JPH0748527A - Optical meterial having antireflection layer and production thereof - Google Patents
Optical meterial having antireflection layer and production thereofInfo
- Publication number
- JPH0748527A JPH0748527A JP5196533A JP19653393A JPH0748527A JP H0748527 A JPH0748527 A JP H0748527A JP 5196533 A JP5196533 A JP 5196533A JP 19653393 A JP19653393 A JP 19653393A JP H0748527 A JPH0748527 A JP H0748527A
- Authority
- JP
- Japan
- Prior art keywords
- antireflection layer
- optical material
- substrate
- refractive index
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Surface Treatment Of Optical Elements (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、反射防止層を有する光
学材料及びその製造方法に係わり、更に詳しく述べるな
らば、本発明は、ディスプレー装置の表示面、その表面
カバー材料、タッチパネル、窓ガラス、ショーウインド
ー用ガラス、ＴＶブラウン管の表示面、液晶表示装置の
表示面、計器のカバーガラス、時計のカバーガラス、偏
光用フィルム、眼鏡用レンズ、カメラ用レンズ、及び陰
極線管の前面映像面などのような映り込みの防止を必要
としている光を透過するような光学材料基体表面の塗装
に有用な反射防止層形成用塗布液を用いて得られる反射
防止層を有する光学材料及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical material having an antireflection layer and a method for producing the same, and more specifically, the present invention relates to a display surface of a display device, a surface cover material thereof, a touch panel and a window glass. , Glass for show windows, display surface of TV cathode ray tube, display surface of liquid crystal display, instrument cover glass, watch cover glass, polarizing film, spectacle lens, camera lens, and cathode ray tube front image plane. The present invention relates to an optical material having an antireflection layer obtained by using a coating liquid for forming an antireflection layer, which is useful for coating the surface of an optical material substrate that transmits light that requires the prevention of glare, and a method for producing the same.
【０００２】[0002]
【従来の技術】一般に、画像表示用材料、例えばディス
プレー装置の表示面に外部の光が反射し、あるいは、外
部映像が映り、表示面の画像を不明瞭にするなどの問題
点が知られている。このため、ディスプレー装置の表示
面などの光学材料用基体の表面に単層あるいは多層から
なる反射防止層を形成することが行われている。従来、
反射防止層を形成する方法としては、真空蒸着法、スパ
ッタリング法、イオンプレーディング法、ＣＶＤ法等の
蒸着法により、ガラスまたはプラスチックよりなる光学
材料基体の表面に直接あるいは該基体の表面に有機物質
よりなるハードコート層やプライマーコート層を形成し
た上で、シリカその他の無機材料を被着させる方法が知
られている。また、シリカコーティング液をスプレー法
により表面に吹き付け、凸凹の膜を形成し、光散乱によ
り反射防止効果を付与させたＴＶブラウン管も提案され
ている。2. Description of the Related Art Generally, there are known problems that image display materials, for example, external light is reflected on a display surface of a display device, or external images are displayed to obscure the image on the display surface. There is. Therefore, a single-layer or multi-layer antireflection layer is formed on the surface of the optical material substrate such as the display surface of the display device. Conventionally,
The antireflection layer may be formed by a vapor deposition method such as a vacuum vapor deposition method, a sputtering method, an ion plating method, or a CVD method, directly on the surface of the optical material substrate made of glass or plastic, or on the surface of the substrate by an organic substance. There is known a method of forming a hard coat layer or a primer coat layer made of, and then depositing silica or another inorganic material. Further, there has been proposed a TV Braun tube in which a silica coating liquid is sprayed on the surface by a spray method to form an uneven film, and an antireflection effect is imparted by light scattering.
【０００３】[0003]
【発明が解決しようとする課題】ところが、従来の蒸着
法によって反射防止層を形成する方法においては、製造
が困難であり、生産性が低いことから、得られる光学材
料が高価となるという欠点があり、さらに光学材料用基
体の特性が発現されなくなったり、あるいは損なわれる
という問題がある。例えば、基体がプラスチックである
場合には、プラスチック基体の耐衝撃性が格段に低下す
るようになる。また、蒸着法では基体を３００℃以上に
加熱することが必要とされるが、プラスチック基体はそ
のような高温に加熱することはできず、低加熱温度で蒸
着を行なうと、形成される膜は基体に対する密着性が不
充分なものとなる。また、シリカコーティング液をスプ
レー法によって形成された凸凹の膜では、画像の解像度
が著しく低下するといった問題点がある。However, in the conventional method of forming the antireflection layer by the vapor deposition method, it is difficult to manufacture and the productivity is low, so that the obtained optical material is expensive. In addition, there is a problem that the characteristics of the substrate for optical materials are not expressed or damaged. For example, when the substrate is plastic, the impact resistance of the plastic substrate is markedly reduced. Further, in the vapor deposition method, it is necessary to heat the substrate to 300 ° C. or higher, but the plastic substrate cannot be heated to such a high temperature, and when vapor deposition is carried out at a low heating temperature, the formed film is Adhesion to the substrate becomes insufficient. Further, the uneven film formed by spraying the silica coating liquid has a problem that the resolution of the image is remarkably lowered.
