JP5230079B2 - Anti-reflective material - Google Patents
Anti-reflective material Download PDFInfo
- Publication number
- JP5230079B2 JP5230079B2 JP2006097814A JP2006097814A JP5230079B2 JP 5230079 B2 JP5230079 B2 JP 5230079B2 JP 2006097814 A JP2006097814 A JP 2006097814A JP 2006097814 A JP2006097814 A JP 2006097814A JP 5230079 B2 JP5230079 B2 JP 5230079B2
- Authority
- JP
- Japan
- Prior art keywords
- refractive index
- hard coat
- low refractive
- layer
- coat layer
- 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 59
- 230000003667 anti-reflective effect Effects 0.000 title claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 51
- -1 acrylate compound Chemical class 0.000 claims description 41
- 229920005989 resin Polymers 0.000 claims description 34
- 239000011347 resin Substances 0.000 claims description 34
- 239000010419 fine particle Substances 0.000 claims description 33
- 239000000377 silicon dioxide Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 24
- 239000011882 ultra-fine particle Substances 0.000 claims description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 16
- 230000005855 radiation Effects 0.000 claims description 15
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 14
- 229910001887 tin oxide Inorganic materials 0.000 claims description 14
- 239000011342 resin composition Substances 0.000 claims description 13
- 239000011787 zinc oxide Substances 0.000 claims description 9
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 6
- 229920005992 thermoplastic resin Polymers 0.000 claims description 5
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 4
- 229910003437 indium oxide Inorganic materials 0.000 claims description 3
- 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
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- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
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- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-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でき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 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（ＡＲ）を有する反射防止材料がその表面に貼られている。 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, an antireflection material having an antireflection function (AR) is generally affixed to the surface in order to further improve the visibility.
従来、ＡＲについてはスパッタリング等により反射防止機能を有する層をフィルム上に形成する方法が主であった。しかしながら、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、最近では塗工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、この塗工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 AR, a method of forming a layer having an antireflection function on a film by sputtering or the like has been mainly used. However, vacuum deposition methods such as sputtering are expensive, have insufficient adhesion to plastic films, and it is difficult to form a uniform film over a large area. Laminating a plurality of different layers has been performed. The reflectance of AR produced by sputtering is usually 0.3% or less, but the reflectance of the film produced by this 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”).
塗工により作製される反射防止材料の一つである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。 The LR film, which is one of the antireflection materials produced by coating, has a basic structure in which a high refractive index layer and a low refractive index layer are sequentially laminated on a base. An arbitrary layer can be provided between the refractive index layer, between the high 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)
塗工により作製される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 the high refractive index layer material of the LR film produced by 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、この塗工により作製される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、耐薬品性、耐殺傷性や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 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 reflectance, this LR film is required to have high wear resistance, chemical resistance, killing resistance, antifouling properties, etc., and recently its surface has antistatic properties. Has come to be demanded. 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、耐擦傷性、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 antistatic properties and high refractive index of antireflective materials, but they have low reflectivity, antistatic properties, scratch resistance, abrasion resistance, chemical resistance, and contamination resistance. An anti-reflection material having balanced characteristics in the above has not been realized yet.
また、低反射性、帯電防止性、耐擦傷性、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、上記機能を同時に満足する反射防止材料を安価な手段で得ることができない。 In addition, as a method of simultaneously imparting these functions of low reflectivity, antistatic properties, scratch resistance, abrasion resistance, chemical resistance, and antifouling properties, development of multi-layered films is underway, Multi-layering, that is, a process of coating on the base material a plurality of times is required, which increases costs. In addition, it is difficult to adjust the balance between the layers by multilayering, and an antireflection material that simultaneously satisfies the above functions cannot be obtained by inexpensive means.
このような状況に鑑み、本発明は、透明基体上に特定のハードコート層と低屈折率層設けることで、低反射性、経済性に優れ、かつ導電性、耐擦傷性、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安価に提供することを目的とする。 In view of such circumstances, the present invention provides a specific hard coat layer and a low refractive index layer on a transparent substrate, so that it is excellent in low reflectivity and economy, and has conductivity, scratch resistance, and abrasion resistance. An object of the present invention is to provide an antireflection material capable of functioning in a well-balanced antifouling property at a low cost.
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、低屈折率層が順次積層されてなり、該ハードコート層は、放射線硬化型樹脂及び熱可塑性樹脂を含むハードコート樹脂組成物と導電性無機超微粒子との硬化物からなり、該低屈折率層が中空シリカ微粒子を含有する組成物からなり、該放射線硬化型樹脂のハードコート樹脂組成物に占める割合が重量比率で１０〜３５％であり、該熱可塑性樹脂の重量平均分子量が８０００〜１５００００であり、該低屈折率層の表面抵抗が１０１１Ω／□未満であることを特徴とする。 The antireflection material of the present invention is obtained by sequentially laminating a hard coat layer and a low refractive index layer on a translucent substrate, and the hard coat layer comprises a hard coat resin composition containing a radiation curable resin and a thermoplastic resin. a cured product of the object and the conductive inorganic ultrafine particles, made from a composition low refractive index layer contains the hollow silica fine particles, a percentage of the hard coat resin composition of the radiation-curable resin in a weight ratio of 10 was 35%, weight average molecular weight of the thermoplastic resin is 8,000 to 150,000, a surface resistivity of the low refractive index layer is characterized by a 10 11 Ω / □ under.
本発明の反射防止材料に用いられる放射線硬化型樹脂の一つが、（メタ）アクリロイル基を有する（メタ）アクリレート化合物であることを特徴とする。 One of the radiation curable resins used in the antireflection material of the present invention is a (meth) acrylate compound having a (meth) acryloyl group.
本発明の反射防止材料に用いられる中空シリカ微粒子は、平均粒子径０．５〜２００ｎｍ、屈折率１．３４〜１．４４であることを特徴とする。 The hollow silica fine particles used in the antireflection material of the present invention have an average particle diameter of 0.5 to 200 nm and a refractive index of 1.34 to 1.44.
