JP4296098B2 - Anti-glare film - Google Patents
Anti-glare film Download PDFInfo
- Publication number
- JP4296098B2 JP4296098B2 JP2004001502A JP2004001502A JP4296098B2 JP 4296098 B2 JP4296098 B2 JP 4296098B2 JP 2004001502 A JP2004001502 A JP 2004001502A JP 2004001502 A JP2004001502 A JP 2004001502A JP 4296098 B2 JP4296098 B2 JP 4296098B2
- Authority
- JP
- Japan
- Prior art keywords
- particles
- resin
- film
- antiglare
- refractive index
- 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.)
- Expired - Lifetime
Links
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- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
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Description
本発明は、各種ディスプレイに用いられる防眩フィルム及びこのフィルムを備えた表示装置に関する。 The present invention relates to an antiglare film used for various displays and a display device including the film.
一般に、陰極管表示装置（ＣＲＴ）、プラズマディスプレイパネル（ＰＤＰ）、液晶ディスプレイ（ＬＣＤ）などの画像表示装置において、外光の反射によるコントラスト低下や視認性劣化を防止するために、光学干渉の原理を利用して反射率を低減する反射防止フィルムが、これらのディスプレイの最表面に配置されている。一方、反射防止フィルムの一種である防眩フィルムは、反射光を適度に散乱させることにより、映り込みを防止し視認性を向上させるために、バインダー樹脂中に微粒子を分散して表面に凹凸構造を形成したフィルムであって、ＬＣＤの最表面には通常、この防眩フィルムが装着されている。 In general, in an image display device such as a cathode ray tube display (CRT), a plasma display panel (PDP), a liquid crystal display (LCD), etc., the principle of optical interference is used to prevent a decrease in contrast and a deterioration in visibility due to reflection of external light. An antireflective film that reduces the reflectivity by using is used on the outermost surface of these displays. On the other hand, the antiglare film, which is a kind of antireflection film, has a concavo-convex structure on the surface by dispersing fine particles in the binder resin in order to prevent reflection and improve visibility by appropriately scattering the reflected light. The antiglare film is usually mounted on the outermost surface of the LCD.
近年、画像の高品位化に伴い、防眩フィルムも単に反射光を散乱させるだけでなく、最表面をフッ素樹脂などの薄膜でコートすることにより、反射率自体を低くする技術が確立されてきた。例えば、特開平７−２８７１０２号公報（特許文献１）には、（１）透明基材フィルムの表裏面の少なくとも一面に表面層である低屈折率層が、他の層を介して形成されており、（２）該他の層の少なくとも一層がバインダー樹脂を主体とするハードコート層であって、該ハードコート層は低屈折率層と直接接しており、（３）該ハードコート層の屈折率が、該ハードコート層の前記低屈折率層側とは反対側の面に接する層の屈折率よりも高い反射防止フィルムが開示されている。この文献には、粒径４００ｎｍ以下であり、かつ屈折率１．５以上である高屈折率微粒子を用い、ハードコート層の屈折率を大きくすることにより、反射率を低減させることが記載されている。 In recent years, with the improvement of image quality, anti-glare films have been established not only to scatter reflected light but also to reduce the reflectance itself by coating the outermost surface with a thin film such as a fluororesin. . For example, in Japanese Patent Laid-Open No. 7-287102 (Patent Document 1), (1) a low refractive index layer as a surface layer is formed on at least one of the front and back surfaces of a transparent substrate film via another layer. (2) at least one of the other layers is a hard coat layer mainly composed of a binder resin, and the hard coat layer is in direct contact with the low refractive index layer, and (3) the refraction of the hard coat layer An antireflection film having a higher refractive index than the refractive index of a layer in contact with the surface of the hard coat layer opposite to the low refractive index layer side is disclosed. This document describes that the reflectance is reduced by increasing the refractive index of the hard coat layer using high refractive index fine particles having a particle size of 400 nm or less and a refractive index of 1.5 or more. Yes.
特許文献１のフィルムを防眩フィルムに応用した例として、例えば、特開２００１−１００００４号公報（特許文献２）には、基材上に、少なくとも１層の、屈折率が１．３８〜１．４９の含フッ素樹脂を含んで成る低屈折率層を設けたフィルムであって、該基材と低屈折率層の間に屈折率が１．５７〜２であるバインダを含む防眩層を設けた防眩性反射防止フィルムが開示されている。この文献には、防眩層のバインダが粒径１００ｎｍ以下の金属酸化物超微粒子と３官能以上の（メタ）アクリレートモノマーとの混合物の硬化物であること、防眩層が、さらに平均粒径１〜１０μｍであり、かつ架橋アクリル樹脂、架橋ポリスチレンなどで構成された防眩性粒子を含むことが記載されている。また、特開２００１−１００００５号公報（特許文献３）には、特許文献２と同様のフィルムについて、さらに、無機微粒子、硬化性樹脂および防汚性素材からなる塗布液の塗膜を熱または電離放射線により硬化してミクロボイドを形成した防眩性反射防止フィルムが開示されている。これらのフィルムでは、防眩層に防眩性粒子や無機超微粒子を含有させることにより、反射率が低減したり、硬度及び耐擦傷性が向上している。 As an example in which the film of Patent Document 1 is applied to an antiglare film, for example, in Japanese Patent Application Laid-Open No. 2001-100004 (Patent Document 2), a refractive index of at least one layer on a substrate is 1.38 to 1. 49. A film provided with a low refractive index layer comprising a fluorine-containing resin of .49, comprising an antiglare layer comprising a binder having a refractive index of 1.57 to 2 between the substrate and the low refractive index layer An antiglare antireflection film provided is disclosed. In this document, the binder of the antiglare layer is a cured product of a mixture of ultrafine metal oxide particles having a particle size of 100 nm or less and a trifunctional or higher (meth) acrylate monomer, and the antiglare layer further has an average particle size. It describes that it contains 1 to 10 μm and includes antiglare particles composed of a crosslinked acrylic resin, a crosslinked polystyrene or the like. Japanese Patent Laid-Open No. 2001-100005 (Patent Document 3) discloses a film similar to that of Patent Document 2, in which a coating film of a coating solution made of inorganic fine particles, a curable resin, and an antifouling material is further heated or ionized. An antiglare antireflection film which is cured by radiation to form microvoids is disclosed. In these films, by adding antiglare particles and inorganic ultrafine particles to the antiglare layer, the reflectance is reduced, and the hardness and scratch resistance are improved.
一方、近年、液晶テレビなど、ＬＣＤが一般家庭に普及するにつれて、耐擦傷性のさらなる向上と、反射率の低下とが同時に求められ、このような状況に対応するために、バインダー樹脂中に分散する超微粒子の比率も向上している。 On the other hand, in recent years, as LCDs such as liquid crystal televisions have spread to general households, further improvement in scratch resistance and reduction in reflectance have been demanded at the same time. The ratio of ultrafine particles to be improved is also improved.
しかし、前述の従来のフィルムでは、一定以上の量の超微粒子をバインダー樹脂に分散すると、反射光の散乱性は変化しないにもかかわらず、透過光の散乱性が異常に上昇し、画像の鮮明性、輝度、コントラストなどが低下する。
従って、本発明の目的は、高い耐擦傷性を有するとともに、鮮明な画像を表示できる防眩フィルム及びその製造方法、このフィルムを備えた表示装置を提供することにある。 Accordingly, an object of the present invention is to provide an antiglare film having high scratch resistance and capable of displaying a clear image, a method for producing the same, and a display device including the film.
本発明の他の目的は、透過光の散乱性が抑制され、高い輝度及びコントラストで画像を表示できる防眩フィルム及びその製造方法、このフィルムを備えた表示装置を提供することにある。 Another object of the present invention is to provide an antiglare film capable of displaying an image with high brightness and contrast while suppressing the scattering of transmitted light, a method for producing the same, and a display device including the film.
本発明のさらに他の目的は、反射率が低く、防眩性が高い防眩フィルム及びその製造方法、このフィルムを備えた表示装置を提供することにある。 Still another object of the present invention is to provide an antiglare film having a low reflectance and a high antiglare property, a method for producing the same, and a display device including the film.
本発明者は、前記課題を達成するため鋭意検討した結果、防眩層を構成するバインダー樹脂及び球状樹脂粒子の双方に、無機微粒子を含有させると、高い耐擦傷性を有するとともに、鮮明な画像を表示できることを見出し、本発明を完成した。 As a result of intensive studies to achieve the above-mentioned problems, the present inventor has high scratch resistance and a clear image when both the binder resin and the spherical resin particles constituting the antiglare layer contain inorganic fine particles. The present invention has been completed.
