JP2011076081A - Optical laminated body, polarizing plate, and display device using the same - Google Patents
Optical laminated body, polarizing plate, and display device using the same Download PDFInfo
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- JP2011076081A JP2011076081A JP2010196767A JP2010196767A JP2011076081A JP 2011076081 A JP2011076081 A JP 2011076081A JP 2010196767 A JP2010196767 A JP 2010196767A JP 2010196767 A JP2010196767 A JP 2010196767A JP 2011076081 A JP2011076081 A JP 2011076081A
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- optical
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- optical functional
- light resistance
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Landscapes
- Liquid Crystal (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Optical Elements Other Than Lenses (AREA)
- Polarising Elements (AREA)
Abstract
Description
本発明は光学積層体、偏光板およびそれを用いた表示装置に関する。 The present invention relates to an optical laminate, a polarizing plate, and a display device using the same.
液晶表示装置(LCD)やプラズマディスプレイ(PDP)等の表示装置は、表示装置表面に蛍光燈などの室内照明、窓からの太陽光の入射、操作者の影などの写り込みにより、画像の視認性が妨げられる。そのため、これらのディスプレイ表面には、画像の視認性を向上させるために、表面反射光を拡散し、外光の正反射を抑え、外部環境の写り込みを防ぐことができる(防眩性を有する)微細凹凸構造を形成させた防眩フィルムなどの、機能性フィルムが最表面に設けられている。 Display devices such as liquid crystal displays (LCDs) and plasma displays (PDPs) are capable of visually recognizing images by reflecting indoor lighting such as fluorescent lamps, sunlight from windows, and operator shadows on the display surface. Sex is disturbed. Therefore, on these display surfaces, in order to improve the visibility of the image, the surface reflected light can be diffused, regular reflection of external light can be suppressed, and reflection of the external environment can be prevented (has antiglare properties). ) A functional film such as an antiglare film having a fine relief structure is provided on the outermost surface.
これら機能性フィルムは、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。)等の透光性基体上に、微細凹凸構造を形成させた防眩層を一層設けたものや、光拡散層上に低屈折率層を積層したものが、一般に製造販売されており、層構成の組み合わせにより所望の機能を提供する機能性フィルムの開発が進められている。 These functional films have an antiglare layer in which a fine concavo-convex structure is formed on a translucent substrate such as polyethylene terephthalate (hereinafter referred to as “PET”) or triacetyl cellulose (hereinafter referred to as “TAC”). One layer provided and one obtained by laminating a low refractive index layer on a light diffusing layer are generally manufactured and sold, and development of a functional film that provides a desired function by a combination of layer configurations is in progress.
ディスプレイの最表面については、静電気による塵埃付着や液晶表示動作の不具合などの問題があり、帯電防止機能を持った光学積層体が求められている。特に、ディスプレイの高コントラスト化に伴い、塵埃の付着が目立ちやすくなったという理由もあり、帯電防止機能を持った光学積層体が求められている。 On the outermost surface of the display, there are problems such as dust adhering due to static electricity and defects in liquid crystal display operation, and an optical laminate having an antistatic function is required. In particular, with the increase in contrast of displays, the adhesion of dust has become more conspicuous, and therefore an optical laminate having an antistatic function is required.
帯電防止機能を持った帯電防止防眩フィルムとして、透明基材フィルム上に透明導電層および防眩層を順次積層したものが提案されている(例えば、特許文献1参照)。 As an antistatic antiglare film having an antistatic function, a film in which a transparent conductive layer and an antiglare layer are sequentially laminated on a transparent substrate film has been proposed (for example, see Patent Document 1).
また、帯電防止性を付与させるために4級アンモニウム塩性化合物を含有させ、防眩性を付与させるために透光性微粒子を添加した樹脂層を塗布することで、1層構成の帯電防止防眩フィルムを得ることができる(例えば、特許文献2、3参照)。 In addition, by adding a resin layer containing a quaternary ammonium salt compound for imparting antistatic properties and adding light-transmitting fine particles for imparting antiglare properties, the antistatic preventive agent having a single layer structure is provided. A dazzling film can be obtained (see, for example, Patent Documents 2 and 3).
また、導電材料として、ポリアニリンやポリチオフェン等の有機導電材料を用いた光学積層体が提案されている。有機系導電材料は、無機系材料に比べて耐光性に劣るため、帯電防止性能が保持できないこととなるため改良が求められている。ここで、耐光性改善のため、ガラス転移点が高い樹脂と混合する方法が提案されている(例えば、特許文献4参照)。 In addition, an optical laminate using an organic conductive material such as polyaniline or polythiophene as a conductive material has been proposed. An organic conductive material is inferior in light resistance as compared with an inorganic material, and therefore cannot be maintained in antistatic performance, so that improvement is required. Here, in order to improve light resistance, a method of mixing with a resin having a high glass transition point has been proposed (for example, see Patent Document 4).
ディスプレイに使用される光学積層体には、帯電防止性能が求められている。ここで、屋外用途での使用にも耐え得るように、太陽光等の光により帯電防止性能が変化しないような耐光性が求められる。また、ディスプレイに使用される偏光板の保護フィルムは、偏光子とトリアセチルセルロース系保護フィルムを貼合する際に、ケン化等の処理を行い偏光子と保護フィルムの接着性を向上させることが通常行われている。このため、トリアセチルセルロース系保護フィルム上に積層される光学機能層や光学積層体には、帯電防止性能が変化しないような耐ケン化性が求められる。 An optical laminate used for a display is required to have antistatic performance. Here, light resistance is required such that the antistatic performance is not changed by light such as sunlight so that it can withstand use in outdoor applications. Moreover, the protective film of the polarizing plate used for a display can improve the adhesiveness of a polarizer and a protective film by processing, such as saponification, when bonding a polarizer and a triacetylcellulose type protective film. Usually done. For this reason, the saponification resistance that does not change the antistatic performance is required for the optical functional layer and the optical laminate laminated on the triacetyl cellulose-based protective film.
特許文献1のように、帯電防止機能を持った帯電防止防眩フィルムとして、透明基材フィルム上に、透明導電層および防眩層を順次積層したものが提案されているが、この構成では、帯電防止性、防眩性等に優れるが、透明基材フィルム上に2層積層した構成のためコストが高くなる問題がある。 As in Patent Document 1, an antistatic antiglare film having an antistatic function has been proposed in which a transparent conductive layer and an antiglare layer are sequentially laminated on a transparent substrate film. Although it is excellent in antistatic property, anti-glare property, etc., there is a problem that the cost increases due to the constitution in which two layers are laminated on the transparent substrate film.
特許文献2、3のように、帯電防止性を付与させるために4級アンモニウム塩系化合物を含有させ、防眩性を付与させるために透光性微粒子を添加した樹脂層を塗布することで、透明基材フィルム上に1層積層した構成の光学積層体を得ることができるが、この構成ではケン化処理により導電性が低下するなどの問題が生じる。 As in Patent Documents 2 and 3, by applying a resin layer containing a quaternary ammonium salt compound for imparting antistatic properties and adding translucent fine particles for imparting antiglare properties, Although an optical laminate having a structure in which one layer is laminated on a transparent substrate film can be obtained, problems such as a decrease in conductivity due to a saponification treatment occur in this configuration.
ポリアニリンやポリチオフェン等の導電性高分子を用いた光学積層体は、有機系導電材料が無機系材料に比べて耐光性に劣るため、帯電防止性能が保持できないこととなるため改良が求められている。ここで、特許文献4のように耐光性改善のため、ガラス転移点が高い樹脂と混合する方法が提案されているが、ここで用いられるガラス転移点の高い樹脂自身の硬度が低いことにより表面硬度が低く、耐スクラッチ性が低下する問題がある。 An optical laminate using a conductive polymer such as polyaniline or polythiophene is required to be improved because an organic conductive material is inferior in light resistance as compared with an inorganic material and thus cannot retain antistatic performance. . Here, as in Patent Document 4, a method of mixing with a resin having a high glass transition point is proposed for improving light resistance, but the surface of the resin itself having a high glass transition point used here is low due to its low hardness. There is a problem that hardness is low and scratch resistance is lowered.
本発明は、上記現状に鑑みて、一層構成で、優れた帯電防止性能を有し、かつ耐光性、耐ケン化性および耐スクラッチ性に優れた光学積層体、偏光板およびそれを用いた表示装置を提供することを目的とするものである。 In view of the above-described present situation, the present invention has an optical laminate, a polarizing plate, and a display using the same, having a single-layer structure, excellent antistatic performance, and excellent light resistance, saponification resistance, and scratch resistance. The object is to provide an apparatus.
本発明は下記の技術的構成により、上記課題を達成したものである。 The present invention achieves the above-mentioned object by the following technical configuration.
(1)透光性基体上に、直接あるいは他の層を介して、少なくとも導電材料を含有する光学機能層を少なくとも設けた光学積層体であって、該光学積層体表面のカーボンアーク式耐光性試験後の表面抵抗率が1.0×1012Ω/□以下であり、かつカーボンアーク式耐光性試験前後の表面抵抗率の比(R2/R1;R1=カーボンアーク式耐光性試験前の表面抵抗率、R2=カーボンアーク式耐光性試験後の表面抵抗率)が104以下であることを特徴とする光学積層体。
(2)カーボンアーク式耐光性試験後の飽和帯電圧が、1.5kV以下であることを特徴とする前記(1)に記載の光学積層体。
(3)前記光学機能層が、樹脂成分と、透光性微粒子あるいは凝集により凹凸を形成できる無機成分の少なくとも一種とを含有してなることを特徴とする前記(1)または(2)に記載の光学積層体。
(4)前記光学機能層が、電離放射線硬化型フッ化アクリレートを含有することを特徴とする前記(1)乃至(3)のいずれかに記載の光学積層体。
(5)前記光学機能層が、π共役系導電性高分子と高分子ドーパントの複合体を含有することを特徴とする前記(1)乃至(4)のいずれかに記載の光学積層体。
(6)ケン化処理後の表面抵抗率が1.0×1010Ω/□以下であることを特徴とする前記(1)乃至(5)のいずれかに記載の光学積層体。
(7)前記(1)乃至(6)のいずれかに記載の光学積層体が、偏光基体上に積層されてなることを特徴とする偏光板。
(8)前記(1)乃至(6)のいずれかに記載の光学積層体が具備されてなることを特徴とする表示装置。
(1) An optical laminate in which at least an optical functional layer containing at least a conductive material is provided on a translucent substrate directly or via another layer, and the carbon arc light resistance of the surface of the optical laminate is provided. Surface resistivity after test is 1.0 × 10 12 Ω / □ or less, and ratio of surface resistivity before and after carbon arc type light resistance test (R2 / R1; R1 = surface before carbon arc type light resistance test) Resistivity, R2 = surface resistivity after carbon arc light resistance test) is 10 4 or less.
(2) The optical laminate according to (1) above, wherein the saturation voltage after the carbon arc light resistance test is 1.5 kV or less.
(3) The optical functional layer contains a resin component and at least one inorganic component capable of forming irregularities by light-transmitting fine particles or aggregation, as described in (1) or (2) above Optical laminate.
(4) The optical layered body according to any one of (1) to (3), wherein the optical functional layer contains an ionizing radiation curable fluorinated acrylate.
(5) The optical layered body according to any one of (1) to (4), wherein the optical functional layer contains a complex of a π-conjugated conductive polymer and a polymer dopant.
(6) The optical layered body according to any one of (1) to (5) above, wherein the surface resistivity after saponification is 1.0 × 10 10 Ω / □ or less.
(7) A polarizing plate, wherein the optical laminate according to any one of (1) to (6) is laminated on a polarizing substrate.
(8) A display device comprising the optical laminate according to any one of (1) to (6).
本発明によれば、一層構成で、優れた帯電防止性能を有し、かつ耐光性、耐ケン化性および耐スクラッチ性に優れた光学積層体、偏光板およびそれを用いた表示装置を提供することができる。 According to the present invention, there are provided an optical laminate, a polarizing plate and a display device using the same, which have a single layer structure, excellent antistatic performance, and excellent light resistance, saponification resistance and scratch resistance. be able to.
本形態に係る光学積層体は、透光性基体上に、樹脂成分と導電材料を含有する光学機能層が積層されたものを基本構成とする。光学機能層の形成材料として、透光性微粒子あるいは凝集により凹凸を形成することができる無機成分を加えることにより、さらに防眩性を具備した光学機能層を提供することができる。
ここで、前記光学機能層は直接または他の層を介して透光性基体に積層され、透光性基体の片面に積層されていても両面に積層されていてもよい。更には、光学積層体は他の層を有していてもよい。ここで他の層としては、例えば、光拡散層、防汚層、偏光基体、低反射層、他の機能付与層(例えば、帯電防止層、紫外線・近赤外線(NIR)吸収層、ネオンカット層、電磁波シールド層、ハードコート層)、を挙げることができる。また、当該他の層の位置は、例えば、偏光基体の場合には前記光学機能層とは反対面の前記透光性基体上とし、低反射層の場合には前記光学機能層上とし、他の機能性付与層の場合には前記光学機能層の下層とする。偏光基体、透光性基体および光学機能層が順次積層されてなる積層体は、偏光板として使用することができる。以下、本最良形態に係る光学積層体の各構成要素(透光性基体、樹脂成分等)を詳述する。
The optical laminate according to this embodiment has a basic configuration in which an optical functional layer containing a resin component and a conductive material is laminated on a translucent substrate. As an optical functional layer forming material, an optical functional layer further having antiglare properties can be provided by adding translucent fine particles or an inorganic component capable of forming irregularities by aggregation.
Here, the optical functional layer may be laminated on the translucent substrate directly or via another layer, and may be laminated on one side or both sides of the translucent substrate. Furthermore, the optical layered body may have other layers. Here, as other layers, for example, a light diffusion layer, an antifouling layer, a polarizing substrate, a low reflection layer, other function-imparting layers (for example, an antistatic layer, an ultraviolet / near infrared (NIR) absorption layer, a neon cut layer, etc. , Electromagnetic wave shielding layer, hard coat layer). In addition, the position of the other layer is, for example, on the light-transmitting substrate opposite to the optical function layer in the case of a polarizing substrate, and on the optical function layer in the case of a low reflection layer. In the case of the functional provision layer, it is the lower layer of the optical functional layer. A laminate in which a polarizing substrate, a translucent substrate, and an optical functional layer are sequentially laminated can be used as a polarizing plate. Hereinafter, each component (translucent substrate, resin component, etc.) of the optical laminate according to the best mode will be described in detail.
