質量部で含まれていることを特徴とする［１］〜［９］のいずれか１項に記載の導電性積層体。
［１１］ 前記機能層上にさらに剥離層を有することを特徴とする［１］〜［１０］のいずれか１項に記載の導電性積層体。
［１２］ 前記機能層上にさらに部材を有することを特徴とする［１］〜［１０］のいずれか１項に記載の導電性積層体。
［１３］ 前記部材がガラスであることを特徴とする［１２］に記載の導電性積層体。
[1] A conductive laminate having a structure in which an inorganic oxide transparent conductive layer, a transparent film-like substrate, a functional layer containing an ultraviolet absorber and a pressure-sensitive adhesive are sequentially laminated.
[2] The conductive laminate according to [1], wherein the transparent film-like substrate is a laminate of a plurality of layers.
[3] The conductive laminate according to [1] or [2], wherein the functional layer side surface of the transparent film substrate is a layer containing a crosslinked polymer.
[4] The conductive laminate according to [3], wherein the layer containing the crosslinked polymer is a layer containing an acrylic resin and has a thickness of 0.5 to 20 μm.
[5] The conductive laminate according to any one of [1] to [4], wherein the functional layer side surface of the transparent film substrate is a layer containing a cross-linked polymer of polyfunctional acrylate. body.
[6] The conductive laminate according to any one of [1] to [5], wherein the inorganic oxide transparent conductive layer is an ITO layer or an IGZO layer.
[7] The conductive laminate according to any one of [1] to [6], wherein the pressure-sensitive adhesive is a pressure-sensitive adhesive polymerized by a solution polymerization method using an organic solvent.
[8] The conductive laminate according to any one of [1] to [6], wherein the adhesive is an active energy ray-curable adhesive.
[9] The conductive laminate according to any one of [1] to [8], wherein the functional layer has an ultraviolet transmittance at a wavelength of 380 nm of less than 5%.
[10] The ultraviolet absorber contains at least one compound that is oily or liquid at 23 ° C., and is contained in an amount of 0.5 to 8 parts by mass with respect to 100 parts by mass of the solid content of the functional layer. The conductive laminate according to any one of [1] to [9], wherein:
[11] The conductive laminate according to any one of [1] to [10], further including a release layer on the functional layer.
[12] The conductive laminate according to any one of [1] to [10], further including a member on the functional layer.
[13] The conductive laminate according to [12], wherein the member is glass.
［１４］ 透明フィルム状基材の片面に無機酸化物透明導電層を有する無機酸化物透明導電体の気泡発生低減シートであって、
紫外線吸収剤と粘着剤を含むことを特徴とする気泡発生低減シート。
［１５］ 透明フィルム状基材の片面に無機酸化物透明導電層を有する無機酸化物透明導電体の亀裂発生低減シートであって、
紫外線吸収剤と粘着剤を含むことを特徴とする亀裂発生低減シート。
[14] A bubble generation reducing sheet of an inorganic oxide transparent conductor having an inorganic oxide transparent conductive layer on one side of a transparent film-shaped substrate,
A bubble generation-reducing sheet comprising an ultraviolet absorber and an adhesive.
[15] A crack generation reducing sheet of an inorganic oxide transparent conductor having an inorganic oxide transparent conductive layer on one side of a transparent film-shaped substrate,
A crack generation-reducing sheet comprising an ultraviolet absorber and an adhesive.
［１６］ 透明フィルム状基材の片面に無機酸化物透明導電層を有する無機酸化物透明導電体の気泡発生低減方法であって、
前記無機酸化物透明導電層が形成されている面とは反対側の面に、紫外線吸収剤と粘着剤を含有する機能層を積層することを特徴とする気泡発生低減方法。
［１７］ 透明フィルム状基材の片面に無機酸化物透明導電層を有する無機酸化物透明導電体の亀裂発生低減方法であって、
前記無機酸化物透明導電層が形成されている面とは反対側の面に、紫外線吸収剤と粘着剤を含有する機能層を積層することを特徴とする亀裂発生低減方法。
[16] A method for reducing bubble generation in an inorganic oxide transparent conductor having an inorganic oxide transparent conductive layer on one side of a transparent film-shaped substrate,
A method for reducing bubble generation, comprising laminating a functional layer containing an ultraviolet absorber and an adhesive on a surface opposite to a surface on which the inorganic oxide transparent conductive layer is formed.
[17] A method for reducing cracks in an inorganic oxide transparent conductor having an inorganic oxide transparent conductive layer on one side of a transparent film-shaped substrate,
A crack generation reduction method comprising laminating a functional layer containing an ultraviolet absorber and an adhesive on a surface opposite to a surface on which the inorganic oxide transparent conductive layer is formed.
本発明の導電性積層体は、長時間過酷な条件に置いた場合であっても、気泡や亀裂の発生を低減することができる。また、本発明の気泡発生低減シートと亀裂発生低減シートは、導電性積層体に貼り合わせることにより、導電性積層体における気泡や亀裂の発生を低減することができる。さらに、本発明の気泡発生低減方法と亀裂発生低減方法によれば、簡単な方法で導電性積層体における気泡や亀裂の発生を低減することができる。 The conductive laminate of the present invention can reduce the occurrence of bubbles and cracks even when placed under harsh conditions for a long time. In addition, the bubble generation reduction sheet and the crack generation reduction sheet of the present invention can reduce the generation of bubbles and cracks in the conductive laminate by being bonded to the conductive laminate. Furthermore, according to the bubble generation reduction method and crack generation reduction method of the present invention, it is possible to reduce the generation of bubbles and cracks in the conductive laminate by a simple method.
以下において、本発明について詳細に説明する。以下に記載する構成要件の説明は、本発明の代表的な実施態様や具体例に基づいてなされることがあるが、本発明はそのような実施態様や具体例に限定されるものではない。なお、本明細書において「〜」を用いて表される数値範囲は、「〜」の前後に記載される数値を下限値および上限値として含む範囲を意味する。 Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments and specific examples of the present invention, but the present invention is not limited to such embodiments and specific examples. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
［導電性積層体］
＜構成の特徴＞
図１に示すように、本発明の導電性積層体（１）は、無機酸化物透明導電層（１１）、透明フィルム状基材（１２）、紫外線吸収剤と粘着剤を含有する機能層（１３）を順に積層体した構造を有することを特徴とする。そこで、以下において、本発明の導電性積層体を構成する無機酸化物透明導電層、透明フィルム状基材、機能層について順に詳しく説明する。
[Conductive laminate]
<Features of configuration>
As shown in FIG. 1, the conductive laminate (1) of the present invention comprises an inorganic oxide transparent conductive layer (11), a transparent film substrate (12), a functional layer containing an ultraviolet absorber and an adhesive ( 13) It has the structure which laminated | stacked in order. Therefore, in the following, the inorganic oxide transparent conductive layer, the transparent film-like substrate, and the functional layer constituting the conductive laminate of the present invention will be described in detail in order.
