JP5150055B2 - Anti-reflective material - Google Patents
Anti-reflective material Download PDFInfo
- Publication number
- JP5150055B2 JP5150055B2 JP2006042128A JP2006042128A JP5150055B2 JP 5150055 B2 JP5150055 B2 JP 5150055B2 JP 2006042128 A JP2006042128 A JP 2006042128A JP 2006042128 A JP2006042128 A JP 2006042128A JP 5150055 B2 JP5150055 B2 JP 5150055B2
- Authority
- JP
- Japan
- Prior art keywords
- refractive index
- hard coat
- coat layer
- low refractive
- coating
- 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.)
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- 239000000463 material Substances 0.000 title claims description 41
- 230000003667 anti-reflective effect Effects 0.000 title description 4
- -1 polysiloxane Polymers 0.000 claims description 48
- 239000000758 substrate Substances 0.000 claims description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 239000011882 ultra-fine particle Substances 0.000 claims description 17
- 239000010419 fine particle Substances 0.000 claims description 16
- 229910001887 tin oxide Inorganic materials 0.000 claims description 16
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 230000005855 radiation Effects 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 9
- 239000011342 resin composition Substances 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- 238000005299 abrasion Methods 0.000 claims description 8
- 238000002834 transmittance Methods 0.000 claims description 8
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- 125000000524 functional group Chemical group 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
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- 210000002268 wool Anatomy 0.000 claims description 4
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- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920005992 thermoplastic resin Polymers 0.000 claims description 3
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- 230000000052 comparative effect Effects 0.000 description 9
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- 238000002310 reflectometry Methods 0.000 description 8
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- 239000011324 bead Substances 0.000 description 3
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- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
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- 239000004925 Acrylic resin Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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Description
本発明は、ＬＣＤやＰＤＰ等のディスプレイ表面に設ける反射防止材料に関し、特に塗工により安価に供給することが出来る反射防止材料に関するものである。 The present invention relates to an antireflection material provided on a display surface such as an LCD or a PDP, and more particularly to an antireflection material that can be supplied at low cost by coating.
近年、ＬＣＤやＰＤＰ等のディスプレイが発達し、携帯電話から大型ＴＶまで、数多くの用途に様々なサイズの製品が製造・販売されるようになってきた。これらのディスプレイでは、視認性をより高めるために一般にその表面に反射防止機能を有する層を設けてある。この反射防止技術を大別すると、外光の映り込みを防止するための防眩、いわゆるＡｎｔｉ−Ｇｌａｒｅ（以下、「ＡＧ」という。）と、光の干渉効果を利用して反射率自体を低く抑えるための反射防止、いわゆるＡｎｔｉ−Ｒｅｆｌｅｃｔｉｏｎ（以下、「ＡＲ」という。）がある。 In recent years, displays such as LCDs and PDPs have been developed, and products of various sizes have been manufactured and sold for many applications ranging from mobile phones to large-sized TVs. In these displays, a layer having an antireflection function is generally provided on the surface in order to further improve the visibility. The anti-reflection technology is roughly classified into anti-glare for preventing reflection of external light, so-called Anti-Glare (hereinafter referred to as “AG”), and the light reflection effect to reduce the reflectivity itself. There is so-called anti-reflection (hereinafter referred to as “AR”) for preventing reflection.
従来、ＡＧについては、サンドブラスト法やエンボス法等により基材表面を直接粗面化する方法、基材表面にフィラーを含有させたハードコート層を設ける方法及び基材表面に海島構造による多孔質膜を形成する方法等で反射防止材料表面に凹凸を形成し、ＡＲについてはスパッタリング等により形成する方法が主であった。しかしながら、後者のスパッタリング等の真空成膜方法は、コストが高く、プラスチックフィルムとの密着性が不十分で、また大面積に均一な成膜を行うことが難しいことから、最近ではウェットコーティングにより屈折率の異なる複数の層を積層することが行われてきた。スパッタリングで作製されたＡＲの反射率は０．３％以下が普通であるが、このウェットコーティングで作製された膜の反射率はこれよりも高く１．０％前後のものが多いため、ＡＲと区別してＬｏｗ Ｒｅｆｌｅｃｔｉｏｎ（以下、「ＬＲ」という。）と呼ばれている。 Conventionally, for AG, a method of directly roughening the surface of a substrate by a sandblasting method or an embossing method, a method of providing a hard coat layer containing a filler on the surface of the substrate, and a porous film having a sea-island structure on the surface of the substrate The main method is to form irregularities on the surface of the antireflective material by the method of forming the AR, and to form AR by sputtering or the like. However, the latter vacuum deposition method such as sputtering is expensive, has insufficient adhesion to a plastic film, and it is difficult to form a uniform film over a large area. Laminating a plurality of layers having different rates has been performed. The reflectivity of AR made by sputtering is usually 0.3% or less, but the reflectivity of a film made by this wet coating is higher than this, and many of them are around 1.0%. For distinction, this is called Low Reflection (hereinafter referred to as “LR”).
ウェットコーティングにより作製されるＬＲフィルムは、基体上に高屈折率層、低屈折率層を順次積層したものが基本的な構成であり、必要に応じて基体と高屈折率層との間、高屈折率層と低屈折率層との間、低屈折率層上、に任意の層を設けることができる。なお、ここで高屈折率、低屈折率というのは絶対的な屈折率を規定するものではなく、２つの層の屈折率を相対的に比較して高い低いと称しているものであり、両者が下記式１の関係を有する時に最も反射率が低くなるとされている。 An LR film produced by wet coating has a basic structure in which a high refractive index layer and a low refractive index layer are sequentially laminated on a substrate. An arbitrary layer can be provided between the refractive index layer and the low refractive index layer and on the low refractive index layer. Here, the high refractive index and the low refractive index do not define an absolute refractive index, but are referred to as high and low relative to the relative refractive indexes of the two layers. Is considered to have the lowest reflectivity when the following relationship is satisfied.
ｎ２＝（ｎ１）１／２・・・（式１）
（ｎ１は高屈折率層の屈折率、ｎ２は低屈折率層の屈折率）
n 2 = (n 1 ) 1/2 (Expression 1)
(N 1 is the refractive index of the high refractive index layer, n 2 is the refractive index of the low refractive index layer)
ウェットコーティングにより作製されるＬＲフィルムの高屈折率層材料としては、屈折率を高めるために、塩素や臭素、硫黄等の元素を含有する有機高分子を使用したり、酸化チタン、酸化ジルコニウム、酸化亜鉛等の高屈折率の金属酸化物超微粒子を層中に分散させたりすることが一般的である。また低屈折率層では、含フッ素系の有機高分子や低屈折率のシリカ、フッ化マグネシウム等を使用したり、微粒子を堆積させて空孔を設け空気の混入による低屈折率化を図る等が行われている。 As a high refractive index layer material of LR film produced by wet coating, an organic polymer containing elements such as chlorine, bromine and sulfur is used to increase the refractive index, and titanium oxide, zirconium oxide, and oxidation are used. It is common to disperse high refractive index ultrafine metal oxides such as zinc in the layer. In the low refractive index layer, fluorine-containing organic polymer, low refractive index silica, magnesium fluoride, etc. are used, or fine particles are deposited to provide pores to reduce the refractive index by mixing air. Has been done.
ところで、近年大型ＴＶ用途のディスプレイの需要が大幅に伸びてきたことから、このウェットコーティングにより作製されるＬＲフィルムの需要も高まっている。ＬＲフィルムとしては、ポリエチレンテレフタレート（以下、「ＰＥＴ」という。）やトリアセチルセルロース（以下、「ＴＡＣ」という。）等の透明フィルム上に、ハードコート層、低屈折率層を順次積層した２層系や、ハードコート層、高屈折率層、低屈折率層を順次積層した３層系の構成を有するものが一般に製造販売されている。このＬＲフィルムには、低反射率であることの他に、高い耐磨耗性や耐薬品性、防汚性等が求められ、最近ではその表面に帯電防止性を持たせることが求められるようにもなってきた。このことは、帯電による埃付着を防ぐと共に、付着した埃の拭き取り性を向上させたいという市場の要求から発生したもので、表面抵抗として１０７〜１０１１Ω／□が必要とされている。なお、Ω／□は、表面抵抗率の単位であり、□は単位面積を意味し、Ω／ｓｑと表記する場合もある。 By the way, since the demand for displays for large TVs has increased greatly in recent years, the demand for LR films produced by this wet coating is also increasing. As the LR film, two layers in which a hard coat layer and a low refractive index layer are sequentially laminated on a transparent film such as polyethylene terephthalate (hereinafter referred to as “PET”) or triacetyl cellulose (hereinafter referred to as “TAC”). In general, a system having a three-layer structure in which a hard coat layer, a high refractive index layer, and a low refractive index layer are sequentially laminated is manufactured and sold. In addition to low reflectivity, this LR film is required to have high wear resistance, chemical resistance, antifouling properties, etc., and recently it is required to have antistatic properties on its surface. It has become. This is caused by a market demand to prevent dust adhesion due to electrification and improve the wiping property of the adhered dust, and a surface resistance of 10 7 to 10 11 Ω / □ is required. Note that Ω / □ is a unit of surface resistivity, □ means a unit area, and may be expressed as Ω / sq.
反射防止材料の表面に帯電防止性を持たせるためには、上記ＬＲフィルムの場合と同様、ハードコート層、高屈折率層、低屈折率層のいずれか、または複数の層に帯電防止性を付与する必要がある。この帯電防止性を付与するための材料としては、界面活性剤、導電性高分子、導電性無機微粒子等が挙げられるが、特に導電性無機微粒子を塗膜中に分散させる方法が、低抵抗実現に有効なため、多く利用されている。 In order to impart antistatic properties to the surface of the antireflective material, as in the case of the LR film, the hard coat layer, the high refractive index layer, the low refractive index layer, or a plurality of layers are provided with antistatic properties. It is necessary to grant. Examples of the material for imparting this antistatic property include surfactants, conductive polymers, conductive inorganic fine particles, etc. Low resistance is achieved especially by the method of dispersing conductive inorganic fine particles in the coating film. Because it is effective, it is widely used.
導電性無機微粒子は、帯電防止の観点から最表面に配置されることが好ましいが、これらの材料は一般に屈折率が高いため、反射防止性を考慮すると低屈折率層の下側の層に含有させ、導電性と共に高屈折率も付与する方が好ましいとされている。 The conductive inorganic fine particles are preferably disposed on the outermost surface from the viewpoint of antistatic. However, since these materials generally have a high refractive index, they are contained in the lower layer of the low refractive index layer in consideration of antireflection properties. In addition, it is preferable to provide a high refractive index as well as conductivity.