<透光性基体>
本最良形態に係る透光性基体としては、透光性である限り特に限定されず、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、トリアセチルセルロース(TAC)、ポリエチレンナフタレート(PEN)、ポリメチルメタクリレート(PMMA)、ポリカーボネート(PC)、ポリイミド(PI)、ポリエチレン(PE)、ポリプロピレン(PP)、ポリビニルアルコール(PVA)、ポリ塩化ビニル(PVC)、シクロオレフィンコポリマー(COC)、含ノルボルネン樹脂、ポリエーテルスルホン、セロファン、芳香族ポリアミド等の各種樹脂フィルムを好適に使用することができる。なお、PDP、LCDに用いる場合は、PETフィルム、TACフィルムおよび含ノルボルネン樹脂フィルムから選ばれる1種を使用することがより好ましい。
<Translucent substrate>
The translucent substrate according to the best mode is not particularly limited as long as it is translucent, and glass such as quartz glass and soda glass can be used. PET, triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyimide (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), polyvinyl chloride (PVC), cycloolefin copolymer (COC) Various resin films such as norbornene-containing resin, polyethersulfone, cellophane, and aromatic polyamide can be suitably used. In addition, when using for PDP and LCD, it is more preferable to use 1 type chosen from a PET film, a TAC film, and a norbornene-containing resin film.
これら透光性基体の透明性は高いものほど良好であるが、全光線透過率(JIS
K7105)としては80%以上、より好ましくは90%以上が良い。また、透光性基体の厚さとしては、軽量化の観点からは薄い方が好ましいが、その生産性やハンドリング性を考慮すると、1〜700μmの範囲のもの、好ましくは25〜250μmを使用することが好適である。
Although the transparency of these light-transmitting substrate, the better the high total light transmittance (JIS
K7105) is 80% or more, more preferably 90% or more. Further, the thickness of the translucent substrate is preferably thin from the viewpoint of weight reduction, but considering the productivity and handling properties, the thickness of the translucent substrate is in the range of 1 to 700 μm, preferably 25 to 250 μm. Is preferred.
透光性基体表面に、アルカリ処理、コロナ処理、プラズマ処理、スパッタ処理などのトリートメント処理、界面活性剤、シランカップリング剤などのプライマーコーティング、Si蒸着などの薄膜ドライコーティングなどを施すことで、透光性基体と光学機能層との密着性を向上させ、当該光学機能層の物理的強度、耐薬品性を向上させることができる。また、透光性基体と光学機能層との間に他の層を設ける場合も、上記同様の方法で、各層界面の密着性を向上させ、当該光学機能層の物理的強度、耐薬品性を向上させることができる。 The surface of the translucent substrate is treated with alkali treatment, corona treatment, plasma treatment, sputtering treatment and other primer treatments, primer coatings such as surfactants and silane coupling agents, and thin film dry coatings such as Si deposition. The adhesion between the optical substrate and the optical functional layer can be improved, and the physical strength and chemical resistance of the optical functional layer can be improved. Also, when another layer is provided between the translucent substrate and the optical functional layer, it is possible to improve the adhesion of each layer interface by the same method as described above, and to improve the physical strength and chemical resistance of the optical functional layer. Can be improved.
<光学機能層>
光学機能層は、樹脂成分と導電材料を含有し、当該樹脂成分を硬化させて形成されるものである。光学機能層には樹脂成分と導電材料に加えて、透光性微粒子あるいは凝集により凹凸を形成できる無機成分を加えると、さらに防眩性を具備するため好ましい。
<Optical function layer>
The optical functional layer contains a resin component and a conductive material, and is formed by curing the resin component. In addition to the resin component and the conductive material, it is preferable to add a light-transmitting fine particle or an inorganic component capable of forming irregularities by agglomeration to the optical functional layer because it further has antiglare properties.
[樹脂成分]
光学機能層を構成する樹脂成分としては、硬化後の皮膜として十分な強度を持ち、透明性のあるものを特に制限なく使用できる。前記樹脂成分としては熱硬化型樹脂、熱可塑型樹脂、電離放射線硬化型樹脂、二液混合型樹脂などがあげられるが、これらのなかでも、電子線や紫外線照射による硬化処理にて、簡易な加工操作にて効率よく硬化することができる電離放射線硬化型樹脂が好適である。
[Resin component]
As the resin component constituting the optical functional layer, a resin having sufficient strength as a cured film and having transparency can be used without particular limitation. Examples of the resin component include a thermosetting resin, a thermoplastic resin, an ionizing radiation curable resin, and a two-component mixed resin. Among these, simple curing can be performed by electron beam or ultraviolet irradiation. An ionizing radiation curable resin that can be efficiently cured by a processing operation is preferable.
電離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、ペンタエリスリトールトリア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、多官能ウレタンアクリレート、エポキシアクリレート、ポリエーテルアクリレート、アルキットアクリレート、メラミンアクリレート、シリコーンアクリレート等のアクリレート化合物、不飽和ポリエステル、テトラメチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、ビスフェノールAジグリシジルエーテルや各種脂環式エポキシ等のエポキシ系化合物、3−エチル−3−ヒドロキシメチルオキセタン、1,4−ビス{[(3−エチル−3−オキセタニル)メトキシ]メチル}ベンゼン、ジ[1−エチル(3−オキセタニル)]メチルエーテル等のオキセタン化合物を挙げることができる。これらは単独、もしくは複数混合して使用することができる。
これら電離放射線硬化型樹脂の中で、(メタ)アクリロイルオキシ基が3個以上の多官能モノマーや、多官能ウレタンアクリレートは、硬化速度が上がることや硬化物の硬度が向上させることができる。また、導電材料と混合させて使用した場合、高度に架橋した分子鎖内に導電材料が固定されるために、ケン化処理や耐光性試験による導電材料成分の脱落等の不具合が起こりにくくなり、ケン化処理による導電性の低下や耐光性試験による帯電防止性の低下が起こりにくくなるといった効果が奏される。
また、多官能ウレタンアクリレートを使用した場合については、硬化物の硬度や柔軟性などを付与することができ、さらに塗料化した際に粘度を上昇させる効果を付与することができるため、製膜性を向上させることができる。
Examples of the ionizing radiation curable resin include monomers and oligomers having radical polymerizable functional groups such as acryloyl group, methacryloyl group, acryloyloxy group, and methacryloyloxy group, and cationic polymerizable functional groups such as epoxy group, vinyl ether group, and oxetane group. In addition, a composition in which prepolymers are used alone or appropriately mixed is used. Examples of monomers include methyl acrylate, methyl methacrylate, methoxy polyethylene methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, ethylene glycol dimethacrylate, dipentaerythritol hexaacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, and the like. it can. As oligomers and prepolymers, polyester acrylate, polyurethane acrylate, polyfunctional urethane acrylate, epoxy acrylate, polyether acrylate, acrylate compounds such as alkit acrylate, melamine acrylate, silicone acrylate, unsaturated polyester, tetramethylene glycol diglycidyl ether, Epoxy compounds such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A diglycidyl ether and various alicyclic epoxies, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[((3- Oxeta such as ethyl-3-oxetanyl) methoxy] methyl} benzene, di [1-ethyl (3-oxetanyl)] methyl ether Mention may be made of the compound. These can be used alone or in combination.
Among these ionizing radiation curable resins, polyfunctional monomers having 3 or more (meth) acryloyloxy groups and polyfunctional urethane acrylates can increase the curing speed and improve the hardness of the cured product. Also, when used by mixing with a conductive material, highly crosslinked intramolecular chain to conductive material is fixed, it becomes defect occurs hardly dropout or the like of the conductive material component by saponification and light resistance tests, There is an effect that a decrease in conductivity due to a saponification treatment and a decrease in antistatic property due to a light resistance test are less likely to occur.
In addition, when polyfunctional urethane acrylate is used, the hardness and flexibility of the cured product can be imparted, and further, the effect of increasing the viscosity when formed into a paint can be imparted. Can be improved.
電離放射線硬化型樹脂として、電離放射線硬化型フッ化アクリレートを使用することができる。電離放射線硬化型フッ化アクリレートは、他のフッ化アクリレートと比較して電離放射線硬化型であることにより、分子間での架橋が起きるため耐薬品性に優れ、ケン化処理後にも十分な防汚性を発現するといった効果が奏される。
導電材料と混合して使用した場合には、フッ化アクリレートのフッ素成分が光学機能層の表層付近に偏在することにより、ケン化処理や耐光性試験による導電材料成分の脱落等の不具合が起こりにくくなり、ケン化処理による帯電防止性の低下や耐光性試験による帯電防止性の低下が起こりにくくなるといった効果が奏される。ここで、図1を用いて「表層」を説明する。図1は透光性基体10上に、光学機能層20が積層されてなる光学積層体1である。なお、図1においては光学機能層の一例として防眩層を記載している。光学機能層として防眩層を具備した光学積層体は防眩性を有する防眩フィルムとして使用することができるため好ましい。透光性基体10に対して、光学機能層20の距離が離れている面側が表層21である。
ここで、フッ素系の界面活性剤を電離放射線硬化型フッ化アクリレートに置き換えて使用した場合、(1)フッ素成分が過剰に表面にブリードアウトし導電剤の機能を損ねる、(2)フッ素系界面活性剤が電離放射線硬化型でないため、ケン化処理時に成分が脱落し、併せて導電成分の脱落も生じ帯電防止性が消失する等の不具合が生じる。
電離放射線硬化型フッ化アクリレートとしては、例えば、2−(パーフルオロデシル)エチルメタクリレート、2−(パーフルオロ−7−メチルオクチル)エチルメタクリレート、3−(パーフルオロ−7−メチルオクチル)−2−ヒドロキシプロピルメタクリレート、2−(パーフルオロ−9−メチルデシル)エチルメタクリレート、3−(パーフルオロ−8−メチルデシル)−2−ヒドロキシプロピルメタクリレート、3−パーフルオロオクチル−2−ヒドロキシルプロピルアクリレート、2−(パーフルオロデシル)エチルアクリレート、2−(パーフルオロ−9−メチルデシル)エチルアクリレート、ペンタデカフルオロオクチル(メタ)アクリレート、ウナデカフルオロヘキシル(メタ)アクリレート、ノナフルオロペンチル(メタ)アクリレート、ヘプタフルオロブチル(メタ)アクリレート、オクタフルオロペンチル(メタ)アクリレート、ペンタフルオロプロピル(メタ)アクリレート、トリフルオロ(メタ)アクリレート、トリフルオロイソプロピル(メタ)アクリレート、トリフルオロエチル(メタ)アクリレート、下記化合物(i)〜(xxx)などを用いることができる。尚、下記化合物はいずれもアクリレートの場合を示したものであり、式中のアクリロイル基はいずれもメタクリロイル基に変更可能である。
An ionizing radiation curable fluorinated acrylate can be used as the ionizing radiation curable resin. Ionizing radiation curable fluorinated acrylates are ionizing radiation curable compared to other fluorinated acrylates, resulting in excellent chemical resistance due to cross-linking between molecules and sufficient antifouling even after saponification treatment. The effect of expressing sex is achieved.
When used in admixture with conductive materials, by fluorine component fluorinated acrylate is unevenly distributed in the vicinity of the surface layer of the optical functional layer, defect occurs hardly dropout or the like of the conductive material component by saponification and light resistance test Thus, there is an effect that a decrease in antistatic property due to saponification treatment and a decrease in antistatic property due to a light resistance test are less likely to occur. Here, the “surface layer” will be described with reference to FIG. FIG. 1 shows an optical laminate 1 in which an optical functional layer 20 is laminated on a translucent substrate 10. In FIG. 1, an antiglare layer is shown as an example of the optical functional layer. An optical laminate having an antiglare layer as the optical functional layer is preferable because it can be used as an antiglare film having antiglare properties. The surface side where the distance of the optical functional layer 20 is separated from the translucent substrate 10 is the surface layer 21.
Here, when the fluorosurfactant is replaced with ionizing radiation curable fluorinated acrylate, (1) the fluorine component excessively bleeds out to the surface and impairs the function of the conductive agent. (2) Fluorine interface Since the activator is not an ionizing radiation curable type, the components are dropped during the saponification treatment, and the conductive components are also dropped, resulting in the loss of antistatic properties.
Examples of the ionizing radiation curable fluorinated acrylate include 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluoro-7-methyloctyl) ethyl methacrylate, 3- (perfluoro-7-methyloctyl) -2- Hydroxypropyl methacrylate, 2- (perfluoro-9-methyldecyl) ethyl methacrylate, 3- (perfluoro-8-methyldecyl) -2-hydroxypropyl methacrylate, 3-perfluorooctyl-2-hydroxylpropyl acrylate, 2- (per Fluorodecyl) ethyl acrylate, 2- (perfluoro-9-methyldecyl) ethyl acrylate, pentadecafluorooctyl (meth) acrylate, unadecafluorohexyl (meth) acrylate, nonafluoropentyl (meth) ) Acrylate, heptafluorobutyl (meth) acrylate, octafluoropentyl (meth) acrylate, pentafluoropropyl (meth) acrylate, trifluoro (meth) acrylate, trifluoroisopropyl (meth) acrylate, trifluoroethyl (meth) acrylate, The following compounds (i) to (xxx) can be used. The following compounds all show the case of acrylate, and any acryloyl group in the formula can be changed to a methacryloyl group.
これらは、単独若しくは複数種類混合して使用することも可能である。フッ化アクリレートの内、ウレタン結合を持つフッ化アルキル基含有ウレタンアクリレートが、硬化物の耐スクラッチ性と伸び及び柔軟性の点より好ましい。また、フッ化アクリレートの中でも、多官能フッ化アクリレートが好適である。尚、ここでの多官能フッ化アクリレートとは2個以上(好適には3個以上、より好適には4個以上)の(メタ)アクリロイルオキシ基を有するものを意味する。 These can be used alone or in combination. Of the fluorinated acrylates, a fluorinated alkyl group-containing urethane acrylate having a urethane bond is preferred from the viewpoint of scratch resistance, elongation and flexibility of the cured product. Of the fluorinated acrylates, polyfunctional fluorinated acrylates are preferred. Here, the polyfunctional fluorinated acrylate means one having 2 or more (preferably 3 or more, more preferably 4 or more) (meth) acryloyloxy groups.
電離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。なお、用いられる放射線としては、紫外線、可視光線、赤外線、電子線のいずれであってもよい。また、これらの放射線は、偏光であっても無偏光であってもよい。
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 ionizing radiation curable resin can be cured by irradiation with an electron beam as it is, but in the case of curing by ultraviolet irradiation, it is necessary to add a photopolymerization initiator. In addition, as a radiation used, any of an ultraviolet-ray, visible light, infrared rays, and an electron beam may be sufficient. Further, these radiations may be polarized or non-polarized.
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.