【０００４】本発明は、上記事情に鑑みてなされたもの
で、光学材料用基体の耐衝撃性などの特性が損なわれる
ことなく、かつ反射防止層の密着性が十分であり、画像
の解像度が低下することがない反射防止層を有する光学
材料を容易に、生産性良く、低コストで得ることができ
る反射防止層を有する光学材料の製造方法を提供するこ
とにある。The present invention has been made in view of the above circumstances, and does not impair the impact resistance and other characteristics of the substrate for optical materials, has sufficient adhesion of the antireflection layer, and has a high image resolution. An object of the present invention is to provide a method for producing an optical material having an antireflection layer, which can easily obtain an optical material having an antireflection layer that does not deteriorate at high productivity at low cost.
【０００５】[0005]
【課題を解決するための手段】本発明者は、多孔質シリ
カよりなる無機微粉末をバインダーに混合することによ
って、前記課題を解決しうることを見いだし、本発明を
完成した。即ち、本発明の反射防止層を有する光学材料
は、屈折率が１．４６以上の光を透過する光学材料用基
体と、この光学材料用基体の表面を覆う反射防止層とか
らなる光学材料であって、該反射防止層は平均粒径０．
３〜１００ｎｍの多孔質シリカよりなる無機微粉末がバ
インダー中に分散したものからなり、前記光学材料用基
体よりも０．０２以上低い屈折率を有し、かつ厚さが５
０〜５０００ｎｍのものであることを特徴とする。ま
た、上記反射防止層を有する光学材料においては、光学
材料用基体の屈折率が１．４６以上であることが好まし
い。The present inventor has found that the above problems can be solved by mixing an inorganic fine powder of porous silica with a binder, and completed the present invention. That is, the optical material having an antireflection layer of the present invention is an optical material comprising an optical material substrate that transmits light having a refractive index of 1.46 or more and an antireflection layer that covers the surface of the optical material substrate. Therefore, the antireflection layer has an average particle size of 0.
An inorganic fine powder made of porous silica having a particle size of 3 to 100 nm is dispersed in a binder, has a refractive index of 0.02 or more lower than that of the optical material substrate, and has a thickness of 5
It is characterized in that it is from 0 to 5000 nm. Further, in the optical material having the antireflection layer, it is preferable that the refractive index of the optical material substrate is 1.46 or more.
【０００６】また、本発明の反射防止層を有する光学材
料の製造方法は、屈折率が１．４６以上の光を透過する
光学材料用基体の表面に平均粒径０．３〜１００ｎｍの
多孔質シリカよりなる無機微粉末とバインダーとを含有
する反射防止層形成用塗布液を塗布し、前記無機微粉末
がバインダー中に分散したものからなり、前記光学材料
用基体よりも０．０２以上低い屈折率を有し、かつ厚さ
５０〜５０００ｎｍである反射防止層を形成することを
特徴とする。The method for producing an optical material having an antireflection layer of the present invention is a porous material having an average particle diameter of 0.3 to 100 nm on the surface of an optical material substrate having a refractive index of 1.46 or more. A coating liquid for forming an antireflection layer containing an inorganic fine powder of silica and a binder is applied, and the inorganic fine powder is dispersed in the binder. The refractive index is 0.02 or more lower than that of the optical material substrate. And an antireflection layer having a thickness of 50 to 5000 nm is formed.