本発明の反射防止材料のハードコート層における導電性無機超微粒子の重量比率は、７５％以上であることを特徴とする。 The weight ratio of the conductive inorganic ultrafine particles in the hard coat layer of the antireflection material of the present invention is 75% or more.
本発明の反射防止材料に用いられる導電性無機超微粒子は、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から選ばれる少なくとも一つからなることを特徴とする。
The conductive inorganic ultrafine particles used in the antireflection material of the present invention are 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. It consists of at least one of the above.
本発明の反射防止材料のハードコート層の硬化後の屈折率は、１．６〜１．８であることを特徴とする。 The refractive index after curing of the hard coat layer of the antireflection material of the present invention is 1.6 to 1.8.
本発明の反射防止材料の低屈折率層の硬化後の屈折率は、１．３６〜１．４２であることを特徴とする。 The refractive index after curing of the low refractive index layer of the antireflection material of the present invention is 1.36 to 1.42.
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、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.
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し、低屈折率層に中空シリカを含有する組成物用いることにより、低反射性、導電性、耐擦傷性、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り、特に低反射性については、２層系反射防止材料としては著しい効果を可能とするものである。 The antireflective material of the present invention comprises a hard coat layer and a low refractive index layer formed on a light-transmitting substrate, and a composition containing hollow silica in the low refractive index layer. It has an excellent balance of scratch resistance, abrasion resistance, and antifouling properties, and can also reduce costs by reducing the coating process. Especially for low reflectivity, it is a two-layer system. As an antireflection material, a remarkable effect is possible.
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。 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.
これら透光性基体の透明性は高いものほど好ましいが、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、反射防止材料生産時の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 handling property at the time of production of the antireflection material, the one in the range of 1 to 700 μm, preferably 25 to 250 μm is used. 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.
本発明の反射防止材料のハードコート層に用いられる放射線硬化型樹脂としては、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。 The radiation curable resin used for the hard coat layer of the antireflection material of the present invention includes radical polymerizable functional groups such as acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, epoxy group, vinyl ether group, oxetane group. A monomer, oligomer, or prepolymer having a cationically polymerizable functional group such as singly or appropriately mixed is 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.
上記放射線硬化型樹脂のうち（メタ）アクリロイル基を有する（メタ）アクリレート化合物が好適に用いられる。（メタ）アクリレート化合物は、ハードコート層の硬度向上に効果があり、特に分子内に３個以上の（メタ）アクリロイル基を有するものが有効である。 Of the radiation curable resins, a (meth) acrylate compound having a (meth) acryloyl group is preferably used. The (meth) acrylate compound is effective for improving the hardness of the hard coat layer, and in particular, those having three or more (meth) acryloyl groups in the molecule are effective.
ハードコート層に用いられるハードコート樹脂組成物中の（メタ）アクリロイル基を有する（メタ）アクリレート化合物の割合は、重量比で１０％以上が好ましく、１０〜８０％がより好ましく、１０〜５０％がより好ましく、１０〜３５％が更に好ましい。放射線硬化型樹脂の重量比が１０％未満では、導電性は良好な状態を示すものの耐溶剤性や膜硬度が低下するので好ましくない。放射線硬化型樹脂の重量比が８０％を超えると、耐溶剤性や膜硬度は良好であるものの、使用する樹脂の組み合わせによっては導電性が低下するのでの好ましくない場合がある。 The ratio of the (meth) acrylate compound having a (meth) acryloyl group in the hard coat resin composition used for the hard coat layer is preferably 10% or more, more preferably 10 to 80%, and more preferably 10 to 50%. Is more preferable, and 10 to 35% is still more preferable. If the weight ratio of the radiation curable resin is less than 10%, the conductivity is good, but the solvent resistance and film hardness are lowered, which is not preferable. If the weight ratio of the radiation curable resin exceeds 80%, the solvent resistance and film hardness are good, but the conductivity may be lowered depending on the combination of the resins used, which may be undesirable.
上記放射線硬化型樹脂は、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できる。 The radiation curable resin can be cured by electron beam irradiation as it is, but when 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.
本発明の反射防止材料のハードコート層に用いられるハードコート樹脂組成物は、上記放射線硬化型樹脂に加えて、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できる。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。 The hard coat resin composition used for the hard coat layer of the antireflection material of the present invention can be used by adding a polymer resin in addition to the radiation curable resin 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.
本発明の反射防止材料のハードコート層に用いられるハードコート樹脂組成物は、重量平均分子量８０００〜１５００００を有する樹脂を含むものであり、ハードコート樹脂組成物を構成する樹脂が放射線硬化型樹脂であるか否かを問わない（請求項１、請求項２）。重量平均分子量が８０００以下の場合、導電性微粒子の分散性が向上し、光透過率も高くなるものの、表面抵抗値が高くなるので好ましくない。重量平均分子量が１５００００以上の場合、導電性微粒子への樹脂吸着量が増加するため表面抵抗値が高くなり好ましくない。上記重量平均分子量を有する樹脂のハードコート樹脂組成物に占める割合は、重量比率で６５％以上が好ましい。６５％未満では、上記重量平均分子量を有する樹脂を含めることの効果が現れ難くなる。 The hard coat resin composition used for the hard coat layer of the antireflective material of the present invention contains a resin having a weight average molecular weight of 8000 to 150,000, and the resin constituting the hard coat resin composition is a radiation curable resin. It does not matter whether or not there is (Claim 1, Claim 2). A weight average molecular weight of 8000 or less is not preferable because the dispersibility of the conductive fine particles is improved and the light transmittance is increased, but the surface resistance value is increased. When the weight average molecular weight is 150,000 or more, the amount of resin adsorbed on the conductive fine particles increases, so that the surface resistance value becomes high, which is not preferable. The proportion of the resin having the weight average molecular weight in the hard coat resin composition is preferably 65% or more by weight. If it is less than 65%, the effect of including a resin having the above weight average molecular weight hardly appears.