また、電離放射線硬化型樹脂にレベリング剤等の添加剤を含有させることができる。レベリング剤は、塗膜表面の張力均一化を図り塗膜形成前に欠陥を直す働きがあり、上記電離放射線硬化型樹脂より界面張力、表面張力共に低い物質が用いられる。 Moreover, additives, such as a leveling agent, can be contained in ionizing radiation curable resin. The leveling agent has a function of uniforming the tension on the surface of the coating film and correcting defects before forming the coating film, and a substance having a lower interfacial tension and surface tension than the ionizing radiation curable resin is used.
電離放射線硬化型樹脂等の樹脂成分の配合量は、光学機能層を構成する樹脂組成物中の固形成分の全質量に対して、50質量%以上含有され、60質量%以上が好適である。上限値は特に限定されないが、例えば、99.6質量%である。50質量%未満では、十分な硬度が得られないなどの問題がある。
なお、電離放射線硬化型樹脂等の樹脂成分の固形分には、後述する無機成分以外の全固形分が含まれてなるものであって、電離放射線硬化型樹脂等の樹脂成分の固形分のみならず、その他の任意成分の固形分も含む。
The compounding amount of the resin component such as ionizing radiation curable resin is 50% by mass or more, and preferably 60% by mass or more with respect to the total mass of the solid component in the resin composition constituting the optical functional layer. Although an upper limit is not specifically limited, For example, it is 99.6 mass%. If it is less than 50% by mass, there is a problem that sufficient hardness cannot be obtained.
The solid content of the resin component such as ionizing radiation curable resin includes all solid content other than the inorganic component described later, and only the solid content of the resin component such as ionizing radiation curable resin. In addition, the solid content of other optional components is included.
[導電材料]
本発明の光学機能層は導電材料を含む。導電材料の添加により、光学積層体の表面における塵埃付着を有効に防止することができる。導電材料の具体例としては、第4級アンモニウム塩、ピリジニウム塩、第1〜第3アミノ基等のカチオン性基を有する各種のカチオン性化合物、スルホン酸塩基、硫酸エステル塩基、リン酸エステル塩基、ホスホン酸塩基等のアニオン性基を有するアニオン性化合物、アミノ酸系、アミノ硫酸エステル系等の両性化合物、アミノアルコール系、グリセリン系、ポリエチレングリコール系等のノニオン性化合物、スズおよびチタンのアルコキシドのような有機金属化合物およびそれらのアセチルアセトナート塩のような金属キレート化合物等が挙げられ、さらに上記に列記した化合物を高分子量化した化合物が挙げられる。また、第3級アミノ基、第4級アンモニウム基、または金属キレート部を有し、かつ、電離放射線により重合可能なモノマーまたはオリゴマー、或いは官能基を有するカップリング剤のような有機金属化合物等の重合性化合物もまた帯電防止剤として使用できる。
[Conductive material]
The optical functional layer of the present invention contains a conductive material. The addition of the conductive material, it is possible to effectively prevent the dust deposition on the surface of the optical stack. Specific examples of conductive materials include quaternary ammonium salts, pyridinium salts, various cationic compounds having a cationic group such as primary to tertiary amino groups, sulfonate groups, sulfate ester bases, phosphate ester bases, anionic compounds having an anionic group such as phosphonate, such as amino acid-based, amphoteric compounds such as amino acid esters, amino alcohols, glycerin-based, nonionic compounds such as polyethylene glycol-based, tin and titanium alkoxide Examples thereof include metal chelate compounds such as organometallic compounds and acetylacetonate salts thereof, and compounds obtained by increasing the molecular weight of the compounds listed above. In addition, a monomer or oligomer having a tertiary amino group, a quaternary ammonium group, or a metal chelate portion and polymerizable by ionizing radiation, or an organometallic compound such as a coupling agent having a functional group, etc. Polymerizable compounds can also be used as antistatic agents.
また、導電性微粒子が挙げられる。導電性微粒子の具体例としては、金属酸化物からなるものを挙げることができる。そのような金属酸化物としては、ZnO、CeO2、Sb2O2、Sb2O3、Sb2O5、SnO2、ITOと略して呼ばれることの多い酸化インジウム錫、In2O3、Al2O3、アンチモンドープ酸化錫(略称;ATO)、アルミニウムドープ酸化亜鉛(略称;AZO)等を挙げることができる。微粒子とは、1ミクロン以下の、いわゆるサブミクロンの大きさのものを指し、好ましくは、平均粒径が0.1nm〜0.1μmのものである。 Moreover, electroconductive fine particles are mentioned. Specific examples of the conductive fine particles include those made of a metal oxide. Examples of such metal oxides include ZnO, CeO 2 , Sb 2 O 2 , Sb 2 O 3 , Sb 2 O 5 , SnO 2 , and indium tin oxide, which is often abbreviated as ITO, In 2 O 3 , Al 2 O 3 , antimony-doped tin oxide (abbreviation: ATO), aluminum-doped zinc oxide (abbreviation: AZO), and the like can be given. The fine particles refer to those having a so-called submicron size of 1 micron or less, and preferably those having an average particle size of 0.1 nm to 0.1 μm.
また、導電材料の別の具体例としては、π共役系導電性高分子が挙げられる。π共役系導電性高分子は、主鎖がπ共役系で構成されている高分子であれば特に限定されず、例えば、脂肪族共役系のポリアセチレン、ポリアセン、ポリアズレン、芳香族共役系のポリフェニレン、複素環式共役系のポリピロール、ポリチオフェン、ポリイソチアナフテン、含ヘテロ原子共役系のポリアニリン、ポリチエニレンビニレン、混合型共役系のポリ(フェニレンビニレン)、分子中に複数の共役鎖を持つ共役系である複鎖型共役系、これらの導電性ポリマーの誘導体、及び、これらの共役高分子鎖を飽和高分子にグラフトまたはブロック共重した高分子である導電性複合体からなる群より選択される少なくとも一種を挙げることができる。なかでも、ポリチオフェン、ポリアニリン、ポリピロール等の共役系導電性高分子を使用することがより好ましい。上記π共役系導電性高分子を使用することによって、優れた帯電防止性能を発揮すると同時に、光学積層体の全光線透過率を高めるとともにヘイズ値を下げることも可能になる。また、導電性向上や、帯電防止性能向上を目的として、有機スルホン酸や塩化鉄等の陰イオンを、ドーパント(電子供与剤)として添加し、複合体として使用することもできる。ドーパント添加効果も踏まえ、特にπ共役系導電性高分子と高分子ドーパントとの複合体は透明性、帯電防止性が高く、好ましい。
π共役系導電性高分子と高分子ドーパントの複合体として、ポリスチレンスルホン酸ドープポリ(3,4−エチレンジオキシチオフェン)(PEDOT−PSSと略す)は、比較的熱安定性が高く、塗膜成形後の透明性が有利となる点で好ましい。
導電材料は、樹脂組成物中の固形成分の全質量に対して、0.3〜20.0質量%が必須に含有され、0.5〜15.0質量%が特に好適である。導電材料の配合量が0.3質量%よりも少ないと、帯電防止性が発現しにくくなる。導電材料の配合量が20質量%よりも多いと、透明性が損なわれる恐れが有る。
ここで、π共役系導電性高分子と高分子ドーパントの複合体を電離放射線硬化型樹脂と混合し放射線により硬化させた場合、複合体が光学機能層中(面内及び深さ方向)に均一に分散し、ケン化処理や耐光性試験による帯電防止性の低下が起こりにくいという効果を奏する。さらに、電離放射線硬化型樹脂として、1分子中に3(より好ましくは4、更に好ましくは5)個以上の(メタ)アクリロイルオキシ基を有する単量体もしくはオリゴマー、プレポリマーで、例えば多官能アクリレート、多官能ウレタンアクリレートまたは多官能フッ化アクリレートとを混合して使用することにより、放射線硬化後は強固に架橋した樹脂成分の分子の隙間にπ共役系導電性高分子と高分子ドーパントの複合体が固定されることにより、ケン化処理や耐光性試験による帯電防止性の低下がおこりにくくなる。また、π共役系導電性高分子と高分子ドーパントの複合体が光学機能層の表層付近に偏在せず、厚さ方向にも適度に分散することにより、耐光性試験による帯電防止性の低下が抑制できる。
導電材料のうちπ共役系導電性高分子と高分子ドーパントの複合体は、他の導電材料に比べ比較的少ない添加量で帯電防止性が得られる。このため、防眩性を付与するための透光性微粒子や凝集により凹凸を形成することができる無機成分との混合が比較的容易にできる点から好ましい。
耐光性試験による帯電防止性の低下を改善するために、樹脂成分と導電材料の混合物に紫外線吸収剤を添加する方法がある。しかしながら、この方法では樹脂成分として硬度が優れる電離放射線硬化型樹脂を使用した場合、紫外線の照射による硬化を妨げられるという不具合が生じるため、光学積層体に求められる耐スクラッチ性が減少しやすくなる。本発明では、紫外線吸収剤を使わずとも耐光性による帯電防止性の低下を抑制できるため、従来困難であった耐スクラッチ性と帯電防止性を両立することができる。
As another specific example of the conductive materials include π-conjugated conductive polymer. The π-conjugated conductive polymer is not particularly limited as long as the main chain is a polymer composed of π-conjugated system. For example, aliphatic conjugated polyacetylene, polyacene, polyazulene, aromatic conjugated polyphenylene, Heterocyclic conjugated polypyrrole, polythiophene, polyisothianaphthene, heteroatom-containing polyaniline, polythienylene vinylene, mixed conjugated poly (phenylene vinylene), conjugated systems with multiple conjugated chains in the molecule Selected from the group consisting of a double-chain conjugated system, a derivative of these conductive polymers, and a conductive complex that is a polymer obtained by grafting or block-copolymerizing these conjugated polymer chains to a saturated polymer. At least one can be mentioned. Among these, it is more preferable to use a conjugated conductive polymer such as polythiophene, polyaniline, and polypyrrole. By using the π-conjugated conductive polymer, excellent antistatic performance can be exhibited, and at the same time, the total light transmittance of the optical laminate can be increased and the haze value can be decreased. In addition, for the purpose of improving conductivity and antistatic performance, anions such as organic sulfonic acid and iron chloride can be added as a dopant (electron donor) and used as a composite. In consideration of the effect of dopant addition, a composite of a π-conjugated conductive polymer and a polymer dopant is particularly preferable because of its high transparency and antistatic properties.
Polystyrene sulfonate doped poly (3,4-ethylenedioxythiophene) (abbreviated as PEDOT-PSS) as a complex of π-conjugated conductive polymer and polymer dopant has relatively high thermal stability and coating film formation. This is preferable in that later transparency is advantageous.
The conductive material essentially contains 0.3 to 20.0 mass% with respect to the total mass of solid components in the resin composition, and 0.5 to 15.0 mass% is particularly preferable. If the amount of the conductive material is less than 0.3 wt%, the antistatic property is hardly exhibited. When the blending amount of the conductive material is more than 20% by mass, the transparency may be impaired.
Here, when a complex of π-conjugated conductive polymer and polymer dopant is mixed with ionizing radiation curable resin and cured by radiation, the complex is uniform in the optical functional layer (in-plane and in the depth direction). The antistatic property is hardly lowered by the saponification treatment or the light resistance test. Further, as an ionizing radiation curable resin, a monomer, oligomer, or prepolymer having 3 (more preferably 4, more preferably 5) or more (meth) acryloyloxy groups in one molecule, such as a polyfunctional acrylate Using a mixture of polyfunctional urethane acrylate or polyfunctional fluorinated acrylate, a composite of a π-conjugated conductive polymer and a polymeric dopant in the gaps between the resin component molecules that are strongly crosslinked after radiation curing By fixing the antistatic property, the antistatic property is hardly lowered by the saponification treatment or the light resistance test. In addition, the composite of the π-conjugated conductive polymer and the polymer dopant is not unevenly distributed near the surface layer of the optical functional layer and is appropriately dispersed in the thickness direction, thereby reducing the antistatic property by the light resistance test. Can be suppressed.
Among the conductive materials, a composite of a π-conjugated conductive polymer and a polymer dopant can provide antistatic properties with a relatively small addition amount compared to other conductive materials. For this reason, it is preferable from the point that mixing with the translucent fine particle for providing anti-glare property and the inorganic component which can form an unevenness | corrugation by aggregation is comparatively easy.
There is a method of adding an ultraviolet absorber to a mixture of a resin component and a conductive material in order to improve a decrease in antistatic property due to a light resistance test. However, in this method, when an ionizing radiation curable resin having excellent hardness is used as the resin component, there is a problem that curing due to irradiation of ultraviolet rays is hindered, so that the scratch resistance required for the optical laminate tends to decrease. In the present invention, since a decrease in antistatic property due to light resistance can be suppressed without using an ultraviolet absorber, both scratch resistance and antistatic property, which have been difficult in the past, can be achieved.
[透光性微粒子]
光学機能層に透光性微粒子を含有させることで、光学機能層の表層に凹凸を形成させることができる。透光性微粒子としては、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樹脂微粒子、シリカ、アルミナ、チタニア、ジルコニア、酸化カルシウム、酸化錫、酸化インジウム、酸化アンチモン等の無機系透光性微粒子を使用することができる。
透光性微粒子の屈折率は、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樹脂マトリックスとの屈折率差が大きくなり過ぎ、全光線透過率が低下する。また、透光性微粒子と樹脂成分との屈折率の差は、0.2以下が好ましい。透光性微粒子の平均粒径は、0.3〜10μmの範囲のものが好ましく、1〜8μmがより好ましい。粒径が0.3μmより小さい場合は防眩性が低下するため、また10μmより大きい場合は、ギラツキを発生すると共に、表面凹凸の程度が大きくなり過ぎて表面が白っぽくなってしまうため好ましくない。また、上記樹脂中に含まれる透光性微粒子の割合は特に限定されないが、樹脂組成物100質量部に対し、1〜20質量部とするのが防眩機能、ギラツキ等の特性を満足する上で好ましく、樹脂層表面の微細な凹凸形状とヘイズ値をコントロールし易い。ここで、「屈折率」は、JIS K−7142に従った測定値を指す。また、「平均粒径」は、電子顕微鏡で実測した100個の粒子の直径の平均値を指す。
[Translucent fine particles]
By including translucent fine particles in the optical functional layer, irregularities can be formed on the surface layer of the optical functional layer. As the translucent fine particles, organic translucent resin fine particles made of acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyethylene resin, epoxy resin, silicone resin, polyvinylidene fluoride, polyfluoroethylene resin, silica, Inorganic light-transmitting fine particles such as alumina, titania, zirconia, calcium oxide, tin oxide, indium oxide, and antimony oxide can be used.