この例としては、特許文献１では、２層系（導電層／低屈折率層）、３層系（導電層／高屈折率層／低屈折率層）の導電層中に分散される金属酸化物の透明導電性超微粒子としてアンチモンドープ酸化錫、アルミドープ酸化亜鉛の針状もしくは球状の微粒子を使用する記載がある。また、特許文献２では、導電性微粒子（Ａ成分）、屈折率２．０以上の誘電体微粒子（Ｂ成分）、およびバインダー（Ｃ成分）からなり、その組成がＡ成分１００重量部に対して、Ｂ成分５〜１００重量部、Ｃ成分５〜１００重量で構成される高屈折率導電性材料組成物が開示されており、導電性微粒子として酸化インジウム錫、酸化錫、酸化アンチモン錫、酸化亜鉛アルミニウムから選択されるとの記載がある。さらに、特許文献３では、プラズマ法で製造された正方晶系酸化錫微粒子とアクリレート化合物とアルコール系溶剤で構成される紫外線硬化型透明導電性塗料組成物が開示されている。 As an example of this, Patent Document 1 discloses a metal oxide dispersed in a conductive layer of a two-layer system (conductive layer / low refractive index layer) or a three-layer system (conductive layer / high refractive index layer / low refractive index layer). There is a description of using needle-like or spherical fine particles of antimony-doped tin oxide or aluminum-doped zinc oxide as transparent conductive ultrafine particles. Moreover, in patent document 2, it consists of electroconductive fine particles (A component), dielectric fine particles (B component) with a refractive index of 2.0 or more, and a binder (C component), and the composition is based on 100 parts by weight of the A component. , A high refractive index conductive material composition comprising 5 to 100 parts by weight of B component and 5 to 100 parts by weight of C component is disclosed, and indium tin oxide, tin oxide, antimony tin oxide, and zinc oxide as conductive fine particles are disclosed. There is a description that it is selected from aluminum. Further, Patent Document 3 discloses an ultraviolet curable transparent conductive coating composition composed of tetragonal tin oxide fine particles produced by a plasma method, an acrylate compound, and an alcohol solvent.
反射防止材料の帯電防止と高屈折率に関し、この他にも多数の特許出願がされているが、低反射性、帯電防止性、耐磨耗性、耐薬品性、耐汚染性等においてバランスの取れた特性を有する反射防止材料は未だ実現していない。 Many other patent applications have been filed regarding anti-static materials and anti-reflective materials with a high refractive index, but there is a balance in terms of low reflectivity, anti-static properties, wear resistance, chemical resistance, stain resistance, etc. An antireflection material having excellent characteristics has not been realized yet.
また、低反射性、帯電防止性、耐磨耗性、耐薬品性、防汚性というこれら機能を同時に付与する方法として、多層に積層した膜の開発が進められているが、多層化、つまり複数回基材上に塗工する工程が必要となりコストが多く掛かる。また、多層化による各層間のバランスを調整することが難しく、実際には使用する目的に応じてこれらの機能の一部を選択・実現しているに過ぎない。 In addition, as a method of simultaneously imparting these functions of low reflectivity, antistatic properties, abrasion resistance, chemical resistance, and antifouling properties, development of multi-layered films is underway. A process of coating on the substrate a plurality of times is required, which increases costs. In addition, it is difficult to adjust the balance between layers due to the multi-layering, and actually, only a part of these functions are selected and realized according to the purpose of use.
このような状況に鑑み、本発明は、透明基体上にハードコート層ともう一層設けることで、低反射性、経済性に優れ、かつ導電性、耐磨耗性、防汚性をバランスよく機能させることのできる反射防止材料を提供するものである。 In view of such circumstances, the present invention provides a hard coat layer and a further layer on a transparent substrate, so that it is excellent in low reflectivity and economy, and has a good balance of conductivity, wear resistance and antifouling properties. An antireflection material that can be made to provide is provided.
本発明の反射防止材料は、透光性基体上に、少なくともハードコート層、低屈折率層を順次積層し、ハードコート層は、粒径５〜５０ｎｍである導電性無機超微粒子と酸性官能基を有する熱可塑性樹脂とを含有する放射線硬化型樹脂組成物が含有され、膜厚が１．０〜５．０μｍ、硬化後の屈折率が１．６〜１．８であり、低屈折率層は含フッ素ポリシロキサンが含有され、硬化後の屈折率が１．３６〜１．４２であり、ハードコート層に含まれる導電性無機超微粒子が、酸化錫、リンドープ酸化錫、アンチモンドープ酸化錫（ＡＴＯ）、酸化インジウム錫（ＩＴＯ）、酸化インジウム、酸化亜鉛、アルミニウムドープ酸化亜鉛から選ばれる少なくとも一つからなり、導電性無機超微粒子の重量比率が７５％以上であり、上記低屈折率層表面で測定する表面抵抗が１０１１Ω／□未満であり、全光線透過率が９０％以上、ヘイズが２％以下であることを特徴とする。 The antireflection material of the present invention is formed by sequentially laminating at least a hard coat layer and a low refractive index layer on a translucent substrate, and the hard coat layer comprises conductive inorganic ultrafine particles having a particle size of 5 to 50 nm and acidic functional groups. A radiation curable resin composition containing a thermoplastic resin having a thickness of 1.0 to 5.0 μm, a refractive index after curing of 1.6 to 1.8, and a low refractive index layer Has a refractive index after curing of 1.36 to 1.42, and the conductive inorganic ultrafine particles contained in the hard coat layer are tin oxide, phosphorus-doped tin oxide, antimony-doped tin oxide ( ATO), indium tin oxide (ITO), indium oxide, zinc oxide, aluminum-doped zinc oxide, the conductive inorganic ultrafine particles have a weight ratio of 75% or more, and the surface of the low refractive index layer A surface resistance of 10 11 Ω / □ under measuring a total light transmittance of 90% or more, and the haze is 2% or less.
本発明の反射防止材料の平均反射率は、１％以下であることを特徴とする。 The average reflectance of the antireflection material of the present invention is characterized in that it is under 1% or less.
本発明の反射防止材料のスチールウールによる耐磨耗性試験後のヘイズの変化量は、０．５％以下であることを特徴とする。 The amount of change in haze after an abrasion resistance test with steel wool of the antireflection material of the present invention is 0.5% or less.
本発明の反射防止材料のハードコート層は、透光性樹脂微粒子を含有し、上記ハードコート層表面に微細な凹凸を有することを特徴とする。 The hard coat layer of the antireflection material of the present invention contains translucent resin fine particles, and has fine irregularities on the surface of the hard coat layer.
本発明の反射防止材料は、透光性基体上にハードコート層と低屈折率層を形成することで、低反射特性、導電性、耐磨耗性、防汚性のバランスに優れるものであり、塗工工程を少なくすることでコストの低減も併せて可能とするものである。 The antireflection material of the present invention has an excellent balance of low reflection characteristics, conductivity, abrasion resistance, and antifouling properties by forming a hard coat layer and a low refractive index layer on a translucent substrate. The cost can be reduced by reducing the coating process.
本発明に使用される透光性基体としては、石英ガラスやソーダガラス等のガラスも使用可能であるが、ＰＥＴ、ＴＡＣ、ポリエチレンナフタレート（ＰＥＮ）、ポリメチルメタクリレート（ＰＭＭＡ）、ポリカーボネート（ＰＣ）、ポリイミド（ＰＩ）、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、ポリビニルアルコール（ＰＶＡ）、ポリ塩化ビニル（ＰＶＣ）、シクロオレフィンコポリマー（ＣＯＣ）、含ノルボルネン樹脂、ポリエーテルスルホン、セロファン、芳香族ポリアミド等の各種樹脂フィルムを好適に使用することができる。なお、ＰＤＰ、ＬＣＤに用いる場合は、ＰＥＴ、ＴＡＣフィルムがより好ましい。 As the translucent substrate used in the present invention, glass such as quartz glass and soda glass can be used, but PET, TAC, polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC). , Polyimide (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cycloolefin copolymer (COC), norbornene resin, polyethersulfone, cellophane, aromatic polyamide, etc. These various resin films can be suitably used. In addition, when using for PDP and LCD, PET and a TAC film are more preferable.
これら透光性基体の透明性は高いものほど良好であるが、光線透過率（ＪＩＳ Ｋ７３６１−１）としては８０％以上、より好ましくは９０％以上が良い。また、透明基体の厚さとしては、軽量化の観点からは薄い方が好ましいが、その生産性やハンドリング性を考慮すると、１〜７００μｍの範囲のもの、好ましくは２５〜２５０μｍを使用することが好適である。 The higher the transparency of these translucent substrates, the better. However, the light transmittance (JIS K7361-1) is 80% or more, more preferably 90% or more. Further, the thickness of the transparent substrate is preferably thin from the viewpoint of weight reduction, but considering the productivity and handling properties, the thickness of the transparent substrate is in the range of 1 to 700 μm, preferably 25 to 250 μm. Is preferred.
また、透光性基体に、アルカリ処理、コロナ処理、プラズマ処理、スパッタ処理等の表面処理や、界面活性剤、シランカップリング剤等の塗布、またはＳｉ蒸着などの表面改質処理を行うことにより、透光性基体とハードコート層との密着性を向上させることができる。 In addition, by performing surface treatment such as alkali treatment, corona treatment, plasma treatment and sputtering treatment, surface treatment such as surfactant and silane coupling agent, or surface modification treatment such as Si deposition on the translucent substrate. The adhesion between the translucent substrate and the hard coat layer can be improved.
本発明のハードコート層に含有される導電性無機超微粒子としては、酸化錫、リンドープ酸化錫、アンチモンドープ酸化錫（ＡＴＯ）、酸化インジウム錫（ＩＴＯ）、酸化インジウム、酸化亜鉛、アルミニウムドープ酸化亜鉛、五酸化アンチモンが挙げられ、特に好ましいのは酸化錫、ＩＴＯ、酸化亜鉛であり、これらはいずれも屈折率が２．０近傍と高いため、導電性だけでなくこれを含有するハードコート層の屈折率を高める働きも担うことが出来る。 The conductive inorganic ultrafine particles contained in the hard coat layer of the present invention include tin oxide, phosphorus-doped tin oxide, antimony-doped tin oxide (ATO), indium tin oxide (ITO), indium oxide, zinc oxide, and aluminum-doped zinc oxide. Antimony pentoxide is particularly preferable, and tin oxide, ITO, and zinc oxide are particularly preferable. Since these materials each have a high refractive index of about 2.0, not only conductivity but also a hard coat layer containing the same. It can also serve to increase the refractive index.