すなわち、本発明の防眩フィルムは、基材と、この基材の上に形成された防眩層とで構成されたフィルムであって、前記防眩層が、バインダー樹脂（Ｉ）と球状樹脂粒子（II）とで構成され、かつ前記バインダー樹脂（Ｉ）及び球状樹脂粒子（II）が、ともに平均粒径１００ｎｍ以下の無機粒子(III)を含む。前記バインダー樹脂（Ｉ）及び球状樹脂粒子（II）は、それぞれ、架橋ポリマー中に１重量％以上の無機粒子(III)が分散した複合樹脂で構成されていてもよい。前記バインダー樹脂（Ｉ）は、架橋ポリマー中に１０重量％以上の無機粒子が分散した複合樹脂で構成され、かつ前記球状樹脂粒子（II）は、架橋ポリマー中に１重量％以上の無機粒子が分散した複合樹脂で構成されていてもよい。前記バインダー樹脂（Ｉ）及び球状樹脂粒子（II）に含まれる無機粒子(III)は、同一又は異なって、周期表４Ａ族金属、２Ｂ族金属、３Ｂ族金属、４Ｂ族金属、５Ｂ族金属、６Ｂ族元素などを含む化合物（例えば、周期表４Ａ族金属を含む無機酸塩及び／又は酸化物など）であってもよい。前記バインダー樹脂（Ｉ）と前記球状樹脂粒子（II）との割合（重量比）は、前者／後者＝９９／１〜８０／２０程度であってもよい。前記防眩フィルムにおいて、球状樹脂粒子（II）の平均粒径は２〜１０μｍ程度であり、かつ無機粒子(III)の平均粒径は５〜５０ｎｍ程度であるとともに、ナノサイズ無機粒子を含むバインダー樹脂（Ｉ）及びナノサイズ無機粒子を含む球状樹脂粒子（II）の屈折率が、それぞれ、１．６１〜２程度であり、かつ前記バインダー樹脂（Ｉ）と前記球状樹脂粒子（II）との屈折率差が０〜０．０５程度であってもよい。前記防眩フィルムは、防眩層の上に、さらに低屈折率層を形成してもよい。前記低屈折率層の屈折率は１．３５〜１．４５程度であり、かつ厚みが０．０５〜０．２μｍ程度であってもよい。 That is, the antiglare film of the present invention is a film composed of a base material and an antiglare layer formed on the base material, and the antiglare layer comprises a binder resin (I) and a spherical resin. The binder resin (I) and the spherical resin particles (II) both contain inorganic particles (III) having an average particle size of 100 nm or less. Each of the binder resin (I) and the spherical resin particles (II) may be composed of a composite resin in which 1% by weight or more of inorganic particles (III) are dispersed in a crosslinked polymer. The binder resin (I) is composed of a composite resin in which 10% by weight or more of inorganic particles are dispersed in a crosslinked polymer, and the spherical resin particle (II) is 1% by weight or more of inorganic particles in the crosslinked polymer. You may be comprised with the disperse | distributed composite resin. The inorganic particles (III) contained in the binder resin (I) and the spherical resin particles (II) are the same or different, and include a periodic table group 4A metal, group 2B metal, group 3B metal, group 4B metal, group 5B metal, A compound containing a Group 6B element or the like (for example, an inorganic acid salt and / or oxide containing a Group 4A metal of the periodic table) may be used. The ratio (weight ratio) between the binder resin (I) and the spherical resin particles (II) may be about the former / the latter = 99/1 to 80/20. In the antiglare film, the spherical resin particles (II) have an average particle size of about 2 to 10 μm, the inorganic particles (III) have an average particle size of about 5 to 50 nm, and a binder containing nano-sized inorganic particles The refractive index of the spherical resin particles (II) containing the resin (I) and nano-sized inorganic particles is about 1.61 to 2, respectively, and the binder resin (I) and the spherical resin particles (II) The refractive index difference may be about 0 to 0.05. The antiglare film may further form a low refractive index layer on the antiglare layer. The low refractive index layer may have a refractive index of about 1.35 to 1.45 and a thickness of about 0.05 to 0.2 μm.
本発明には、基材の上に、平均粒径１００ｎｍ以下の無機粒子(III)を含むバインダー樹脂（Ｉ）と、平均粒径１００ｎｍ以下の無機粒子(III)を含む球状樹脂粒子（II）とで構成された防眩層を形成した後、この防眩層の上に、低屈折率層を形成して防眩性反射防止フィルムを製造する方法も含まれる。さらに、本発明には、前記フィルムを備えている表示装置も含まれる。 In the present invention, a binder resin (I) containing inorganic particles (III) having an average particle size of 100 nm or less and spherical resin particles (II) containing inorganic particles (III) having an average particle size of 100 nm or less on a substrate. And a method of producing an antiglare antireflection film by forming a low refractive index layer on the antiglare layer after forming the antiglare layer composed of Furthermore, the present invention includes a display device including the film.
本発明では、無機微粒子が、バインダー樹脂及び球状粒子の双方に含まれるため、高い耐擦傷性を有するとともに、鮮明な画像を表示できる防眩フィルムが得られる。特に、この防眩フィルムは、透過光の散乱性が抑制され、高い輝度及びコントラストで画像を表示できる。さらに、この防眩フィルムを低屈折率層と組み合わせると、反射率が低く、高い防眩性を有する防眩反射防止フィルムが得られる。 In the present invention, since the inorganic fine particles are contained in both the binder resin and the spherical particles, an antiglare film having high scratch resistance and capable of displaying a clear image is obtained. In particular, this antiglare film can suppress the scattering of transmitted light and can display an image with high luminance and contrast. Furthermore, when this antiglare film is combined with a low refractive index layer, an antiglare antireflection film having low reflectance and high antiglare properties can be obtained.
本発明の防眩フィルムは、基材と、この基材の上に形成された防眩層とで構成されている。防眩層の上には、さらに低屈折率層が形成されていてもよい。 The antiglare film of the present invention is composed of a base material and an antiglare layer formed on the base material. A low refractive index layer may be further formed on the antiglare layer.
［基材］
基材としては、用途に応じて選択でき、透明な材質で形成されている限り、特に限定されず、無機物質（ガラス、シリカ、アルミナなど）などで構成されていてもよいが、通常、透明樹脂で構成されたプラスチックフィルムが使用される。透明樹脂としては、例えば、熱可塑性樹脂［セルロース誘導体、オレフィン系樹脂（脂環式オレフィン系樹脂を含む）、ハロゲン含有樹脂、ビニルアルコール系樹脂、有機酸ビニルエステル系樹脂、（メタ）アクリル系樹脂、スチレン系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ポリカーボネート系樹脂、ポリエーテル系樹脂、ポリスルホン系樹脂、熱可塑性ポリウレタン樹脂、ポリスルホン系樹脂、ポリフェニレンエーテル系樹脂など］、ゴム又は熱可塑性エラストマー［ポリブタジエン、ポリイソプレンなどのジエン系ゴム、スチレン−ブタジエン共重合体、アクリロニトリル−ブタジエン共重合体、アクリルゴム、ウレタンゴム、シリコーンゴムなど］、熱又は光硬化性樹脂又は前駆体［エポキシ樹脂、不飽和ポリエステル樹脂、ジアリルフタレート樹脂、シリコーン樹脂、ポリウレタン系樹脂、エポキシ（メタ）アクリレート、ウレタン（メタ）アクリレート、ポリエステル（メタ）アクリレートなど］などが挙げられる。これらの透明樹脂は、単独で又は二種以上組み合わせて使用できる。
[Base material]
The base material can be selected according to the application and is not particularly limited as long as it is formed of a transparent material, and may be composed of an inorganic substance (glass, silica, alumina, etc.), but is usually transparent. A plastic film made of resin is used. Transparent resins include, for example, thermoplastic resins [cellulose derivatives, olefin resins (including alicyclic olefin resins), halogen-containing resins, vinyl alcohol resins, organic acid vinyl ester resins, (meth) acrylic resins. Styrene resin, polyester resin, polyamide resin, polycarbonate resin, polyether resin, polysulfone resin, thermoplastic polyurethane resin, polysulfone resin, polyphenylene ether resin, etc.], rubber or thermoplastic elastomer [polybutadiene, Diene rubber such as polyisoprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, acrylic rubber, urethane rubber, silicone rubber, etc.], heat or photo-curing resin or precursor [epoxy resin, unsaturated polyester resin Diallyl phthalate resins, silicone resins, polyurethane resins, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, etc.] and the like. These transparent resins can be used alone or in combination of two or more.
これらの透明樹脂のうち、セルロース誘導体［セルロースアセテート（セルロースジアセテート、セルローストリアセテートなど）、セルロースプロピオネート、セルロースブチレート、セルロースアセテートプロピオネート、セルロースアセテートブチレートなどのセルロースＣ2-6有機酸エステルなど］、ポリアミド系樹脂（ポリアミド６、ポリアミド６６など）、ポリカーボネート系樹脂（ビスフェノールＡ型ポリカーボネートなど）、スチレン系樹脂［ポリスチレン（ＧＰＰＳ）など］、オレフィン系樹脂（脂環式オレフィン系樹脂など）などが好ましい。 Among these transparent resins, cellulose derivatives [cellulose C 2-6 organic acids such as cellulose acetate (cellulose diacetate, cellulose triacetate, etc.), cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, etc. Ester etc.], polyamide resins (polyamide 6, polyamide 66 etc.), polycarbonate resins (bisphenol A type polycarbonate etc.), styrene resins [polystyrene (GPPS) etc.], olefin resins (alicyclic olefin resins etc.) Etc. are preferable.
基材の厚みは、特に限定されず、例えば、１〜１０００μｍ、好ましくは５〜５００μｍ、さらに好ましくは１０〜３００μｍ（特に３０〜１００μｍ）程度である。 The thickness of a base material is not specifically limited, For example, it is 1-1000 micrometers, Preferably it is 5-500 micrometers, More preferably, it is about 10-300 micrometers (especially 30-100 micrometers).