The refractive index of the translucent 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 resin matrix becomes large. Too much, the total light transmittance decreases. Further, the difference in refractive index between the translucent fine particles and the resin component is preferably 0.2 or less. The average particle diameter of the translucent fine particles is preferably in the range of 0.3 to 10 μm, and more preferably 1 to 8 μm. When the particle size is smaller than 0.3 μm, the antiglare property is lowered. When the particle size is larger than 10 μm, it is not preferable because glare occurs and the surface unevenness becomes too large and the surface becomes whitish. Further, the ratio of the light-transmitting fine particles contained in the resin is not particularly limited, but 1 to 20 parts by mass with respect to 100 parts by mass of the resin composition is sufficient for satisfying characteristics such as an antiglare function and glare. Preferably, it is easy to control the fine uneven shape and haze value on the surface of the resin layer. Here, "refractive index" refers to the measurements in accordance with JIS K-7142. Further, “average particle diameter” refers to an average value of the diameters of 100 particles actually measured with an electron microscope.
[凝集により凹凸を形成することができる無機成分]
また、本発明の光学機能層は無機成分の凝集を利用して凹凸を形成し作製することができる。用いられる無機成分としては、光学機能層中に含有され、製膜時に凝集し表面凹凸を形成するものであればよい。無機成分としては、シリカゾル、ジルコニアゾルなどの金属酸化物ゾル、アエロジル、膨潤性粘土、層状有機粘土などがある。これらの無機成分の中でも、安定的に表面凹凸を形成できる点より、層状有機粘土が好ましい。層状有機粘土が安定的に表面凹凸を形成できる理由としては、層状有機粘土が樹脂成分(有機物成分)と相溶性が高く、凝集性をも有しているため、第一の相と第二の相が入り組んだ構造を形成しやすく、製膜時に表面凹凸を形成しやすくなることが挙げられる。
本発明において、層状有機粘土とは、膨潤性粘土の層間に有機オニウムイオンを導入したものをいう。層状有機粘土は、特定の溶媒に対して分散性が低く、光学機能層形成用塗料として層状有機粘土および特定の性質を具備した溶媒を使用すると、当該溶媒の選択により、光学機能層に微粒子を含有させることなく、表面凹凸を有する光学機能層を形成する。
[Inorganic component capable of forming irregularities by aggregation]
Further, the optical functional layer of the present invention can be produced by forming irregularities by utilizing aggregation of inorganic components. Any inorganic component may be used as long as it is contained in the optical functional layer and aggregates during film formation to form surface irregularities. Examples of the inorganic component include metal oxide sols such as silica sol and zirconia sol, aerosil, swellable clay, and layered organic clay. Among these inorganic components, layered organic clay is preferable from the viewpoint that surface irregularities can be stably formed. The reason why the layered organic clay can stably form surface irregularities is that the layered organic clay is highly compatible with the resin component (organic component) and also has cohesiveness. It is easy to form an intricate structure, and surface irregularities can be easily formed during film formation.
In the present invention, the layered organic clay refers to an organic onium ion introduced between the layers of the swellable clay. The layered organic clay has low dispersibility with respect to a specific solvent. When a layered organic clay and a solvent having specific properties are used as a coating material for forming an optical functional layer, fine particles are formed in the optical functional layer by selecting the solvent. An optical functional layer having surface irregularities is formed without inclusion.
(膨潤性粘土)
膨潤性粘土は、陽イオン交換能を有し、該膨潤性粘土の層間に水を取り込んで膨潤するものであればよく、天然物であっても合成物(置換体、誘導体を含む)であってもよい。また、天然物と合成物との混合物であってもよい。
膨潤性粘土としては、例えば、雲母、合成雲母、バーミキュライト、モンモリロナイト、鉄モンモリロナイト、バイデライト、サポナイト、ヘクトライト、スチーブンサイト、ノントロナイト、マガディアイト、アイラライト、カネマイト、層状チタン酸、スメクタイト、合成スメクタイト等を挙げることができる。これらの膨潤性粘土は、1種を使用してもよいし、複数を混合して使用してもよい。
(Swelling clay)
The swellable clay is not limited as long as it has a cation exchange ability and swells by taking water between the layers of the swellable clay. Even if it is a natural product, it is a synthetic product (including substitution products and derivatives). May be. Moreover, the mixture of a natural product and a synthetic product may be sufficient.
Examples of the swellable clay include mica, synthetic mica, vermiculite, montmorillonite, iron montmorillonite, beidellite, saponite, hectorite, stevensite, nontronite, magadiite, isallite, kanemite, layered titanic acid, smectite, and synthetic smectite. Etc. These swellable clays may be used alone or in combination.
(有機オニウムイオン)
有機オニウムイオンは、膨潤性粘土の陽イオン交換性を利用して有機化することができるものであれば制限されない。
オニウムイオンとしては、例えば、ジメチルジステアリルアンモニウム塩やトリメチルステアリルアンモニウム塩などの第4級アンモニウム塩や、ベンジル基やポリオキシエチレン基を有するアンモニウム塩を用いたり、ホスホニウム塩やピリジニウム塩やイミダゾリウム塩からなるイオンを用いたりすることができる。塩としては、例えば、Cl−、Br−、NO3 −、OH−、CH3COO−等の陰イオンとの塩を挙げることができる。塩としては、第4級アンモニウム塩を使用することが好ましい。
有機オニウムイオンの官能基は制限されないが、アルキル基、ベンジル基、ポリオキシプロピレン基またはフェニル基のいずれかを含む材料を使用すると、防眩性を発揮させやすくなるため好ましい。
(Organic onium ion)
The organic onium ion is not limited as long as it can be organicized using the cation exchange property of the swellable clay.
Examples of onium ions include quaternary ammonium salts such as dimethyl distearyl ammonium salt and trimethyl stearyl ammonium salt, ammonium salts having a benzyl group or a polyoxyethylene group, phosphonium salts, pyridinium salts, and imidazolium salts. The ion which consists of can be used. Examples of the salt include salts with anions such as Cl − , Br − , NO 3 − , OH − , and CH 3 COO − . As the salt, a quaternary ammonium salt is preferably used.
The functional group of the organic onium ion is not limited, but it is preferable to use a material containing any one of an alkyl group, a benzyl group, a polyoxypropylene group, and a phenyl group because antiglare properties are easily exhibited.
アルキル基の好ましい範囲は、炭素数1〜30であり、例えばメチル、エチル、プロピル、イソプロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、オクタデシル等が挙げられる。 The preferred range of the alkyl group is 1 to 30 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, octadecyl, etc. Is mentioned.
ポリオキシプロピレン基〔(CH2CH(CH3)O)nH又は(CH2CH2CH2O)nH〕のnの好ましい範囲は1〜50であり、さらに好ましくは5〜50であり、その付加モル数が多いほど、有機溶媒に対する分散性は良くなるが、過剰になり過ぎると、生成物が粘着性を帯びるようになるので、溶媒に対する分散性に重点をおけばnの数は、20〜50がより好ましい。また、nの数が5〜20である場合には、生成物が非粘着性で粉砕性がすぐれている。また、分散性とハンドリングの点から、第4級アンモニウム全体のnの総数は5〜50が好ましい。 The preferable range of n in the polyoxypropylene group [(CH 2 CH (CH 3 ) O) n H or (CH 2 CH 2 CH 2 O) n H] is 1 to 50, more preferably 5 to 50. The more the number of moles added, the better the dispersibility in the organic solvent, but if it is too much, the product will become sticky, so if the emphasis is placed on the dispersibility in the solvent, the number of n is 20-50 are more preferable. Moreover, when the number of n is 5-20, a product is non-adhesive and the grindability is excellent. Further, from the viewpoint of dispersibility and handling, the total number of n in the quaternary ammonium is preferably 5-50.
該第4級アンモニウム塩の具体的例としては、テトラアルキルアンモニウムクロリド、テトラアルキルアンモニウムブロミド、ポリオキシプロピレン・トリアルキルアンモニウムクロリド、ポリオキシプロピレン・トリアルキルアンモニウムブロミド、ジ(ポリオキシプロピレン)・ジアルキルアンモニウムクロリド、ジ(ポリオキシプロピレン)・ジアルキルアンモニウムブロミド、トリ(ポリオキシプロピレン)・アルキルアンモニウムクロリド、トリ(ポリオキシプロピレン)・アルキルアンモニウムブロミド等を挙げることができる。 Specific examples of the quaternary ammonium salt include tetraalkylammonium chloride, tetraalkylammonium bromide, polyoxypropylene / trialkylammonium chloride, polyoxypropylene / trialkylammonium bromide, di (polyoxypropylene) / dialkylammonium. Examples thereof include chloride, di (polyoxypropylene) · dialkylammonium bromide, tri (polyoxypropylene) · alkylammonium chloride, tri (polyoxypropylene) · alkylammonium bromide and the like.
一般式(I)の第4級アンモニウムイオンにおいて、R1で好ましいものはメチル基又はベンジル基である。R2で好ましいものは炭素数1〜12のアルキル基であり、特に好ましいものは炭素数1〜4のアルキル基である。R3で好ましいものは炭素数1〜25のアルキル基である。R4で好ましいものは炭素数1〜25のアルキル基、(CH2CH(CH3)O)nH基又は(CH2CH2CH2O)nH基である。nは5〜50であるものが好ましい。 In the quaternary ammonium ion of the general formula (I), R 1 is preferably a methyl group or a benzyl group. R 2 is preferably an alkyl group having 1 to 12 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms. R 3 is preferably an alkyl group having 1 to 25 carbon atoms. R 4 is preferably an alkyl group having 1 to 25 carbon atoms, a (CH 2 CH (CH 3 ) O) n H group or a (CH 2 CH 2 CH 2 O) n H group. n is preferably 5 to 50.
層状有機粘土の配合量は、樹脂組成物中の固形成分の全質量に対して、0.1〜10質量%が含有され、0.2〜5質量%が特に好適である。層状有機粘土の配合量が0.1質量%では十分な数の表面凹凸が形成されなくなり防眩性が不十分になる問題がある。層状有機粘土の配合量が10質量%超では、表面凹凸数が多くなり、視認性が損なわれる問題がある。 The compounding amount of the layered organic clay is 0.1 to 10% by mass and particularly preferably 0.2 to 5% by mass with respect to the total mass of the solid components in the resin composition. When the blending amount of the layered organic clay is 0.1% by mass, a sufficient number of surface irregularities are not formed and the antiglare property is insufficient. When the blending amount of the layered organic clay exceeds 10% by mass, the number of surface irregularities increases and there is a problem that visibility is impaired.
溶剤としては、防眩性を得るための表面凹凸を形成させる溶媒としては、第1の溶媒および第2の溶媒を含有することが好ましい。
上記の本発明の樹脂組成物に、第1の溶媒および第2の溶媒を加えることによって、本発明の光学機能層を形成することができる塗料とすることができる。本発明の光学機能層を形成することができる塗料は上記の第1の溶媒と第2の溶媒を含有してなるため、従来光学機能層の表面凹凸形状を作成するために必須と考えられていた微粒子を添加せずとも、光学機能層の表面凹凸形状を作成することができるものである。
As a solvent, it is preferable to contain the 1st solvent and the 2nd solvent as a solvent which forms the surface unevenness | corrugation for obtaining anti-glare property.
By adding the first solvent and the second solvent to the above-described resin composition of the present invention, a coating material that can form the optical functional layer of the present invention can be obtained. Since the coating material capable of forming the optical functional layer of the present invention contains the first solvent and the second solvent described above, it has been conventionally considered essential for creating the uneven surface shape of the optical functional layer. without addition of fine particles, it is capable of creating a surface irregularity shape of the optical functional layer.
第1の溶媒とは、層状有機粘土に実質的に濁りを生じさせずに、透明性を有した状態で分散させることができるものをいう。実質的に濁りを生じないとは、全く濁りが生じないものに加え、濁りが生じていないと同視しうるものも含むものである。第1の溶媒として具体的には、層状有機粘土100質量部に対して、1000質量部の第1の溶媒を添加して混合した混合液のヘイズ値が10%以下のものをいう。第1の溶媒を添加して混合した混合液のヘイズ値は8%以下であることが好ましく、6%以下であることがさらに好ましい。なお、混合液のヘイズ値の下限値は特に限定されないが、例えば、0.1%である。
第1の溶媒としては、例えば、いわゆる極性の小さい溶媒(非極性溶媒)を使用することができる。これは、層状有機粘土は有機化処理しているため、上記溶媒によって分散しやすくなるためである。層状有機粘土の種類によって使用できる第1の溶媒は異なるが、例えば、層状有機粘土として合成スメクタイトを使用した場合、第1の溶媒としては、ベンゼン、トルエン、キシレン等の芳香族溶剤を使用することができる。これらの第1の溶媒は一種で使用しても複数を混合して使用してもよい。
A 1st solvent means what can be disperse | distributed in the state with transparency, without producing turbidity substantially in layered organic clay. “Substantially no turbidity” includes not turbidity at all, but also includes those that can be regarded as not turbid. Specifically, the first solvent is one having a haze value of 10% or less of a mixed solution obtained by adding 1000 parts by mass of the first solvent to 100 parts by mass of the layered organic clay. The haze value of the mixed solution obtained by adding and mixing the first solvent is preferably 8% or less, and more preferably 6% or less. The lower limit of the haze value of the mixture is not particularly limited, for example, 0.1%.
As the first solvent, for example, a so-called small-polar solvent (nonpolar solvent) can be used. This is because the layered organoclay is organically treated and thus easily dispersed by the solvent. The first solvent that can be used differs depending on the type of layered organic clay, but for example, when synthetic smectite is used as the layered organic clay, an aromatic solvent such as benzene, toluene, xylene, etc. should be used as the first solvent. Can do. These first solvents may be used alone or in combination.
第2の溶媒とは、層状有機粘土に濁りを生じさせた状態で分散させることができるものをいう。第2の溶媒として具体的には、層状有機粘土100質量部に対して、1000質量部の第2の溶媒を添加して混合した混合液のヘイズ値が30%以上のものをいう。第2の溶媒を添加して混合した混合液のヘイズ値は40%以上であることが好ましく、50%以上であることがさらに好ましい。なお、混合液のヘイズ値の上限値は特に限定されないが、例えば、99%である。
第2の溶媒としては、例えば、いわゆる極性溶媒を使用することができる。これは、層状有機粘土は有機化処理しているため、上記溶媒によって分散しにくくなるためである。層状有機粘土の種類によって使用できる第2の溶媒は異なるが、例えば、層状有機粘土として合成スメクタイトを使用した場合、第2の溶媒としては水、メタノール、エタノール、プロパノール、イソプロパノール、メチルエチルケトン、イソプロピルアルコール等を使用することができる。これらの第2の溶媒は一種で使用しても複数を混合して使用してもよい。
A 2nd solvent means what can be disperse | distributed in the state which made the layered organic clay turbid. Specifically, the second solvent is one having a haze value of 30% or more of a mixed solution obtained by adding 1000 parts by mass of the second solvent to 100 parts by mass of the layered organic clay. The haze value of the mixed solution obtained by adding the second solvent and mixing is preferably 40% or more, and more preferably 50% or more. In addition, although the upper limit of the haze value of a liquid mixture is not specifically limited, For example, it is 99%.