＜無機酸化物透明導電層＞
本発明の導電性積層体を構成する無機酸化物透明導電層は、導電性を有し、可視光線を透過する透明な無機酸化物から構成されるものである。そのような無機酸化物として。スズ、亜鉛、インジウム、ガリウムチタン、珪素、ジルコニウム、金、銀、銅、マグネシウム、アルミニウム、パラジウム、アンチモン、タングステンの酸化物などを挙げることができる。これらの元素を２種以上含む酸化物を用いてもよい。好ましい無機酸化物透明導電層として、ＩＴＯ層やＩＧＺＯ層などを例示することができる。
<Inorganic oxide transparent conductive layer>
The inorganic oxide transparent conductive layer constituting the conductive laminate of the present invention is composed of a transparent inorganic oxide having conductivity and transmitting visible light. As such an inorganic oxide. Examples include tin, zinc, indium, gallium titanium, silicon, zirconium, gold, silver, copper, magnesium, aluminum, palladium, antimony, and oxides of tungsten. An oxide containing two or more of these elements may be used. Examples of preferred inorganic oxide transparent conductive layers include ITO layers and IGZO layers.
本発明における無機酸化物透明導電層の形成方法は特に制限されない。透明フィルム状基材上に、例えば、真空蒸着法、スパッタリング法、イオンプレーティング法により形成することが可能である。
また、無機酸化物透明導電層の厚みも特に制限されない。通常は１ｎｍ以上とし、例えば５ｎｍ以上、あるいは１０ｎｍ以上にすることができる。上限については、例えば１ｍｍ以下としたり、１μｍ以下としたり、０．１μｍ以下としたり、０．０３μｍ以下とすることができる。
The method for forming the inorganic oxide transparent conductive layer in the present invention is not particularly limited. It can be formed on a transparent film-like substrate by, for example, a vacuum deposition method, a sputtering method, or an ion plating method.
Further, the thickness of the inorganic oxide transparent conductive layer is not particularly limited. Usually, it is 1 nm or more, for example, 5 nm or more, or 10 nm or more. For example, the upper limit may be 1 mm or less, 1 μm or less, 0.1 μm or less, or 0.03 μm or less.
＜透明フィルム状基材＞
本発明の導電性積層体を構成する透明フィルム状基材は、可視光線を透過する透明な材料から構成されているフィルム状の材料から構成される。典型的な構成材料は透明な樹脂である。例えば、ポリエチレンテレフタレート（ＰＥＴ）フィルム、ポリエチレンナフタレートフィルム、ポリプロピレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリプロピレンナフタレートフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、セロファン、ジアセチルセルロースフィルム、トリアセチルセルロースフィルム、アセチルセルロースブチレートフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム、ポリビニルアルコールフィルム、エチレン−酢酸ビニル共重合体フィルム、ポリスチレンフィルム、ポリカーボネートフィルム、ポリメチルペンテンフィルム、ポリスルホンフィルム、ポリエーテルエーテルケトンフィルム、ポリエーテルスルホンフィルム、ポリエーテルイミドフィルム、ポリイミドフィルム、フッ素樹脂フィルム、ポリアミドフィルム、アクリル樹脂フィルム等が挙げられる。これらの中では、耐熱性に優れること等から、ＰＥＴが好ましく用いられる。
<Transparent film substrate>
The transparent film-like base material constituting the conductive laminate of the present invention is made of a film-like material made of a transparent material that transmits visible light. A typical constituent material is a transparent resin. For example, polyethylene terephthalate (PET) film, polyethylene naphthalate film, polypropylene terephthalate film, polybutylene terephthalate film, polypropylene naphthalate film, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film , Polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether ether ketone film, polyether sulfone film, poly Etherimide film Polyimide film, a fluororesin film, a polyamide film, and acrylic resin film. Among these, PET is preferably used because of its excellent heat resistance.
また、本発明の導電性積層体を構成する透明フィルム状基材は、透明な架橋重合体を含むものであることも好ましい。そのような架橋重合体として、多官能モノマーの重合体を挙げることができる。好ましくは３官能以上の多官能モノマーを含む重合性モノマーの重合体であり、より好ましくは４官能以上の多官能モノマーを含む重合性モノマーの重合体である。例えば、３官能以上の多官能モノマーと２官能モノマーの混合モノマーの共重合体なども好ましく例示することができる。なお、ここでいうモノマーには、オリゴマーも含まれる。 Moreover, it is also preferable that the transparent film-form base material which comprises the electroconductive laminated body of this invention contains a transparent crosslinked polymer. An example of such a crosslinked polymer is a polymer of a polyfunctional monomer. Preferred is a polymer of a polymerizable monomer containing a trifunctional or higher polyfunctional monomer, and more preferred is a polymer of a polymerizable monomer containing a tetrafunctional or higher polyfunctional monomer. For example, a copolymer of a mixed monomer of a trifunctional or higher polyfunctional monomer and a bifunctional monomer can be preferably exemplified. In addition, an oligomer is also contained in the monomer here.
架橋重合体を得るために使用しうるモノマーの種類は特に制限されないが、例えば、アクリルモノマーなどを好ましく例示することができる。例えば、ジプロピレングリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ポリエチレングリコール（質量平均分子量６００）ジ（メタ）アクリレート、プロピレンオキサイド変性ネオペンチルグリコールジ（メタ）アクリレート、変性ビスフェノールＡジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、ポリエチレングリコール（質量平均分子量４００）ジ（メタ）アクリレート等の２官能（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（メタ）アクリレート、トリメチロールプロパンエトキシトリ（メタ）アクリレート、ポリエーテルトリ（メタ）アクリレート、グリセリンプロポキシトリ（メタ）アクリレート等の３官能(メタ)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、ペンタエリスリトールエトキシテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、プロピオン酸変性ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールモノヒドロキシペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等の４官能以上の（メタ）アクリレートが挙げられる。
重合性不飽和基を有する有機化合物のモノマーまたはオリゴマーは、熱硬化性であってもよいし、活性エネルギー線硬化性であってもよい。
Although the kind of monomer which can be used in order to obtain a crosslinked polymer is not restrict | limited in particular, For example, an acrylic monomer etc. can be illustrated preferably. For example, dipropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol (mass average molecular weight 600) di (meth) acrylate, propylene oxide modified neo Bifunctional (meth) acrylates such as pentyl glycol di (meth) acrylate, modified bisphenol A di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, polyethylene glycol (mass average molecular weight 400) di (meth) acrylate, Pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, polyether tri (meth) acrylate , Trifunctional (meth) acrylates such as glycerol propoxytri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, propionic acid modified dipenta Examples include tetra- or higher functional (meth) acrylates such as erythritol penta (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
The monomer or oligomer of the organic compound having a polymerizable unsaturated group may be thermosetting or active energy ray curable.