［防眩層］
防眩層は、バインダー樹脂（Ｉ）と平均粒径１〜１０μｍの球状樹脂粒子（II）とで構成されている。さらに、前記バインダー樹脂（Ｉ）及び球状樹脂粒子（II）は、ともに平均粒径１００ｎｍ以下の無機粒子(III)を含む。
[Anti-glare layer]
The antiglare layer is composed of a binder resin (I) and spherical resin particles (II) having an average particle diameter of 1 to 10 μm. Furthermore, both the binder resin (I) and the spherical resin particles (II) contain inorganic particles (III) having an average particle size of 100 nm or less.
（Ｉ）バインダー樹脂
本発明のバインダー樹脂（Ｉ）は、熱可塑性樹脂［オレフィン系樹脂（ポリエチレン、ポリプロピレンなど）、アクリル系樹脂（ポリメタクリル酸メチルなど）、スチレン系樹脂（ポリスチレンなど）、塩化ビニル系樹脂（ポリ塩化ビニルなど）、ポリエステル樹脂（ポリエチレンテレフタレートなど）、ポリアミド樹脂（ポリアミド６など）など］や熱硬化性樹脂［エポキシ樹脂、フェノール樹脂、ウレタン樹脂、不飽和ポリエステル樹脂、ビニルエステル樹脂、ジアリルフタレート樹脂、シリコーン樹脂、アミノ樹脂（尿素樹脂、メラミン樹脂など）など］などで構成され、前記無機粒子(III)を含んでいるが、好ましくは、架橋ポリマー中に前記無機粒子(III)が分散した複合樹脂で構成できる。架橋ポリマーは、熱や活性エネルギー線（紫外線や電子線など）などにより硬化又は架橋させることにより生成でき、例えば、架橋アクリル系樹脂、架橋スチレン系樹脂、架橋ウレタン系樹脂、架橋ポリエステル系樹脂などが挙げられる。これらの架橋ポリマーのうち、光学的特性の点から、架橋アクリル系樹脂、架橋スチレン系樹脂、特に架橋アクリル系樹脂が好ましい。架橋アクリル系樹脂を形成するための重合性モノマー又はオリゴマーとしては、（メタ）アクリロイル基を有するモノマー又はオリゴマーが使用できる。
(I) Binder Resin The binder resin (I) of the present invention is a thermoplastic resin [olefin resin (polyethylene, polypropylene, etc.), acrylic resin (polymethyl methacrylate, etc.), styrene resin (polystyrene, etc.), vinyl chloride. Resin (polyvinyl chloride etc.), polyester resin (polyethylene terephthalate etc.), polyamide resin (polyamide 6 etc.) and thermosetting resin [epoxy resin, phenol resin, urethane resin, unsaturated polyester resin, vinyl ester resin, Diallyl phthalate resin, silicone resin, amino resin (urea resin, melamine resin, etc.) and the like, and contains the inorganic particles (III). Preferably, the inorganic particles (III) are contained in the crosslinked polymer. It can be composed of a dispersed composite resin. The crosslinked polymer can be generated by curing or crosslinking with heat or active energy rays (such as ultraviolet rays or electron beams). For example, a crosslinked acrylic resin, a crosslinked styrene resin, a crosslinked urethane resin, or a crosslinked polyester resin can be used. Can be mentioned. Among these crosslinked polymers, a crosslinked acrylic resin, a crosslinked styrene resin, particularly a crosslinked acrylic resin is preferable from the viewpoint of optical properties. As the polymerizable monomer or oligomer for forming the crosslinked acrylic resin, a monomer or oligomer having a (meth) acryloyl group can be used.
（メタ）アクリロイル基を有するモノマーとしては、例えば、単官能性モノマー［（メタ）アクリル酸エステルなどの（メタ）アクリル系モノマー、ビニルピロリドンなどのビニル系モノマー、イソボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレートなどの橋架環式炭化水素基を有する（メタ）アクリレートなど］、複数の（メタ）アクリロイル基を有する多官能性モノマー［エチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ブタンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート（ＮＰＧＤＡ）、ヘキサンジオールジ（メタ）アクリレートなどのアルキレングリコールジ（メタ）アクリレート；ジエチレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、ポリオキシテトラメチレングリコールジ（メタ）アクリレートなどの（ポリ）オキシアルキレングリコールジ（メタ）アクリレート；トリシクロデカンジメタノールジ（メタ）アクリレート、アダマンタンジ（メタ）アクリレートなどの橋架環式炭化水素基を有するジ（メタ）アクリレート；トリメチロールプロパントリ（メタ）アクリレート（ＴＭＰＴＡ）、トリメチロールエタントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート（ＰＥＴＡ）、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート（ＤＰＨＡ）などの多官能性モノマーなど］が例示できる。これらのモノマーは、単独で又は二種以上組み合わせて使用できる。 Examples of the monomer having a (meth) acryloyl group include a monofunctional monomer [(meth) acrylic monomer such as (meth) acrylic acid ester, vinyl monomer such as vinylpyrrolidone, isobornyl (meth) acrylate, adamantyl (meta ) (Meth) acrylates having bridged cyclic hydrocarbon groups such as acrylates, etc.], polyfunctional monomers having multiple (meth) acryloyl groups [ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butane Dialkylene glycol di (meth) acrylates such as diol di (meth) acrylate, neopentyl glycol di (meth) acrylate (NPGDA), hexanediol di (meth) acrylate; , (Poly) oxyalkylene glycol di (meth) acrylate such as dipropylene glycol di (meth) acrylate, polyoxytetramethylene glycol di (meth) acrylate; tricyclodecane dimethanol di (meth) acrylate, adamantane di (meth) Di (meth) acrylate having a bridged cyclic hydrocarbon group such as acrylate; trimethylolpropane tri (meth) acrylate (TMPTA), trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate (PETA), penta Multifunctional monomers such as erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate (DPHA), etc.] It can be shown. These monomers can be used alone or in combination of two or more.
重合性オリゴマーとしては、例えば、ビスフェノールＡ−アルキレンオキサイド付加体の（メタ）アクリレート、エポキシ（メタ）アクリレート（ビスフェノールＡ型エポキシ（メタ）アクリレート、ノボラック型エポキシ（メタ）アクリレートなど）、ポリエステル（メタ）アクリレート（例えば、脂肪族ポリエステル型（メタ）アクリレート、芳香族ポリエステル型（メタ）アクリレートなど）、（ポリ）ウレタン（メタ）アクリレート（ポリエステル型ウレタン（メタ）アクリレート、ポリエーテル型ウレタン（メタ）アクリレートなど）、シリコーン（メタ）アクリレートなどが例示できる。これらのオリゴマーは、単独で又は二種以上組み合わせて使用できる。 Examples of the polymerizable oligomer include (meth) acrylate, bisphenol A-alkylene oxide adduct (meth) acrylate, epoxy (meth) acrylate (bisphenol A type epoxy (meth) acrylate, novolac type epoxy (meth) acrylate, etc.), and polyester (meth). Acrylate (for example, aliphatic polyester type (meth) acrylate, aromatic polyester type (meth) acrylate, etc.), (poly) urethane (meth) acrylate (polyester type urethane (meth) acrylate, polyether type urethane (meth) acrylate, etc.) ), Silicone (meth) acrylate, and the like. These oligomers can be used alone or in combination of two or more.
これらのオリゴマー及びモノマーのうち、耐擦傷性を向上させる点から、少なくとも複数の（メタ）アクリロイル基を有するモノマー又はオリゴマー、例えば、ＮＰＧＤＡ、ＴＭＰＴＡ、ＰＥＴＡ、ＤＰＨＡなどの多官能性モノマーを使用するのが好ましい。 Among these oligomers and monomers, from the viewpoint of improving scratch resistance, monomers or oligomers having at least a plurality of (meth) acryloyl groups, for example, polyfunctional monomers such as NPGDA, TMPTA, PETA, DPHA are used. Is preferred.
架橋ポリマーは、反応開始剤を用いて得ることができる。反応開始剤（例えば、光重合開始剤）としては、例えば、アセトフェノン類又はプロピオフェノン類、ベンジル類、ベンゾイン類、ベンゾフェノン類、チオキサントン類、アシルホスフィンオキシド類などが例示できる。反応開始剤の割合は、重合性モノマー及びオリゴマーの合計１００重量部に対して０．１〜３０重量部、好ましくは０．５〜２０重量部、さらに好ましくは１〜１５重量部程度であってもよい。さらに、架橋ポリマーは、反応促進剤、例えば、第三級アミン類（ジアルキルアミノ安息香酸エステルなど）、ホスフィン系光重合促進剤などを用いて得てもよい。 The crosslinked polymer can be obtained using a reaction initiator. Examples of the reaction initiator (for example, photopolymerization initiator) include acetophenones or propiophenones, benzyls, benzoins, benzophenones, thioxanthones, acylphosphine oxides, and the like. The ratio of the reaction initiator is 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, more preferably about 1 to 15 parts by weight with respect to 100 parts by weight of the total of the polymerizable monomer and oligomer. Also good. Furthermore, the crosslinked polymer may be obtained using a reaction accelerator, for example, a tertiary amine (such as a dialkylaminobenzoate ester), a phosphine photopolymerization accelerator, or the like.