As the second solvent, for example, a so-called polar solvent can be used. This is because the layered organoclay has been organically treated and thus is difficult to disperse by the solvent. The second solvent that can be used differs depending on the type of layered organic clay, but for example, when synthetic smectite is used as the layered organic clay, the second solvent is water, methanol, ethanol, propanol, isopropanol, methyl ethyl ketone, isopropyl alcohol, etc. Can be used. These second solvents may be used alone or in combination.
ここで、第1の溶媒および第2の溶媒を混合して使用すると、防眩性を得るための表面凹凸を形成させやすくなるため好ましい。第1の溶媒と第2の溶媒の混合比としては質量比で、10:90〜90:10の範囲であれば、防眩性を得るための表面凹凸を形成させやすくなるため好ましい。第1の溶媒と第2の溶媒の混合比としては質量比で、15:85〜85:15の範囲であることが好ましく、20:80〜80:20の範囲であることが好ましい。第1の溶媒が10質量部未満では未溶解物による外観欠点が発生する問題がある。第1の溶媒が90質量部超では十分な防眩性を得るための表面凹凸が得られない問題がある。 Here, it is preferable to use a mixture of the first solvent and the second solvent because surface irregularities for obtaining antiglare properties can be easily formed. The mixing ratio of the first solvent and the second solvent is preferably a mass ratio in the range of 10:90 to 90:10 because surface irregularities for obtaining antiglare properties can be easily formed. The mixing ratio of the first solvent and the second solvent is preferably in the range of 15:85 to 85:15, and more preferably in the range of 20:80 to 80:20, by mass ratio. If the first solvent is less than 10 parts by mass, there is a problem in that appearance defects due to undissolved substances occur. If the first solvent exceeds 90 parts by mass, there is a problem that surface irregularities for obtaining sufficient antiglare property cannot be obtained.
また、樹脂組成物と、溶媒(第1の溶媒と第2の溶媒を合わせたもの)の配合量は質量比で、70:30〜30:70の範囲であればよい。
樹脂組成物が30質量部未満では、乾燥ムラなどが生じ外観が悪くなるとともに、表面凹凸数が多くなり視認性が損なわれる問題がある。
樹脂組成物が70質量部超では、固形分の溶解性が損なわれやすくなるため、製膜できなくなる問題がある。
Moreover, the compounding quantity of a resin composition and a solvent (what combined the 1st solvent and the 2nd solvent) should just be the range of 70: 30-30: 70 by mass ratio.
When the resin composition is less than 30 parts by mass, there are problems that drying unevenness occurs and the appearance is deteriorated, the number of surface irregularities is increased, and visibility is impaired.
If the resin composition exceeds 70 parts by mass, the solubility of the solid content tends to be impaired, so that there is a problem that the film cannot be formed.
無機成分により凹凸を形成する方法と微粒子により凹凸を付ける方法と組み合わせる場合
無機成分の凝集により凹凸を形成する方法と微粒子により凹凸を付ける方法と組み合わせることができる。樹脂組成物に透光性の微粒子を添加することにより、当該光学機能層の表面凹凸の形状や数を調整しやすくなる。
光学機能層形成用塗料に微粒子を添加して光学機能層を形成した場合、無機成分の凝集により形成された凸部の縁部(光学機能層の凹部)に微粒子が偏在する。
凸部の縁部に微粒子が偏在する理由としては、次のように考える。
微粒子は、塗布後の塗布層内で無機材料成分が対流ドメイン内で凝集構造を形成するのと同時に、この凝集構造の縁部に偏在し始める。乾燥工程により、塗液の流動性が無くなった時点で微粒子は固定化され、最終的に凸部の縁部に偏在することとなる。
微粒子の添加により、無機成分の凝集により形成される表面凹凸の形状を調整できる優位点がある。光学機能層表面の形状を調整することによって、光学機能層表面の耐擦傷性および表面硬度を向上させることができる。
When combining the method of forming irregularities with an inorganic component and the method of applying irregularities with fine particles, it can be combined with the method of forming irregularities by aggregation of inorganic components and the method of forming irregularities with fine particles. By adding translucent fine particles to the resin composition, it becomes easy to adjust the shape and number of surface irregularities of the optical functional layer.
When the optical functional layer is formed by adding fine particles to the coating for forming the optical functional layer, the fine particles are unevenly distributed at the edge of the convex portion (the concave portion of the optical functional layer) formed by aggregation of the inorganic components.
The reason why the fine particles are unevenly distributed at the edge of the convex portion is considered as follows.
The fine particles begin to be unevenly distributed at the edge of the aggregate structure at the same time as the inorganic material component forms an aggregate structure in the convection domain in the coating layer after coating. When the fluidity of the coating liquid is lost by the drying step, the fine particles are fixed and finally unevenly distributed at the edge of the convex portion.
By adding fine particles, there is an advantage that the shape of surface irregularities formed by aggregation of inorganic components can be adjusted. By adjusting the shape of the surface of the optical functional layer, the scratch resistance and surface hardness of the surface of the optical functional layer can be improved.
<光学積層体>
上記の構成成分を含む光学機能層形成用塗料を、透光性基体上に直接あるいは他の層を介して塗布した後、熱、あるいは電離放射線(例えば電子線または紫外線照射)を照射して該光学機能層形成用塗料を硬化させることにより光学機能層を形成させ、本発明の光学積層体を得ることができる。なお、光学機能層の構成成分として、透光性微粒子あるいは凝集により凹凸を形成できる無機成分の少なくとも一種を含まない場合であっても、上記の第1の溶媒と第2の溶媒を使用することができる。
光学機能層は透光性基体の片面に形成されていても両面に形成されていてもよい。
<Optical laminate>
After coating the optical functional layer-forming paint containing the above-mentioned components directly on the translucent substrate or through another layer, the coating is irradiated with heat or ionizing radiation (for example, electron beam or ultraviolet irradiation). The optical functional layer can be formed by curing the coating material for forming an optical functional layer to obtain the optical laminate of the present invention. In addition, even if it is a case where at least one kind of inorganic component capable of forming irregularities by translucent fine particles or agglomeration is not included as a component of the optical functional layer, the first solvent and the second solvent described above should be used. Can do.
The optical functional layer may be formed on one side or both sides of the translucent substrate.
光学機能層の厚さは1.0〜12.0μmの範囲であることが好ましく、より好ましくは2.0〜11.0μmの範囲であり、さらに好ましくは3.0〜10.0μmの範囲である。光学機能層が1.0μmより薄い場合は、紫外線硬化時に酸素阻害による硬化不良を起こし、光学機能層の耐スクラッチ性が劣化しやすくなる。光学機能層が12.0μmより厚い場合は、光学機能層の硬化収縮によるカールの発生や、マイクロクラックの発生、透光性基体との密着性の低下、さらには光透過性の低下が生じてしまう。そして、膜厚の増加に伴う必要塗料量の増加によるコストアップの原因ともなる。 The thickness of the optical functional layer is preferably in the range of 1.0 to 12.0 μm, more preferably in the range of 2.0 to 11.0 μm, and still more preferably in the range of 3.0 to 10.0 μm. is there. When the optical functional layer is thinner than 1.0 μm, curing failure due to oxygen inhibition occurs during ultraviolet curing, and the scratch resistance of the optical functional layer is likely to deteriorate. When the optical functional layer is thicker than 12.0 μm, curling due to curing shrinkage of the optical functional layer, generation of microcracks, decrease in adhesion to the translucent substrate, and further decrease in light transmission may occur. End up. And it becomes a cause of the cost increase by the increase in the amount of required coating materials accompanying the increase in film thickness.
上記光学積層体の光学機能層表面から測定した表面抵抗率は1.0×1012Ω/□以下であることが必要である。1.0×1012Ω/□を超えると、充分な帯電防止性能が得られないおそれがある。上記表面抵抗率は、好ましくは、静電荷が帯電するが、すぐ減衰する範囲1.0×1012Ω/□〜1.0×1010Ω/□であり、より好ましくは帯電が少ない1.0×1010Ω/□以下であり、1.0×109Ω/□以下が特に好ましい。下限値は限定されないが、例えば1.0×106Ω/□以下である。
上記光学積層体を、PVA(PATTERNED VERTICAL ALIGNMENT)液晶に搭載する場合には、上記表面抵抗率は1.0×1010Ω/□以下である必要が有る。これを超えると、ディスプレイ表面への静電気の帯電による液晶反転など、画像表示の不具合が生じる。
The surface resistivity measured from the surface of the optical functional layer of the optical laminate is required to be 1.0 × 10 12 Ω / □ or less. If it exceeds 1.0 × 10 12 Ω / □, sufficient antistatic performance may not be obtained. The surface resistivity is preferably in the range of 1.0 × 10 12 Ω / □ to 1.0 × 10 10 Ω / □ in which the electrostatic charge is charged, but decays immediately. It is 0 × 10 10 Ω / □ or less, and 1.0 × 10 9 Ω / □ or less is particularly preferable. The lower limit is not limited, but is, for example, 1.0 × 10 6 Ω / □ or less.
When the optical laminated body is mounted on a PVA (PATTERNED VERTICAL ALIGNMENT) liquid crystal, the surface resistivity needs to be 1.0 × 10 10 Ω / □ or less. Exceeding this causes problems in image display, such as liquid crystal inversion due to electrostatic charging of the display surface.
上記光学積層体は、最表面における飽和帯電圧が1.5kV以下であることが好ましい。飽和帯電圧を1.5kV以下にするためには、光学機能層内に良好な導電性を示す導電材料を添加することや、導電材料の添加量を増やすことにより達成できる。飽和帯電圧と表面抵抗率は相関があり、飽和帯電圧は、表面抵抗率が低いほど低くなる。
上記飽和帯電圧が1.5kV超であると、特にIPS モードの液晶ディスプレイにおいては、水平方向に配された電極間に電位をかけるので、液晶ディスプレイの表面の帯電により、表示が乱れやすくなるおそれがある。
上記飽和帯電圧は、1.0kV以下であることがより好ましく、0.5kV以下であることが更に好ましい。下限値は限定されないが、例えば0.01kVである。
The optical layered body preferably has a saturation voltage at the outermost surface of 1.5 kV or less. The saturation voltage can be reduced to 1.5 kV or less by adding a conductive material exhibiting good conductivity in the optical functional layer or increasing the amount of the conductive material added. Saturated charging voltage and the surface resistivity is correlated, saturated electrification voltage, the surface resistivity as lower lower.
When the saturation band voltage is more than 1.5 kV, in particular, in an IPS mode liquid crystal display, a potential is applied between the electrodes arranged in the horizontal direction, so that the display may be easily disturbed due to charging of the surface of the liquid crystal display. There is.
The saturation voltage is more preferably 1.0 kV or less, and further preferably 0.5 kV or less. Although a lower limit is not limited, For example, it is 0.01 kV.
上記飽和帯電圧は、JIS L1094に準拠して測定することができ、半減期測定法を挙げることができる。上記半減期測定法は、スタティックオネストメータH−0110(シシド静電気社製、測定条件;印加電圧10kV、距離20mm、25℃、40%RH)等の市販の測定器を使用して測定することができる。
具体的な測定方法としては、例えば、試料(4cm×4cm)をターンテーブルに固定し回転させて電圧を印可し、上記測定器により試料表面の耐電圧値(kV)を測定する。時間に対する耐電圧の減衰曲線を描くことにより、半減期(帯電量が初期値の半分に達するまでの時間)と飽和帯電圧を測定できる。
The saturation voltage can be measured according to JIS L1094, and a half-life measurement method can be mentioned. The half-life assay, static Honest Meter H-0110 (Shishido Electrostatic Ltd., measurement condition: applied voltage 10 kV, distance 20mm, 25 ℃, 40% RH) can be measured using a commercially available measuring instrument, such as it can.
As a specific measuring method, for example, a sample (4 cm × 4 cm) is fixed on a turntable and rotated to apply a voltage, and the withstand voltage value (kV) on the sample surface is measured by the measuring instrument. By drawing a decay curve of withstand voltage with respect to time, the half-life (time until the charge amount reaches half of the initial value) and the saturation voltage can be measured.
ディスプレイに用いられる防眩層やハードコート層などの光学機能層が設けられた光学積層体は、屋外での使用を想定し、耐光性が求められる。耐光性の試験は、太陽光で自然暴露により行う方法があるが、劣化が生じるまでに長時間が必要であるため、通常人工光を照射する促進試験が行なわれる。促進試験には、光源として紫外線カーボンアークランプを用いる、カーボンアーク式耐光性試験機が使用できる。カーボンアーク式耐光性試験機による試験条件は、JIS K 5600−7−5に定められており、本明細書においてはこの試験条件に準じて測定した値を使用している。
耐光性試験機に発せされる紫外線により、透光性基体上に設けられた光学機能層は、分子鎖の開裂等の構造変化により特性の劣化が生じる恐れがある。このため、透光性基体上に積層される光学機能層や光学積層体には、耐光性が求められ、特に耐光性試験による帯電防止性の劣化の低減が求められる。
An optical layered body provided with optical functional layers such as an antiglare layer and a hard coat layer used in displays is assumed to be used outdoors and is required to have light resistance. There is a method of performing a light resistance test by natural exposure with sunlight. However, since a long time is required until the deterioration occurs, an accelerated test in which artificial light is irradiated is usually performed. For the accelerated test, a carbon arc type light resistance tester using an ultraviolet carbon arc lamp as a light source can be used. Test conditions by the carbon arc type light resistance tester are defined in JIS K 5600-7-5, and values measured according to the test conditions are used in this specification.
The optical function layer provided on the light-transmitting substrate may be deteriorated due to structural changes such as molecular chain cleavage due to ultraviolet rays emitted from the light resistance tester. For this reason, the optical functional layer and the optical layered body laminated on the light-transmitting substrate are required to have light resistance, and in particular, to reduce deterioration of antistatic property by a light resistance test.