重量平均分子量の測定は、特開２００１−１８７８５７号公報に記載と同様の方法で行った。ゲルパミエーションクロマトグラフィー（ＧＰＣ）により測定し、下記条件において、得られたアクリル系粘着剤のうち固形分１ｇを１００ｍｌの１，１，１，３，３，３−ヘキサフルオロ−２−プロパノールに添加し十分攪拌したのち、これを０．４５μｍのメンブランフィルターでろ過したろ液を試料とした。また、標準メチルメタクリレートは、米国プレッシャーケミカル社製の標準メチルメタクリレートを使用した。 The weight average molecular weight was measured by the same method as described in JP-A No. 2001-187857. Measured by gel permeation chromatography (GPC). Under the following conditions, 1 g of solid content of the obtained acrylic pressure-sensitive adhesive was added to 100 ml of 1,1,1,3,3,3-hexafluoro-2-propanol. After adding and stirring sufficiently, the filtrate which filtered this with the 0.45 micrometer membrane filter was made into the sample. As the standard methyl methacrylate, standard methyl methacrylate manufactured by Pressure Chemical Co., USA was used.
装置；米国ウオーターズ社製、高温高速ゲル浸透クロマトグラム（モデル１５０−Ｃ、ＡＬＣ／ＧＰＣ）
カラム；昭和電工社製、ＳＨＯＤＥＸ ＧＰＣ ＨＦＩＰ−８０５（１本）、ＨＦＩＰ−８０３（１本）
測定温度；４０℃
流速；１ｍｌ／分
Apparatus: manufactured by Waters, USA, high-temperature high-speed gel permeation chromatogram (model 150-C, ALC / GPC)
Column; manufactured by Showa Denko KK, SHODEX GPC HFIP-805 (1), HFIP-803 (1)
Measurement temperature: 40 ° C
Flow rate: 1 ml / min
本発明の反射防止材料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できる。 As the conductive inorganic ultrafine particles contained in the hard coat layer of the antireflection material of the present invention, tin oxide, phosphorus-doped tin oxide, antimony-doped tin oxide (ATO), indium tin oxide (ITO), indium oxide, zinc oxide, Examples include aluminum-doped zinc oxide and antimony pentoxide, and tin oxide, ITO, and zinc oxide are particularly preferable. Since these materials each have a high refractive index of around 2.0, they contain not only conductivity but also this. It can also serve to increase the refractive index of the hard coat layer.
上記導電性無機超微粒子の粒径は、１〜３００ｎｍの範囲であることが好ましく、より好ましくは５〜１００ｎｍ、更に好ましくは５〜５０ｎｍである。導電性無機超微粒子の粒径が１ｎｍ未満では均一な分散が困難になり、一方３００ｎｍを超えると透明性が低下する。 The particle diameter of the conductive inorganic ultrafine particles is preferably in the range of 1 to 300 nm, more preferably 5 to 100 nm, still more preferably 5 to 50 nm. When the particle diameter of the conductive inorganic ultrafine particles is less than 1 nm, uniform dispersion becomes difficult. On the other hand, when the particle diameter exceeds 300 nm, the transparency is lowered.
また、本発明では、導電性無機超微粒子をハードコート層に用いられるハードコート樹脂組成物中に安定して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。 Further, in the present invention, in order to stably disperse the conductive inorganic ultrafine particles in the hard coat resin composition used in the hard coat layer, the surface of the conductive inorganic ultrafine particles can be treated with various coupling agents as necessary. Can be modified. 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７５〜９５％が好ましく、より好ましくは８０〜９０％である。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擦傷性が低下する。 The proportion of the conductive inorganic ultrafine particles in the hard coat layer is preferably 75 to 95% by weight, more preferably 80 to 90%. If it is less than 75%, good conductivity is difficult to obtain, and if it exceeds 95%, the haze value increases and the scratch resistance of the hard coat layer decreases.
本発明の反射防止材料のハードコート層は、主に上述の導電性無機超微粒子と放射線硬化型樹脂を含むハードコート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、放射線硬化型樹脂を含むハードコート樹脂組成物と有機溶剤からなる塗料を透光性基体上に塗工し、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、放射線硬化型樹脂を含むハードコート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、透光性基体への濡れ性、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 of the antireflective material of the present invention is mainly composed of a cured product of a hard coat resin composition containing the above-described conductive inorganic ultrafine particles and a radiation curable resin. A paint comprising a hard coat resin composition containing ultrafine particles and a radiation curable resin and an organic solvent is applied onto a translucent substrate, 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 hard coat resin composition containing the radiation curable resin and is suitable for the dispersion of the conductive inorganic ultrafine particles. Specifically, in consideration of coating suitability such as wettability to a light-transmitting substrate, viscosity, and drying speed, an alcohol type, an ester type, a ketone type, an ether type, or an aromatic hydrocarbon is used alone or in combination. Solvents can be used.
ハードコート層の硬化後の厚さは１〜５μｍの範囲であり、より好ましくは２〜４μｍの範囲である。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すことによる低反射率層との密着性への影響と思われる耐擦傷性、耐磨耗性が劣り、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、透光性基体とハードコート層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要因ともなる。 The thickness of the hard coat layer after curing is in the range of 1 to 5 μm, more preferably in the range of 2 to 4 μm. When the hard coat layer is thinner than 1 μm, the scratch resistance and wear resistance, which are considered to affect the adhesion with the low reflectance layer due to the curing failure due to oxygen inhibition in the ultraviolet curing type, are inferior, and from 5 μm If it is thick, curling will occur due to curing shrinkage of the resin, micro cracks will occur in the hard coat layer, the adhesion between the translucent substrate and the hard coat layer will decrease, and the light transmission will also decrease To do. And it becomes a factor of cost increase by the increase in the amount of required coating materials accompanying the increase in film thickness.