また、架橋重合体は、無機粒子および／または有機粒子を含有していてもよい。無機粒子および／または有機粒子を含有すると、塗膜の硬化収縮が抑制される点で好ましい。無機粒子としては、例えば、二酸化ケイ素粒子、二酸化チタン粒子、酸化ジルコニウム粒子、酸化アルミニウム粒子、二酸化スズ粒子、五酸化アンチモン粒子、三酸化アンチモン粒子などの無機酸化物粒子を挙げることができる。また、有機粒子としては、例えば、アクリル樹脂、ポリスチレン、ポリシロキサン、メラミン樹脂、ベンゾグアナミン樹脂、ポリテトラフルオロエチレン、セルロースアセテート、ポリカーボネート、ポリアミドなどの樹脂粒子などを挙げることができる。 The crosslinked polymer may contain inorganic particles and / or organic particles. When inorganic particles and / or organic particles are contained, it is preferable in that curing shrinkage of the coating film is suppressed. Examples of the inorganic particles include inorganic oxide particles such as silicon dioxide particles, titanium dioxide particles, zirconium oxide particles, aluminum oxide particles, tin dioxide particles, antimony pentoxide particles, and antimony trioxide particles. Examples of the organic particles include resin particles such as acrylic resin, polystyrene, polysiloxane, melamine resin, benzoguanamine resin, polytetrafluoroethylene, cellulose acetate, polycarbonate, and polyamide.
無機粒子を用いる場合は、カップリング剤により処理した反応性無機酸化物粒子を用いることが好ましい。有機粒子を用いる場合は、カップリング剤により処理した反応性有機酸化物粒子を用いることが好ましい。カップリング剤により処理することにより、アクリル系重合体との間の結合力を高めることができる。その結果、表面硬度や耐擦傷性を向上させることができ、さらに無機酸化物粒子および有機粒子の分散性を向上させることができるため、好ましい。 When using inorganic particles, it is preferable to use reactive inorganic oxide particles treated with a coupling agent. When organic particles are used, it is preferable to use reactive organic oxide particles treated with a coupling agent. By treating with a coupling agent, the bonding strength with the acrylic polymer can be increased. As a result, the surface hardness and scratch resistance can be improved, and further, the dispersibility of the inorganic oxide particles and the organic particles can be improved, which is preferable.
カップリング剤としては、例えば、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリエトキシアルミニウム等が挙げられる。これらは１種を単独で使用してもよいし、２種以上を併用してもよい。カップリング剤の処理量は、無機酸化物粒子または有機粒子１００質量部に対して、０．１〜２０質量部であることが好ましく、１〜１０質量部であることがより好ましい。 Examples of the coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-mercaptopropyltrimethoxy. Examples thereof include silane, γ-aminopropyltriethoxysilane, and γ-aminopropyltriethoxyaluminum. These may be used individually by 1 type and may use 2 or more types together. The amount of the coupling agent to be treated is preferably 0.1 to 20 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the inorganic oxide particles or the organic particles.
本発明の導電性積層体を構成する透明フィルム状基材は、単層であっても、複数の層から構成されるものであってもよい。複数の層から構成されるものである場合は、上記のＰＥＴなどの透明樹脂フィルム上に架橋重合体フィルムを積層した構造などを好ましく例示することができる。ＰＥＴなどの透明樹脂フィルム上に架橋重合体フィルムを積層する場合は、積層前にＰＥＴなどの透明樹脂フィルムを表面処理しておいてもよい。表面処理としては、例えば、サンドブラスト処理や溶剤処理等の凹凸化処理、コロナ放電処理、クロム酸処理、火炎処理、熱風処理、オゾン・紫外線照射処理等の表面酸化処理などが挙げられる。特に透明フィルム状基材が架橋重合体を含む場合に、本発明の効果をより発揮させることができる。 The transparent film-like substrate constituting the conductive laminate of the present invention may be a single layer or a plurality of layers. In the case of being composed of a plurality of layers, a structure in which a cross-linked polymer film is laminated on the transparent resin film such as the above-mentioned PET can be preferably exemplified. When a crosslinked polymer film is laminated on a transparent resin film such as PET, the transparent resin film such as PET may be surface-treated before lamination. Examples of the surface treatment include surface roughening treatment such as sandblast treatment and solvent treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. In particular, when the transparent film-like substrate contains a crosslinked polymer, the effect of the present invention can be exhibited more.
本発明の導電性積層体を構成する透明フィルム状基材の厚みは特に制限されないが、例えば、１０μｍ以上にすることができ、２０μｍ以上、５０μｍ以上の範囲内で選択することも可能である。上限は用途によって異なるが、例えば１ｃｍ以下、１ｍｍ以下、３００μｍ以下の範囲内で選択することも可能である。また、架橋重合体を含む層の厚みは、０．５〜２０μｍであることが好ましい。 The thickness of the transparent film-like substrate constituting the conductive laminate of the present invention is not particularly limited, but can be, for example, 10 μm or more, and can be selected within a range of 20 μm or more and 50 μm or more. Although an upper limit changes with uses, it is also possible to select within the range of 1 cm or less, 1 mm or less, and 300 micrometers or less, for example. Moreover, it is preferable that the thickness of the layer containing a crosslinked polymer is 0.5-20 micrometers.
＜機能層＞
本発明の導電性積層体を構成する機能層は、紫外線吸収剤と粘着剤を含有する層である。
<Functional layer>
The functional layer which comprises the electroconductive laminated body of this invention is a layer containing a ultraviolet absorber and an adhesive.
（１）機能層の粘着剤
粘着剤としては、アクリル重合体を好ましく例示することができる。その中でも、官能基を持たない（メタ）アクリル酸アルキルエステルを主成分とし、これに官能基を有する（メタ）アクリル酸系単量体との共重合体を用いることが好ましい。官能基を有する（メタ）アクリル酸系単量体は架橋剤を用いる場合の反応点なり、架橋により粘着力や凝集力や耐熱性の制御が可能となるためである。
官能基を持たない（メタ）アクリル酸アルキルエステルと（メタ）アクリル酸系アルキルエステル以外の官能基を有する（メタ）アクリル酸系単量体の使用量は、共重合体を構成する全単量体質量中に占める割合として０．１〜２０質量％とすることが好ましい。より好ましくは０．５〜１５質量％であり、さらに好ましくは１〜１０質量％である。なお、本発明における「（メタ）アクリル酸」とは、アクリル酸およびメタリル酸の総称である。
(1) Functional layer pressure-sensitive adhesive As the pressure-sensitive adhesive, an acrylic polymer can be preferably exemplified. Among them, it is preferable to use a copolymer of (meth) acrylic acid alkyl ester having no functional group as a main component and a (meth) acrylic acid monomer having a functional group. This is because the (meth) acrylic acid monomer having a functional group is a reaction point when a crosslinking agent is used, and the adhesive force, cohesive force and heat resistance can be controlled by crosslinking.
The amount of the (meth) acrylic acid alkyl ester having a functional group other than the (meth) acrylic acid alkyl ester having no functional group and the (meth) acrylic acid alkyl ester is the total amount of the copolymer constituting the copolymer. It is preferable to set it as 0.1-20 mass% as a ratio occupied in body mass. More preferably, it is 0.5-15 mass%, More preferably, it is 1-10 mass%. In the present invention, “(meth) acrylic acid” is a general term for acrylic acid and methacrylic acid.
アクリル重合体を構成する官能基を持たない（メタ）アクリル酸アルキルエステルの単量体としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソノニル（メタ）アクリレート、ラウリル（メタ）アクリレート等の（メタ）アクリル酸アルキルエステル単量体が挙げられるが、これらは必要に応じ２種類以上を併用しても良い。 Examples of monomers of (meth) acrylic acid alkyl ester having no functional group constituting the acrylic polymer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. (Meth) acrylic acid alkyl ester monomers such as isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate and lauryl (meth) acrylate However, these may be used in combination of two or more if necessary.