液晶ディスプレイに使用される偏光板は、防眩層やハードコート層などの光学機能層が設けられたトリアセチルセルロース系保護フィルムと、染色されたポリビニルアルコールを延伸処理することにより得られる偏光子と、トリアセチルセルロース系保護フィルムが積層されることにより構成されている。なお、本明細書においては「偏光子」と「偏光基体」の文言を使用しているが、これらは同一のものを示している。
偏光子とトリアセチルセルロース系保護フィルムを貼合する際には、ケン化処理を行い、偏光子と保護フィルムの接着性を向上させる。ここで、ケン化処理は、防眩層等の塗工層(光学機能層)が設けられていないトリアセチルセルロースフィルム表面の親水化を目的として行われる。しかしながら、ケン化処理は光学機能層等の塗工層が設けられたフィルム全体を各種溶液に浸漬することにより行なわれるため、トリアセチルセルロースに設けられた光学機能層等の塗工層表面も処理されることとなる。
ケン化処理によるトリアセチルセルロース表面の親水化は、水の接触角の測定により確認でき、トリアセチルセルロースフィルム表面の水の接触角が、処理前に55°以上のものが、処理後に20°以下となればケン化処理が適切に行なわれているといえる。
ケン化処理は、アルカリ水溶液に浸漬、水洗、酸水溶液への浸漬による中和、水洗、および熱乾燥を通じて行なわれる。ここで、ケン化処理により、トリアセチルセルロースに設けられた塗工層を形成する成分のアルカリ水溶液や酸水溶液への溶出などによる特性の劣化の恐れが生じる。このため、トリアセチルセルロース系保護フィルム上に積層される光学機能層や光学積層体には、耐ケン化性が求められ、特にケン化処理による帯電防止性の劣化の低減が求められる。
さらに、偏光板に用いられる、トリアセチルセルロース系保護フィルムは、ケン化処理された防眩層等の塗工層が表面に表出され使用されるため、トリアセチルセルロース系保護フィルム上に積層される光学機能層や光学積層体には耐ケン化性と耐光性を併せて持つ必要が有る。
The polarizing plate used for the liquid crystal display is a triacetyl cellulose-based protective film provided with an optical functional layer such as an antiglare layer or a hard coat layer, and a polarizer obtained by stretching a dyed polyvinyl alcohol. The triacetylcellulose-based protective film is laminated. In the present specification, the terms “polarizer” and “polarizing substrate” are used, but these indicate the same thing.
When laminating a polarizer and a triacetyl cellulose-based protective film, a saponification treatment is performed to improve the adhesion between the polarizer and the protective film. Here, the saponification treatment is performed for the purpose of hydrophilizing the surface of the triacetyl cellulose film in which a coating layer (optical functional layer) such as an antiglare layer is not provided. However, since the saponification treatment is performed by immersing the entire film provided with a coating layer such as an optical functional layer in various solutions, the surface of the coating layer such as an optical functional layer provided on triacetyl cellulose is also treated. Will be.
Hydrophilization of the surface of triacetyl cellulose by saponification treatment can be confirmed by measuring the contact angle of water, and the contact angle of water on the surface of the triacetyl cellulose film is 55 ° or more before treatment, but 20 ° or less after treatment. Then, it can be said that the saponification process is appropriately performed.
The saponification treatment is performed through immersion in an alkaline aqueous solution, washing with water, neutralization by immersion in an aqueous acid solution, washing with water, and heat drying. Here, the saponification treatment may cause deterioration of characteristics due to elution of the components forming the coating layer provided on the triacetyl cellulose into an alkaline aqueous solution or an acid aqueous solution. For this reason, the optical functional layer and the optical laminate laminated on the triacetyl cellulose-based protective film are required to have saponification resistance, and in particular, to reduce deterioration of antistatic properties due to saponification treatment.
Furthermore, the triacetylcellulose-based protective film used for the polarizing plate is laminated on the triacetylcellulose-based protective film because a coating layer such as a saponified antiglare layer is exposed on the surface and used. The optical functional layer and the optical laminate need to have both saponification resistance and light resistance.
光学機能層を含む本発明の光学積層体は、耐光性及び耐ケン化性に優れたものとなる。
すなわち、本発明の光学機能層および光学積層体は、放射照度500W/m2(測定波長範囲300〜700nm)、ブラックパネル温度50±5℃条件下での80時間の条件でのカーボンアーク式耐光性試験後の表面抵抗率R2と、未処理時の表面抵抗率R1との比(R2/R1)が104以下であることが必要であり、103以下であることが好ましく、102以下であることが特に好ましい。また、本発明の光学機能層および光学積層体は、未処理時の表面抵抗率R1と、ケン化処理後の表面抵抗率R3との比(R3/R1)が10以下であることが好ましく、5.0以下であることがさらに好ましく、1.0以下であることが特に好ましい。また、ケン化処理および放射照度500W/m2(測定波長範囲300〜700nm)、ブラックパネル温度50±5℃条件下での80時間の条件でのカーボンアーク式耐光性試験後の表面抵抗率R4と未処理時の表面抵抗率R1との比(R4/R1)が104以下であることが好ましく、103以下であることがさらに好ましく、102以下であることが特に好ましい。
The optical layered body of the present invention including the optical functional layer has excellent light resistance and saponification resistance.
That is, the optical functional layer and the optical laminate of the present invention have a carbon arc type light resistance under conditions of irradiance of 500 W / m 2 (measurement wavelength range of 300 to 700 nm) and a black panel temperature of 50 ± 5 ° C. for 80 hours. The ratio (R2 / R1) between the surface resistivity R2 after the property test and the surface resistivity R1 when untreated is required to be 10 4 or less, preferably 10 3 or less, and preferably 10 2 or less. It is particularly preferred that In the optical functional layer and the optical laminate of the present invention, the ratio (R3 / R1) of the surface resistivity R1 when untreated and the surface resistivity R3 after saponification treatment is preferably 10 or less, It is more preferably 5.0 or less, and particularly preferably 1.0 or less. Further, surface resistivity R4 after carbon arc light resistance test under conditions of saponification treatment and irradiance of 500 W / m 2 (measurement wavelength range of 300 to 700 nm) and black panel temperature of 50 ± 5 ° C. for 80 hours. And the surface resistivity R1 when untreated (R4 / R1) is preferably 10 4 or less, more preferably 10 3 or less, and particularly preferably 102 2 or less.
本発明の光学機能層および光学積層体は、画像鮮明性が5.0〜80.0の範囲(JIS K7105に従い0.5mm光学くしを用いて測定した値)が好ましく、20.0〜75.0がより好ましい。画像鮮明性が5.0未満ではコントラストが悪化し、80.0を超えると防眩性が悪化するため、ディスプレイ表面に用いる光学積層体に適さなくなる。 The optical function layer and optical laminate of the present invention preferably have an image sharpness in the range of 5.0 to 80.0 (value measured using a 0.5 mm optical comb in accordance with JIS K7105), and 20.0 to 75. 0 is more preferable. If the image clarity is less than 5.0, the contrast deteriorates, and if it exceeds 80.0, the antiglare property deteriorates, so that it is not suitable for an optical laminate used for the display surface.
本発明の光学機能層および光学積層体は、JIS K7105による全光線透過率が91.0%以上が好ましく、92.0%がより好ましく、更に好ましくは93.0%以上である。全光線透過率が91.0%未満ではコントラストが悪化し、ディスプレイ表面に用いる光学積層体に適さなくなる。 In the optical functional layer and the optical layered body of the present invention, the total light transmittance according to JIS K7105 is preferably 91.0% or more, more preferably 92.0%, and further preferably 93.0% or more. When the total light transmittance is less than 91.0%, the contrast is deteriorated and the optical laminate used for the display surface is not suitable.
本発明の光学積層体は、光学機能層の表面に微細な凹凸形状を有する。ここで、当該微細な凹凸形状は、好適には、ASME95に従い求められる平均傾斜から計算される平均傾斜角度が0.2〜1.4の範囲にあり、より好ましくは0.25〜1.2、更に好ましくは0.25〜1.0である。平均傾斜角度が0.2未満では防眩性が悪化し、平均傾斜角度が1.4を超えるとコントラストが悪化するため、ディスプレイ表面に用いる光学積層体に適さなくなる。 The optical layered body of the present invention has a fine uneven shape on the surface of the optical functional layer. Here, the fine concavo-convex shape preferably has an average inclination angle calculated from an average inclination obtained according to ASME 95 in the range of 0.2 to 1.4, more preferably 0.25 to 1.2. More preferably, it is 0.25 to 1.0. When the average inclination angle is less than 0.2, the antiglare property is deteriorated, and when the average inclination angle exceeds 1.4, the contrast is deteriorated, so that it is not suitable for the optical laminate used for the display surface.
また、本発明の光学積層体は、光学機能層の微細な凹凸形状として、表面粗さRaが0.05〜0.2μmであることが好ましく、0.05〜0.15μmであることがさらに好ましく、0.05〜0.10μmであることが特に好ましい。表面粗さRaが0.05μm未満であると、光学積層体の防眩性が不十分になる。表面粗さRaが0.2μm超であると、光学積層体のコントラストが悪化する。 In the optical layered body of the present invention, the surface roughness Ra is preferably 0.05 to 0.2 μm, and more preferably 0.05 to 0.15 μm, as the fine uneven shape of the optical functional layer. Preferably, it is 0.05-0.10 micrometer. When the surface roughness Ra is less than 0.05 μm, the antiglare property of the optical laminate is insufficient. If the surface roughness Ra is more than 0.2 μm, the contrast of the optical laminate is deteriorated.
<光学積層体の製造方法>
透光性基体上に光学機能層形成用塗料を塗布する手法としては、通常の塗工方式や印刷方式が適用される。具体的には、エアドクターコーティング、バーコーティング、ブレードコーティング、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、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、ダムコーティング、ディップコーティング、ダイコーティング等のコーティングや、グラビア印刷等の凹版印刷、スクリーン印刷等の孔版印刷等の印刷等が使用できる。
<Method for producing optical laminate>
As a method for applying the coating material for forming an optical functional layer on the translucent substrate, a normal coating method or printing method is applied. More specifically, air doctor coating, bar coating, blade coating, knife coating, reverse coating, transfer roll coating, gravure roll coating, kiss coating, cast coating, spray coating, slot orifice coating, calendar coating, dam coating, dip coating Coating such as die coating, intaglio printing such as gravure printing, printing such as stencil printing such as screen printing, and the like can be used.
以下、本発明を実施例を用いて説明するが、本発明はこれらに制限されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not restrict | limited to these.
(製造例1)合成スメクタイトの製造
10Lのビーカーに水4L を入れ、3号水ガラス(SiO2 28%、Na2 O9%、モル比3.22)860g を溶解し、95%硫酸162g を撹拌しながら一度に加えてケイ酸塩溶液を得る。次に水1L にMgCl2 ・6H2 O一級試薬(純度98%)560g を溶解し、これを前記ケイ酸溶液に加えて均質混合溶液を調製した。これを2N −NaOH溶液3.6L 中に撹拌しながら5分間で滴下した。得られた反応沈澱物を、直ちに日本ガイシ(株)製のクロスフロー方式による濾過システム〔クロスフロー濾過器(セラミック膜フィルター:孔径2μm、チューブラータイプ、濾過面積400cm2)、加圧:2kg/cm2、濾布:テトロン1310〕で濾過及び充分に水洗した後、水200mlとLi(OH)・H2 O 14.5gとよりなる溶液を加えてスラリー状とした。これをオートクレーブに移し、41kg/cm2、250℃で3時間、水熱反応させた。冷却後反応物を取出し、80℃で乾燥し、粉砕して下記式の合成スメクタイトを得た。この合成スメクタイトを分析したところ、次の組成のものが得られた。Na0.4 Mg2.6 Li0.4 Si4 O10(OH)2
また、メチレンブルー吸着法で測定した陽イオン交換容量が110ミリ当量/100g であった。
(Production Example 1) Production of synthetic smectite 4L of water was placed in a 10L beaker, 860 g of No. 3 water glass (SiO 2 28%, Na 2 O 9%, molar ratio 3.22) was dissolved, and 162% of 95% sulfuric acid was stirred. Add at once while obtaining a silicate solution. Next, 560 g of MgCl 2 · 6H 2 O primary reagent (purity 98%) was dissolved in 1 L of water, and this was added to the silicic acid solution to prepare a homogeneous mixed solution. This was added dropwise over 5 minutes while stirring 2N -NaOH solution 3.6 L. The obtained reaction precipitate was immediately filtered by a cross flow method (cross flow filter (ceramic membrane filter: pore size 2 μm, tubular type, filtration area 400 cm 2 ), manufactured by NGK Co., Ltd., pressure: 2 kg / cm 2 , filter cloth: Tetoron 1310] and sufficiently washed with water, and then a solution consisting of 200 ml of water and 14.5 g of Li (OH) · H 2 O was added to form a slurry. This was transferred to an autoclave and subjected to a hydrothermal reaction at 41 kg / cm 2 and 250 ° C. for 3 hours. After cooling, the reaction product was taken out, dried at 80 ° C., and pulverized to obtain a synthetic smectite represented by the following formula. When this synthetic smectite was analyzed, the following composition was obtained. Na 0.4 Mg 2.6 Li 0.4 Si 4 O 10 (OH) 2
The cation exchange capacity measured by the methylene blue adsorption method was 110 meq / 100 g.
(製造例2)合成スメクタイト系層状有機粘土Aの製造
製造例1で合成した合成スメクタイト20g を水道水1000mlに分散させて懸濁液とした。該合成スメクタイトの陽イオン交換容量の1.00倍相当量の次式(II)の第四級アンモニウム塩(98%含有品)を溶解した水溶液500mlを、前記合成スメクタイト懸濁液に添加し、撹拌しながら室温で2時間反応させた。生成物を固液分離、洗浄して副生塩類を除去した後、乾燥して合成スメクタイト系層状有機粘土Aを得た。
(Production Example 2) Production of synthetic smectite-based layered organic clay A 20 g of synthetic smectite synthesized in Production Example 1 was dispersed in 1000 ml of tap water to obtain a suspension. 500 ml of an aqueous solution in which a quaternary ammonium salt of the following formula (II) (containing 98%) corresponding to 1.00 times the cation exchange capacity of the synthetic smectite is dissolved, is added to the synthetic smectite suspension; The reaction was allowed to proceed for 2 hours at room temperature with stirring. The product was subjected to solid-liquid separation and washing to remove by-product salts, and then dried to obtain a synthetic smectite-based layered organic clay A.