無機粒子(III)は、例えば、周期表２Ａ族金属（マグネシウム、カルシウム、ストロンチウムなど）、４Ａ族金属（チタン、ジルコニウムなど）、２Ｂ族金属（亜鉛など）、３Ｂ族金属（アルミニウム、ガリウム、インジウムなど）、４Ｂ族金属（ケイ素、スズなど）、５Ｂ族金属（アンチモン、ビスマスなど）、６Ｂ族元素（硫黄など）などを含む化合物（例えば、無機酸金属塩、酸化物、炭酸塩、リン酸塩、硫化物など）で構成されていてもよい。 Inorganic particles (III) are, for example, periodic table group 2A metals (magnesium, calcium, strontium, etc.), group 4A metals (titanium, zirconium, etc.), group 2B metals (zinc, etc.), group 3B metals (aluminum, gallium, indium). Etc.) Compounds containing Group 4B metals (silicon, tin, etc.), Group 5B metals (antimony, bismuth, etc.), Group 6B elements (sulfur, etc.) (for example, inorganic acid metal salts, oxides, carbonates, phosphoric acids) Salt, sulfide, etc.).
これらの金属又は元素を含む化合物としては、無機酸塩、酸化物、金属硫化物などが好ましい。このような化合物としては、具体的には、無機酸塩として、例えば、チタン酸金属塩（チタン酸カリウム、チタン酸バリウム、チタン酸鉛、チタン酸ストロンチウム、チタン酸ビスマス、チタン酸ビスマス、チタン酸マグネシウム、チタン酸ネオジウム、チタン酸カルシウムなど）、スズ酸金属塩（スズ酸亜鉛など）、アンチモン酸金属塩（アンチモン酸ナトリウムなど）などの無機酸金属塩などが挙げられる。 As the compound containing these metals or elements, inorganic acid salts, oxides, metal sulfides and the like are preferable. Specific examples of such a compound include inorganic acid salts such as metal titanate (potassium titanate, barium titanate, lead titanate, strontium titanate, bismuth titanate, bismuth titanate, titanate. Inorganic acid metal salts such as magnesium, neodymium titanate, calcium titanate), metal stannate (such as zinc stannate), metal antimonate (such as sodium antimonate), and the like.
酸化物としては、例えば、酸化チタン、酸化ジルコニウム、酸化亜鉛、酸化アルミニウム、酸化インジウム、酸化スズ、酸化アンチモン（三酸化アンチモン、四酸化アンチモン、五酸化アンチモンなど）などが挙げられる。 Examples of the oxide include titanium oxide, zirconium oxide, zinc oxide, aluminum oxide, indium oxide, tin oxide, and antimony oxide (such as antimony trioxide, antimony tetroxide, and antimony pentoxide).
金属硫化物としては、例えば、硫化チタン、硫化ジルコニウム、硫化アルミニウム、硫化インジウム、硫化アンチモンなどが挙げられる。 Examples of the metal sulfide include titanium sulfide, zirconium sulfide, aluminum sulfide, indium sulfide, and antimony sulfide.
また、無機粒子に帯電防止効果（例えば、フィルムの表面抵抗値１０9Ω／□以下程度の導電性）を付与するために、ＩＴＯ（インジウム−チタン−オキサイド）、ＡＴＯ（アンチモン−チタン−オキサイド）、酸化亜鉛−アルミニウムなどの導電性化合物を使用してもよい。これらの化合物は、単独で又は二種以上組み合わせて使用できる。 Further, in order to impart an antistatic effect to the inorganic particles (for example, a conductivity of a film having a surface resistance of about 10 9 Ω / □ or less), ITO (indium-titanium-oxide), ATO (antimony-titanium-oxide) A conductive compound such as zinc oxide-aluminum may be used. These compounds can be used alone or in combination of two or more.
これらの無機粒子のうち、周期表４Ａ族金属を含む化合物（チタン酸金属塩、酸化チタン、酸化ジルコニウムなど）、特に、チタンを含む化合物（例えば、チタン酸バリウムなどのチタン酸金属塩や、アナターゼ型又はルチル型の二酸化チタンなど）が好ましい。 Among these inorganic particles, compounds containing Group 4A metal of periodic table (metal titanate, titanium oxide, zirconium oxide, etc.), particularly compounds containing titanium (for example, metal titanate such as barium titanate, anatase, etc.) Type or rutile type titanium dioxide).
無機粒子(III)の平均粒径は、１００ｎｍ以下（例えば、５〜１００ｎｍ）であり、好ましくは５〜７０ｎｍ（例えば、５〜５０ｎｍ）、さらに好ましくは１０〜４０ｎｍ程度である。 The average particle diameter of the inorganic particles (III) is 100 nm or less (for example, 5 to 100 nm), preferably 5 to 70 nm (for example, 5 to 50 nm), and more preferably about 10 to 40 nm.
バインダー樹脂（Ｉ）中における無機粒子(III)の割合は１重量％以上（例えば、５〜９５重量％）の範囲から選択でき、通常、１０重量％以上（例えば、１０〜９０重量％）、好ましくは３０〜９０重量％（例えば、３５〜９０重量％）、さらに好ましくは４０〜９０重量％（特に５０〜９０重量％）程度である。バインダー樹脂中に無機粒子(III)を分散させると、反射防止効果と耐擦傷性を向上できる。 The ratio of the inorganic particles (III) in the binder resin (I) can be selected from the range of 1% by weight or more (for example, 5 to 95% by weight), and usually 10% by weight or more (for example, 10 to 90% by weight), The amount is preferably about 30 to 90% by weight (for example, 35 to 90% by weight), more preferably about 40 to 90% by weight (particularly 50 to 90% by weight). When the inorganic particles (III) are dispersed in the binder resin, the antireflection effect and the scratch resistance can be improved.
バインダー樹脂（Ｉ）の（見かけ上の）屈折率は高く、例えば、１．６１〜２、好ましくは１．６２〜１．９５、さらに好ましくは１．６３〜１．９程度である。屈折率が高いため、反射防止性が高い。無機粒子(III)は、平均粒径が光の波長よりも小さく、かつポリマー中に分散しているため、光の散乱が生じず、光学的には均一な物質として挙動し、防眩層が前記屈折率を有するようになる。 The (apparent) refractive index of the binder resin (I) is high, for example, about 1.61-2, preferably 1.62-1.95, and more preferably about 1.63-1.9. Since the refractive index is high, the antireflection property is high. Inorganic particles (III) have an average particle size smaller than the wavelength of light and are dispersed in the polymer, so there is no light scattering, and they behave as optically uniform substances, and the antiglare layer It has the refractive index.
（II）球状樹脂粒子
本発明の防眩層には、凹凸構造を形成し、防眩性を向上する点から、球状樹脂粒子（II）が含まれる。球状樹脂粒子（II）の形状は、楕円体状などであってもよいが、光散乱特性の点から、真球状または略真球状であるのが好ましい。球状樹脂粒子（II）の平均粒子径は、例えば、１〜１０μｍ、好ましくは２〜１０μｍ、さらに好ましくは２〜８μｍ（特に２〜５μｍ）程度である。
(II) Spherical resin particles The antiglare layer of the present invention contains spherical resin particles (II) from the viewpoint of forming an uneven structure and improving antiglare properties. The shape of the spherical resin particles (II) may be an ellipsoidal shape, but is preferably a true sphere or a substantially true sphere from the viewpoint of light scattering characteristics. The average particle diameter of the spherical resin particles (II) is, for example, about 1 to 10 μm, preferably 2 to 10 μm, and more preferably about 2 to 8 μm (particularly 2 to 5 μm).
球状樹脂粒子（II）は、前記バインダー樹脂と同様に、前記無機粒子(III)を含んでおり、好ましくは、架橋ポリマー中に前記無機粒子(III)が分散した複合樹脂で構成されている。架橋ポリマーとしては、前記バインダー樹脂と同様の架橋ポリマーが使用でき、前記バインダー樹脂における架橋ポリマーと同一又は異なってもよいが、架橋スチレン系樹脂、架橋アクリル系樹脂、特に、架橋スチレン系樹脂が好ましい。 Similar to the binder resin, the spherical resin particles (II) contain the inorganic particles (III), and are preferably composed of a composite resin in which the inorganic particles (III) are dispersed in a crosslinked polymer. As the cross-linked polymer, the same cross-linked polymer as the binder resin can be used and may be the same as or different from the cross-linked polymer in the binder resin. .