本発明の反射防止材料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。帯電防止性能としては１０７未満の低い表面抵抗は必要ない。１０９Ω／□を超える場合、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。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 antireflection material of the present invention is preferably 10 7 to 10 9 Ω / □. For antistatic performance, a low surface resistance of less than 10 7 is not necessary. When it exceeds 10 9 Ω / □, the surface resistance of the outermost surface when a low refractive index layer is provided thereon becomes 10 11 Ω / □ or more, and 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である。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。 Moreover, the refractive index after hardening of a hard-coat layer is 1.6-1.8. 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含有・分散し、ハードコート層表面に微細な凹凸を形成することにより、防眩（ＡＧ）性能を付与することができる。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性が低下し、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い好ましくない。 In the present invention, antiglare (AG) performance can be imparted by containing and dispersing translucent resin fine particles in the hard coat layer described above and forming fine irregularities on the surface of the hard coat layer. 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. When the particle size is 10 μm or more, glare is generated, and the degree of surface irregularities becomes too large, and the surface becomes whitish.
本発明の反射防止材料の低屈折率層は、中空シリカ微粒子を含むことが必須である。上記のアルコキシシランから成るマトリックス中に中空シリカ微粒子を添加することにより、低屈折率化が可能となる。中空シリカ微粒子は内部に空気を含有しているため、屈折率が１．２８〜１．４０と、通常のシリカ微粒子の屈折率（１．４６）と比較して著しく低い。中空シリカ微粒子は、多孔性シリカ微粒子を有機珪素化合物等で表面を被覆し、その細孔入口を閉塞して作製される。また、この中空シリカ微粒子を上記アルコキシシランから成るマトリックス中に添加した場合、中空シリカ微粒子は中空であるために、マトリックスがシリカ微粒子内部に浸漬することが無く、従って屈折率の上昇を防ぐことができる。 The low refractive index layer of the antireflection material of the present invention must contain hollow silica fine particles. By adding hollow silica fine particles into the matrix composed of the above alkoxysilane, the refractive index can be lowered. Since the hollow silica fine particles contain air inside, the refractive index is 1.28 to 1.40, which is significantly lower than the refractive index (1.46) of ordinary silica fine particles. The hollow silica fine particles are produced by covering the surface of porous silica fine particles with an organic silicon compound or the like and closing the pore inlets. Further, when the hollow silica fine particles are added to the above-mentioned matrix composed of alkoxysilane, the hollow silica fine particles are hollow, so that the matrix is not immersed in the silica fine particles, and thus the increase in the refractive index is prevented. it can.
中空シリカ微粒子の平均粒径は、重量平均粒子径で０．５〜２００ｎｍの範囲内であれは良い。平均粒径が２００ｎｍよりも大きくなると、低屈折率層の表面においてレイリー散乱によって光が散乱され、白っぽく見え、その透明性が低下する。平均粒径が０．５ｎｍ未満であると、中空シリカ微粒子が凝集しやすくなってしまい、塗工安定性が悪化する。 The average particle diameter of the hollow silica fine particles may be within the range of 0.5 to 200 nm in terms of weight average particle diameter. When the average particle size is larger than 200 nm, light is scattered by Rayleigh scattering on the surface of the low refractive index layer, and it looks whitish and its transparency is lowered. If the average particle size is less than 0.5 nm, the hollow silica fine particles are easily aggregated, and the coating stability is deteriorated.
本発明の反射防止材料の低屈折率層は、好適にアルコキシシラン中に中空シリカが分散されてなる。 The low refractive index layer of the antireflection material of the present invention is preferably formed by dispersing hollow silica in alkoxysilane.
低屈折率層に用いられるアルコキシシランは、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。
Ｒ1 a−ＳｉＸ４−ａ ０≦ａ≦２ ［１］
Ｘ3Ｓｉ−Ｒ2−ＳｉＸ3 ［２］
Ｙ−（Ｓｉ（ＯＲ3）2Ｏ）n−Ｙ ［３］
（ＸはＣｌ、Ｂｒ、ＮＣＯ、ＯＲ4のいずれかを示す。ＹはＨまたは炭素数が１〜２０の有機基を示す。Ｒ1、Ｒ2、Ｒ3、Ｒ4は炭素数が１〜２０の有機基を示す。ｎは１〜３０の整数を示す。）
Ｒ５ a−ＳｉＸ４−ａ １≦ａ≦２ ［４］
Ｘ3Ｓｉ−Ｒ６−ＳｉＸ3 ［５］
（ＸはＣｌ、Ｂｒ、ＮＣＯ、ＯＲ4のいずれかを示す。Ｒ５とＲ６は少なくともひとつのフッ素原子を含む有機基を示す。）
The alkoxysilane used for the low refractive index layer is obtained by curing a hydrolyzable silane compound and / or a mixture containing at least a hydrolyzate thereof and a curing accelerator. A mixture of at least one silane compound represented by the general formulas [1] to [3] and at least one fluorinated silane compound represented by the general formulas [4] and [5] is used.
R 1 a -SiX 4-a 0 ≦ a ≦ 2 [1]
X 3 Si—R 2 —SiX 3 [2]
Y— (Si (OR 3 ) 2 O) n —Y [3]
(X represents any one of Cl, Br, NCO, and OR 4. Y represents H or an organic group having 1 to 20 carbon atoms. R 1 , R 2 , R 3 , and R 4 represent 1 to C carbon atoms. 20 represents an organic group, and n represents an integer of 1 to 30.)
R 5 a -SiX 4-a 1 ≦ a ≦ 2 [4]
X 3 Si—R 6 —SiX 3 [5]
(X represents any one of Cl, Br, NCO and OR 4. R 5 and R 6 represent an organic group containing at least one fluorine atom.)