(製造例3)電離放射線硬化型フッ化アクリレート B液の合成
500mlの反応フラスコ中、イソホロンジイソシアナート22.2g(0.1モル)のMIBK(メチルイソブチルケトン)100ml溶液に、エアーバブリングを行いながらペンタエリスリトールトリアクリレート59.6g(0.20モル)のMIBK50ml溶液を25℃で滴下した。滴下終了後、ジブチル錫ジラウレート0.3gを加え更に70℃で4時間加熱撹拌を行った。反応終了後、反応溶液を5%塩酸100mlで洗浄した。有機層を分取した後、40℃以下で溶媒を減圧留去することで無色透明粘稠液体のウレタンアクリレート80.5gを得た。200ml反応フラスコに、調製したウレタンアクリレート40.8g(0.05モル)、パーフルオロオクチルエチルメルカプタン71.9g(0.15モル)、MIBK60gを投入し均一とした。この混合溶液に25℃でトリエチルアミン1.0gを徐々に加えた。加え終わった後、さらに50℃で3時間撹拌した。反応終了後、50℃以下の条件でエバポレーターを用いて、トリエチルアミンを減圧留去し、さらに真空ポンプで乾燥することで、構造式1で示されるフッ素化アルキル基含有ウレタンアクリレートを含有し、アクリロイル基とパーフルオロオクチルエチルメルカプタンとの付加反応の位置が前記構造式1とは異なる化合物を更に含む混合物からなる電離放射線硬化型フッ化アクリレートB液を得た。
(Production Example 3) Synthesis of ionizing radiation curable fluorinated acrylate solution B In a 500 ml reaction flask, air bubbling was performed on 100 ml of MIBK (methyl isobutyl ketone) in 22.2 g (0.1 mol) of isophorone diisocyanate. Then, a solution of 59.6 g (0.20 mol) of pentaerythritol triacrylate in 50 ml of MIBK was added dropwise at 25 ° C. After completion of dropping, 0.3 g of dibutyltin dilaurate was added, and the mixture was further stirred with heating at 70 ° C. for 4 hours. After completion of the reaction, the reaction solution was washed with 100 ml of 5% hydrochloric acid. After separating the organic layer, the solvent was distilled off under reduced pressure at 40 ° C. or less to obtain 80.5 g of a colorless transparent viscous liquid urethane acrylate. Into a 200 ml reaction flask, 40.8 g (0.05 mol) of the prepared urethane acrylate, 71.9 g (0.15 mol) of perfluorooctylethyl mercaptan, and 60 g of MIBK were added to make uniform. To this mixed solution, 1.0 g of triethylamine was gradually added at 25 ° C. After the addition was completed, the mixture was further stirred at 50 ° C. for 3 hours. After completion of the reaction, triethylamine is distilled off under reduced pressure using an evaporator under conditions of 50 ° C. or lower, and further dried with a vacuum pump, thereby containing a fluorinated alkyl group-containing urethane acrylate represented by Structural Formula 1, and an acryloyl group. An ionizing radiation curable fluorinated acrylate B liquid comprising a mixture further containing a compound in which the position of the addition reaction between and perfluorooctylethyl mercaptan is different from that of the structural formula 1 was obtained.
(製造例4)ポリスチレンスルホン酸の合成
1000mlのイオン交換水に206gのスチレンスルホン酸ナトリウムを溶解し、80℃で撹拌しながら、予め10mlの水に溶解した1.14gの過硫酸アンモニウム酸化剤溶液を20分間滴下し、この溶液を12時間撹拌した。得られたスチレンスルホン酸ナトリウム含有溶液に10質量%に希釈した硫酸を1000ml添加し、限外ろ過法を用いてポリスチレンスルホン酸含有溶液の約1000ml溶液を除去し、残液に2000mlのイオン交換水を加え、限外ろ過法を用いて約2000ml溶液を除去した。上記の限外ろ過操作を3回繰り返した。さらに、得られたろ液に約2000mlのイオン交換水を添加し、限外ろ過法を用いて約2000ml溶液を除去した。この限外ろ過操作を3回繰り返した。得られた溶液中の水を減圧除去して、無色のポリスチレンスルホン酸の固形物を得た。
(Production Example 4) Synthesis of polystyrene sulfonic acid 206 g of sodium styrene sulfonate was dissolved in 1000 ml of ion-exchanged water, and 1.14 g of ammonium persulfate oxidizing agent solution previously dissolved in 10 ml of water was stirred at 80 ° C. The solution was added dropwise for 20 minutes and the solution was stirred for 12 hours. To the obtained sodium styrenesulfonate-containing solution, 1000 ml of sulfuric acid diluted to 10% by mass was added, about 1000 ml of the polystyrenesulfonic acid-containing solution was removed using an ultrafiltration method, and 2000 ml of ion-exchanged water was added to the remaining liquid. And about 2000 ml solution was removed using ultrafiltration. The above ultrafiltration operation was repeated three times. Further, about 2000 ml of ion-exchanged water was added to the obtained filtrate, and about 2000 ml of solution was removed using an ultrafiltration method. This ultrafiltration operation was repeated three times. Water in the obtained solution was removed under reduced pressure to obtain a colorless polystyrene sulfonic acid solid.
(製造例5)ポリスチレンスルホン酸ドープポリ(3,4−エチレンジオキシチオフェン)(PSS−PEDOT)の合成
14.2gの3,4−エチレンジオキシチオフェンと、36.7gの製造例4で合成したポリスチレンスルホン酸を2000mlのイオン交換水に溶かした溶液とを20℃で混合した。これにより得られた混合溶液を20℃に保ち、掻き混ぜながら、200mlのイオン交換水に溶かした29.64gの過硫酸アンモニウムと8.0gの硫酸第二鉄の酸化触媒溶液とをゆっくり添加し、3時間撹拌して反応させた。得られた反応液に2000mlのイオン交換水を添加し、限外ろ過法を用いて約2000ml溶液を除去した。この操作を3回繰り返した。そして、得られた溶液に200mlの10質量%に希釈した硫酸と2000mlのイオン交換水とを加え、限外ろ過法を用いて約2000mlの溶液を除去し、これに2000mlのイオン交換水を加え、限外ろ過法を用いて約2000mlの液を除去した。この操作を3回繰り返した。さらに、得られた溶液に2000mlのイオン交換水を加え、限外ろ過法を用いて約2000mlの溶液を除去した。この操作を5回繰り返し、1.5質量%の青色のポリスチレンスルホン酸ドープポリ(3,4−エチレンジオキシチオフェン)(PSS−PEDOT)の水溶液を得た。
(Production Example 5) Synthesis of polystyrene sulfonate-doped poly (3,4-ethylenedioxythiophene) (PSS-PEDOT) Synthesis was performed in 14.2 g of 3,4-ethylenedioxythiophene and 36.7 g of Production Example 4. A solution of polystyrene sulfonic acid dissolved in 2000 ml of ion-exchanged water was mixed at 20 ° C. Keeping thus obtained mixed solution to 20 ° C., stirred while slowly adding an oxidation catalyst solution of ammonium persulfate and 8.0g of ferric sulfate 29.64g dissolved in ion-exchanged water 200 ml, The reaction was stirred for 3 hours. 2000 ml of ion-exchanged water was added to the resulting reaction solution, and about 2000 ml of solution was removed using an ultrafiltration method. This operation was repeated three times. Then, 200 ml of sulfuric acid diluted to 10% by mass and 2000 ml of ion-exchanged water are added to the resulting solution, and about 2000 ml of solution is removed using an ultrafiltration method, and 2000 ml of ion-exchanged water is added thereto. About 2000 ml of liquid was removed using an ultrafiltration method. This operation was repeated three times. Furthermore, 2000 ml of ion-exchanged water was added to the obtained solution, and about 2000 ml of the solution was removed using an ultrafiltration method. This operation was repeated 5 times to obtain an aqueous solution of 1.5% by mass of blue polystyrenesulfonic acid doped poly (3,4-ethylenedioxythiophene) (PSS-PEDOT).
(製造例6)ポリスチレンスルホン酸ドープポリ(3,4−エチレンジオキシチオフェン)(PSS−PEDOT)のイソプロピルアルコール分散液 C液の作成
製造例5で合成したポリスチレンスルホン酸ドープポリ(3,4−エチレンジオキシチオフェン)(PSS−PEDOT)の1.5質量%の水分散液100gをフラスコにとり、イソプロピルアルコール100gを添加、撹拌しながら、10%塩酸を0.5ml添加した。その後30分撹拌を継続した後、1時間放置した。得られたゲル状物を、グラスフィルターを用いて減圧ろ過、その後イソプロピルアルコール200gを添加、減圧ろ過という操作を8回繰り返した。固形分が完全に乾燥しない状態でグラスフィルターから取り出し、加熱質量減少から固形分質量を算出、固形分7.8%の湿潤青色固体15gを得た。イソプロピルアルコール15gをビーカーにとり、アミンアルキレンオキシド付加物(商品名:エソミンC/15、ライオンアクゾ社製)0.4gを添加した後、得られた湿潤青色固体15gを加えて、乳化分散機(商品名:TKホモディスパー、特殊機化工業製)を用い、回転数4000rpmで10分処理を行い、PSS−PEDOTイソプロピルアルコール分散液(C液)を得た(固形分濃度5%、水含有量20%以下)。
得られたPSS−PEDOTイソプロピルアルコール分散液(固形分濃度5%、水含有量20%以下)の平均粒子径をナノトラック粒子径分布測定装置UPA−EX150(日機装株式会社製)を使用し、モノディスパースモードにて測定した。ここで、平均粒子径(d50)は20nm、d90は40nmであった。
(Production Example 6) polystyrene sulfonic acid doped poly (3,4-ethylenedioxythiophene) (PSS-PEDOT) of isopropyl alcohol dispersion liquid C Creating Production Example 5 Synthesis polystyrene sulfonate-doped poly (3,4-ethylene di 100 g of a 1.5 mass% aqueous dispersion of (oxythiophene) (PSS-PEDOT) was placed in a flask, 100 g of isopropyl alcohol was added, and 0.5 ml of 10% hydrochloric acid was added with stirring. Thereafter, stirring was continued for 30 minutes, and then left for 1 hour. The obtained gel-like product was filtered under reduced pressure using a glass filter, and then 200 g of isopropyl alcohol was added, followed by vacuum filtration for 8 times. The solid content was taken out from the glass filter in a state where it was not completely dried, and the solid content mass was calculated from the reduced heating mass to obtain 15 g of a wet blue solid having a solid content of 7.8%. After taking 15 g of isopropyl alcohol in a beaker and adding 0.4 g of an amine alkylene oxide adduct (trade name: Esomine C / 15, manufactured by Lion Akzo), 15 g of the obtained wet blue solid is added, and an emulsifying disperser (product) name: TK homodisper using Tokushu Kika Kogyo), the 10-minute treatment at a rotation speed of 4000 rpm, PSS-PEDOT isopropyl alcohol dispersion (C solution) (solid content concentration 5%, water content 20 %Less than).
The average particle size of the obtained PSS-PEDOT isopropyl alcohol dispersion (solid content concentration 5%, water content 20% or less) was measured using a nanotrack particle size distribution analyzer UPA-EX150 (manufactured by Nikkiso Co., Ltd.). Measured in disperse mode. Here, the average particle diameter (d50) was 20 nm, and d90 was 40 nm.
(製造例7)4級アンモニウム塩基含有コポリマーD液 製造例
撹拌装置、窒素ガス導入管、温度計および還流冷却管を備えたフラスコに、n−ブチルメタクリレート 40g、ライトエステルDQ−100(共栄化学社製)50g、N,N−ジメチルアミノエチルメタクリレート5g、アクリル酸5g、メタノール
60g、メチルセロソルブ60gを仕込み、フラスコ内に窒素ガスを導入しながら30分撹拌して窒素置換を行った後、フラスコ内の内容物を75℃まで昇温した。次いでAIBN(アゾビスイソブチロニトリル)0.5gをフラスコ内に添加した。フラスコ内の内容物を75℃に維持しながら1時間毎にAIBN0.5gを2回添加した。最初のAIBNの添加から9時間後室温まで冷却してポリマー濃度45%の4級アンモニウム塩基含有コポリマーD液を得た。得られた共重合体について、GPCによる測定を行ったところ、質量平均分子量は100,000であった。また、ポリマーのSP値を測定したところ12.15であった。
(Production Example 7) Quaternary ammonium base-containing copolymer D solution Production example In a flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer, and a reflux condenser, n-butyl methacrylate 40 g, light ester DQ-100 (Kyoei Chemical Co., Ltd.) Ltd.) 50 g, N, N-dimethylaminoethyl methacrylate 5g, acrylic acid 5g, methanol 60 g, was charged with methyl cellosolve 60 g, after stirred for 30 minutes while introducing nitrogen gas nitrogen substitution in the flask, the flask Was heated to 75 ° C. Next, 0.5 g of AIBN (azobisisobutyronitrile) was added into the flask. While maintaining the contents in the flask at 75 ° C., 0.5 g of AIBN was added twice every hour. Nine hours after the first AIBN addition, the mixture was cooled to room temperature to obtain a quaternary ammonium base-containing copolymer D solution having a polymer concentration of 45%. When the obtained copolymer was measured by GPC, the mass average molecular weight was 100,000. Moreover, it was 12.15 when SP value of the polymer was measured.
前記、層状有機粘土A、電離放射線硬化型フッ化アクリレートB液、PSS−PEDOTイソプロピルアルコール分散液C液を含む表1記載の所定の混合物をディスパーにて30分間撹拌することによって得られた光学機能層形成用の塗料を、膜厚80μm、全光線透過率92%からなる透明基体のTACフィルム(富士フィルム社製;TD80UL)の片面上にロールコーティング方式にて塗布(ラインスピード;20m/分)し、30〜50℃で20秒間予備乾燥を経た後、100℃で1分間乾燥し、窒素雰囲気(窒素ガス置換)中で紫外線照射(ランプ;集光型高圧水銀灯、ランプ出力;120W/cm、灯数:4灯、照射距離;20cm)を行うことで塗工膜を硬化させた。このようにして、厚さ5.5μmの光学機能層を有する実施例1の光学積層体を得た。 Optical function obtained by stirring the predetermined mixture described in Table 1 containing the layered organic clay A, ionizing radiation curable fluorinated acrylate B liquid, and PSS-PEDOT isopropyl alcohol dispersion C liquid with a disper for 30 minutes. A layer-forming coating material is applied on one side of a transparent substrate TAC film (Fuji Film Co., Ltd .; TD80UL) with a film thickness of 80 μm and a total light transmittance of 92% (line speed: 20 m / min) Then, after preliminary drying at 30 to 50 ° C. for 20 seconds, drying at 100 ° C. for 1 minute, and irradiation with ultraviolet rays in a nitrogen atmosphere (nitrogen gas replacement) (lamp; condensing high-pressure mercury lamp, lamp output; 120 W / cm, The coating film was cured by performing the number of lamps: 4 lamps, irradiation distance: 20 cm). Thus, the optical laminated body of Example 1 which has an optical functional layer with a thickness of 5.5 micrometers was obtained.