また、官能基を有する（メタ）アクリル酸系単量体としては（メタ）アクリル酸、マレイン酸、無水マレイン酸、イタコン酸、フマル酸、無水フマル酸等のカルボキシル基含有単量体、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、２−ヒドロキシブチル（メタ）アクリレート、ポリエチレングリコール（メタ）アクリレート等の水酸基含有単量体、（メタ）アクリルアミド、モルホリルアクリルアミド、Ｎ，Ｎ−ジメチルアミノエチルアクリレート、Ｎ−ｔｅｒｔ−ブチルアミノエチルアクリレート等のアミノ基含有(メタ)アクリル酸エステル、グリシジル（メタ）アクリレート等のエポキシ基などが挙げられ、これらは必要に応じ２種類以上を併用しても良い。 In addition, examples of the (meth) acrylic acid monomer having a functional group include (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, fumaric anhydride and other carboxyl group-containing monomers, 2- Hydroxyl-containing monomers such as hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, (meth) acrylamide, morpholyacrylamide, N , N-dimethylaminoethyl acrylate, N-tert-butylaminoethyl acrylate and other amino group-containing (meth) acrylic acid esters, glycidyl (meth) acrylate and other epoxy groups, and the like. May be used in combination.
粘着剤を重合する際には、例えば、溶液重合法を適用することができる。
溶液重合法としては、イオン重合法やラジカル重合法など挙げられる。その際に使用される溶媒としては、例えば、テトラヒドロフラン、クロロホルム、酢酸エチル、トルエン、ヘキサン、アセトン、メチルエチルケトンなどが挙げられる。
本発明では、有機溶剤を用いた溶液重合法や活性エネルギー線硬化型の粘着剤を用いることが好ましい。
When polymerizing the pressure-sensitive adhesive, for example, a solution polymerization method can be applied.
Examples of the solution polymerization method include an ionic polymerization method and a radical polymerization method. Examples of the solvent used at that time include tetrahydrofuran, chloroform, ethyl acetate, toluene, hexane, acetone, methyl ethyl ketone, and the like.
In the present invention, it is preferable to use a solution polymerization method using an organic solvent or an active energy ray-curable pressure-sensitive adhesive.
本発明で用いる粘着剤が前記官能基を有する単量体を用いた共重合体の場合は、架橋剤を配合することにより架橋処理を施すことができる。
架橋剤としては、例えば、イソシアネート化合物、エポキシ化合物、オキサゾリン化合物、アジリジン化合物、金属キレート化合物、ブチル化メラミン化合物などが挙げられ、これらは必要に応じ２種類以上を併用しても良い。
これら架橋剤の中でも、アクリル重合体を容易に架橋できることから、イソシアネート化合物、エポキシ化合物が好ましい。
イソシアネート化合物としては、例えば、トリレンジイソシアネート、キシリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネートなどが挙げられる。
エポキシ化合物としては、例えば、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル、テトラグリシジルキシレンジアミン、１，３−ビス（Ｎ，Ｎ−ジグリシジルアミノメチル）シクロヘキサン、トリメチロールプロパンポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ソルビトールポリグリシジルエーテルなどが挙げられる。
架橋剤の含有量は、所望とする粘着物性に応じて適宜選択することが好ましい。
In the case where the pressure-sensitive adhesive used in the present invention is a copolymer using the monomer having the functional group, a crosslinking treatment can be performed by blending a crosslinking agent.
As a crosslinking agent, an isocyanate compound, an epoxy compound, an oxazoline compound, an aziridine compound, a metal chelate compound, a butylated melamine compound, etc. are mentioned, for example, These may use 2 or more types together as needed.
Among these crosslinking agents, an isocyanate compound and an epoxy compound are preferable because the acrylic polymer can be easily crosslinked.
Examples of the isocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diester. Glycidyl ether, tetraglycidyl xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc. Can be mentioned.
It is preferable that the content of the crosslinking agent is appropriately selected according to the desired pressure-sensitive adhesive properties.
（２）機能層の紫外線吸収剤
機能層に用いる紫外線吸収剤は、紫外領域に極大吸収波長を有するものの中から選択することができる。本発明では、特に波長３５０ｎｍ以上に極大吸収波長を有する紫外線吸収剤を用いることが好ましい。波長３５０ｎｍ以上に極大吸収波長を有する紫外線吸収剤として、例えば下記一般式（１）または（２）で示される化合物を挙げることができる。
(2) Ultraviolet absorber for functional layer The ultraviolet absorber used for the functional layer can be selected from those having a maximum absorption wavelength in the ultraviolet region. In the present invention, it is particularly preferable to use an ultraviolet absorber having a maximum absorption wavelength at a wavelength of 350 nm or more. Examples of the ultraviolet absorber having a maximum absorption wavelength at a wavelength of 350 nm or longer include compounds represented by the following general formula (1) or (2).
上式において、Ｒ1は、水素原子、ハロゲン原子、炭素数１〜４のアルコキシ基、ニトロ基またはシアノ基を表し、Ｒ2は、水素原子または炭素数１〜８のアルキル基を表し、Ｒ3は、アルキル基系構造体を表す。 In the above formula, R 1 represents a hydrogen atom, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, a nitro group or a cyano group, R 2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R 3 represents an alkyl group structure.
上式において、Ｒ4、Ｒ5およびＲ6は、水素原子、水酸基、アルキル基系構造体またはハロゲン原子であって、Ｒ4、Ｒ5およびＲ6のすべてが水素原子であることはない。 In the above formula, R 4 , R 5 and R 6 are a hydrogen atom, a hydroxyl group, an alkyl group structure or a halogen atom, and all of R 4 , R 5 and R 6 are not hydrogen atoms.
アルキル基系構造体とは、置換もしくは無置換のアルキル基や、置換もしくは無置換のアルコキシ基などのアルキル基を主とする置換基を含む概念である。 The alkyl group structure is a concept including a substituent mainly composed of an alkyl group such as a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkoxy group.
中でも、基本骨格の芳香環に分子量の大きなアルキル基を導入することにより相溶性を向上させ、２３℃で液状または油状を示す紫外線吸収剤を、特に好ましく用いることができる。ここで、２３℃で液状または油状を示すとは、希釈溶剤がなくても紫外線吸収剤のみで流動性がある状態を意味する。 Among them, an ultraviolet absorber that improves the compatibility by introducing an alkyl group having a large molecular weight into the aromatic ring of the basic skeleton and exhibits a liquid state or an oil state at 23 ° C. can be particularly preferably used. Here, being liquid or oily at 23 ° C. means a state in which there is fluidity only with an ultraviolet absorber even without a diluting solvent.