これらの導電性無機超微粒子の粒径は、５〜５０ｎｍである。導電性無機超微粒子の粒径が５ｎｍ未満では均一な分散が困難になり、一方５０ｎｍを超えると透明性が低下するという不都合を生じるからである。 These conductive inorganic ultrafine particles have a particle size of 5 to 50 nm. This is because when the particle diameter of the conductive inorganic ultrafine particles is less than 5 nm, uniform dispersion becomes difficult, while when it exceeds 50 nm, the transparency is lowered.
ハードコート層に使用される放射線硬化型樹脂組成物としては、アクリロイル基、メタクリロイル基、アクリロイルオキシ基、メタクリロイルオキシ基等のラジカル重合性官能基や、エポキシ基、ビニルエーテル基、オキセタン基等のカチオン重合性官能基を有するモノマー、オリゴマー、プレポリマーを単独で、または適宜混合した組成物が用いられる。モノマーの例としては、アクリル酸メチル、メチルメタクリレート、メトキシポリエチレンメタクリレート、シクロヘキシルメタクリレート、フェノキシエチルメタクリレート、エチレングリコールジメタクリレート、ジペンタエリスリトールヘキサアクリレート、トリメチロールプロパントリメタクリレート等を挙げることができる。オリゴマー、プレポリマーとしては、ポリエステルアクリレート、ポリウレタンアクリレート、エポキシアクリレート、ポリエーテルアクリレート、アルキットアクリレート、メラミンアクリレート、シリコーンアクリレート等のアクリレート化合物、不飽和ポリエステル、テトラメ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、ネオペンチルグリコールジグリシジルエーテル、ビスフェノールＡジグリシジルエーテルや各種脂環式エポキシ等のエポキシ系化合物、３−エチル−３−ヒドロキシメチルオキセタン、１，４−ビス｛［（３−エチル−３−オキセタニル）メトキシ］メチル｝ベンゼン、ジ［１−エチル（３−オキセタニル）］メチルエーテル等のオキセタン化合物を挙げることができる。これらは単独、もしくは複数混合して使用することができる。 Radiation curable resin compositions used for the hard coat layer include radical polymerizable functional groups such as acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, and cationic polymerization such as epoxy group, vinyl ether group, oxetane group, etc. The composition which mixed the monomer, oligomer, and prepolymer which have a functional functional group individually or suitably was used. Examples of the monomer include methyl acrylate, methyl methacrylate, methoxypolyethylene methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, ethylene glycol dimethacrylate, dipentaerythritol hexaacrylate, trimethylolpropane trimethacrylate, and the like. As oligomers and prepolymers, polyester acrylate, polyurethane acrylate, epoxy acrylate, polyether acrylate, alkit acrylate, acrylate compounds such as melamine acrylate, silicone acrylate, unsaturated polyester, tetramethylene glycol diglycidyl ether, propylene glycol diglycidyl ether , Neopentyl glycol diglycidyl ether, epoxy compounds such as bisphenol A diglycidyl ether and various alicyclic epoxies, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl And oxetane compounds such as methoxy] methyl} benzene and di [1-ethyl (3-oxetanyl)] methyl ether.These can be used alone or in combination.
上記放射線硬化型樹脂組成物は、そのままで電子線照射により硬化可能であるが、紫外線照射による硬化を行う場合は、光重合開始剤の添加が必要である。光重合開始剤としては、アセトフェノン系、ベンゾフェノン系、チオキサントン系、ベンゾイン、ベンゾインメチルエーテル等のラジカル重合開始剤、芳香族ジアゾニウム塩、芳香族スルホニウム塩、芳香族ヨードニウム塩、メタロセン化合物等のカチオン重合開始剤を単独または適宜組み合わせて使用することが出来る。 The radiation curable resin composition can be cured by electron beam irradiation as it is, but in the case of curing by ultraviolet irradiation, it is necessary to add a photopolymerization initiator. Photopolymerization initiators include radical polymerization initiators such as acetophenone, benzophenone, thioxanthone, benzoin, and benzoin methyl ether, and cationic polymerization starts such as aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, and metallocene compounds. The agents can be used alone or in appropriate combination.
本発明では、上記放射線硬化型樹脂組成物に加えて、その重合硬化を妨げない範囲で高分子樹脂を添加使用することが出来る。この高分子樹脂は、後述するハードコート層塗料に使用される有機溶剤に可溶な熱可塑性樹脂であり、具体的にはアクリル樹脂、アルキッド樹脂、ポリエステル樹脂等が挙げられ、これらの樹脂中には、導電性無機超微粒子との親和性を増すために、カルボキシル基やリン酸基、スルホン酸基等の酸性官能基を有することが好ましい。 In the present invention, in addition to the radiation curable resin composition, a polymer resin can be added and used as long as the polymerization and curing is not hindered. This polymer resin is a thermoplastic resin that is soluble in an organic solvent used in the hard coat layer coating described later, and specifically includes acrylic resins, alkyd resins, polyester resins, and the like. In order to increase the affinity with the conductive inorganic ultrafine particles, it is preferable to have an acidic functional group such as a carboxyl group, a phosphate group, or a sulfonate group.
また、本発明では、導電性無機超微粒子を上記の放射線硬化型樹脂組成物中に安定に分散させるために導電性無機超微粒子の表面を、必要に応じて各種カップリング剤により修飾することができる。このカップリング剤としては、シランカップリング剤、アルミニウム、チタニウム、ジルコニウム等の金属アルコキシド、脂肪酸等の有機酸およびその塩、リン酸化合物等が挙げられる。 In the present invention, the surface of the conductive inorganic ultrafine particles may be modified with various coupling agents as required in order to stably disperse the conductive inorganic ultrafine particles in the radiation curable resin composition. it can. Examples of the coupling agent include silane coupling agents, metal alkoxides such as aluminum, titanium, and zirconium, organic acids such as fatty acids and salts thereof, and phosphoric acid compounds.
ハードコート層中に占める導電性無機超微粒子の割合は、重量比率で７５％以上であり、好ましくは重量比率で７５〜９５％であり、より好ましくは８０〜９０％である。この割合が７５％未満では良好な導電性が得られにくく、９５％を超えると、ヘイズ値が上昇すると共にハードコート層の耐磨耗性が低下するといった問題が生じやすい。 The ratio of the conductive inorganic ultrafine particles in the hard coat layer is 75% or more by weight, preferably 75 to 95% by weight, and more preferably 80 to 90%. If this ratio is less than 75%, good conductivity is difficult to obtain, and if it exceeds 95%, the haze value increases and the wear resistance of the hard coat layer tends to decrease.
ハードコート層は、主に上述の導電性無機超微粒子と放射線硬化型樹脂組成物の硬化物により構成されるが、その形成方法は、導電性無機超微粒子と放射線硬化型樹脂組成物と有機溶剤からなる塗料を塗工し、有機溶剤を揮発させた後に電子線または紫外線照射により硬化せしめるものである。ここで使用される有機溶剤としては、放射線硬化型樹脂組成物を溶解すると共に、導電性無機超微粒子の分散に適したものを選ぶ必要がある。具体的には、基材への濡れ性、粘度、乾燥速度といった塗工適性を考慮して、アルコール系、エステル系、ケトン系、エーテル系、芳香族炭化水素から選ばれた単独または混合溶剤を使用することができる。 The hard coat layer is mainly composed of the above-described conductive inorganic ultrafine particles and a cured product of the radiation curable resin composition, and the formation method thereof is the conductive inorganic ultrafine particles, the radiation curable resin composition, and the organic solvent. The coating composition is applied and the organic solvent is volatilized, and then cured by electron beam or ultraviolet irradiation. As the organic solvent used here, it is necessary to select a solvent that dissolves the radiation curable resin composition and is suitable for dispersing conductive inorganic ultrafine particles. Specifically, in consideration of coating suitability such as wettability to the substrate, viscosity, and drying speed, a single or mixed solvent selected from alcohols, esters, ketones, ethers, and aromatic hydrocarbons is used. Can be used.
ハードコート層の厚さは１．０〜５．０μｍの範囲であり、より好ましくは２．０〜４．０μｍの範囲がよい。ハードコート層が１μｍより薄い場合は、紫外線硬化型時に酸素阻害による硬化不良を起こし、ハードコート層の耐磨耗性が劣化し、５μｍより厚い場合は、樹脂の硬化収縮によりカールが発生したり、ハードコート層にマイクロクラックが発生したり、透光性基体との密着性が低下したり、さらには光透過性が低下したりする。そして、膜厚の増加に伴う必要塗料量の増加によりコストアップの原因ともなる。 The thickness of the hard coat layer is in the range of 1.0 to 5.0 μm, more preferably in the range of 2.0 to 4.0 μm. When the hard coat layer is thinner than 1 μm, curing failure due to oxygen inhibition occurs in the ultraviolet curing type, and the wear resistance of the hard coat layer is deteriorated. When it is thicker than 5 μm, curling occurs due to curing shrinkage of the resin. In addition, microcracks are generated in the hard coat layer, adhesion to the light-transmitting substrate is lowered, and light transmittance is further lowered. And it becomes a cause of cost increase by the increase in the amount of required coating materials accompanying the increase in film thickness.
本発明のハードコート層までの段階の表面抵抗は、１０７〜１０９Ω／□であることが好ましい。帯電防止性であればこれ以上低い表面抵抗は必要なく、また１０９Ω／□を超えるようであれば、その上に低屈折率層を設けた際の最表面の表面抵抗が１０１１Ω／□以上になってしまい、十分な帯電防止性を発揮できないので好ましくない。また、ハードコート層の表面硬度は、鉛筆硬度試験（ＪＩＳ Ｋ５６００−５−４）で、Ｈ以上の硬度であり、２Ｈ以上もしくは３Ｈ以上の硬度がより好ましい。 The surface resistance at the stage up to the hard coat layer of the present invention is preferably 10 7 to 10 9 Ω / □. If it is antistatic, a lower surface resistance is not necessary, and if it exceeds 10 9 Ω / □, the surface resistance of the outermost surface when a low refractive index layer is provided is 10 11 Ω / □. It becomes more than □, which is not preferable because sufficient antistatic properties cannot be exhibited. Further, the surface hardness of the hard coat layer is a hardness of H or higher in a pencil hardness test (JIS K5600-5-4), and a hardness of 2H or higher or 3H or higher is more preferable.