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としては、Ｓｉ（ＯＣＨ3）4、Ｓｉ（ＯＣ2Ｈ5）4、Ｓｉ（ＯＣ3Ｈ7）4、Ｓｉ〔ＯＣＨ（ＣＨ3）2〕〕4、Ｓｉ（ＯＣ4Ｈ9）4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、ＣＦ3（ＣＨ2）2Ｓｉ（ＯＣＨ3）3、ＣＦ3ＣＦ2（ＣＨ2）2Ｓｉ（ＯＣＨ3）3、ＣＦ3（ＣＦ2）2（ＣＨ2）2Ｓｉ（ＯＣＨ3）3、ＣＦ3（ＣＦ2）3（ＣＨ2）2Ｓｉ（ＯＣＨ3）3、ＣＦ3（ＣＦ2）4（ＣＨ2）2Ｓｉ（ＯＣＨ3）3、ＣＦ3（ＣＦ2）5（ＣＨ2）2Ｓｉ（ＯＣＨ3）3、ＣＦ3（ＣＦ2）6（ＣＨ2）2Ｓｉ（ＯＣＨ3）3、ＣＦ3（ＣＦ2）7（ＣＨ2）2Ｓｉ（ＯＣＨ3）3、ＣＦ3（ＣＦ2）8（ＣＨ2）2Ｓｉ（ＯＣＨ3）3、ＣＦ3（ＣＦ2）9（ＣＨ2）2Ｓｉ（ＯＣＨ3）3、ＣＦ3（ＣＨ2）2Ｓｉ（ＯＣ2Ｈ5）3、ＣＦ3ＣＦ2（ＣＨ2）2Ｓｉ（ＯＣ2Ｈ5）3、ＣＦ3（ＣＦ2）2（ＣＨ2）2Ｓｉ（ＯＣ2Ｈ5）3、ＣＦ3（ＣＦ2）3（ＣＨ2）2Ｓｉ（ＯＣ2Ｈ5）3、ＣＦ3（ＣＦ2）4（ＣＨ2）2Ｓｉ（ＯＣ2Ｈ5）3、ＣＦ3（ＣＦ2）5（ＣＨ2）2Ｓｉ（ＯＣ2Ｈ5）3、ＣＦ3（ＣＦ2）6（ＣＨ2）2Ｓｉ（ＯＣ2Ｈ5）3、ＣＦ3（ＣＦ2）7（ＣＨ2）2Ｓｉ（ＯＣ2Ｈ5）3、ＣＦ3（ＣＦ2）8（ＣＨ2）2Ｓｉ（ＯＣ2Ｈ5）3、ＣＦ3（ＣＦ2）9（ＣＨ2）2Ｓｉ（ＯＣ2Ｈ5）3等が挙げられる。 Specific examples of the hydrolyzable silane compound include Si (OCH 3 ) 4 , Si (OC 2 H 5 ) 4 , Si (OC 3 H 7 ) as silane compounds having a hydrolyzable group having 4 silicon atoms. 4 , Si [OCH (CH 3 ) 2 ]] 4 , Si (OC 4 H 9 ) 4 and the like, but are not limited thereto. Further, the fluorine-containing silane compound, CF 3 (CH 2) 2 Si (OCH 3) 3, CF 3 CF 2 (CH 2) 2 Si (OCH 3) 3, CF 3 (CF 2) 2 (CH 2) 2 Si (OCH 3 ) 3 , CF 3 (CF 2 ) 3 (CH 2 ) 2 Si (OCH 3 ) 3 , CF 3 (CF 2 ) 4 (CH 2 ) 2 Si (OCH 3 ) 3 , CF 3 (CF 2 ) 5 (CH 2 ) 2 Si (OCH 3 ) 3 , CF 3 (CF 2 ) 6 (CH 2 ) 2 Si (OCH 3 ) 3 , CF 3 (CF 2 ) 7 (CH 2 ) 2 Si (OCH 3 ) 3 , CF 3 (CF 2 ) 8 (CH 2 ) 2 Si (OCH 3 ) 3 , CF 3 (CF 2 ) 9 (CH 2 ) 2 Si (OCH 3 ) 3 , CF 3 (CH 2 ) 2 Si ( OC 2 H 5) 3, CF 3 CF 2 (CH 2) 2 Si (OC 2 H 5) 3, CF 3 (CF 2) 2 (CH 2) 2 Si (OC 2 H 5) 3, CF 3 (C 2) 3 (CH 2) 2 Si (OC 2 H 5) 3, CF 3 (CF 2) 4 (CH 2) 2 Si (OC 2 H 5) 3, CF 3 (CF 2) 5 (CH 2) 2 Si (OC 2 H 5 ) 3 , CF 3 (CF 2 ) 6 (CH 2 ) 2 Si (OC 2 H 5 ) 3 , CF 3 (CF 2 ) 7 (CH 2 ) 2 Si (OC 2 H 5 ) 3 CF 3 (CF 2 ) 8 (CH 2 ) 2 Si (OC 2 H 5 ) 3 , CF 3 (CF 2 ) 9 (CH 2 ) 2 Si (OC 2 H 5 ) 3 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］：ａ＝０）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ため一概には言えないが、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 (general formula [1]: a = 0) and a fluorine-containing hydrolyzable silane compound as appropriate. In this case, the mixing ratio varies depending on the type of the silane compound, so it cannot be said unconditionally. However, with respect to 100 parts by weight of the silane compound having four hydrolyzable groups on the silicon atom, the fluorine-containing hydrolyzable silane compound is 1 to 500 parts by weight, more preferably 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。この場合は、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 mixture of silane compound-water-solvent or a small amount of a strong acid (hydrochloric acid, etc.), leave it at room temperature for several hours to several days, dilute to a coating concentration, and cure Add an accelerating ingredient 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.
本発明の反射防止材料の低屈折率層は、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 of the antireflection 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ハードコート層上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できる。 A low refractive index layer can be provided on the hard coat layer 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 that 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.
本発明の反射防止材料における低屈折率層の表面抵抗は、１０１１Ω／□未満であることが好ましく、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 in the antireflection material of the present invention is preferably less than 10 11 Ω / □, 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と低屈折率層との屈折率の関係は、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。この範囲内を外れると低反射性が低下する。 The refractive index relationship between 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 The refractive index after curing is 1.36 to 1.42. Outside this range, the low reflectivity is reduced.
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、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、反射防止材料表面のスチールウールによる耐擦傷性試験では、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 scratch resistance test with steel wool on the antireflection material 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.