本発明における紫外線吸収剤の含有量は、機能層の固形分（特にアクリル重合体）１００質量部に対して０．５〜８質量部であることが好ましく、３〜８質量部であることがより好ましく、４〜６質量部であることがさらに好ましい。本発明における紫外線吸収剤の含有量は、３８０ｎｍでの紫外線透過率が５％未満となる量に調整することが好ましい。含有量が３質量部以上であれば、機能層厚みが２５μｍの時、３８０ｎｍの波長の光での透過率が２％以下になるため、本発明の効果がより得られやすくなる。また、８質量部以下であれば、粘着特性を損ねることがないため好ましく、さらに４〜６質量部であれば、さらに安定して２％以下の透過率が得られるため好ましい。本発明では、２種以上の紫外線吸収剤を併用してもよい。 In the present invention, the content of the ultraviolet absorber is preferably 0.5 to 8 parts by mass, and preferably 3 to 8 parts by mass with respect to 100 parts by mass of the solid content (particularly acrylic polymer) of the functional layer. More preferably, it is 4-6 mass parts. The content of the ultraviolet absorber in the present invention is preferably adjusted to such an amount that the ultraviolet transmittance at 380 nm is less than 5%. When the content is 3 parts by mass or more, when the functional layer thickness is 25 μm, the transmittance with light having a wavelength of 380 nm is 2% or less, so that the effect of the present invention is more easily obtained. Moreover, if it is 8 mass parts or less, since an adhesive characteristic is not impaired, it is preferable, and if it is 4-6 mass parts, since the transmittance | permeability of 2% or less is obtained more stably, it is preferable. In the present invention, two or more ultraviolet absorbers may be used in combination.
（３）機能層に併用可能な添加剤
本発明の機能層に併用することができる添加剤として、ヒンダードアミン系化合物に代表される光安定剤を好ましく例示することができる。また、ヒンダードフェノール系化合物に代表される酸化防止剤を併用することも好ましい。酸化防止剤は、一般にラジカル連鎖停止剤とよばれる一次酸化防止剤と、過酸化物分解剤として作用する二次酸化防止剤とに分類される。一次酸化防止剤としては、ヒンダードフェノール系酸化防止剤、アミン系酸化防止剤、ラクトン系酸化防止剤が挙げられる。また、二次酸化防止剤としては、リン系酸化防止剤、イオウ系酸化防止剤が挙げられる。
これら酸化防止剤は１種を単独で使用してもよいし、２種以上を併用してもよい。
(3) Additives that can be used in combination with the functional layer Preferred examples of additives that can be used in the functional layer of the present invention include light stabilizers typified by hindered amine compounds. It is also preferable to use an antioxidant typified by a hindered phenol compound. Antioxidants are generally classified into primary antioxidants called radical chain terminators and secondary antioxidants that act as peroxide decomposers. Examples of the primary antioxidant include hindered phenol antioxidants, amine antioxidants, and lactone antioxidants. Examples of secondary antioxidants include phosphorus antioxidants and sulfur antioxidants.
These antioxidants may be used alone or in combination of two or more.
併用される添加剤の含有量は、アクリル重合体１００質量部に対して０．０３〜１．５質量部であることが好ましく、０．０５〜１．０質量部であることがより好ましい。含有量が前記下限値以上であれば、高温、低温及び湿熱環境下にて長期間にわたって使用した際の紫外線の吸収性を確実に維持でき、前記上限値以下であれば、３８０ｎｍでの透過率上昇や粘着特性の低下をより防止できる。 The content of the additive used in combination is preferably 0.03 to 1.5 parts by mass and more preferably 0.05 to 1.0 parts by mass with respect to 100 parts by mass of the acrylic polymer. If the content is equal to or higher than the lower limit value, it is possible to reliably maintain the absorbency of ultraviolet rays when used over a long period of time in a high temperature, low temperature and wet heat environment, and if the content is equal to or lower than the upper limit value, the transmittance at 380 nm. It is possible to further prevent the rise and the deterioration of the adhesive property.
機能層には、必要に応じて、粘着付与剤、シランカップリング剤、金属腐食防止剤などの上記以外の添加剤が含まれてもよい。粘着付与剤として、例えば、ロジン系樹脂、テルペン系樹脂、テルペンフェノール系樹脂、クマロンインデン系樹脂、スチレン系樹脂、キシレン系樹脂、フェノール系樹脂、石油樹脂などが挙げられる。シランカップリング剤としては、例えば、メルカプトアルコキシシラン化合物（例えば、メルカプト基置換アルコキシオリゴマー等）などが挙げられる。金属腐食防止剤としては金属と錯体を形成し金属表面に皮膜を作ることにより腐食を防止するタイプが好ましく、特にベンゾトリアゾール系金属腐食防止剤が好ましい。 The functional layer may contain additives other than the above, such as a tackifier, a silane coupling agent, and a metal corrosion inhibitor, as necessary. Examples of the tackifier include rosin resin, terpene resin, terpene phenol resin, coumarone indene resin, styrene resin, xylene resin, phenol resin, and petroleum resin. Examples of the silane coupling agent include mercaptoalkoxysilane compounds (for example, mercapto group-substituted alkoxy oligomers). As the metal corrosion inhibitor, a type that prevents a corrosion by forming a complex with a metal and forming a film on the metal surface is preferable, and a benzotriazole-based metal corrosion inhibitor is particularly preferable.
機能層の厚みは１０〜１００μｍとすることが好ましく、１５〜５０μｍとすることがより好ましい。厚みが１０μｍ以上であれば、充分な粘着力を確保でき、長時間使用しても浮きや剥がれが生じにくくなる上に、紫外線を充分に吸収できる。また、機能層の厚みが１００μｍ以下であれば、ディスプレイの大きさに粘着シートをカットする際にカット刃などに粘着剤が付着して不良率が上がるなどのトラブルが生じにくいという利点がある。 The thickness of the functional layer is preferably 10 to 100 μm, and more preferably 15 to 50 μm. When the thickness is 10 μm or more, sufficient adhesive strength can be secured, and even when used for a long time, it is difficult for floating and peeling to occur, and ultraviolet rays can be sufficiently absorbed. In addition, when the thickness of the functional layer is 100 μm or less, there is an advantage that troubles such as an increase in the defect rate due to adhesion of the adhesive to the cutting blade when the adhesive sheet is cut to the size of the display are obtained.
＜剥離層＞
本発明の導電性積層体の機能層表面には、さらに剥離層が形成されていてもよい。導電性積層体の機能層は粘着剤を含有しているため、露出していると意図しない物品と粘着してしまったり、機能層自体が劣化してしまったりするおそれがある。このため、機能層を物理的および化学的に保護するために、機能層の表面に剥離層を設けておき、使用する際に剥離層を剥離して機能層を露出させたうえで、他の部材へ貼り合わせることができる。
<Peeling layer>
A release layer may be further formed on the functional layer surface of the conductive laminate of the present invention. Since the functional layer of the conductive laminate contains an adhesive, if it is exposed, it may stick to an unintended article or the functional layer itself may deteriorate. For this reason, in order to physically and chemically protect the functional layer, a release layer is provided on the surface of the functional layer, and when used, the release layer is peeled off to expose the functional layer. Can be attached to a member.