また、ハードコート層の硬化後の屈折率は１．６〜１．８が好ましい。屈折率が１．６未満では、上層に低屈折率層を設けても十分な低反射率を達成できず、また、屈折率が１．８よりも高くなれば、透光性基体との屈折率差が大きくなり過ぎて低屈折率層を設けた際の干渉ムラが大きくなるという問題を生じる。 The refractive index after curing of the hard coat layer is preferably 1.6 to 1.8. If the refractive index is less than 1.6, sufficient low reflectance cannot be achieved even if a low refractive index layer is provided on the upper layer, and if the refractive index is higher than 1.8, refraction with the translucent substrate is not possible. There is a problem that the unevenness of interference is increased when the low refractive index layer is provided due to the rate difference becoming too large.
本発明では、以上説明したハードコート層中に透光性樹脂微粒子を分散・含有せしめて、ハードコート層表面に微細な凹凸を形成し、いわゆるＡＧを作製することができる。ここで使用される透光性樹脂微粒子としては、アクリル樹脂、ポリスチレン樹脂、スチレン−アクリル共重合体、ポリエチレン樹脂、エポキシ樹脂、シリコーン樹脂、ポリフッ化ビニリデン、ポリフッ化エチレン系樹脂等よりなる有機透光性粒子を使用することができる。透光性樹脂微粒子の屈折率は、１．４０〜１．７５が好ましく、屈折率が１．４０未満または１．７５より大きい場合は、透光性基体あるいはハードコート層との屈折率差が大きくなり過ぎ、透過率が低下する。透光性粒子の粒径は０．３〜１０μｍの範囲のものが好ましく、１〜５μｍがより好ましい。粒径が０．３μｍ以下の場合はＡＧ性が低下するため、また１０μｍ以上の場合は、ギラツキを発生すると共に、表面凹凸の程度が大きくなり過ぎて表面が白っぽくなってしまうため好ましくない。 In the present invention, translucent resin fine particles are dispersed and contained in the hard coat layer described above, and fine irregularities are formed on the surface of the hard coat layer, so-called AG can be produced. As the translucent resin fine particles used here, an organic translucent resin made of acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyethylene resin, epoxy resin, silicone resin, polyvinylidene fluoride, polyfluoroethylene resin, or the like. Sex particles can be used. The refractive index of the translucent resin fine particles is preferably 1.40 to 1.75. When the refractive index is less than 1.40 or greater than 1.75, the difference in refractive index from the translucent substrate or the hard coat layer is small. It becomes too large and the transmittance decreases. The particle diameter of the translucent particles is preferably in the range of 0.3 to 10 μm, more preferably 1 to 5 μm. When the particle size is 0.3 μm or less, the AG property is lowered, and when the particle size is 10 μm or more, glare is generated and the surface unevenness becomes too large and the surface becomes whitish.
本発明では、上述のハードコート層上に設ける低屈折率層は含フッ素ポリシロキサンで構成される。この含フッ素ポリシロキサンは、加水分解性シラン化合物及び／またはその加水分解物と硬化促進剤とを少なくとも含有する混合物が硬化したものであり、この加水分解性シラン化合物としては、下記一般式［１］〜［３］で示されるシラン化合物の少なくとも１種類と、一般式［４］、［５］で示される含フッ素シラン化合物の少なくとも１種類との混合物が使用される。 In the present invention, the low refractive index layer provided on the hard coat layer is composed of fluorine-containing polysiloxane. This fluorine-containing polysiloxane is obtained by curing a hydrolyzable silane compound and / or a mixture containing at least a hydrolyzate thereof and a curing accelerator, and the hydrolyzable silane compound has the following general formula [1 A mixture of at least one of the silane compounds represented by the formulas [3] to [3] and at least one of the fluorinated silane compounds represented by the general formulas [4] and [5] is used.
加水分解性シラン化合物の具体例としては、ケイ素原子が４個の加水分解基を有するシラン化合物が挙げられ、具体的には、テトラメトキシシラン、テトラエトキシシラン、テトラ（１−プロポキシ）シラン、テトラ（２−プロポキシ）シラン、テトラ（１−ブトキシ）シラン、テトラクロロシラン、テトラブロモシラン、テトライソシアナートシラン、ジメトキシシロキサンオリゴマー、ジエトキシシロキサンオリゴマー等が挙げられるが、これらに限定されるものではない。また、含フッ素シラン化合物としては、３，３，３−トリフルオロプロピルトリメトキシシラン、３，３，３−トリフルオロプロピルトリエトキシシラン、３，３，３−トリフルオロプロピルトリプロポキシシラン、３，３，３−トリフルオロプロピルトリクロロシラン、３，３，３−トリフルオロプロピルトリイソシアナートシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−テトラヒドロパーフルオロヘキシルトリメトキシシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−テトラヒドロパーフルオロヘキシルトリエトキシシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−テトラヒドロパーフルオロヘキシルトリプロポキシシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−テトラヒドロパーフルオロヘキシルトリクロロシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−テトラヒドロパーフルオロヘキシルトリイソシアナートシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−テトラヒドロパーフルオロノニルトリメトキシシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−テトラヒドロパーフルオロノニルトリエトキシシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−テトラヒドロパーフルオロノニルトリプロポキシシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−テトラヒドロパーフルオロノニルトリクロロシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−テトラヒドロパーフルオロノニルトリイソシアナートシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−テトラヒドロパーフルオロデシルトリメトキシシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−テトラヒドロパーフルオロデシルトリエトキシシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−テトラヒドロパーフルオロデシルトリプロポキシシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−テトラヒドロパーフルオロデシルトリクロロシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−テトラヒドロパーフルオロデシルトリイソシアナートシラン、１−ヘプタフルオロイソプロポキシプロピルトリメトキシシラン、１−ヘプタフルオロイソプロポキシプロピルトリエトキシシラン、１−ヘプタフルオロイソプロポキシプロピルトリプロポキシシラン、１−ヘプタフルオロイソプロポキシプロピルトリクロロシラン、１−ヘプタフルオロイソプロポキシプロピルトリイソシアナートシラン、１，４−ビス（トリメトキシシリル）−２，２，３，３−テトラフルオロブタン、１，５−ビス（トリメトキシシリル）−２，２，３，３，４，４−ヘキサフルオロペンタン等が挙げられる。中でも、屈折率、反応性、溶媒溶解性の観点から１Ｈ，１Ｈ，２Ｈ，２Ｈ−テトラヒドロパーフルオロデシルトリエトキシシランが好適である。 Specific examples of the hydrolyzable silane compound include a silane compound having a hydrolyzable group having 4 silicon atoms. Specifically, tetramethoxysilane, tetraethoxysilane, tetra (1-propoxy) silane, tetra Examples include (2-propoxy) silane, tetra (1-butoxy) silane, tetrachlorosilane, tetrabromosilane, tetraisocyanatosilane, dimethoxysiloxane oligomer, diethoxysiloxane oligomer, and the like, but are not limited thereto. Examples of the fluorine-containing silane compound include 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3,3,3-trifluoropropyltripropoxysilane, 3, 3,3-trifluoropropyltrichlorosilane, 3,3,3-trifluoropropyltriisocyanatosilane, 1H, 1H, 2H, 2H-tetrahydroperfluorohexyltrimethoxysilane, 1H, 1H, 2H, 2H-tetrahydroper Fluorohexyltriethoxysilane, 1H, 1H, 2H, 2H-tetrahydroperfluorohexyltripropoxysilane, 1H, 1H, 2H, 2H-tetrahydroperfluorohexyltrichlorosilane, 1H, 1H, 2H, 2H-tetrahydroperfluorohexyltri Sodium silane, 1H, 1H, 2H, 2H-tetrahydroperfluorononyltrimethoxysilane, 1H, 1H, 2H, 2H-tetrahydroperfluorononyltriethoxysilane, 1H, 1H, 2H, 2H-tetrahydroperfluorononyltripropoxy Silane, 1H, 1H, 2H, 2H-tetrahydroperfluorononyltrichlorosilane, 1H, 1H, 2H, 2H-tetrahydroperfluorononyltriisocyanatosilane, 1H, 1H, 2H, 2H-tetrahydroperfluorodecyltrimethoxysilane, 1H, 1H, 2H, 2H-tetrahydroperfluorodecyltriethoxysilane, 1H, 1H, 2H, 2H-tetrahydroperfluorodecyltripropoxysilane, 1H, 1H, 2H, 2H-tetrahydroperful Rhodecyltrichlorosilane, 1H, 1H, 2H, 2H-tetrahydroperfluorodecyltriisocyanate silane, 1-heptafluoroisopropoxypropyltrimethoxysilane, 1-heptafluoroisopropoxypropyltriethoxysilane, 1-heptafluoroisopropoxy Propyltripropoxysilane, 1-heptafluoroisopropoxypropyltrichlorosilane, 1-heptafluoroisopropoxypropyltriisocyanatosilane, 1,4-bis (trimethoxysilyl) -2,2,3,3-tetrafluorobutane, Examples include 1,5-bis (trimethoxysilyl) -2,2,3,3,4,4-hexafluoropentane. Among these, 1H, 1H, 2H, 2H-tetrahydroperfluorodecyltriethoxysilane is preferable from the viewpoint of refractive index, reactivity, and solvent solubility.