架橋スチレン系樹脂としては、例えば、架橋ポリスチレン、架橋ポリビニルトルエン、架橋スチレン−メタクリル酸メチル共重合体などが挙げられる。架橋スチレン系樹脂において、スチレン系モノマーとしては、スチレン、アルキル置換スチレン（例えば、ビニルトルエン、ビニルキシレン、ｐ−エチルスチレン、ｐ−イソプロピルスチレン、ブチルスチレン、ｐ−ｔ−ブチルスチレンなど）、ハロゲン置換スチレン（例えば、クロロスチレン、ブロモスチレンなど）、α位にアルキル基が置換したα−アルキル置換スチレン（例えば、α−メチルスチレンなど）などが例示できる。共重合性モノマーとしては、例えば、（メタ）アクリル酸、（メタ）アクリル酸メチルなどの（メタ）アクリル酸エステルなどが挙げられる。これらのモノマーは、単独で又は二種以上組み合わせて使用できる。架橋剤としては、例えば、複数のビニル基を有する化合物（ジビニルベンゼンなど）や、前記バインダー樹脂の項で例示された複数の（メタ）アクリロイル基を有する多官能性モノマーなどが挙げられる。これらの架橋剤は、単独で又は二種以上組み合わせて使用できる。架橋スチレン系樹脂のうち、透明性の点から、架橋ポリスチレンが好ましい。 Examples of the cross-linked styrene resin include cross-linked polystyrene, cross-linked polyvinyl toluene, and cross-linked styrene-methyl methacrylate copolymer. In the crosslinked styrene-based resin, styrene-based monomers include styrene, alkyl-substituted styrene (for example, vinyl toluene, vinyl xylene, p-ethyl styrene, p-isopropyl styrene, butyl styrene, pt-butyl styrene, etc.), halogen-substituted Examples thereof include styrene (for example, chlorostyrene, bromostyrene, etc.), α-alkyl-substituted styrene (for example, α-methylstyrene, etc.) having an alkyl group substituted at the α-position. Examples of the copolymerizable monomer include (meth) acrylic acid esters such as (meth) acrylic acid and methyl (meth) acrylate. These monomers can be used alone or in combination of two or more. Examples of the crosslinking agent include a compound having a plurality of vinyl groups (divinylbenzene and the like) and a polyfunctional monomer having a plurality of (meth) acryloyl groups exemplified in the section of the binder resin. These crosslinking agents can be used alone or in combination of two or more. Of the cross-linked styrene resins, cross-linked polystyrene is preferable from the viewpoint of transparency.
球状樹脂粒子（II）に含まれる無機粒子(III)の種類は、前記バインダー樹脂（Ｉ）の無機粒子(III)と同じであってもよく、異なっていてもよいが、バインダー樹脂（Ｉ）及び球状樹脂粒子（II）に含まれる無機粒子のうち、少なくとも一方が、周期表４Ａ族金属を含む化合物［特に、無機酸塩（例えば、チタン酸バリウムなどのチタン酸金属塩）及び／又は酸化物（例えば、アナターゼ型又はルチル型の二酸化チタン）］であるのが好ましい。 The kind of inorganic particles (III) contained in the spherical resin particles (II) may be the same as or different from the inorganic particles (III) of the binder resin (I), but the binder resin (I) And at least one of the inorganic particles contained in the spherical resin particles (II) is a compound containing a Group 4A metal of the periodic table [particularly, an inorganic acid salt (for example, a metal titanate such as barium titanate) and / or oxidation. Product (for example, anatase type or rutile type titanium dioxide)].
球状樹脂粒子（II）中における無機粒子(III)の割合は１重量％以上の範囲から選択でき、通常、３重量％以上（例えば、３〜９０重量％）、好ましくは５〜８０重量％、さらに好ましくは１０〜７０重量％（特に１５〜５０重量％）程度である。球状樹脂粒子中に無機粒子を分散させると、適度な光散乱特性を示し、防眩性と表示画像の鮮明性とを両立できるとともに、耐擦傷性も優れる。 The proportion of the inorganic particles (III) in the spherical resin particles (II) can be selected from the range of 1% by weight or more, and usually 3% by weight or more (for example, 3 to 90% by weight), preferably 5 to 80% by weight, More preferably, it is about 10 to 70% by weight (particularly 15 to 50% by weight). When inorganic particles are dispersed in the spherical resin particles, an appropriate light scattering characteristic is exhibited, and both the antiglare property and the sharpness of the display image can be achieved, and the scratch resistance is also excellent.
球状粒子（II）の製造方法としては、例えば、特開２００３−２６９３２号公報に記載されたエマルジョンを利用した乳化重合法などが使用できる。例えば、架橋スチレン系樹脂の場合、乳化剤（アニオン界面活性剤など）、架橋剤（ジビニルベンゼンなど）、開始剤（アゾビスイソブチロニトリルなど）の存在下、スチレン単量体及び無機粒子(III)を水性溶媒中に乳化分散させて乳化重合する方法、乳化剤、開始剤、スチレン系単量体及び無機粒子(III)を水性溶媒中で乳化重合してシード粒子を生成させた後、シード粒子の存在下、少なくともスチレン系単量体を重合する多段重合法で得ることができる。 As a method for producing the spherical particles (II), for example, an emulsion polymerization method using an emulsion described in JP-A No. 2003-26932 can be used. For example, in the case of a crosslinked styrene resin, a styrene monomer and inorganic particles (III) in the presence of an emulsifier (such as an anionic surfactant), a crosslinking agent (such as divinylbenzene), and an initiator (such as azobisisobutyronitrile). ) Is emulsified and dispersed in an aqueous solvent, and emulsion polymerization is performed. After the emulsifier, initiator, styrene monomer and inorganic particles (III) are emulsion-polymerized in an aqueous solvent to produce seed particles, seed particles are produced. Can be obtained by a multistage polymerization method in which at least a styrene monomer is polymerized.
球状樹脂粒子（II）の（見かけ上の）屈折率は、前記バインダー樹脂（Ｉ）と同様の理由で、例えば、１．６１〜２、好ましくは１．６２〜１．９５、さらに好ましくは１．６３〜１．９程度であり、屈折率が高いと、反射防止性が高い。なお、光散乱特性の点から、この球状樹脂粒子（II）の屈折率は、バインダー樹脂（Ｉ）の屈折率に極力一致するのが好ましい。バインダー樹脂（Ｉ）と球状樹脂粒子（II）との屈折率差は、例えば、０〜０．０５、好ましくは０〜０．０３、さらに好ましくは０〜０．０２（特に０〜０．０１）程度である。 The (apparent) refractive index of the spherical resin particles (II) is, for example, 1.61-2, preferably 1.62-1.95, more preferably 1 for the same reason as the binder resin (I). When the refractive index is high, the antireflection property is high. From the viewpoint of light scattering characteristics, the refractive index of the spherical resin particles (II) preferably matches the refractive index of the binder resin (I) as much as possible. The refractive index difference between the binder resin (I) and the spherical resin particles (II) is, for example, 0 to 0.05, preferably 0 to 0.03, more preferably 0 to 0.02 (particularly 0 to 0.01). )
球状樹脂粒子（II）において、無機粒子(III)を架橋樹脂中に分散することにより、球状樹脂粒子（II）の硬度をさらに向上し、防眩層の耐擦傷性を向上するほか、防眩層の上に、さらに低屈折率層を形成する場合、低屈折率層との密着性を向上できる。 In spherical resin particles (II), by dispersing inorganic particles (III) in the cross-linked resin, the hardness of the spherical resin particles (II) is further improved and the anti-glare layer is improved in scratch resistance. When a low refractive index layer is further formed on the layer, adhesion with the low refractive index layer can be improved.
前記バインダー樹脂（Ｉ）と球状樹脂粒子（II）との割合（重量比）は、適度な凹凸を形成し防眩性を付与する点から、例えば、前者／後者＝９９／１〜８０／２０であり、好ましくは９７／３〜８５／１５、さらに好ましくは９６／４〜８０／２０（特に９６／４〜９０／１０）程度である。 The ratio (weight ratio) between the binder resin (I) and the spherical resin particles (II) is, for example, the former / the latter = 99/1 to 80/20 from the viewpoint of forming appropriate irregularities and imparting antiglare properties. It is preferably 97/3 to 85/15, more preferably about 96/4 to 80/20 (particularly 96/4 to 90/10).
防眩層の厚みは、例えば、１〜１０μｍ（例えば、３〜１０μｍ）、好ましくは２〜８μｍ（例えば、３〜８μｍ）、さらに好ましくは３〜６μｍ（特に３〜５μｍ）程度である。 The thickness of the antiglare layer is, for example, about 1 to 10 μm (for example, 3 to 10 μm), preferably about 2 to 8 μm (for example, 3 to 8 μm), and more preferably about 3 to 6 μm (particularly 3 to 5 μm).
［低屈折率層］
前記防眩層の上には、さらに低屈折率層を形成してもよい。低屈折率層は、慣用の低屈折率層、例えば、特開２００１−１００００６号公報に記載の低屈折率層などが使用できる。このような低屈折率層は、例えば、含フッ素モノマーやシラン化合物などの重合（又は架橋）体などで構成されていてもよい。さらに、低屈折率層は、塗膜強度を向上させるために、無機フィラーを含んでもよい。無機フィラーを含む場合、熱、水分、電離放射線などにより重合した含フッ素モノマーやシラン化合物中に、無機フィラーが分散しているのが好ましい。
[Low refractive index layer]
A low refractive index layer may be further formed on the antiglare layer. As the low refractive index layer, a conventional low refractive index layer, for example, a low refractive index layer described in JP-A-2001-100006 can be used. Such a low refractive index layer may be composed of, for example, a polymerized (or crosslinked) product such as a fluorine-containing monomer or a silane compound. Furthermore, the low refractive index layer may contain an inorganic filler in order to improve the coating film strength. When the inorganic filler is included, it is preferable that the inorganic filler is dispersed in the fluorine-containing monomer or silane compound polymerized by heat, moisture, ionizing radiation or the like.