剥離層としては、例えば、各種プラスチックフィルムにシリコーン等の剥離剤を塗布して剥離剤層を形成したもの、ポリプロピレンフィルム単体などが挙げられ、通常の粘着シート用の剥離シートとして用いられているものを利用することができる。 Examples of the release layer include those in which a release agent layer such as silicone is applied to various plastic films to form a release agent layer, and a polypropylene film alone, which is used as a release sheet for ordinary pressure-sensitive adhesive sheets Can be used.
＜導電性積層体の形成方法＞
本発明の導電性積層体の形成方法としては、例えば、剥離層上に粘着剤と紫外線吸収剤を含む機能層形成用組成物を塗布し、乾燥して機能層を形成した後に、機能層に無機酸化物透明導電層付き透明フィルム状基材を貼り合わせる方法や、無機酸化物透明導電層付き透明フィルム状基材に機能層形成用組成物を塗布し、乾燥して機能層を形成した後に、機能層に剥離層を貼り合わせる方法などが挙げられる。機能層形成用組成物の塗布方法としては、例えば、メイヤーバーコータ、ロールコータ、ナイフコータ、グラビアコータ、リップコータ、カーテンコータ、ダイコータ等を用いた塗布方法が挙げられる。
<Method for forming conductive laminate>
As a method for forming the conductive laminate of the present invention, for example, a functional layer-forming composition containing an adhesive and an ultraviolet absorber is applied on a release layer and dried to form a functional layer. After laminating a transparent film-like substrate with an inorganic oxide transparent conductive layer and applying a composition for forming a functional layer on a transparent film-like substrate with an inorganic oxide transparent conductive layer and drying to form a functional layer And a method of attaching a release layer to the functional layer. Examples of the application method of the functional layer forming composition include an application method using a Mayer bar coater, a roll coater, a knife coater, a gravure coater, a lip coater, a curtain coater, a die coater or the like.
［気泡発生低減シートおよび亀裂発生低減シート］
本発明の気泡発生低減シートおよび亀裂発生低減シートは、上記の機能層からなるシートであり、粘着剤と紫外線吸収剤を含むことを特徴とする。このようなシートを、透明フィルム状基材の片面に無機酸化物透明導電層を有する無機酸化物透明導電体に貼り合わせることにより、無機酸化物透明導電体における気泡の発生や亀裂の発生を効果的に抑えることができる。特に、高湿度条件下や屋外において長期間使用した場合に、気泡の発生や亀裂の発生を効果的に抑えることができる。シートの貼り合わせは、無機酸化物透明導電層が形成されている面とは反対側の面に対して行う。すなわち、無機酸化物透明導電体の透明フィルム状基材側に対してシートを貼り合わせる。
[Bubble generation reduction sheet and crack generation reduction sheet]
The bubble generation-reducing sheet and crack generation-reducing sheet of the present invention are sheets composed of the functional layers described above, and include an adhesive and an ultraviolet absorber. By bonding such a sheet to an inorganic oxide transparent conductor having an inorganic oxide transparent conductive layer on one side of a transparent film-like substrate, it is possible to effectively generate bubbles and cracks in the inorganic oxide transparent conductor. Can be suppressed. In particular, when used under high humidity conditions or outdoors for a long period of time, it is possible to effectively suppress the generation of bubbles and cracks. The sheets are bonded to the surface opposite to the surface on which the inorganic oxide transparent conductive layer is formed. That is, a sheet | seat is bonded together with respect to the transparent film-like base material side of an inorganic oxide transparent conductor.
本発明の気泡発生低減シートおよび亀裂発生低減シートは、貼り合わせ前には両面に剥離シートを積層しておくことが好ましい。剥離シートの詳細については、上記の剥離層の記載を参照することができる。 The bubble generation reducing sheet and crack generation reducing sheet of the present invention are preferably laminated with release sheets on both sides before bonding. For the details of the release sheet, the description of the release layer can be referred to.
無機酸化物透明導電体に本発明の気泡発生低減シートまたは亀裂発生低減シートを貼り合わせた後に、さらに気泡発生低減シートまたは亀裂発生低減シートの粘着性露出表面に別の部材を貼り合わせることができる。例えば、ガラスなどの支持性を有する部材や、光学部材などに対して幅広く適用することが可能である。その種類やサイズなどについては、特に制限されない。 After the bubble generation reducing sheet or crack generation reducing sheet of the present invention is bonded to the inorganic oxide transparent conductor, another member can be further bonded to the adhesive exposed surface of the bubble generation reducing sheet or crack generation reducing sheet. . For example, it can be widely applied to a member having supportability such as glass or an optical member. There are no particular restrictions on the type or size.
以下に実施例と比較例を挙げて本発明の特徴をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。なお、例中の「部」及び「％」は、特に断らない限りそれぞれ「質量部」及び「質量％」を意味する。 The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below. In the examples, “parts” and “%” mean “parts by mass” and “% by mass” unless otherwise specified.
気泡発生低減シートの作製
（実施例１）
＜粘着剤の調製＞
攪拌機、温度計、還流冷却機、滴下装置、窒素導入管を備えた反応装置に、窒素ガスを封入後、溶媒である酢酸エチルを添加した。次いで、反応装置内に、アクリル単量体であるブチルアクリレート６５質量部、メチルアクリレート３５質量部、アクリル酸２部と、重合開始剤である２，２´−アゾイソブチロニトリル０．１質量部を添加し、攪拌しながら窒素ガス気流中、溶媒の還流温度で８時間重合した。反応終了後、トルエンを添加してアクリル重合体溶液を得た。このアクリル重合体固形分１００質量部に、光安定剤としてヒンダードアミン系化合物（品名：ＴＩＮＵＶＩＮ１４４、ＢＡＳＦ社製）２．０質量部、さらに酸化防止剤としてヒンダードフェノール系化合物（商品名：ＩＲＧＡＮＯＸ １５２０Ｌ、ＢＡＳＦ社製）０．０８質量部を添加して粘着剤主剤とした。
次いで、該粘着剤主剤固形分１００質量部に対して、架橋剤であるトリレンジイソシアネート（品名：コロネートＬ、日本ポリウレタン社製）１部、波長３５３ｎｍに極大吸収波長を有するベンゾトリアゾール系液状紫外線吸収剤（品名：ＴＩＮＵＶＩＮ１０９、ＢＡＳＦ社製）４．０質量部を混合して粘着剤溶液を得た。
Production of bubble generation reduction sheet (Example 1)
<Preparation of adhesive>
Nitrogen gas was sealed in a reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, and then ethyl acetate as a solvent was added. Next, in the reactor, 65 parts by mass of butyl acrylate as an acrylic monomer, 35 parts by mass of methyl acrylate, 2 parts of acrylic acid, and 0.1 mass of 2,2′-azoisobutyronitrile as a polymerization initiator. The polymer was polymerized for 8 hours at the reflux temperature of the solvent in a nitrogen gas stream while stirring. After completion of the reaction, toluene was added to obtain an acrylic polymer solution. To 100 parts by mass of this acrylic polymer solid content, 2.0 parts by mass of a hindered amine compound (product name: TINUVIN 144, manufactured by BASF) as a light stabilizer, and a hindered phenol compound (trade name: IRGANOX 1520L) as an antioxidant. 0.08 parts by mass) (manufactured by BASF) was added to obtain an adhesive main agent.