また、本発明の加水分解性シラン化合物として、上記の化合物の他に皮膜形成剤および帯電防止剤としての機能を有するカチオン変性シラン化合物を含有されることも出来る。カチオン変性シラン化合物の具体例としては、オクタデシルジメチル［３−（トリメトキシシリル）プロピル］アンモニウムクロライド、３−（Ｎ−スチルメチル−２−アミノエチルアミノ）−プロピルトリメトキシシラン塩酸塩、Ｎ（３−トリメトキシシリルプロピル）−Ｎ−メチル−Ｎ，Ｎ−ジアリルアンモニウムクロライド、Ｎ，Ｎ−ジデシル−Ｎ−メチル−Ｎ−（３−トリメトキシシリルプロピル）アンモニウムクロライド、オクタデシルジメチル（３−トリメトキシシリルプロピル）アンモニウムクロライド、テトラデシルジメチル（３−トリメトキシシリルプロピル）アンモニウムクロライド、Ｎ−トリメトキシシリルプロピル−Ｎ，Ｎ，Ｎ−トリ−ｎ−ブチルアンモニウムクロライド、Ｎ−トリメトキシシリルプロピル−Ｎ，Ｎ，Ｎ−トリメチルアンモニウムクロライド、トリメトキシシリルプロピル（ポリエチレンイミン）、ジメトキシメチルシリルプロピル変性（ポリエチレンイミン）等が挙げられる。 Moreover, as a hydrolysable silane compound of this invention, the cation modified silane compound which has a function as a film forming agent and an antistatic agent other than said compound can also be contained. Specific examples of the cation-modified silane compound include octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, 3- (N-stilmethyl-2-aminoethylamino) -propyltrimethoxysilane hydrochloride, N (3- Trimethoxysilylpropyl) -N-methyl-N, N-diallylammonium chloride, N, N-didecyl-N-methyl-N- (3-trimethoxysilylpropyl) ammonium chloride, octadecyldimethyl (3-trimethoxysilylpropyl) ) Ammonium chloride, tetradecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, N-trimethoxysilylpropyl-N, N, N-tri-n-butylammonium chloride, N-trimethoxysilylpropyl-N, , N- trimethylammonium chloride, trimethoxysilylpropyl (polyethylenimine), and the like dimethoxymethylsilylpropyl modified (polyethyleneimine) and the like.
低屈折率層の屈折率と塗膜強度のバランスを取るためには、以上の加水分解性シラン化合物の中で、低屈折率層の塗膜強度を向上させるためには、ケイ素原子に４個の加水分解性基を有するシラン化合物（一般式［１］においてａ＝０の化合物）と、含フッ素加水分解性シラン化合物とを適宜混合して使用することが好ましい。この際の混合比はシラン化合物の種類により異なるが、ケイ素原子に４個の加水分解性基を有するシラン化合物１００重量部に対して、含フッ素加水分解性シラン化合物は１〜５００重量部、更に好適には２０〜３００重量部が好ましく用いられる。 In order to balance the refractive index of the low refractive index layer and the coating film strength, among the above hydrolyzable silane compounds, in order to improve the coating strength of the low refractive index layer, four silicon atoms are used. It is preferable to use a silane compound having a hydrolyzable group (a compound of a = 0 in the general formula [1]) and a fluorine-containing hydrolyzable silane compound as appropriate. The mixing ratio at this time varies depending on the type of the silane compound, but the fluorine-containing hydrolyzable silane compound is 1 to 500 parts by weight with respect to 100 parts by weight of the silane compound having four hydrolyzable groups on the silicon atom. Suitably 20 to 300 parts by weight are preferably used.
上記の加水分解性シラン化合物は、通常アルコール溶剤に溶解して部分的に加水分解と重縮合を進行させておき、これを塗工後に加熱により重縮合を更に進めて硬化膜を形成することになる。これらの加水分解・重縮合反応を促進するために、加水分解性シラン化合物及び／またはその加水分解物１００重量部に対して、１〜３０重量部の範囲で硬化促進剤が添加・使用される。この硬化促進剤としては、硝酸、塩酸等の鉱酸やシュウ酸、酢酸等の有機酸、オルトリン酸、ベンゼンスルホン酸、Ｐ−トルエンスルホン酸等の酸性触媒が、またアンモニア等の塩基性触媒が挙げられる。 The hydrolyzable silane compound is usually dissolved in an alcohol solvent and partially hydrolyzed and polycondensed, and after coating, the polycondensation is further advanced by heating to form a cured film. Become. In order to accelerate these hydrolysis and polycondensation reactions, a curing accelerator is added and used in the range of 1 to 30 parts by weight with respect to 100 parts by weight of the hydrolyzable silane compound and / or the hydrolyzate thereof. . Examples of the curing accelerator include mineral acids such as nitric acid and hydrochloric acid, organic acids such as oxalic acid and acetic acid, acidic catalysts such as orthophosphoric acid, benzenesulfonic acid and P-toluenesulfonic acid, and basic catalysts such as ammonia. Can be mentioned.
これらの硬化促進成分は、シラン化合物と混合した後、直接塗布・製膜することも可能であるが、シラン化合物に予め水を加えて加水分解した後、硬化促進成分を加えて塗布・製膜しても良い。この場合、シラン化合物−水−溶剤混合物またはこれに微量の強酸（塩酸等）を加えた混合物を調整後、室温で数時間から数日放置し、塗工用の濃度に希釈して、硬化促進成分を加えて塗工・製膜する。また、水の不存在下、シラン化合物をシュウ酸等のシラン重合触媒を用いてオリゴマーにした後、硬化促進成分を加えて塗布・製膜してもよい。この場合は、シラン化合物−溶剤−カルボン酸触媒混合物を室温から１００℃の範囲で加熱することで行い、他の場合と同様に希釈後、硬化促進成分を加えて使用する。 These curing accelerating components can be directly applied and formed into a film after mixing with the silane compound. However, after water is added to the silane compound in advance and hydrolyzed, the hardening accelerating component is added and applied to form a film. You may do it. In this case, after preparing a silane compound-water-solvent mixture or a mixture obtained by adding a trace amount of a strong acid (hydrochloric acid, etc.), it is allowed to stand at room temperature for several hours to several days and diluted to a coating concentration to accelerate curing. Add ingredients to coat and form a film. Alternatively, in the absence of water, the silane compound may be oligomerized using a silane polymerization catalyst such as oxalic acid, and then a curing accelerating component may be added for coating and film formation. In this case, the silane compound-solvent-carboxylic acid catalyst mixture is heated in the range of room temperature to 100 ° C., and after dilution, the curing accelerating component is added and used as in other cases.
本発明の低屈折率層塗料は以下の塗料調製、塗工、乾燥、及び重合、硬化のプロセスにより作製される。塗料は、任意の溶媒に上記シラン化合物を溶解し、必要に応じて加水分解またはオリゴマー化した後、上記硬化促進成分を混合することによって調製できる。この場合、目的とする塗工膜厚を得るためにシラン化合物の濃度を、通常０．１〜５０重量％程度、好ましくは０．５〜３０重量％程度に調製する。溶媒としては、少なくとも加水分解したシラン化合物を溶解できる極性溶媒を含んでいる必要がある。また乾燥時の揮発性の点で沸点が５０〜１５０℃の溶剤が用いられる。このような溶剤としてはメタノール、エタノール、１−プロパノール、２−プロパノール、ブタノール等のアルコール類、エチレングリコール、プロピレングリコール、ヘキシレングリコール等のグリコール類、エチルセロソルブ、ブチルセロソルブ、エチルカルビトール、ブチルカルビトール、ジエチルセロソルブ、ジエチルカルビトール等のグリコールエーテル類、アセトン、メチルエチルケトン、メチルイソブチルケトンなどのケトン類、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチルなどのエステル類、ベンゼン、トルエン、キシレン等の芳香族炭化水素類、Ｎ−メチルピロリドン、ジメチルフォルムアミド等の含窒素類、クロロホルム、塩化メチレン、トリクロロエチレンなどのハロゲン化炭化水素類などが用いられるが、これらに限定されるものではない。また、上記溶媒は単独、もしくは混合して用いることができる。 The low refractive index layer coating material of the present invention is produced by the following coating preparation, coating, drying, polymerization, and curing processes. The coating material can be prepared by dissolving the silane compound in an arbitrary solvent, hydrolyzing or oligomerizing as necessary, and then mixing the curing accelerating component. In this case, in order to obtain the target coating film thickness, the concentration of the silane compound is usually adjusted to about 0.1 to 50% by weight, preferably about 0.5 to 30% by weight. As the solvent, it is necessary to contain at least a polar solvent capable of dissolving the hydrolyzed silane compound. A solvent having a boiling point of 50 to 150 ° C. is used from the viewpoint of volatility during drying. Such solvents include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, glycols such as ethylene glycol, propylene glycol, hexylene glycol, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol. , Glycol ethers such as diethyl cellosolve and diethyl carbitol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate, aromatics such as benzene, toluene and xylene Hydrocarbons, nitrogen-containing compounds such as N-methylpyrrolidone and dimethylformamide, and halogenated hydrocarbons such as chloroform, methylene chloride, and trichloroethylene are used. The present invention is not limited to these. Moreover, the said solvent can be used individually or in mixture.
上記調製した塗料を用いて、塗工または印刷手法により透明支持基体の片面もしくは両面に低屈折率層を設けることができる。具体的には、エアドクターコーティング、ブレードコーティング、ワイヤードクターコーティング、ナイフコーティング、リバースコーティング、トランスファロールコーティング、グラビアロールコーティング、マイクログラビアコーティング、キスコーティング、キャストコーティング、スプレーコーティング、スロットオリフィスコーティング、カレンダーコーティング、電着コーティング、ディップコーティング、ダイコーティング等の塗工手法や、フレキソ印刷等の凸版印刷、ダイレクトグラビア印刷、オフセットグラビア印刷等の凹版印刷、オフセット印刷等の平版印刷、スクリーン印刷等の孔版印刷等の印刷手法を挙げることができる。尚、上記のようにして形成される低屈折率層の厚さは、屈折率と光の波長との関係を考慮して層の厚さを適宜決定すればよく、特に限定されるものではないが、７０〜１２０ｎｍ程度が好適である。この程度の厚さであれば、下層のハードコート層の表面抵抗を一桁程度上昇させるだけであるため、低屈折率層の表面抵抗を１０１１Ω／□未満に抑えることが出来る。 A low refractive index layer can be provided on one side or both sides of the transparent support substrate by coating or printing using the prepared paint. Specifically, air doctor coating, blade coating, wire doctor coating, knife coating, reverse coating, transfer roll coating, gravure roll coating, micro gravure coating, kiss coating, cast coating, spray coating, slot orifice coating, calendar coating, Coating methods such as electrodeposition coating, dip coating, die coating, relief printing such as flexographic printing, intaglio printing such as direct gravure printing, offset gravure printing, lithographic printing such as offset printing, stencil printing such as screen printing, etc. A printing method can be mentioned. The thickness of the low refractive index layer formed as described above is not particularly limited, as long as the thickness of the layer is appropriately determined in consideration of the relationship between the refractive index and the wavelength of light. However, about 70 to 120 nm is preferable. With such a thickness, the surface resistance of the lower hard coat layer is only increased by an order of magnitude, so the surface resistance of the low refractive index layer can be suppressed to less than 10 11 Ω / □.