含フッ素モノマーとしては、例えば、フルオロオレフィン類（例えば、フルオロエチレン、ビニリデンフルオライド、テトラフルオロエチレン、ヘキサフルオロエチレン、ヘキサフルオロプロピレン、パーフルオロ−２，２−ジメチルー１，３−ジオキソールなど）などが挙げられる。これらの含フッ素モノマーは、反応性基を有するアクリル系モノマー（例えば、（メタ）アクリル酸、グリシジル（メタ）アクリレート、メチロール（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレートなどのヒドロキシＣ2-6アルキル（メタ）アクリレート、アリル（メタ）アクリレートなど）などの架橋性モノマーで架橋してもよく、オレフィン類（エチレン、プロピレンなど）、アクリル系モノマー（（メタ）アクリル酸、（メタ）アクリル酸メチル、などの（メタ）アクリル酸エステルなど）、スチレン系モノマー（スチレン、ジビニルベンゼンなど）の共重合性モノマーと共重合してもよい。 Examples of the fluorine-containing monomer include fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.). Can be mentioned. These fluorine-containing monomers are acrylic monomers having a reactive group (for example, hydroxy C 2-6 alkyl such as (meth) acrylic acid, glycidyl (meth) acrylate, methylol (meth) acrylate, hydroxyethyl (meth) acrylate). (Meth) acrylate, allyl (meth) acrylate, etc.) may be cross-linked, such as olefins (ethylene, propylene, etc.), acrylic monomers ((meth) acrylic acid, methyl (meth) acrylate, (Meth) acrylic acid esters, etc.) and styrene monomers (styrene, divinylbenzene, etc.) copolymerizable monomers.
シラン化合物としては、例えば、パーフルオロアルキル基含有シラン化合物［例えば、（ヘプタデカフルオロ−１，１，２，２−テトラデシル）トリエトキシシラン］などが例示できる。 Examples of the silane compound include perfluoroalkyl group-containing silane compounds [eg, (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane].
低屈折率層に用いられる無機フィラーとしては、例えば、前記特開２００１−１００００６号公報に記載のフィラーや、前記無機粒子(III)で例示された粒子などが使用できるが、シリカやフッ化マグネシウムなどの低屈折率のフィラー、特にシリカが好ましい。 As the inorganic filler used in the low refractive index layer, for example, the filler described in JP-A-2001-100006, the particles exemplified in the inorganic particles (III), and the like can be used. A low refractive index filler such as silica is particularly preferable.
無機フィラーの平均粒径は０．１μｍ以下、好ましくは０．０５μｍ以下（例えば、０．０１〜０．０５μｍ）、さらに好ましくは０．０１〜０．０４μｍ程度である。 The average particle size of the inorganic filler is 0.1 μm or less, preferably 0.05 μm or less (for example, 0.01 to 0.05 μm), more preferably about 0.01 to 0.04 μm.
低屈折率層中における無機フィラーの割合は、例えば、１重量％以上であってもよく、例えば、５〜９０重量％程度である。また、無機フィラーは、カップリング剤（チタンカップリング剤、シランカップリング剤）により表面改質されていてもよい。 The proportion of the inorganic filler in the low refractive index layer may be, for example, 1% by weight or more, for example, about 5 to 90% by weight. The inorganic filler may be surface-modified with a coupling agent (titanium coupling agent, silane coupling agent).
低屈折率層の厚みは、例えば、０．０５〜０．２μｍ程度であり、好ましくは０．０６〜０．１５μｍ、さらに好ましくは０．０７〜０．１２μｍ程度である。 The thickness of the low refractive index layer is, for example, about 0.05 to 0.2 μm, preferably 0.06 to 0.15 μm, and more preferably about 0.07 to 0.12 μm.
［防眩フィルム及びその製造方法］
本発明の防眩フィルムの厚みは、１〜５００μｍ程度の範囲から選択でき、好ましくは３〜３００μｍ、さらに好ましくは５〜２００μｍ（特に１０〜１００μｍ）程度である。
[Anti-glare film and method for producing the same]
The thickness of the antiglare film of the present invention can be selected from the range of about 1 to 500 μm, preferably 3 to 300 μm, more preferably about 5 to 200 μm (particularly 10 to 100 μm).
本発明の防眩フィルムには、必要に応じて、その表面に、帯電防止層（例えば、カーボンブラックなどの導電剤を含む光硬化性樹脂で構成された導電性薄膜など）などの薄膜を形成してもよい。これらの薄膜の厚みは、例えば、０．０１〜１０μｍ、好ましくは０．０３〜１μｍ、さらに好ましくは０．０５〜０．１μｍ程度である。 A thin film such as an antistatic layer (for example, a conductive thin film composed of a photocurable resin containing a conductive agent such as carbon black) is formed on the surface of the antiglare film of the present invention as necessary. May be. The thickness of these thin films is, for example, about 0.01 to 10 μm, preferably about 0.03 to 1 μm, and more preferably about 0.05 to 0.1 μm.
本発明の防眩フィルムは、透明性及び光散乱性に優れ、かつ高い防眩性を有する。本発明のフィルムのヘイズは、例えば、２〜２０％、好ましくは３〜１５％、さらに好ましくは３〜１０％程度である。なお、ヘイズは、ヘイズメーター（例えば、日本電色（株）製、ＮＤＨ５０００Ｗ）を用いて、ＪＩＳ Ｋ６７１４に基づいて測定できる。 The antiglare film of the present invention is excellent in transparency and light scattering properties and has high antiglare properties. The haze of the film of the present invention is, for example, about 2 to 20%, preferably about 3 to 15%, and more preferably about 3 to 10%. Haze can be measured based on JIS K6714 using a haze meter (for example, NDH5000W manufactured by Nippon Denshoku Co., Ltd.).
本発明の防眩フィルムの透過鮮明度は、例えば、２０〜９０％、好ましくは３０〜９０％、好ましくは４０〜９０％程度である。透過画像鮮明度は、写像性測定器（たとえば、スガ試験機（株）製ＩＣＭ−１ＤＤ型）により、光学櫛０．５ｍｍ幅を用いて、ＪＩＳ Ｋ７１５０に基づいて測定できる。 The transmission clarity of the antiglare film of the present invention is, for example, about 20 to 90%, preferably about 30 to 90%, and preferably about 40 to 90%. The transmitted image sharpness can be measured based on JIS K7150 using an image comb measuring instrument (for example, ICM-1DD type manufactured by Suga Test Instruments Co., Ltd.) using an optical comb width of 0.5 mm.
本発明の防眩フィルムの積分反射率（視感度換算）は、例えば、１．８％未満、好ましくは１．６％未満（例えば、０．１〜１．６％）、さらに好ましくは１．５％未満（例えば、０．１〜１．５％）程度である。 The integrated reflectance (visibility conversion) of the antiglare film of the present invention is, for example, less than 1.8%, preferably less than 1.6% (for example, 0.1 to 1.6%), more preferably 1. It is about less than 5% (for example, 0.1 to 1.5%).
本発明の防眩フィルムは、例えば、液晶表示装置として用いる場合、片面に接着層を設けることにより、ディスプレイの最表面に配置してもよい。また、本発明の防眩フィルムを偏光板の保護膜として使用してもよい。 For example, when used as a liquid crystal display device, the antiglare film of the present invention may be disposed on the outermost surface of a display by providing an adhesive layer on one side. Moreover, you may use the anti-glare film of this invention as a protective film of a polarizing plate.
本発明の防眩フィルムは、基材の上に、平均粒径１００ｎｍ以下の無機粒子(III)を含むバインダー樹脂（Ｉ）と、平均粒径１００ｎｍ以下の無機粒子(III)を含む球状樹脂粒子（II）とで構成された防眩層を形成することにより製造できる。さらに、得られた防眩層の上に、低屈折率層を形成して、防眩性反射防止フィルムを製造してもよい。具体的には、防眩性フィルムは、例えば、基材の上に、前記バインダー樹脂（Ｉ）及び無機粒子(III)を含む溶液を塗布し、乾燥後、硬化処理して、表面に凹凸構造を有する防眩層を形成してもよい。さらに、防眩性反射防止フィルムは、得られた防眩層の上に、さらにフッ素系モノマーなどを含有する溶液を塗布し、乾燥及び硬化処理してもよい。この方法において、ポリマーの硬化処理は、活性エネルギー線（紫外線、電子線など）の照射や加熱により重合させて硬化させてもよい。また、溶剤は、ポリマーや重合性モノマー又はオリゴマーの種類に応じて適宜選択でき、反応開始剤や硬化剤などを適宜添加してもよい。 The antiglare film of the present invention comprises a binder resin (I) containing inorganic particles (III) having an average particle size of 100 nm or less and spherical resin particles containing inorganic particles (III) having an average particle size of 100 nm or less on a substrate. It can manufacture by forming the glare-proof layer comprised by (II). Furthermore, an antiglare antireflection film may be produced by forming a low refractive index layer on the obtained antiglare layer. Specifically, for example, the antiglare film is formed by applying a solution containing the binder resin (I) and the inorganic particles (III) on a substrate, drying, curing, and forming a concavo-convex structure on the surface. You may form the anti-glare layer which has. Furthermore, the antiglare antireflection film may be further subjected to drying and curing treatment by applying a solution containing a fluorine monomer or the like on the obtained antiglare layer. In this method, the polymer may be cured by polymerization by irradiation with active energy rays (such as ultraviolet rays or electron beams) or heating. Moreover, a solvent can be suitably selected according to the kind of a polymer, a polymerizable monomer, or an oligomer, You may add a reaction initiator, a hardening | curing agent, etc. suitably.