Next, with respect to 100 parts by mass of the pressure-sensitive adhesive main component, 1 part of tolylene diisocyanate (product name: Coronate L, manufactured by Nippon Polyurethane Co., Ltd.), a benzotriazole-based liquid ultraviolet absorption having a maximum absorption wavelength at a wavelength of 353 nm 4.0 parts by mass of an agent (product name: TINUVIN109, manufactured by BASF) was mixed to obtain an adhesive solution.
＜剥離フィルム付き気泡発生低減シートの作製＞
上記粘着剤を、ナイフコータにより、厚さ３８μｍのＰＥＴ剥離フィルム（品名：ＲＬ０７（２）＃３８、王子特殊紙社製）に、乾燥後の塗工量が２５μｍ／ｍ2になるように塗工し、１００℃で２分間乾燥させて、機能層を得た。次いで、該機能層の表面に厚さ３８μｍのＰＥＴ剥離フィルム（品名：ＲＬ０７（Ｌ）＃３８、王子特殊紙社製）に貼合して、機能層が剥離力差のある１対の剥離フィルムに挟まれたＰＥＴ剥離フィルム／機能層／ＰＥＴ剥離フィルムの構成を備える剥離フィルム付き気泡発生低減シートを得た。
<Preparation of bubble generation reduction sheet with release film>
Using a knife coater, apply the above adhesive to a PET release film (product name: RL07 (2) # 38, manufactured by Oji Specialty Paper Co., Ltd.) with a thickness of 38 μm so that the coating amount after drying is 25 μm / m 2. And dried at 100 ° C. for 2 minutes to obtain a functional layer. Next, a pair of release films having a difference in peel force between the functional layers are bonded to a 38 μm thick PET peel film (product name: RL07 (L) # 38, manufactured by Oji Specialty Paper Co., Ltd.) on the surface of the functional layer. A bubble generation reducing sheet with a release film having a configuration of a PET release film / functional layer / PET release film sandwiched between layers was obtained.
（実施例２）
波長３５３ｎｍに極大吸収波長を有するベンゾトリアゾール系液状紫外線吸収剤（品名：ＴＩＮＵＶＩＮ１０９、ＢＡＳＦ社製）の添加量を８．０質量部に変更したこと以外は実施例１と同様にして粘着剤溶液を得た。そして、この粘着剤溶液を用い、実施例１と同様にして剥離フィルム付き気泡発生低減シートを得た。
(Example 2)
A pressure-sensitive adhesive solution was prepared in the same manner as in Example 1 except that the addition amount of a benzotriazole-based liquid ultraviolet absorber having a maximum absorption wavelength at a wavelength of 353 nm (product name: TINUVIN109, manufactured by BASF) was changed to 8.0 parts by mass. Obtained. And using this adhesive solution, it carried out similarly to Example 1, and obtained the bubble generation reduction sheet | seat with a peeling film.
（実施例３）
紫外線吸収剤を波長３５６ｎｍに極大吸収波長を有するヒドロキシフェニルトリアジン系液状紫外線吸収剤（品名：ＴＩＮＵＶＩＮ４７７、ＢＡＳＦ社製）に変更したこと以外は実施例１と同様にして粘着剤溶液を得た。そして、この粘着剤溶液を用い、実施例１と同様にして剥離フィルム付き気泡発生低減シートを得た。
(Example 3)
A pressure-sensitive adhesive solution was obtained in the same manner as in Example 1 except that the ultraviolet absorber was changed to a hydroxyphenyltriazine-based liquid ultraviolet absorber having a maximum absorption wavelength at 356 nm (product name: TINUVIN477, manufactured by BASF). And using this adhesive solution, it carried out similarly to Example 1, and obtained the bubble generation reduction sheet | seat with a peeling film.
（実施例４）
紫外線吸収剤を波長３５６ｎｍに極大吸収波長を有するヒドロキシフェニルトリアジン系液状紫外線吸収剤（品名：ＴＩＮＵＶＩＮ４７７、ＢＡＳＦ社製）の添加量を８．０質量部にしたこと以外は実施例３と同様にして粘着剤溶液を得た。そして、この粘着剤溶液を用い、実施例１と同様にして剥離フィルム付き気泡発生低減シートを得た。
Example 4
The same procedure as in Example 3 was conducted except that the amount of addition of the hydroxyphenyltriazine liquid ultraviolet absorber having a maximum absorption wavelength at a wavelength of 356 nm (product name: TINUVIN477, manufactured by BASF) was 8.0 parts by mass. An adhesive solution was obtained. And using this adhesive solution, it carried out similarly to Example 1, and obtained the bubble generation reduction sheet | seat with a peeling film.
（比較例１）
紫外線吸収剤を添加しないこと以外は実施例１と同様にして粘着剤溶液を得た。そして、この粘着剤溶液を用い、実施例１と同様にして剥離フィルム付き気泡発生低減シートを得た。
(Comparative Example 1)
A pressure-sensitive adhesive solution was obtained in the same manner as in Example 1 except that no ultraviolet absorber was added. And using this adhesive solution, it carried out similarly to Example 1, and obtained the bubble generation reduction sheet | seat with a peeling film.
実施例１〜４で作製した剥離フィルム付き気泡発生低減シートは、剥離フィルム付き亀裂発生低減シートとしても利用できるものである。 The bubble generation reduction sheet with a release film produced in Examples 1 to 4 can also be used as a crack generation reduction sheet with a release film.