＜ハードコート層の作製＞
厚さ１００μｍ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（照射距離１０ｃｍ、照射時間３０秒）を行い、塗工膜を硬化させ、厚さ２．５μｍ、屈折率１．６４のハードコート層を形成した。
<Preparation of hard coat layer>
The following hard coat paint was applied by reverse coating to a PET film (trade name: A4300, manufactured by Toyobo Co., Ltd.) with a thickness of 100 μm, dried at 100 ° C. for 1 minute, and then 120 W / cm concentrating high pressure in a nitrogen atmosphere. Ultraviolet irradiation (irradiation distance 10 cm, irradiation time 30 seconds) was performed with one mercury lamp, the coating film was cured, and a hard coat layer having a thickness of 2.5 μm and a refractive index of 1.64 was formed.
［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
・ジペンタエリスリトールテトラアクリレート １．８部
・平均粒子径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
・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
上記ハードコート塗料のうちの光重合開始剤以外の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、光重合開始剤を溶解させ、ハードコート塗料を作製した。
[Composition of hard coat paint]
・ 7 parts of a polyester resin with a weight average molecular weight of 65000, an acid value of 7 mgKOH / g, and a non-volatile content of 60%, produced by reacting a polybasic acid consisting of isophthalic acid and adipic acid with neopentyl glycol dipentaerythritol tetraacrylate 1.8 parts ITO powder with an average particle size of 0.05 μm and Sn content of 5 mol% with respect to In
34 parts · Mixed solvent in which the weight ratio of n-butanol / xylene is 4/6 · 57.2 parts · Photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Geigy Corporation) 0.2 parts Of the hard coat paints A material other than the photopolymerization initiator and 50 cc of glass beads were placed in a 250 cc container and dispersed for 5 hours in a paint shaker. After dispersion, the photopolymerization initiator was dissolved to prepare a hard coat paint.
＜低屈折率層の作製＞
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、厚さ０．１μｍ、屈折率１．３８の低屈折率層を形成した。その後、低屈折率層の硬化のため、６０℃で１２０時間キュアーし、反射率０．５７％の実施例１の低反射部材を得た
<Preparation of low refractive index layer>
On the hard coat layer, the following low refractive index paint is applied by reverse coating, dried at 100 ° C. for 1 minute to cure the coating film, and has a thickness of 0.1 μm and a refractive index of 1.38. A layer was formed. Thereafter, for curing the low refractive index layer, curing was performed at 60 ° C. for 120 hours to obtain a low reflective member of Example 1 having a reflectance of 0.57%.
［低屈折率塗料の配合］
・中空シリカ含有低屈折率塗料（商品名：ＥＬＣＯＭ ＴＧ１００１ＳＩＣ 触媒化成工業社製 固形分２．８％） ６５部
・イソプロピルアルコール ３５部
[Composition of low refractive index paint]
・ Hollow silica-containing low-refractive index paint (trade name: ELCOM TG1001SIC, manufactured by Catalyst Kasei Kogyo Co., Ltd., solid content: 2.8%) 65 parts ・ Isopropyl alcohol 35 parts
＜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。
<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.
［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０．０５μｍの酸化錫 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
・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
上記ハードコート塗料のうちの光重合開始剤以外の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、光重合開始剤を溶解させハードコート塗料を作製した。
[Composition of hard coat paint]
7 parts of a polyester resin having a weight average molecular weight of 65000, an acid value of 7 mg KOH / g, and a non-volatile content of 60%, produced by reacting a polybasic acid consisting of isophthalic acid and adipic acid with neopentyl glycol 1.8 parts of acrylate, 34 parts of tin oxide having an average primary particle of 0.05 μm, 57.2 parts of a mixed solvent having a weight ratio of n-butanol / xylene of 4/6, a photopolymerization initiator (trade name: Irgacure 907 0.2 parts A material other than the photopolymerization initiator of the hard coat paint and 50 cc of glass beads were placed in a 250 cc container and dispersed in a paint shaker for 5 hours. After dispersion, the photopolymerization initiator 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℃１分間乾燥し塗工膜を硬化させた。このようにして、厚さ０．１μｍ、屈折率１．３８の低屈折率層を形成。その後、低屈折率層の硬化のため、６０℃で１２０時間キュアーし反射率０．６３％の本発明の低反射部材を得た。
<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. In this way, a low refractive index layer having a thickness of 0.1 μm and a refractive index of 1.38 is formed. Thereafter, in order to cure the low refractive index layer, curing was performed at 60 ° C. for 120 hours to obtain a low reflective member of the present invention having a reflectance of 0.63%.
［低屈折率塗料の配合］
・中空シリカ含有低屈折率塗料（商品名：ＥＬＣＯＭ ＴＧ１００１ＳＩＣ、触媒化成工業社製、固形分２．８％） ６５部
・イソプロピルアルコール ３５部
[Composition of low refractive index paint]
・ Hollow silica-containing low refractive index paint (trade name: ELCOM TG1001SIC, manufactured by Catalyst Kasei Kogyo Co., Ltd., solid content 2.8%) 65 parts ・ Isopropyl alcohol 35 parts
＜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１．５２のハードコート層を形成した。
<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 1.52 was formed.
［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
[Composition of hard coat paint]
・ Ultraviolet curable urethane acrylate oligomer (trade name: UV7600B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content concentration: 100% 38 parts ・ Photopolymerization initiator (trade name: Irgacure 184, manufactured by Ciba Geigy) 2 parts ・ 36 parts of methyl ethyl ketone 24 parts of cyclohexanone
＜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℃１分間乾燥し塗工膜を硬化させた。このようにして、厚さ０．１μｍ、屈折率１．３８の低屈折率層を形成。その後、低屈折率層の硬化のため、６０℃で１２０時間キュアーし反射率１．５４％の本発明の低反射部材を得た。
<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. In this way, a low refractive index layer having a thickness of 0.1 μm and a refractive index of 1.38 is formed. Thereafter, in order to cure the low refractive index layer, curing was performed at 60 ° C. for 120 hours to obtain a low reflection member of the present invention having a reflectance of 1.54%.