低屈折率層塗膜の乾燥、及び重合、硬化は、加熱乾燥により溶媒を揮発せしめ、さらに加熱を継続して硬化を進める必要がある。加熱温度は４０℃以上、好ましくは８０〜１２０℃で行う。加熱温度の上限は使用する基体によって異なるが、一般的な透明フィルムは１２０℃以上では軟化して使用できなくなる。 For drying, polymerization, and curing of the low refractive index layer coating film, it is necessary to volatilize the solvent by heat drying, and to continue the curing by further heating. The heating temperature is 40 ° C. or higher, preferably 80 to 120 ° C. Although the upper limit of the heating temperature varies depending on the substrate to be used, a general transparent film becomes soft at 120 ° C. or more and cannot be used.
本発明の低屈折率層の表面抵抗は、１０１１Ω／□未満であることが必須であり、より好ましくは１０１０Ω／□以下である。１０１１Ω／□以上では、十分な帯電防止性を発揮できないので好ましくない。
The surface resistance of the low refractive index layer of the present invention is essential to be less than 10 11 Ω / □ , and more preferably 10 10 Ω / □ or less. A value of 10 11 Ω / □ or more is not preferable because sufficient antistatic properties cannot be exhibited.
本発明の反射防止材料におけるハードコート層および低屈折率層の屈折率の関係は、ハードコート層の硬化後の屈折率が１．６〜１．８の範囲で、かつ低屈折率層の硬化後の屈折率が１．３６〜１．４２であることが望ましく、この範囲内を外れると低反射機能が低下する。 The relationship between the refractive indices of the hard coat layer and the low refractive index layer in the antireflection material of the present invention is such that the refractive index after curing of the hard coat layer is in the range of 1.6 to 1.8, and the low refractive index layer is cured. It is desirable that the later refractive index is 1.36 to 1.42, and if it is out of this range, the low reflection function is lowered.
本発明の反射防止材料は、以上の材料およびその組み合わせを最適化することにより、平均反射率を１％以下に、全光線透過率を９０％以上、ヘイズを２％以下にすることができる。また、表面のスチールウールによる耐磨耗性試験では、ヘイズの変化量を０．５％以下に抑えることができるものである。 The antireflection material of the present invention can have an average reflectance of 1% or less, a total light transmittance of 90% or more, and a haze of 2% or less by optimizing the above materials and combinations thereof. In the abrasion resistance test using steel wool on the surface, the amount of change in haze can be suppressed to 0.5% or less.
以下、本発明を実施例によって説明する。なお、「部」は重量部を意味するものとする。 Hereinafter, the present invention will be described by way of examples. “Part” means part by weight.
＜ハードコート層作製＞
１００μｍ厚さのＰＥＴフィルム（商品名：Ａ４３００、東洋紡績社製）に、下記ハードコート塗料をリバースコーティングにて塗布し、１００℃で１分間乾燥後、窒素雰囲気中で１２０Ｗ／ｃｍ集光型高圧水銀灯１灯で紫外線照射を行い（照射距離１０ｃｍ、照射時間３０秒）、塗工膜を硬化させた。このようにして、厚さ２．５μｍ、屈折率１．６４のハードコート層を形成した。
［ハードコート塗料の配合］
・イソフタル酸及びアジピン酸からなる多塩基酸と、ネオペンチルグリコールを反応させることにより生成する、重量平均分子量６５０００、酸価７ｍｇＫＯＨ／ｇ 不揮発分６０％のポリエステル樹脂 ７部
・ジペンタエリストールテトラアクリレート １．８部
・平均一次粒子径０．０５μｍ、Ｉｎに対するＳｎ含有量が５モル％となるＩＴＯ粉末
３４部
・ｎ−ブタノール／キシレンの重量比が４／６となる混合溶媒 ５７．２部
上記材料とガラスビーズ５０ｃｃを２５０ｃｃ容器に入れペイントシェーカーにて５時間分散した。分散後、光重合開始剤（商品名：イルガキュアー９０７、チバガイギー社製）０．２部を溶解させハードコート塗料を作製した。
<Hard coat layer production>
The following hard coat paint is applied by reverse coating to a 100 μm thick PET film (trade name: A4300, manufactured by Toyobo Co., Ltd.), dried at 100 ° C. for 1 minute, and then 120 W / cm condensing type high pressure in a nitrogen atmosphere. Ultraviolet irradiation was performed with one mercury lamp (irradiation distance 10 cm, irradiation time 30 seconds), and the coating film was cured. In this manner, a hard coat layer having a thickness of 2.5 μm and a refractive index of 1.64 was formed.
[Composition of hard coat paint]
7 parts of polyester resin with a weight average molecular weight of 65000 and an acid value of 7 mg KOH / g non-volatile content of 60% produced by reacting polybasic acid consisting of isophthalic acid and adipic acid with neopentyl glycol dipentaerystol tetraacrylate 1.8 parts ITO powder with an average primary particle size of 0.05 μm and Sn content of 5 mol% with respect to In
34 parts. Mixed solvent having a weight ratio of n-butanol / xylene of 4/6 57.2 parts The above materials and 50 cc of glass beads were placed in a 250 cc container and dispersed in a paint shaker for 5 hours. After dispersion, 0.2 parts of a photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Geigy) was dissolved to prepare a hard coat paint.
＜低屈折率層作製＞
上記ハードコート層上に、下記低屈折率塗料をリバースコーティングにて塗布し、１００℃で１分間乾燥し塗工膜を硬化させた。
［低屈折率塗料の配合］
・含フッ素ポリシロキサン（商品名：ＬＲ２０４−１、日産化学工業社製 固形分濃度 ６．４６％） ７．９部
・メチルイソブチルケトン １２．１部
その後、低屈折率層の硬化のため、６０℃で１２０時間キュアーし，厚さ０．１μｍ、屈折率１．３８，反射率０．８１％の本発明の反射防止材料を得た。
<Production of low refractive index layer>
On the hard coat layer, the following low refractive index paint was applied by reverse coating and dried at 100 ° C. for 1 minute to cure the coating film.
[Composition of low refractive index paint]
Fluorine-containing polysiloxane (trade name: LR204-1, solid concentration 6.46%, manufactured by Nissan Chemical Industries, Ltd.) 7.9 parts, methyl isobutyl ketone 12.1 parts, and then 60 for curing of the low refractive index layer Cure at 120 ° C. for 120 hours to obtain an antireflection material of the present invention having a thickness of 0.1 μm, a refractive index of 1.38, and a reflectance of 0.81%.
＜ハードコート層作製＞
１００μｍ厚さのＰＥＴフィルム（商品名：Ａ４３００、東洋紡績社製）に、下記ハードコート塗料をリバースコーティングにて塗布し、１００℃で１分間乾燥後、窒素雰囲気中で１２０Ｗ／ｃｍ集光型高圧水銀灯１灯で紫外線照射を行い（照射距離１０ｃｍ照射時間３０秒）、塗工膜を硬化させた。このようにして、厚さ２．５μｍ、屈折率１．６１のハードコート層を形成した。
［ハードコート塗料の配合］
・イソフタル酸及びアジピン酸からなる多塩基酸と、ネオペンチルグリコールを反応させることにより生成する、重量平均分子量６５０００、酸価７ｍｇＫＯＨ／ｇ 不揮発分６０％のポリエステル樹脂 ８．４部
・ジペンタエリストールテトラアクリレート ２．１部
・平均一次粒子０．０５μｍの酸化錫 ３２．８部
・ｎ−ブタノール／キシレンの重量比が４／６となる混合溶媒 ５６．７部
上記材料とガラスビーズ５０ｃｃを２５０ｃｃ容器に入れペイントシェーカーにて５時間分散した。分散後、光重合開始剤（商品名：イルガキュアー９０７、チバガイギー社製）０．２部を溶解させハードコート塗料を作製した。
<Hard coat layer production>
The following hard coat paint is applied by reverse coating to a 100 μm thick PET film (trade name: A4300, manufactured by Toyobo Co., Ltd.), dried at 100 ° C. for 1 minute, and then 120 W / cm condensing type high pressure in a nitrogen atmosphere. Ultraviolet irradiation was performed with one mercury lamp (irradiation distance: 10 cm, irradiation time: 30 seconds), and the coating film was cured. In this way, a hard coat layer having a thickness of 2.5 μm and a refractive index of 1.61 was formed.
[Composition of hard coat paint]
8.4 parts of a polyester resin having a weight average molecular weight of 65000 and an acid value of 7 mg KOH / g non-volatile content produced by reacting a polybasic acid consisting of isophthalic acid and adipic acid with neopentyl glycol 8.4 parts dipentaerystol 2.1 parts of tetraacrylate, 32.8 parts of tin oxide with an average primary particle of 0.05 μm, 56.7 parts of a mixed solvent in which the weight ratio of n-butanol / xylene is 4/6 250 cc of the above material and 50 cc of glass beads And dispersed for 5 hours in a paint shaker. After dispersion, 0.2 parts of a photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Geigy) was dissolved to prepare a hard coat paint.
＜低屈折率層作製＞
上記ハードコート層上に、実施例１と同配合の低屈折率塗料をリバースコーティングにて塗布し、１００℃で１分間乾燥し塗工膜を硬化させた。
その後、低屈折率層の硬化のため、６０℃で１２０時間キュアーし、厚さ０．１μｍ、屈折率１．３８、反射率０．７９％の本発明の反射防止材料を得た。
<Production of low refractive index layer>
On the hard coat layer, a low refractive index paint having the same composition as in Example 1 was applied by reverse coating and dried at 100 ° C. for 1 minute to cure the coating film.
Thereafter, in order to cure the low refractive index layer, curing was performed at 60 ° C. for 120 hours to obtain an antireflection material of the present invention having a thickness of 0.1 μm, a refractive index of 1.38, and a reflectance of 0.79%.
＜ハードコート層作製＞
１００μｍ厚さのＰＥＴフィルム（商品名：Ａ４３００、東洋紡績社製）に、下記ハードコート塗料をリバースコーティングにて塗布し、１００℃で１分間乾燥後、窒素雰囲気中で１２０Ｗ／ｃｍ集光型高圧水銀灯１灯で紫外線照射を行い（照射距離１０ｃｍ照射時間３０秒）、塗工膜を硬化させた。このようにして、厚さ２．５μｍ、屈折率１．６０のハードコート層を形成した。
［ハードコート塗料の配合］
・酸化錫含有紫外線硬化型樹脂（商品名：ＥＳＢ−３、大日本塗料社製 固形分濃度 ２９．７％ 固形分中の酸化錫含率８２％）
<Hard coat layer production>
The following hard coat paint is applied by reverse coating to a 100 μm thick PET film (trade name: A4300, manufactured by Toyobo Co., Ltd.), dried at 100 ° C. for 1 minute, and then 120 W / cm condensing type high pressure in a nitrogen atmosphere. Ultraviolet irradiation was performed with one mercury lamp (irradiation distance: 10 cm, irradiation time: 30 seconds), and the coating film was cured. In this way, a hard coat layer having a thickness of 2.5 μm and a refractive index of 1.60 was formed.