導電性積層体の作製
（実施例５）
＜導電性積層体の形成＞
多官能（メタ）アクリルモノマーとして６官能アクリレート（商品名ＤＰＨＡ、ダイセル・サイテック（株）製）６４質量部、ジエチレングリコールジアクリレート（商品名ＳＲ２３０、サートマー社製）２７質量部、光重合開始剤（商品名ＩＲＧＡＣＵＲＥ１８４、ＢＡＳＦ社製）５質量部、および光安定化剤（ＴＩＮＵＶＩＮ１５２、ＢＡＳＦ社製）４質量部を、メチルエチルケトン（ＭＥＫ）およびシクロヘキサノンを１：１で混合した希釈溶剤に固形分が４０質量％となるように混合して組成物（Ａ）を調製した。厚さ５０μｍのＰＥＴフィルム（商品名Ａ４３００、東洋紡績（株）製）を用意し、その上に前記組成物（Ａ）をバー塗工して、８０℃で６０秒間加熱乾燥し、高圧水銀ランプ紫外線照射機（アイグラフィックス社製）を用いて、１６０Ｗ／ｃｍ、ランプ高さ１３ｃｍ、ベルトスピード１０ｍ／分、２ｐａｓｓの条件で窒素雰囲気下にて紫外線を照射して硬化することにより、架橋重合体層とＰＥＴフィルムからなる透明フィルム状基材を作製した。この透明フィルム状基材のＰＥＴフィルム表面上に、真空蒸着法により厚み１２００Å（オングストローム）のＩＴＯ膜を形成して、無機酸化物透明導電層と透明フィルム状基材の積層体を作製した。
次に、この積層体の透明フィルム状基材上に、実施例１で作製した剥離フィルム付き気泡発生低減シートの一方のＰＥＴ剥離フィルムを剥がして露出させた機能層を重ね合わせて２ｋｇ荷重ロールで圧着し、常温で３０分間放置することにより、導電性積層体を作製した。
実施例１の剥離フィルム付き気泡発生低減シートの代わりに、実施例２〜４または比較例１の剥離フィルム付き気泡発生低減シートを用いて、同様にして導電性積層体を作製した。
Production of conductive laminate (Example 5)
<Formation of conductive laminate>
As polyfunctional (meth) acrylic monomer, hexafunctional acrylate (trade name DPHA, manufactured by Daicel Cytec Co., Ltd.) 64 parts by mass, diethylene glycol diacrylate (trade name SR230, manufactured by Sartomer) 27 parts by mass, photopolymerization initiator (product) Name IRGACURE 184 (manufactured by BASF) 5 parts by mass, and light stabilizer (TINUVIN 152, manufactured by BASF) 4 parts by mass in a dilute solvent in which methyl ethyl ketone (MEK) and cyclohexanone are mixed at a ratio of 40% by mass The composition (A) was prepared by mixing so that A PET film (trade name A4300, manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm is prepared, and the composition (A) is bar-coated thereon, followed by heating and drying at 80 ° C. for 60 seconds, and a high-pressure mercury lamp. Using an ultraviolet irradiator (made by Eye Graphics Co., Ltd.), curing by irradiation with ultraviolet rays in a nitrogen atmosphere under the conditions of 160 W / cm, lamp height of 13 cm, belt speed of 10 m / min, and 2 pass, A transparent film-like substrate composed of a combined layer and a PET film was produced. An ITO film having a thickness of 1200 angstroms (angstrom) was formed on the surface of the PET film of the transparent film substrate by a vacuum deposition method to produce a laminate of the inorganic oxide transparent conductive layer and the transparent film substrate.
Next, on the transparent film-like substrate of this laminate, the functional layer exposed by peeling off one PET release film of the bubble generation reducing sheet with release film produced in Example 1 was overlaid with a 2 kg load roll. A conductive laminate was produced by crimping and leaving at room temperature for 30 minutes.
Instead of the bubble generation reducing sheet with release film of Example 1, a conductive laminate was prepared in the same manner using Examples 2 to 4 or the bubble generation reduction sheet with release film of Comparative Example 1.
＜気泡発生評価＞
作製した導電性積層体の剥離フィルムを剥がすことにより露出した機能層を、ガラス板上に重ね合わせて２ｋｇ荷重ロールで圧着し、常温で３０分間放置することにより積層サンプルを作製した。この積層サンプルを、耐候性試験機（キセノンウェザーメーター、スガ試験機製）を用いて、ブラックパネル温度６０℃、相対湿度９０％の環境下、３００〜４００ｎｍの紫外線強度が７０Ｗ／ｍ2の条件で１２０時間処理をして耐久試験を行った。その後、サンプル中の最大径１００μｍ以上の気泡の発生状況を光学顕微鏡により確認した。気泡発生が認められない場合を「○」、気泡発生が認められる場合を「×」と評価した。結果を表１に示す。気泡発生が認められ、「×」と評価された比較例１の気泡発生低減シートを用いたサンプルでは、透明フィルム状基材側の機能層内に気泡が多数発生していることが確認された。
<Bubble generation evaluation>
The functional layer exposed by peeling off the release film of the produced conductive laminate was superimposed on a glass plate, pressure-bonded with a 2 kg load roll, and allowed to stand at room temperature for 30 minutes to produce a laminated sample. Using this weather resistance tester (xenon weather meter, manufactured by Suga Test Instruments Co., Ltd.), the UV intensity at 300 to 400 nm is 70 W / m 2 in an environment with a black panel temperature of 60 ° C. and a relative humidity of 90%. The durability test was conducted after 120 hours of treatment. Thereafter, the generation state of bubbles having a maximum diameter of 100 μm or more in the sample was confirmed by an optical microscope. The case where bubble generation was not recognized was evaluated as “◯”, and the case where bubble generation was observed was evaluated as “x”. The results are shown in Table 1. In the sample using the bubble generation reducing sheet of Comparative Example 1 in which bubble generation was recognized and evaluated as “x”, it was confirmed that many bubbles were generated in the functional layer on the transparent film-like substrate side. .
＜亀裂発生評価＞
気泡発生評価の耐候性試験後のサンプルについて、光学顕微鏡により亀裂の発生を確認した。亀裂が認められない場合を「○」、亀裂が認められる場合を「×」と評価した。結果を表１に示す。亀裂が認められ、「×」と評価された比較例１の気泡発生低減シートを用いたサンプルでは、架橋重合体層に亀裂が多数発生していることが確認された。
<Crack evaluation>
About the sample after the weather resistance test of bubble generation evaluation, generation | occurrence | production of the crack was confirmed with the optical microscope. A case where no crack was observed was evaluated as “◯”, and a case where a crack was observed was evaluated as “x”. The results are shown in Table 1. In the sample using the bubble generation reducing sheet of Comparative Example 1 in which cracks were recognized and evaluated as “x”, it was confirmed that many cracks were generated in the crosslinked polymer layer.
本発明の条件を満たす気泡発生低減シート（亀裂発生低減シート）は、無機酸化物透明導電体の気泡や亀裂の発生を効果的に抑制することができる。これに対して、本発明の条件を満たさないシートは、無機酸化物透明導電体の気泡や亀裂の発生を抑制することができない。 The bubble generation reduction sheet (crack generation reduction sheet) that satisfies the conditions of the present invention can effectively suppress the generation of bubbles and cracks in the inorganic oxide transparent conductor. On the other hand, the sheet | seat which does not satisfy | fill the conditions of this invention cannot suppress generation | occurrence | production of the bubble and crack of an inorganic oxide transparent conductor.
１ 導電性積層体
１１ 無機酸化物透明導電層
１２ 透明フィルム状基材
１３ 機能層
DESCRIPTION OF SYMBOLS 1 Conductive
Claims (2)
前記無機酸化物透明導電層が形成されている面とは反対側の面に、紫外線吸収剤と粘着剤を含有する気泡発生低減シートを積層することを特徴とする気泡発生低減方法。 A method for reducing bubble generation in an inorganic oxide transparent conductor having an inorganic oxide transparent conductive layer on one side of a transparent film-shaped substrate,
A bubble generation reduction method comprising laminating a bubble generation reduction sheet containing an ultraviolet absorber and an adhesive on a surface opposite to a surface on which the inorganic oxide transparent conductive layer is formed.
前記無機酸化物透明導電層が形成されている面とは反対側の面に、紫外線吸収剤と粘着剤を含有する亀裂発生低減シートを積層することを特徴とする亀裂発生低減方法。 A method for reducing the occurrence of cracks in an inorganic oxide transparent conductor having an inorganic oxide transparent conductive layer on one side of a transparent film-shaped substrate,
A crack generation reduction method comprising laminating a crack generation reduction sheet containing an ultraviolet absorber and an adhesive on a surface opposite to a surface on which the inorganic oxide transparent conductive layer is formed.
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