［低屈折率塗料の配合］
・中空シリカ含有低屈折率塗料（商品名：ＥＬＣＯＭ ＴＧ１００１ＳＩＣ、触媒化成工業社製、固形分２．８％） ６５部
・イソプロピルアルコール ３５部
[Composition of low refractive index paint]
・ Hollow silica-containing low refractive index paint (trade name: ELCOM TG1001SIC, manufactured by Catalyst Kasei Kogyo Co., Ltd., solid content 2.8%) 65 parts ・ Isopropyl alcohol 35 parts
＜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１．６４のハードコート層を形成した。
<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 manner, a hard coat layer having a thickness of 2.5 μm and a refractive index of 1.64 was formed.
［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ＺｒＯ含率６８．０％）
[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℃１分間乾燥し塗工膜を硬化させた。このようにして、厚さ０．１μｍ、屈折率１．３８の低屈折率層を形成。その後、低屈折率層の硬化のため、６０℃で１２０時間キュアーし反射率０．７７％の本発明の低反射部材を得た。
<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. In this way, a low refractive index layer having a thickness of 0.1 μm and a refractive index of 1.38 is formed. Thereafter, in order to cure the low refractive index layer, curing was performed at 60 ° C. for 120 hours to obtain a low reflective member of the present invention having a reflectivity of 0.77%.
＜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℃１分間乾燥し塗工膜を硬化させた。このようにして、厚さ０．１μｍ、屈折率１．３８の低屈折率層を形成。その後、低屈折率層の硬化のため、６０℃で１２０時間キュアーし反射率０．９２％の本発明の低反射部材を得た。
<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. In this way, a low refractive index layer having a thickness of 0.1 μm and a refractive index of 1.38 is formed. Thereafter, in order to cure the low refractive index layer, curing was performed at 60 ° C. for 120 hours to obtain a low reflection member of the present invention having a reflectance of 0.92%.
［低屈折率塗料の配合］
・シリカゾル（平均粒子径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
[Composition of low refractive index paint]
Silica sol (ethanol dispersion containing 30% silica ultrafine particles as SiO 2 with an average particle size of 15 nm) 10 parts Film forming agent (tetraethoxysilane hydrolyzate calculated as SiO 2 , solid content concentration 6% ) 15 parts ethanol 53 parts
＜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１．６４のハードコート層を形成した。
<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 manner, a hard coat layer having a thickness of 2.5 μm and a refractive index of 1.64 was formed.
［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
・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
上記ハードコート塗料の内の光重合開始剤以外の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、光重合開始剤を溶解させハードコート塗料を作製した。
[Composition of hard coat paint]
7 parts of a polyester resin having a weight average molecular weight of 65000, an acid value of 7 mg KOH / g, and a non-volatile content of 60%, produced by reacting a polybasic acid consisting of isophthalic acid and adipic acid with neopentyl glycol ITO powder with 1.8 parts of acrylate, average particle size of 0.05 μm, and Sn content of 5 mol% with respect to In
34 parts / mixed solvent in which the weight ratio of n-butanol / xylene is 4/6 57.2 parts / photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Geigy) 0.2 parts A material other than the photopolymerization initiator and 50 cc of glass beads were placed in a 250 cc container and dispersed in a paint shaker for 5 hours. After dispersion, the photopolymerization initiator 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℃１分間乾燥し塗工膜を硬化させた。このようにして、厚さ０．１μｍ、屈折率１．３８の低屈折率層を形成。その後、低屈折率層の硬化のため、６０℃で１２０時間キュアーし反射率０．８１％の本発明の低反射部材を得た。
<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. In this way, a low refractive index layer having a thickness of 0.1 μm and a refractive index of 1.38 is formed. Thereafter, in order to cure the low refractive index layer, curing was performed at 60 ° C. for 120 hours to obtain a low reflective member of the present invention having a reflectance of 0.81%.
［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
[Composition of low refractive index paint]
Fluorine-containing polysiloxane (trade name: LR204-1, manufactured by Nissan Chemical Industries, solid content concentration: 6.46%) 7.9 parts methyl isobutyl ketone 12.1 parts
＜比較例５＞
＜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。
<Comparative Example 5>
<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.
［ハードコート塗料］
・ジペンタエリスリトールヘキサアクリレート ６部
・平均粒子径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 ６０部
[Hard coat paint]
・ 6 parts of dipentaerythritol hexaacrylate ・ ITO powder with an average particle size of 0.05 μm and Sn content of 5 mol% with respect to In
34 parts. 60 parts of a mixed solvent in which the weight ratio of n-butanol / xylene is 4/6.
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。 The above materials and 50 cc of glass beads were placed in a 250 cc container and dispersed for 5 hours using a paint shaker. After the dispersion, 0.2 part 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℃１分間乾燥し塗工膜を硬化させた。このようにして、厚さ０．１μｍ、屈折率１．３８の低屈折率層を形成。その後、低屈折率層の硬化のため、６０℃で１２０時間キュアーし反射率０．６８％の本発明の低反射部材を得た。
<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. In this way, a low refractive index layer having a thickness of 0.1 μm and a refractive index of 1.38 is formed. Thereafter, in order to cure the low refractive index layer, curing was performed at 60 ° C. for 120 hours to obtain a low reflective member of the present invention having a reflectivity of 0.68%.
［低屈折率塗料の配合］
・中空シリカ含有低屈折率塗料（商品名：ＥＬＣＯＭ ＴＧ１００１ＳＩＣ 触媒化成工業社固形分２．８％） ６５部
・イソプロピルアルコール ３５部
[Composition of low refractive index paint]
・ Hollow silica-containing low-refractive index paint (trade name: ELCOM TG1001 SIC: 2.8% solid content by Catalytic Chemical Industry Co., Ltd.) 65 parts ・ Isopropyl alcohol 35 parts
実施例１〜２、比較例１〜５で得られた反射防止材料を用い、全光線透過率、ヘイズ値、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。 Using the antireflection materials obtained in Examples 1 and 2 and Comparative Examples 1 to 5, total light transmittance, haze value, reflectance, surface resistance value, abrasion resistance, and antifouling property were measured by the following methods. ,evaluated.