本発明の防眩フィルムは、高い耐擦傷性を有するとともに、反射率が低く、鮮明な画像を表示できるため、防眩性と耐擦傷性が必要とされる種々の用途、例えば、液晶ディスプレイ（ＬＣＤ）、プラズマディスプレイパネル（ＰＤＰ）、有機発光ダイオード（ＯＬＥＤ）、陰極管表示装置（ＣＲＴ）、タッチパネル付き表示装置、有機エレクトロルミネッセンス（ＥＬ）ディスプレイ、無機ＥＬディスプレイ、フィールドエミッションディスプレイ（ＦＥＤ）などの表示装置に使用できる。特に、本発明の防眩フィルムは、近年一般家庭に普及が著しく、耐擦傷性が必要とされる液晶表示装置に対して有用である。 The antiglare film of the present invention has high scratch resistance, low reflectance, and can display a clear image. Therefore, the antiglare film can be used in various applications that require antiglare and scratch resistance, such as a liquid crystal display ( LCD), plasma display panel (PDP), organic light emitting diode (OLED), cathode ray tube display (CRT), display device with touch panel, organic electroluminescence (EL) display, inorganic EL display, field emission display (FED), etc. Can be used for display devices. In particular, the antiglare film of the present invention has been widely used in general households in recent years, and is useful for liquid crystal display devices that require scratch resistance.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。なお、実施例及び比較例で得られた防眩フィルムの評価方法を以下に示す。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the evaluation method of the anti-glare film obtained by the Example and the comparative example is shown below.
（１）ヘイズ
得られた防眩フィルムのヘイズをヘイズメーター（日本電色（株）製、商品名「ＮＤＨ−５０００Ｗ」）を用いて測定した。
(1) Haze The haze of the obtained antiglare film was measured using a haze meter (manufactured by Nippon Denshoku Co., Ltd., trade name “NDH-5000W”).
（２）反射率
得られた防眩フィルムの裏面に黒フィルムを貼り合わせ、積分球反射強度測定装置（ＨＩＴＡＣＨＩ（株）製、商品名「Ｕ３３００」）を用いて、積分反射率（視感度換算）を測定した。
(2) Reflectivity A black film is pasted on the back surface of the obtained antiglare film, and integrated reflectance (visibility conversion) using an integrating sphere reflection intensity measuring device (trade name “U3300” manufactured by HITACHI). ) Was measured.
（３）鉛筆硬度評価
硬度の指標として、ＪＩＳ Ｋ５４００に準拠して鉛筆硬度を評価した。
(3) Pencil hardness evaluation Pencil hardness was evaluated based on JIS K5400 as an index of hardness.
（４）スチールウール耐擦傷性
耐擦傷性の指標として、＃００００のスチールウールを２５０ｇ／ｃｍ2の加重で１０往復し、キズの本数より評価した。
(4) Scratch resistance of steel wool As an index of scratch resistance, steel wool of # 0000 was reciprocated 10 times with a load of 250 g / cm 2 and evaluated from the number of scratches.
◎：２本以下
○：３〜４本
△：５〜６本
×：７本以上。
◎: 2 or less ○: 3 to 4 Δ: 5 to 6 ×: 7 or more.
（５）防眩性
防眩フィルムの裏面に黒フィルムを貼り合わせ、２ｍの距離より、むき出し蛍光灯（１００００ｃｄ／ｍ2）を映し、その反射像のボケの程度を評価した。
(5) Antiglare property A black film was bonded to the back surface of the antiglare film, and an exposed fluorescent lamp (10000 cd / m 2 ) was projected from a distance of 2 m, and the degree of blur of the reflected image was evaluated.
○：蛍光灯の輪郭がわからない、もしくはわずかにわかる
△：蛍光灯は部分的にボケているが、輪郭が明確に見える
×：蛍光灯がほとんどボケず、輪郭が非常に明確に見える。
○: The outline of the fluorescent lamp is not known or slightly understood. Δ: The fluorescent lamp is partially blurred, but the outline is clearly visible. X: The fluorescent lamp is hardly blurred, and the outline is very clear.
（６）透過鮮明度
防眩フィルムを、写像測定器（スガ試験機（株）製、商品名「ＩＣＭ−１ＤＤ」）を用いて、光学櫛０．５ｍｍ幅を用いて、ＪＩＳ Ｋ７１５０に基づいて測定した。
(6) Transmission clarity Based on JIS K7150, using an anti-glare film using a mapping instrument (Suga Test Instruments Co., Ltd., trade name “ICM-1DD”) with an optical comb width of 0.5 mm. It was measured.
（７）文字ボケ
防眩フィルムを、パソコンに接続した液晶モニタ（１５インチＸＧＡ、ＴＦＴ−ＴＮ方式、正面輝度：３５０ｃｄ／ｍ2、正面コントラスト：３００対１、表面ＡＧなし）の表面に貼り合わせ、文字のボケ具合を評価した。
(7) Text blur An anti-glare film is pasted on the surface of a liquid crystal monitor (15-inch XGA, TFT-TN system, front luminance: 350 cd / m 2 , front contrast: 300 to 1, no surface AG) connected to a personal computer. The character blur was evaluated.
○：文字の輪郭は全くボケない、もしくはわずかにボケる程度
△：文字の輪郭がボケており、多少の違和感を持つ
×：文字の輪郭がボケており、強い違和感を持つ。
○: The outline of the character is not blurred at all or slightly blurred. Δ: The outline of the character is blurred and has a slightly strange feeling. ×: The outline of the character is blurred and has a strong feeling of strangeness.
実施例１
［球状樹脂粒子（II）］
ポリビニルピロリドン（重量平均分子量３万）１００重量部、アニオン界面活性剤（和光純薬（株）製、商品名「エアゾールＯＴ」）６０重量部及びアゾビスイソブチロニトリル１５０重量部をエタノール８５重量部に溶解させ、さらに、ゾルゲル法にて製造したチタン酸バリウム超微粒子（平均粒子径０．０３μｍ）５００重量部を分散させた。この溶液を撹拌しながら窒素気流下でスチレン１０００重量部を投入し、７０℃に昇温させ２４時間重合反応を行い、平均粒径２．１μｍのシード粒子を得た。
Example 1
[Spherical resin particles (II)]
85 parts by weight of ethanol with 100 parts by weight of polyvinylpyrrolidone (weight average molecular weight 30,000), 60 parts by weight of an anionic surfactant (trade name “Aerosol OT” manufactured by Wako Pure Chemical Industries, Ltd.) and 150 parts by weight of azobisisobutyronitrile In addition, 500 parts by weight of barium titanate ultrafine particles (average particle size: 0.03 μm) produced by the sol-gel method were dispersed. While stirring this solution, 1000 parts by weight of styrene was added under a nitrogen stream, the temperature was raised to 70 ° C., and a polymerization reaction was performed for 24 hours to obtain seed particles having an average particle diameter of 2.1 μm.
上記シード粒子１重量部にイオン交換水１００００重量部とラウリル硫酸ナトリウム１０重量部を加え均一に分散させた。ジビニルベンセン２０００重量部及び重合開始剤［２，２′−アゾビス（２，４−ジメチルバレロニトリル）、和光純薬（株）製、商品名「Ｖ−６５」］１００重量部を混合して、ホモジナイザーで微分散乳化した。得られた乳化液をシード粒子分散液に加え、２５℃、２００ｒｐｍの回転数で３時間攪拌して、シード粒子に吸収させた。この分散液に、ポリビニルアルコール（ＰＶＡ）の５重量％水溶液１００００重量部を加えた後、２００ｒｐｍの回転数で攪拌しながら窒素気流下７０℃で１２時間重合を行った。得られた分散液から遠心分離によりポリマー粒子を取り出し、８０℃以上に加熱したイオン交換水及びメタノールで分散剤を完全に洗浄した後、乾燥して粒子を得た。この粒子は、平均粒径５μｍ、Ｃｖ値３であった。この粒子の灰分を測定した結果、粒子中のチタン酸バリウム濃度は２５％であった。この粒子から、沈降法により平均粒子径３μｍ、Ｃｖ値１．１の球状樹脂粒子（II）を分取した。 To 1 part by weight of the seed particles, 10000 parts by weight of ion exchange water and 10 parts by weight of sodium lauryl sulfate were added and dispersed uniformly. 2000 parts by weight of divinyl benzene and 100 parts by weight of a polymerization initiator [2,2′-azobis (2,4-dimethylvaleronitrile), manufactured by Wako Pure Chemical Industries, Ltd., trade name “V-65”] were mixed, It was finely dispersed and emulsified with a homogenizer. The obtained emulsion was added to the seed particle dispersion and stirred for 3 hours at 25 ° C. and 200 rpm to be absorbed by the seed particles. After adding 10,000 parts by weight of a 5% by weight aqueous solution of polyvinyl alcohol (PVA) to this dispersion, polymerization was carried out at 70 ° C. for 12 hours under a nitrogen stream while stirring at a rotation speed of 200 rpm. The polymer particles were taken out from the obtained dispersion by centrifugation, and the dispersant was completely washed with ion-exchanged water and methanol heated to 80 ° C. or higher, and then dried to obtain particles. These particles had an average particle size of 5 μm and a Cv value of 3. As a result of measuring the ash content of the particles, the barium titanate concentration in the particles was 25%. From these particles, spherical resin particles (II) having an average particle diameter of 3 μm and a Cv value of 1.1 were collected by a sedimentation method.