[Composition of hard coat paint]
-Tin oxide-containing UV curable resin (trade name: ESB-3, manufactured by Dainippon Paint Co., Ltd., solid content concentration 29.7%, tin oxide content 82% in solid content)
＜低屈折率層作製＞
上記ハードコート層上に、実施例１と同配合の屈折率塗料をリバースコーティングにて塗布し、１００℃で１分間乾燥し塗工膜を硬化させた。
その後、低屈折率層の硬化のため、６０℃で１２０時間キュアーし、厚さ０．１μｍ、屈折率１．３８、反射率０．８２％の本発明の反射防止材料を得た。
<Production of low refractive index layer>
On the hard coat layer, a refractive index paint having the same composition as that of Example 1 was applied by reverse coating, and dried at 100 ° C. for 1 minute to cure the coating film.
Thereafter, in order to cure the low refractive index layer, curing was performed at 60 ° C. for 120 hours to obtain an antireflection material of the present invention having a thickness of 0.1 μm, a refractive index of 1.38, and a reflectance of 0.82%.
＜比較例１＞
＜ハードコート層作製＞
１００μｍ厚さのＰＥＴフィルム（商品名：Ａ４３００、東洋紡績社製）に、下記ハードコート塗料をリバースコーティングにて塗布し、１００℃で１分間乾燥後、窒素雰囲気中で１２０Ｗ／ｃｍ集光型高圧水銀灯１灯で紫外線照射を行い（照射距離１０ｃｍ照射時間３０秒）、塗工膜を硬化させた。このようにして、厚さ２．５μｍ、屈折率１．６９のハードコート層を形成した。
［ハードコート塗料の配合］
・酸化ジルコニア含有紫外線硬化型樹脂（商品名：ＫＺ７３９１、ＪＳＲ社製 固形分濃度４２％、固形分中のＺｒＯ含率６８．０％）
<Comparative Example 1>
<Hard coat layer production>
The following hard coat paint is applied by reverse coating to a 100 μm thick PET film (trade name: A4300, manufactured by Toyobo Co., Ltd.), dried at 100 ° C. for 1 minute, and then 120 W / cm condensing type high pressure in a nitrogen atmosphere. Ultraviolet irradiation was performed with one mercury lamp (irradiation distance: 10 cm, irradiation time: 30 seconds), and the coating film was cured. In this way, a hard coat layer having a thickness of 2.5 μm and a refractive index of 1.69 was formed.
[Composition of hard coat paint]
-Zirconia-containing UV curable resin (trade name: KZ7391, manufactured by JSR, solid content concentration 42%, ZrO content in solid content 68.0%)
＜低屈折率層作製＞
上記ハードコート層上に、実施例１と同配合の低屈折率塗料をリバースコーティングにて塗布し、１００℃で１分間乾燥し塗工膜を硬化させた。
その後、低屈折率層の硬化のため、６０℃で１２０時間キュアーし、厚さ０．１μｍ、屈折率１．３８、反射率０．８５％の反射防止材料を得た。
<Production of low refractive index layer>
On the hard coat layer, a low refractive index paint having the same composition as in Example 1 was applied by reverse coating and dried at 100 ° C. for 1 minute to cure the coating film.
Thereafter, in order to cure the low refractive index layer, curing was performed at 60 ° C. for 120 hours to obtain an antireflection material having a thickness of 0.1 μm, a refractive index of 1.38, and a reflectance of 0.85%.
＜比較例２＞
＜ハードコート層作製＞
１００μｍ厚さのＰＥＴフィルム（商品名：Ａ４３００、東洋紡績社製）に、下記ハードコート塗料をリバースコーティングにて塗布し、１００℃で１分間乾燥後、窒素雰囲気中で１２０Ｗ／ｃｍ集光型高圧水銀灯１灯で紫外線照射を行い（照射距離１０ｃｍ照射時間３０秒）、塗工膜を硬化させた。このようにして、厚さ２．５μｍ、屈折率１．５２のハードコート層を形成した。
［ハードコート塗料の配合］
・紫外線硬化型ウレタンアクリレートオリゴマー（商品名：ＵＶ７６００Ｂ、日本合成化学工業社製 固形分濃度 １００％） ３８部
・光重合開始剤（商品名：イルガキュアー１８４、チバガイギー社製） ２部
・メチルエチルケトン ３６部
・シクロヘキサノン ２４部
<Comparative example 2>
<Hard coat layer production>
The following hard coat paint is applied by reverse coating to a 100 μm thick PET film (trade name: A4300, manufactured by Toyobo Co., Ltd.), dried at 100 ° C. for 1 minute, and then 120 W / cm condensing type high pressure in a nitrogen atmosphere. Ultraviolet irradiation was performed with one mercury lamp (irradiation distance: 10 cm, irradiation time: 30 seconds), and the coating film was cured. In this way, a hard coat layer having a thickness of 2.5 μm and a refractive index of 1.52 was formed.
[Composition of hard coat paint]
・ UV curable urethane acrylate oligomer (trade name: UV7600B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content 100%) 38 parts ・ Photopolymerization initiator (trade name: Irgacure 184, manufactured by Ciba Geigy) 2 parts ・ Methyl ethyl ketone 36 parts・ Cyclohexanone 24 parts
＜低屈折率層作製＞
上記ハードコート層上に、実施例１と同配合の低屈折率塗料をリバースコーティングにて塗布し、１００℃で１分間乾燥し塗工膜を硬化させた。
その後、低屈折率層の硬化のため、６０℃で１２０時間キュアーし、厚さ０．１μｍ、屈折率１．３８、反射率２．１３％の反射防止材料を得た。
<Production of low refractive index layer>
On the hard coat layer, a low refractive index paint having the same composition as in Example 1 was applied by reverse coating and dried at 100 ° C. for 1 minute to cure the coating film.
Thereafter, in order to cure the low refractive index layer, curing was performed at 60 ° C. for 120 hours to obtain an antireflection material having a thickness of 0.1 μm, a refractive index of 1.38, and a reflectance of 2.13%.
＜比較例３＞
＜ハードコート層作製＞
１００μｍ厚さのＰＥＴフィルム（商品名：Ａ４３００、東洋紡績社製）に、実施例１と同配合のハードコート塗料をリバースコーティングにて塗布し、１００℃で１分間乾燥後、窒素雰囲気中で１２０Ｗ／ｃｍ集光型高圧水銀灯１灯で紫外線照射を行い（照射距離１０ｃｍ照射時間３０秒）、塗工膜を硬化させた。このようにして、厚さ２．５μｍ、屈折率１．６４のハードコート層を形成した。
<Comparative Example 3>
<Hard coat layer production>
On a 100 μm thick PET film (trade name: A4300, manufactured by Toyobo Co., Ltd.), a hard coat paint having the same composition as in Example 1 was applied by reverse coating, dried at 100 ° C. for 1 minute, and then 120 W in a nitrogen atmosphere. / Cm Condensation type high-pressure mercury lamp was irradiated with ultraviolet light (irradiation distance 10 cm, irradiation time 30 seconds) to cure the coating film. In this manner, a hard coat layer having a thickness of 2.5 μm and a refractive index of 1.64 was formed.
＜低屈折率層作製＞
上記ハードコート層上に、下記低屈折率塗料をリバースコーティングにて塗布し、１００℃で１分間乾燥し塗工膜を硬化させた。
［低屈折率塗料の配合］
・シリカゾル（粒子径１５ｎｍでＳｉＯ２として３０重量％のシリカ超微粒子を含有するエタノール分散液） １０部
・皮膜形成剤（テトラエトキシシランの加水分解物 ＳｉＯ２として計算して固形分濃度６％ １５部
・エタノール ５３部
その後、低屈折率層の硬化のため、６０℃で１２０時間キュアーし、厚さ０．１μｍ、屈折率１．３８、反射率０．９２％の反射防止材料を得た。
<Production of low refractive index layer>
On the hard coat layer, the following low refractive index paint was applied by reverse coating and dried at 100 ° C. for 1 minute to cure the coating film.
[Composition of low refractive index paint]
10 parts of silica sol (ethanol dispersion containing 30% by weight of silica as SiO 2 with a particle size of 15 nm) Film forming agent (hydrolyzate of tetraethoxysilane, calculated as SiO 2 , solid content concentration 6% 15 Part / Ethanol 53 parts Thereafter, in order to cure the low refractive index layer, curing was performed at 60 ° C. for 120 hours to obtain an antireflection material having a thickness of 0.1 μm, a refractive index of 1.38 and a reflectance of 0.92%.
＜比較例４＞
＜ハードコート層作製＞
１００μｍ厚さのＰＥＴフィルム（商品名：Ａ４３００、東洋紡績社製）に、下記ハードコート塗料をリバースコーティングにて塗布し、１００℃で１分間乾燥後、窒素雰囲気中で１２０Ｗ／ｃｍ集光型高圧水銀灯１灯で紫外線照射を行い（照射距離１０ｃｍ照射時間３０秒）、塗工膜を硬化させた。このようにして、厚さ２．５μｍ、屈折率１．６１のハードコート層を形成した。
［ハードコート塗料の配合］
・イソフタル酸及びアジピン酸からなる多塩基酸と、ネオペンチルグリコールを反応させることにより生成する、重量平均分子量６５０００、酸価７ｍｇＫＯＨ／ｇ 不揮発分６０％のポリエステル樹脂 １４部
・ジペンタエリストールテトラアクリレート ３．６部
・平均一次粒子０．０５μｍ、Ｉｎに対するＳｎ含有量が５モル％となるＩＴＯ粉末
２８部
・ｎ−ブタノール／キシレンの重量比が４／６となる混合溶媒 ５４．４部
上記材料とガラスビーズ５０ｃｃを２５０ｃｃ容器に入れペイントシェーカーにて５時間分散した。分散後、光重合開始剤（商品名：イルガキュアー９０７、チバガイギー社製）０．２部を溶解させハードコート塗料を作製した。
<Comparative example 4>
<Hard coat layer production>
The following hard coat paint is applied by reverse coating to a 100 μm thick PET film (trade name: A4300, manufactured by Toyobo Co., Ltd.), dried at 100 ° C. for 1 minute, and then 120 W / cm condensing type high pressure in a nitrogen atmosphere. Ultraviolet irradiation was performed with one mercury lamp (irradiation distance: 10 cm, irradiation time: 30 seconds), and the coating film was cured. In this way, a hard coat layer having a thickness of 2.5 μm and a refractive index of 1.61 was formed.