全光線透過率およびヘイズ値は、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３８０〜７８０ｎｍ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。
耐擦傷性は日本スチールウール社製のスチールウール＃００００を板紙耐摩耗試験機（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、その部分のヘイズ値をＨＡＺＥメーターで測定し、下記式２で計算されるヘイズ値の変化量δＨを求めた。ここで、δＨの値が大きいほど耐擦傷性が劣ると見なす。
The total light transmittance and haze value 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 380 to 780 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).
As for scratch resistance, steel wool # 0000 manufactured by Nippon Steel Wool Co., Ltd. is 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 haze value of the portion was measured with a HAZE meter, and the change amount δH of the haze value calculated by the following formula 2 was obtained. Here, it is considered that the greater the value of δH, the lower the scratch resistance.
δＨ＝試験後のヘイズ値−試験前のヘイズ値・・・（式２） δH = haze value after test−haze value before test (formula 2)
耐磨耗性は、綿製の布をヨシミツ精機製鉛筆硬度試験機に取り付け、反射防止材料の低屈折率層面を荷重１Ｋｇで１００往復させた後の表面を目視で確認した。目視で変化が確認できない場合を○、傷、変化が確認できる面積が試験した面積の１／３未満の場合を△、変化が確認できる面積が試験した面積の１／３以上の場合を×とした。 Abrasion resistance was confirmed by visually observing the surface after attaching a cotton cloth to a pencil hardness tester manufactured by Yoshimitsu Seiki and reciprocating the low refractive index layer surface of the antireflective material 100 with a load of 1 kg. When the change cannot be confirmed visually, ○, when the area where the change can be confirmed is less than 1/3 of the tested area, and when the area where the change can be confirmed is 1/3 or more of the tested area, ×. did.
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 ◯.
上記評価方法による評価結果を表１に示す。 Table 1 shows the evaluation results obtained by the above evaluation method.
実施例１および実施例２の反射防止材料は、低反射性、導電性、耐擦傷性、耐磨耗性、防汚性にバランスよく充足するものであった。導電性無機超微粒子をハードコート層に含まない比較例１は、導電性が著しく劣り、反射率も低下しなかった。非導電性微粒子である酸化ジルコニアハードコート層に含む比較例２は、比較例１よりも反射率の改善が見られるものの、導電性が劣るものであった。中空でないシリカ超微粒子を低屈折率層に含む比較例３は、低反射性、耐擦傷性、耐磨耗性、防汚性に劣るものであった。中空シリカ微粒子を低屈折率層に含まない比較例４は、低反射性、耐磨耗性に劣るものであった。平均分子量が８０００〜１５００００の樹脂をハードコート層に含まない比較例５は、導電性無機超微粒子をハードコート層に含むにも関わらず、導電性に劣るものであった。 The antireflection material of Example 1 and Example 2 satisfy | filled the low reflection property, electroconductivity, abrasion resistance, abrasion resistance, and antifouling property with sufficient balance. The comparative example 1 which does not contain electroconductive inorganic ultrafine particles in a hard-coat layer was remarkably inferior, and the reflectance did not fall. Comparative Example 2 included in the zirconia hard coat layer, which is a non-conductive fine particle, was inferior in conductivity, although an improvement in reflectance was seen compared to Comparative Example 1. The comparative example 3 which contains the silica ultrafine particle which is not hollow in a low refractive index layer was inferior to low reflectivity, abrasion resistance, abrasion resistance, and antifouling property. The comparative example 4 which does not contain a hollow silica fine particle in a low-refractive-index layer was inferior to low reflectivity and abrasion resistance. Comparative Example 5 in which the hard coat layer does not contain a resin having an average molecular weight of 8000 to 150,000 was inferior in conductivity even though the conductive inorganic ultrafine particles were contained in the hard coat layer.
以上のように、ハードコート層、低屈折率層の構成を本発明の範囲内に制御することにより、低反射性、導電性、耐擦傷性、耐磨耗性、防汚性をバランスよく充足し、これらバランスを透光性基体上に２層積層するのみで実現できるという塗工（積層）回数低減による経済性も併せて実現できる反射防止材料を提供することができる。
As described above, by controlling the constitution of the hard coat layer and the low refractive index layer within the scope of the present invention, low reflectivity, conductivity, scratch resistance, wear resistance, and antifouling properties are well balanced. And the antireflection material which can also implement | achieve economical efficiency by the frequency | count reduction of the coating (lamination | stacking) that these balance is realizable only by laminating | stacking two layers on a translucent base | substrate can be provided.
Claims (8)
該ハードコート層は、放射線硬化型樹脂及び熱可塑性樹脂を含むハードコート樹脂組成物と導電性無機超微粒子との硬化物からなり、
該低屈折率層が中空シリカ微粒子を含有する組成物からなり、
該放射線硬化型樹脂のハードコート樹脂組成物に占める割合が重量比率で１０〜３５％であり、
該熱可塑性樹脂の重量平均分子量が８０００〜１５００００であり、
該低屈折率層の表面抵抗が１０１１Ω／□未満であることを特徴とする反射防止材料。 On the translucent substrate, a hard coat layer and a low refractive index layer are sequentially laminated,
The hard coat layer comprises a cured product of a hard coat resin composition containing a radiation curable resin and a thermoplastic resin and conductive inorganic ultrafine particles ,
The low refractive index layer is composed of a composition containing hollow silica fine particles,
The proportion of the radiation curable resin in the hard coat resin composition is 10 to 35% by weight,
The weight average molecular weight of the thermoplastic resin is from 8,000 to 150,000,
An antireflection material, wherein the low refractive index layer has a surface resistance of less than 10 11 Ω / □.
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| WO2011033976A1 (en) | 2009-09-18 | 2011-03-24 | 東レ株式会社 | Reflection prevention member and manufacture method for the same |
| JP2012058506A (en) * | 2010-09-09 | 2012-03-22 | Sumitomo Osaka Cement Co Ltd | Optical material, tin oxide fine particle dispersion, tin oxide fine particle dispersion coating material, method for manufacturing optical material, high refractive index film, and antistatic film |
| JP6197472B2 (en) * | 2013-08-13 | 2017-09-20 | コニカミノルタ株式会社 | Hard coat film and radiation image conversion panel using the same |
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