［バインダー樹脂（Ｉ）溶液］
ジルコニア含有紫外線（ＵＶ）硬化型ハードコート液（ＪＳＲ（株）製、商品名「デソライトＺ７４０１」、固形分濃度４８重量％、ジルコニア含有率７１重量％、ジルコニアの平均粒子径０．０２μｍ）５００重量部、光重合開始剤（チバ・スペシャルティ・ケミカルズ社製、イルガキュア９０７）７．５重量部を、メチルエチルケトン及びｎ−ブタノールの混合溶媒（メチルエチルケトン／ｎ−ブタノール＝８／２（重量比））２３０重量部で希釈し、バインダー樹脂（Ｉ）溶液を調製した。この溶液を塗布、紫外線硬化して得られた塗膜はほぼ透明であり、見かけ上の屈折率は１．７３であった。
[Binder resin (I) solution]
Zirconia-containing ultraviolet (UV) curable hard coat liquid (manufactured by JSR Corporation, trade name “Desolite Z7401”, solid content concentration 48 wt%, zirconia content 71 wt%, zirconia average particle size 0.02 μm) 500 wt Parts by weight, 7.5 parts by weight of a photopolymerization initiator (Ciba Specialty Chemicals, Irgacure 907), 230 parts by weight of a mixed solvent of methyl ethyl ketone and n-butanol (methyl ethyl ketone / n-butanol = 8/2 (weight ratio)) The binder resin (I) solution was prepared. The coating film obtained by applying this solution and curing with ultraviolet rays was almost transparent, and the apparent refractive index was 1.73.
［防眩層の塗布］
前記バインダー樹脂溶液に、前記球状樹脂粒子（II）１５重量部を添加し、高速攪拌機にて５０００ｒｐｍで１時間攪拌、分散した後、フィルターでろ過して防眩層用の溶液を調製した。この溶液を、８０μｍのセルローストリアセテートフィルム（富士写真フィルム（株）製、商品名「フジＴＡＣ―ＴＤ８０Ｕ」）上に、バーコーターを用いて塗布し、１００℃にて乾燥後、メタルハライドランプを用いてＵＶ照射し、厚さ３．５μｍの防眩層を形成した。
[Application of antiglare layer]
15 parts by weight of the spherical resin particles (II) were added to the binder resin solution, stirred and dispersed at 5000 rpm for 1 hour with a high-speed stirrer, and then filtered with a filter to prepare a solution for an antiglare layer. This solution was applied on an 80 μm cellulose triacetate film (Fuji Photo Film Co., Ltd., trade name “Fuji TAC-TD80U”) using a bar coater, dried at 100 ° C., and then using a metal halide lamp. UV irradiation was performed to form an antiglare layer having a thickness of 3.5 μm.
［低屈折率層の塗布］
前記防眩層の上に、屈折率１．４２の熱架橋性含フッ素樹脂溶液（ＪＳＲ（株）製、商品名「オプスタ−ＴＴ１００６」、固形分濃度６重量％）をフィルターでろ過後、バーコーターを用いて塗布し、１２０℃にて乾燥後、厚み０．０９μｍの低屈折率層を形成し、防眩フィルムを作製した。得られた防眩フィルムの評価結果を表１に示す。
[Application of low refractive index layer]
On the antiglare layer, a heat-crosslinkable fluororesin solution having a refractive index of 1.42 (manufactured by JSR Corporation, trade name “OPSTA-TT1006”, solid content concentration 6% by weight) is filtered through a filter, After coating using a coater and drying at 120 ° C., a low refractive index layer having a thickness of 0.09 μm was formed to produce an antiglare film. The evaluation results of the obtained antiglare film are shown in Table 1.
比較例１
球状樹脂粒子（II）の代わりに市販の架橋ポリスチレン粒子（平均粒子径３μｍ、Ｃｖ値１．１）を用いる以外は実施例１と同様にして防眩フィルムを作製した。得られた防眩フィルムの評価結果を表１に示す。
Comparative Example 1
An antiglare film was produced in the same manner as in Example 1 except that commercially available crosslinked polystyrene particles (average particle size 3 μm, Cv value 1.1) were used instead of the spherical resin particles (II). The evaluation results of the obtained antiglare film are shown in Table 1.
比較例２
［バインダー樹脂溶液］
ジルコニア含有ＵＶ硬化型ハードコート液（ＪＳＲ（株）製、商品名「デソライトＺ７４０１」、固形分濃度４８重量％、ジルコニア含有率７１重量％、ジルコニアの平均粒子径０．０２μｍ）２３０重量部、ジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ）１３５重量部、光重合開始剤（チバ・スペシャルティ・ケミカルズ社製、イルガキュア９０７）７．５重量部を、メチルエチルケトン及びｎ−ブタノールの混合溶媒（メチルエチルケトン／ｎ−ブタノール＝８／２（重量比））３５０重量部で希釈し、バインダー樹脂溶液を調製した。この溶液を塗布、紫外線硬化して得られた塗膜はほぼ透明であり、見かけ上の屈折率は１．６であった。
Comparative Example 2
[Binder resin solution]
Zirconia-containing UV curable hard coat liquid (manufactured by JSR Corporation, trade name “Desolite Z7401”, solid concentration 48% by weight, zirconia content 71% by weight, zirconia average particle diameter 0.02 μm) 230 parts by weight 135 parts by weight of pentaerythritol hexaacrylate (DPHA) and 7.5 parts by weight of a photopolymerization initiator (manufactured by Ciba Specialty Chemicals, Irgacure 907) are mixed with methyl ethyl ketone and n-butanol (methyl ethyl ketone / n-butanol = 8). / 2 (weight ratio)) was diluted with 350 parts by weight to prepare a binder resin solution. The coating film obtained by applying this solution and curing with ultraviolet rays was almost transparent, and the apparent refractive index was 1.6.
［防眩層の塗布］
前記バインダー樹脂溶液に、架橋ポリスチレン粒子（平均粒子径３μｍ、Ｃｖ値１．１）１５重量部を添加し、高速攪拌機にて５０００ｒｐｍで１時間攪拌、分散した後、フィルターでろ過して防眩層用の溶液を調製した。防眩層用の溶液として、この溶液を用いる以外は実施例１と同様にして、防眩フィルムを作製した。得られた防眩フィルムの評価結果を表１に示す。
[Application of antiglare layer]
15 parts by weight of crosslinked polystyrene particles (average particle size 3 μm, Cv value 1.1) are added to the binder resin solution, and the mixture is stirred and dispersed at 5000 rpm for 1 hour with a high-speed stirrer, and then filtered through a filter to produce an antiglare layer. A solution for was prepared. An antiglare film was produced in the same manner as in Example 1 except that this solution was used as a solution for the antiglare layer. The evaluation results of the obtained antiglare film are shown in Table 1.
実施例１で得られた防眩フィルムは、硬度、耐擦傷性が良好で、かつ反射率が低いうえに、ヘイズが低く、透過鮮明度が高いため、鮮明な表示が可能である。 The antiglare film obtained in Example 1 has good hardness and scratch resistance, low reflectivity, low haze, and high transmission clarity, and therefore can display clearly.
これに対して、比較例１では、通常の架橋ポリスチレン樹脂による微粒子を用いているために、バインダー樹脂との屈折率差による散乱が生じている。その結果、ヘイズが高く、透過鮮明度が低くなり、文字ボケが生じている。 On the other hand, in Comparative Example 1, since fine particles made of ordinary crosslinked polystyrene resin are used, scattering due to a difference in refractive index from the binder resin occurs. As a result, the haze is high, the transmission clearness is low, and character blurring occurs.
その一方で、比較例２では、通常の架橋ポリスチレン樹脂微粒子でも散乱が起こらないように、バインダー樹脂に添加する無機粒子の割合を減らしている。その結果、ヘイズが低く、透過鮮明度が高くなり、文字ボケは生じていないが、鉛筆硬度が下がり耐擦傷性が低下するほか、反射率も高くなり防眩性が低下している。
On the other hand, in Comparative Example 2, the proportion of inorganic particles added to the binder resin is reduced so that scattering does not occur even with ordinary crosslinked polystyrene resin fine particles. As a result, the haze is low, the transmission clearness is high, and character blurring is not generated, but the pencil hardness is lowered and the scratch resistance is lowered, and the reflectance is also high and the antiglare property is lowered.
Claims (12)
A display device comprising the film according to claim 1.
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| JP2008062538A (en) * | 2006-09-08 | 2008-03-21 | Nakajima Kogyo Kk | Glare shielding film |
| JP2008145781A (en) * | 2006-12-11 | 2008-06-26 | Admatechs Co Ltd | Anti-glare film and method of manufacturing the same |
| CN103443661B (en) * | 2011-03-23 | 2016-02-10 | 大日本印刷株式会社 | Optical laminate, polaroid and image display device |
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