[Composition of hard coat paint]
14 parts of a polyester resin having a weight average molecular weight of 65000 and an acid value of 7 mg KOH / g non-volatile content of 60% produced by reacting a polybasic acid consisting of isophthalic acid and adipic acid with neopentyl glycol dipentaerystol tetraacrylate 3.6 parts, average primary particle 0.05 μm, ITO powder with Sn content of 5 mol% with respect to In
28 parts / mixed solvent in which the weight ratio of n-butanol / xylene is 4/6 54.4 parts The above materials and 50 cc of glass beads were placed in a 250 cc container and dispersed in a paint shaker for 5 hours. After dispersion, 0.2 parts of a photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Geigy) was dissolved to prepare a hard coat paint.
＜低屈折率層作製＞
上記ハードコート層上に、実施例１と同配合の低屈折率塗料をリバースコーティングにて塗布し、１００℃で１分間乾燥し塗工膜を硬化させた。
その後、低屈折率層の硬化のため、６０℃で１２０時間キュアーし、厚さ０．１μｍ、屈折率１．３８、反射率０．９５％の反射防止材料を得た。
<Production of low refractive index layer>
On the hard coat layer, a low refractive index paint having the same composition as in Example 1 was applied by reverse coating and dried at 100 ° C. for 1 minute to cure the coating film.
Thereafter, in order to cure the low refractive index layer, curing was performed at 60 ° C. for 120 hours to obtain an antireflection material having a thickness of 0.1 μm, a refractive index of 1.38, and a reflectance of 0.95%.
実施例１〜３、比較例１〜４で得られた反射防止材料を用い、全光線透過率、ＨＡＺＥ、反射率、表面抵抗値、耐磨耗性、および防汚性を下記方法により測定、評価した。
全光線透過率およびＨＡＺＥは、ＨＡＺＥメーター（商品名：ＮＤＨ２０００、日本電色社製）により測定した。
反射率は分光光度計（商品名：ＵＶ３１００、島津製作所社製）を使用し、波長領域４００〜７００ｎｍの範囲の５゜の正反射を測定し、ＪＩＳ Ｚ８７０１に従って視感度補正したＹ値で表した。なお、測定は非測定面を黒マジックで完全に黒塗りした状態で行った。
表面抵抗値は、表面抵抗値高抵抗率計（商品名：ハイレスタ・アップ、三菱化学社製）を使用し測定した。
耐磨耗性は日本スチールウール社製のスチールウール＃００００を板紙耐磨耗試験機（熊谷理機工業社製）に取り付け、反射防止材料の低屈折率層面を荷重２５０ｇにて１０回往復させる。その後、下記式２で計算されるその部分のＨＡＺＥ値の変化δＨを、ＨＡＺＥメーターで測定した。ここで、測定値が大きいほど耐磨耗性が悪いと見なす。
Using the antireflection materials obtained in Examples 1 to 3 and Comparative Examples 1 to 4, the total light transmittance, HAZE, reflectance, surface resistance value, abrasion resistance, and antifouling properties were measured by the following methods, evaluated.
Total light transmittance and HAZE were measured with a HAZE meter (trade name: NDH2000, manufactured by Nippon Denshoku).
The reflectance was expressed as a Y value obtained by using a spectrophotometer (trade name: UV3100, manufactured by Shimadzu Corporation), measuring specular reflection at 5 ° in the wavelength range of 400 to 700 nm, and correcting the visibility according to JIS Z8701. . The measurement was performed with the non-measurement surface completely blackened with black magic.
The surface resistance value was measured using a surface resistance value high resistivity meter (trade name: Hiresta Up, manufactured by Mitsubishi Chemical Corporation).
Wear resistance is steel wool # 0000 manufactured by Nippon Steel Wool Co., Ltd., attached to a paperboard abrasion resistance tester (manufactured by Kumagai Riki Kogyo Co., Ltd.), and the low refractive index layer surface of the antireflection material is reciprocated 10 times at a load of 250 g. . Thereafter, the change δH of the HAZE value of the portion calculated by the following formula 2 was measured with a HAZE meter. Here, it is considered that the greater the measured value, the worse the wear resistance.
δＨ＝試験後のＨＡＺＥ値−試験前のＨＡＺＥ値・・・（式２） δH = HAZE value after test−HAZE value before test (Formula 2)
防汚性は、低屈折率層上にサラダ油をスポイトで１滴滴下した後、リグロインを含ませたワイパー（商品名：クリーンワイパーＳＦ３０Ｃ、クラレ社製）で２０往復ラビングし、更に拭き取った面の光学顕微鏡写真を撮影、サラダ油の付着の有無を確認した。低屈折率層にサラダ油の付着が顕著に認められる場合を×とし、まったく認められない場合を○とした。 The antifouling property was obtained by dropping one drop of salad oil onto the low refractive index layer with a dropper, rubbing 20 times with a wiper containing Ligroin (trade name: Clean Wiper SF30C, manufactured by Kuraray Co., Ltd.), and further wiping the surface. An optical micrograph was taken to confirm the presence or absence of salad oil. The case where the adhesion of salad oil was remarkably recognized in the low refractive index layer was evaluated as x, and the case where it was not recognized at all was evaluated as ◯.
表１の結果から明らかなように、本発明の反射防止材料は、ハードコート層に導電性無機微粒子を含有する放射線硬化型樹脂、また低屈折率層に含フッ素ポリシロキサンを用いることにより、低反射特性、導電性、耐磨耗性、防汚性が得られているのに対し、比較例１では、導電性、耐磨耗性が劣っており、比較例２では、低反射特性、導電性が劣っており、比較例３では耐磨耗性、防汚性が劣っており実用に耐え得るものではなかった。また、比較例４のハードコート層に含まれる導電性無機微粒子の含有量が７５％未満の場合、導電性が劣り実用に耐え得るものではなかった。 As is clear from the results in Table 1, the antireflection material of the present invention has a low resistance by using a radiation curable resin containing conductive inorganic fine particles in the hard coat layer and a fluorine-containing polysiloxane in the low refractive index layer. While the reflection characteristics, conductivity, wear resistance, and antifouling properties are obtained, Comparative Example 1 has poor conductivity and wear resistance, and Comparative Example 2 has low reflection characteristics, conductivity. In Comparative Example 3, the abrasion resistance and antifouling property were inferior and could not withstand practical use. Further, when the content of the conductive inorganic fine particles contained in the hard coat layer of Comparative Example 4 was less than 75%, the conductivity was inferior and could not be practically used.
Claims (4)
上記ハードコート層は、粒径５〜５０ｎｍである導電性無機超微粒子と酸性官能基を有する熱可塑性樹脂とを含有する放射線硬化型樹脂組成物が含有され、膜厚が１．０〜５．０μｍ、硬化後の屈折率が１．６〜１．８であり、
上記低屈折率層は含フッ素ポリシロキサンが含有され、硬化後の屈折率が１．３６〜１．４２であり、
上記ハードコート層に含まれる導電性無機超微粒子が、酸化錫、リンドープ酸化錫、アンチモンドープ酸化錫（ＡＴＯ）、酸化インジウム錫（ＩＴＯ）、酸化インジウム、酸化亜鉛、アルミニウムドープ酸化亜鉛から選ばれる少なくとも一つからなり、
上記導電性無機超微粒子の重量比率が７５％以上であり、
上記低屈折率層表面で測定する表面抵抗が１０１１Ω／□未満であり、全光線透過率が９０％以上、ヘイズが２％以下であることを特徴とする反射防止材料。 On the translucent substrate, at least a hard coat layer and a low refractive index layer are sequentially laminated,
The hard coat layer contains a radiation curable resin composition containing conductive inorganic ultrafine particles having a particle size of 5 to 50 nm and a thermoplastic resin having an acidic functional group, and has a film thickness of 1.0 to 5. 0 μm, the refractive index after curing is 1.6 to 1.8,
The low refractive index layer contains fluorine-containing polysiloxane, and the refractive index after curing is 1.36 to 1.42.
The conductive inorganic ultrafine particles contained in the hard coat layer are at least selected from tin oxide, phosphorus-doped tin oxide, antimony-doped tin oxide (ATO), indium tin oxide (ITO), indium oxide, zinc oxide, and aluminum-doped zinc oxide. Consist of one,
The weight ratio of the conductive inorganic ultrafine particles is 75% or more,
An antireflection material having a surface resistance measured on the surface of the low refractive index layer of less than 10 11 Ω / □, a total light transmittance of 90% or more, and a haze of 2% or less.
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| TW095110637A TWI390239B (en) | 2005-03-29 | 2006-03-28 | Anti-glare film |
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| JP2008241882A (en) * | 2007-03-26 | 2008-10-09 | Aica Kogyo Co Ltd | Coating agent and anti-reflection film |
| WO2010038709A1 (en) | 2008-09-30 | 2010-04-08 | 凸版印刷株式会社 | Antireflection film |
| CN102656486B (en) * | 2009-12-18 | 2014-11-12 | 凸版印刷株式会社 | Antireflection film |
| JP5789163B2 (en) * | 2011-09-29 | 2015-10-07 | 日立マクセル株式会社 | Transparent conductive sheet |
| JP6393970B2 (en) * | 2013-09-30 | 2018-09-26 | 凸版印刷株式会社 | HARD COAT COMPOSITION, HARD COAT FILM, AND ANTI-REFLECTION FILM |
| JP7159564B2 (en) * | 2018-01-30 | 2022-10-25 | 大日本印刷株式会社 | Optical film and image display device |
| CN111421936B (en) * | 2020-02-28 | 2023-11-03 | 江苏晶华新材料科技有限公司 | Reflectivity matching hardening film for ITO (indium tin oxide) coating |
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| JP4014133B2 (en) * | 2001-10-23 | 2007-11-28 | 日東電工株式会社 | Antireflection film, optical element and image display device |
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