光学機能層形成用塗料を表1記載の所定の混合液に変更した以外は、実施例1と同様にして、厚さ5.8μmの光学機能層を有する実施例2の光学積層体を得た。 An optical laminated body of Example 2 having an optical functional layer with a thickness of 5.8 μm was obtained in the same manner as in Example 1 except that the coating material for forming the optical functional layer was changed to the predetermined mixed liquid shown in Table 1. .
[比較例1]
光学機能層形成用塗料を、4級アンモニウム塩基含有コポリマーD液を含む表1記載の所定の混合液に変更した以外は、実施例1と同様にして、厚さ4.0μmの光学機能層を有する比較例1の光学積層体を得た。
[Comparative Example 1]
An optical functional layer having a thickness of 4.0 μm was formed in the same manner as in Example 1 except that the coating for forming the optical functional layer was changed to the predetermined mixed solution described in Table 1 containing the quaternary ammonium base-containing copolymer D solution. The optical laminated body of the comparative example 1 which has was obtained.
[比較例2]
光学機能層形成用塗料を、導電材料を含まない表1記載の所定の混合液に変更した以外は、実施例1と同様にして、厚さ5.6μmの光学機能層を有する比較例2の光学積層体を得た。
[Comparative Example 2]
Comparative Example 2 having an optical functional layer having a thickness of 5.6 μm was obtained in the same manner as in Example 1 except that the coating material for forming the optical functional layer was changed to the predetermined mixed liquid described in Table 1 that did not contain a conductive material. An optical laminate was obtained.
<評価方法>
次に実施例および比較例の光学積層体について、下記の項目について評価を行った。
<Evaluation method>
Next, the following items were evaluated for the optical laminates of Examples and Comparative Examples.
(ケン化処理)
光学積層体のケン化処理は以下の手順に従う。光学積層体を構成するTACフィルム表面の水の接触角を測定したところ、ケン化処理前に55°以上であったものがケン化処理後に20°以下になっていたため、ケン化処理が適切に行われていることを確認した。
(1)55℃、6%の水酸化ナトリウム水溶液に2分間浸漬。
(2)30秒間水洗。
(3)35℃、0.1規定の硫酸に30秒間浸漬。
(4)30秒間水洗。
(5)120℃、1分間、熱風乾燥。
上記で得られた各光学積層体について、初期(ケン化処理および耐候性試験を行っていない段階)の表面抵抗率(R1)、ケン化処理後の表面抵抗率(R3)を測定した。ここで、R3/R1が10未満のものを○、10以上のものを×とした。
(Saponification treatment)
The saponification process of an optical laminated body follows the following procedures. When the contact angle of water on the surface of the TAC film constituting the optical laminate was measured, it was 55 ° or more before the saponification treatment and was 20 ° or less after the saponification treatment. Confirmed that it was done.
(1) Immerse in a 6% sodium hydroxide aqueous solution at 55 ° C. for 2 minutes.
(2) Wash with water for 30 seconds.
(3) Immerse in 0.1 N sulfuric acid at 35 ° C. for 30 seconds.
(4) Wash with water for 30 seconds.
(5) Hot air drying at 120 ° C. for 1 minute.
About each optical laminated body obtained above, the surface resistivity (R1) of the initial stage (the stage which is not performing a saponification process and a weather resistance test) and the surface resistivity (R3) after a saponification process were measured. Here, what R3 / R1 is less than 10 ○, and as × 10 or more.
(耐光性試験)
耐光性試験は、以下の条件にて行った。
試験機 ;カーボンアーク式耐光性試験機(スガ試験機(株)製耐光性試験機)
品 名;「紫外線オートフェードメーターU48AU−B」)
試験条件;ブラックパネル温度;50±5℃
放射照度;500W/m2(測定波長範囲300〜700nm)
照射時間;80時間
上記で得られた光学積層体について、初期(ケン化処理および耐候性試験を行っていない段階)の表面抵抗率(R1)、カーボンアーク式耐光性試験後の表面抵抗率(R2)を測定した。R2/R1が104以下のものを○、104を超えるものを×とした。また、上記で得られた光学積層体について、初期(ケン化処理および耐候性試験を行っていない段階)の表面抵抗率(R1)、ケン化処理およびカーボンアーク式耐光性試験後の表面抵抗率(R4)を測定した。R4/R1が104未満のものを○、104を超えるものを×とした。
(Light resistance test)
The light resistance test was performed under the following conditions.
Testing machine: Carbon arc light resistance tester (Suga Test Instruments Co., Ltd. light resistance tester)
Product name: “UV Auto Fade Meter U48AU-B”)
Test conditions; black panel temperature; 50 ± 5 ° C
Irradiance: 500 W / m 2 (measurement wavelength range 300 to 700 nm)
Irradiation time: 80 hours About the optical laminated body obtained above, the surface resistivity (R1) at the initial stage (stage where saponification treatment and weather resistance test are not performed), the surface resistivity after the carbon arc type light resistance test ( R2) was measured. The case where R2 / R1 was 10 4 or less was evaluated as “◯”, and the case where it exceeded 10 4 was evaluated as “X”. Moreover, about the optical laminated body obtained above, the surface resistivity (R1) of the initial stage (the stage which is not performing a saponification process and a weather resistance test), the surface resistivity after a saponification process and a carbon arc type light resistance test (R4) was measured. The case where R4 / R1 is less than 10 4 is evaluated as ◯, and the case where R4 / R1 exceeds 10 4 is evaluated as ×.
(全光線透過率)
全光線透過率は、JIS K7105に従い、ヘイズメーター(商品名:NDH2000、日本電色社製)を用いて測定した。
(Total light transmittance)
The total light transmittance was measured using a haze meter (trade name: NDH2000, manufactured by Nippon Denshoku) in accordance with JIS K7105.
(ヘイズ値)
ヘイズ値は、JIS K7105に従い、ヘイズメーター(商品名:NDH2000、日本電色社製)を用いて測定した。
(Haze value)
The haze value was measured according to JIS K7105 using a haze meter (trade name: NDH2000, manufactured by Nippon Denshoku).
(表面粗さ)
表面粗さRaは、JIS B0601−1994に従い、表面粗さ測定器(商品名:サーフコーダSE1700α、小坂研究所社製)を用いて測定した。
(Surface roughness)
The surface roughness Ra was measured according to JIS B0601-1994 using a surface roughness measuring instrument (trade name: Surfcorder SE1700α, manufactured by Kosaka Laboratory Ltd.).
(平均傾斜角度)
平均傾斜角度は、ASME95に従い、表面粗さ測定器(商品名:サーフコーダSE1700α、小坂研究所社製)を用いて平均傾斜を求め、次式に従って平均傾斜角度を算出した。
平均傾斜角度=tan−1(平均傾斜)
(Average tilt angle)
The average inclination angle was determined according to ASME95 using a surface roughness measuring instrument (trade name: Surfcorder SE1700α, manufactured by Kosaka Laboratories), and the average inclination angle was calculated according to the following formula.
Average inclination angle = tan −1 (average inclination)
(画像鮮明性)
JIS K7105に従い、写像性測定器(商品名:ICM−1DP、スガ試験機社製)を用い、測定器を透過モードに設定し、光学くし幅0.5mmにて測定した。
(Image clarity)
According to JIS K7105, a measuring device (trade name: ICM-1DP, manufactured by Suga Test Instruments Co., Ltd.) was used, and the measuring device was set to a transmission mode, and measurement was performed at an optical comb width of 0.5 mm.
(防眩性)
防眩性は、画像鮮明性の値が0〜80のとき○、81〜100のとき×とした。
(Anti-glare)
The antiglare property was set to ○ when the value of image clarity was 0 to 80, and × when 81 to 100.
(表面抵抗率)
表面抵抗率は、JIS K6911に従い、高抵抗率計(商品名:Hiresta−UP、三菱化学製)を用いて測定した。測定は、サンプルを20℃ 65%RH環境下で1時間調湿した後、20℃ 65%RHの条件で行った。表面抵抗率の測定は、光学積層体の光学機能層の表面側から、印加電圧250V、印加時間10秒で実施した。
1.0×109Ω/□以下のとき◎、1.0×109Ω/□超1.0×1010Ω/□以下のとき○、1.0×1010Ω/□超〜1.0×1012Ω/□以下のとき△、1.0×1012Ω/□を超えるときを×とした。
(Surface resistivity)
The surface resistivity was measured using a high resistivity meter (trade name: Hiresta-UP, manufactured by Mitsubishi Chemical Corporation) according to JIS K6911. The measurement was carried out under conditions of 20 ° C. and 65% RH after conditioning the sample for 1 hour in an environment of 20 ° C. and 65% RH. The surface resistivity was measured from the surface side of the optical functional layer of the optical laminate with an applied voltage of 250 V and an application time of 10 seconds.
1.0 × 10 9 Ω / □ when: ◎, 1.0 × 10 9 Ω / □ ultra 1.0 × 10 10 Ω / □ when: ○, 1.0 × 10 10 Ω / □ super to 1 .0 × 10 12 Ω / □ when: △, was × when more than 1.0 × 10 12 Ω / □.
(飽和帯電圧)
飽和帯電圧は、スタティックオネストメータH−0110(シシド静電気社製)を用いて、印加電圧10kV、距離20mm、25℃、40%RHの条件下で、JIS L1094に従い測定した。
(Saturation band voltage)
Saturated electrification voltage, using a static Honest Meter H-0110 (manufactured by Shishido Electrostatic, Ltd.), applied voltage 10 kV, distance 20 mm, 25 ° C., under the conditions of RH 40%, measured in accordance with JIS L1094.
(耐スクラッチ性)
日本スチールウール社製のスチールウール#0000を耐磨耗試験機(Fu Chien社製 Abrasion Tester、Model;339)に取り付け、光学機能層面を荷重250g/cm2にて10回往復させた。その後、磨耗部分の傷を蛍光灯下で確認した。傷の数が0本のとき◎、傷の数が1〜10本未満のとき○、傷の数が10〜30本未満のとき△、傷の数が30本以上のとき×とした。
(Scratch resistance)
Steel wool # 0000 manufactured by Nippon Steel Wool Co., Ltd. was attached to an abrasion resistance tester (Abrasion Tester, Model; 339 manufactured by Fu Chien Co., Ltd.), and the optical functional layer surface was reciprocated 10 times at a load of 250 g / cm 2 . Thereafter, scratches on the worn parts were confirmed under a fluorescent lamp. When the number of scratches was 0, ◎, when the number of scratches was less than 1-10, ◯, when the number of scratches was less than 10-30, Δ, and when the number of scratches was 30 or more, x.
(明室コントラスト)
明室コントラストは、実施例及び比較例の光学積層体において、光学機能層の形成面と反対面に、無色透明な粘着層を介して液晶表示装置(商品名:LC−37GX1W、シャープ社製)の画面表面に貼り合せ、液晶表示装置画面の正面上方60°の方向から蛍光灯(商品名:HH4125GL、ナショナル社製)にて液晶ディスプレイ表面の照度が200ルクスとなるようにした後、液晶表示装置を白表示及び黒表示としたときの輝度を色彩輝度計(商品名:BM−5A、トプコン社製)にて測定し、得られた黒表示時の輝度(cd/m2)と白表示時の輝度(cd/m2)を以下の式にて算出した時の値が、800以下のとき×、801以上のとき○とした。
コントラスト=白表示の輝度/黒表示の輝度
(Light room contrast)
Bright room contrast is a liquid crystal display device (trade name: LC-37GX1W, manufactured by Sharp Corporation) through a colorless and transparent adhesive layer on the surface opposite to the surface on which the optical functional layer is formed in the optical laminates of Examples and Comparative Examples. bonded to the screen surface, a fluorescent lamp from the direction of the upper front 60 ° of the liquid crystal display device screen (trade name: HH4125GL, manufactured by National Co.) after the illuminance of the liquid crystal display surface is 200 lux at a liquid crystal display The luminance when the device is in white display and black display is measured with a color luminance meter (trade name: BM-5A, manufactured by Topcon Corporation), and the resulting luminance (cd / m 2 ) and white display in black display are obtained. When the luminance (cd / m 2 ) at the time was calculated by the following formula, the value was 800 when the value was 800 or less, and when the value was 801 or more, the result was ○.
Contrast = Brightness of white display / Brightness of black display
(暗室コントラスト)
暗室コントラストは、実施例及び比較例の光学積層体において、光学機能層の形成面と反対面に、無色透明な粘着層を介して液晶表示装置(商品名:LC−37GX1W、シャープ社製)の画面表面に貼り合せ、暗室条件下で液晶表示装置を白表示及び黒表示としたときの輝度を色彩輝度計(商品名:BM−5A、トプコン社製)にて測定し、得られた黒表示時の輝度(cd/m2)と白表示時の輝度(cd/m2)を以下の式にて算出した時の値が、900〜1100のとき×、1101〜1300のとき△、1301〜1500のとき○とした。
コントラスト=白表示の輝度/黒表示の輝度
(Dark room contrast)
The dark room contrast is that of the liquid crystal display device (trade name: LC-37GX1W, manufactured by Sharp Corporation) through a colorless and transparent adhesive layer on the surface opposite to the surface on which the optical functional layer is formed in the optical laminates of Examples and Comparative Examples. The black display was obtained by measuring the luminance when the liquid crystal display device was set to white display and black display under dark room conditions with a color luminance meter (trade name: BM-5A, manufactured by Topcon Corporation). value when calculated in the luminance (cd / m 2) and the white display of the luminance (cd / m 2) the following equation when there is, × when 900-1100, when 1,101 to 1300 △, 1301 to In the case of 1500, it was rated as “good”.
Contrast = Brightness of white display / Brightness of black display
得られた結果を表2および表3に示した。 The obtained results are shown in Tables 2 and 3.
上記のように本発明によれば、一層構成で、優れた帯電防止性能を有し、かつ耐ケン化性、耐光性および耐スクラッチ性に優れた光学積層体、偏光板およびそれを用いた表示装置を提供することができる。 As described above, according to the present invention, an optical laminate, a polarizing plate, and a display using the same, having a single-layer structure, excellent antistatic performance, and excellent saponification resistance, light resistance, and scratch resistance. An apparatus can be provided.
1 光学積層体
10 透光性基体
20 光学機能層
21 表層
DESCRIPTION OF SYMBOLS 1 Optical laminated body 10 Translucent base | substrate 20 Optical functional layer 21 Surface layer
Claims (8)
A display device comprising the optical layered body according to claim 1.
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