【０００７】以下、本発明を詳しく説明する。本発明に
おいては、反射防止層が形成される光学材料用基体とし
て、その屈折率が１．４６以上の光を透過するガラスま
たはプラスチック基体あるいはこれらの基体の表面に表
面層を形成したものが用いられる。このような基体であ
れは、その材質が限定されるものではなく、無アルカリ
ガラス、アルカリホウケイ酸ガラス、アルミナケイ酸ガ
ラス、鉛ガラス、この他のガラスよりなるもの、またポ
リメチルメタクリレート、ポリカーボネート、ポリスチ
レン、酢酸セルロース、ジエチレングリコールビスアリ
ルカーボネート、ポリウレタン、メタクリレート重合
体、アクリレート重合体、その他の樹脂よりなるものが
使用することができる。The present invention will be described in detail below. In the present invention, a glass or plastic substrate that transmits light having a refractive index of 1.46 or more, or a substrate having a surface layer formed on the surface thereof is used as the optical material substrate on which the antireflection layer is formed. To be Such a substrate is not limited in its material, and is made of non-alkali glass, alkali borosilicate glass, alumina silicate glass, lead glass, other glass, polymethylmethacrylate, polycarbonate, Those made of polystyrene, cellulose acetate, diethylene glycol bisallyl carbonate, polyurethane, methacrylate polymer, acrylate polymer and other resins can be used.
【０００８】本発明において用いられる光学材料用基体
は、その屈折率が１．４６以上のものであることが必要
であり、屈折率が１．４６未満の光学材料用基体を用い
ると、実質的に反射防止効果が発現されない場合があ
る。そして、屈折率が１．５４以上の光学材料用基体を
用いると、十分に優れた反射防止効果が得ることができ
る。このように、光学材料用基体の屈折率は１．４６以
上であることが必要であるが、本発明においては、屈折
率が比較的低くて、例えば１．５４未満のガラスまたは
プラスチック基体に反射防止層を形成する場合に、当該
ガラスまたはプラスチック基体の表面に、屈折率が１．
４６以上、好ましくは１．５４以上の有機物質よりなる
表面層を形成し、これによって表面部分の屈折率を調整
したものを光学材料用基体として用いることができる。
この表面層の屈折率は、この表面層が形成されるガラス
またはプラスチック基体の屈折率と近似していることが
好ましい。この表面層は、ハードコート層としての性質
を有するものとして形成することも可能である。本発明
に用いられる光学材料用基体は、最終的に使用目的に応
じた形態とされ得るものであれば良く、平板、その他の
形態を有するものであっても良い。The optical material substrate used in the present invention must have a refractive index of 1.46 or more. When an optical material substrate having a refractive index of less than 1.46 is used, it is substantially In some cases, the antireflection effect is not exhibited. When a substrate for optical material having a refractive index of 1.54 or more is used, a sufficiently excellent antireflection effect can be obtained. As described above, the refractive index of the substrate for optical material needs to be 1.46 or more, but in the present invention, the refractive index is relatively low, and for example, it is reflected on a glass or plastic substrate of less than 1.54. When forming the prevention layer, the surface of the glass or plastic substrate has a refractive index of 1.
A substrate having a surface layer of 46 or more, preferably 1.54 or more, which is made of an organic substance, and the refractive index of the surface portion of which is adjusted by this, can be used as a substrate for an optical material.
The refractive index of this surface layer is preferably similar to that of the glass or plastic substrate on which it is formed. This surface layer can also be formed to have a property as a hard coat layer. The substrate for optical materials used in the present invention may be any one as long as it can be finally formed into a form according to the purpose of use, and may have a flat plate or other forms.
【０００９】本発明においては、光学材料用基体の表面
を覆うように反射防止層が形成される。この反射防止層
は、多孔質シリカからなる無機微粉末（以下、多孔質シ
リカ微粉末と略す。）をバインダー中に分散させてなる
ものである。この多孔質シリカ微粉末としては、例えば
高度に絡み合った枝別れしたポリマー状に生成したシリ
カを使用することができる。このような多孔質シリカ微
粉末は低密度であり、そのため粒子内に空隙が存在して
いるため、それ自身の屈折率は、通常のシリカ（屈折率
＝１．４６）と比較して著しく屈折率が低い（屈折率＝
１．２〜１．４）。このため優れた反射防止効果を得る
ことができる。反射防止層がこのような優れた反射防止
効果を得るには、少なくとも光学材料用基体の屈折率よ
りも０．０２以上低い屈折率を有することが必要であ
る。このような多孔質シリカ微粉末は、例えば、シリコ
ンのアルコキシドを用い、アルカリの存在下において加
水分解することによって得ることができる。In the present invention, the antireflection layer is formed so as to cover the surface of the optical material substrate. This antireflection layer is formed by dispersing an inorganic fine powder of porous silica (hereinafter abbreviated as porous silica fine powder) in a binder. As the porous silica fine powder, for example, silica produced in a highly entangled branched polymer form can be used. Since such fine porous silica powder has a low density and therefore has voids in the particles, its own refractive index is significantly higher than that of ordinary silica (refractive index = 1.46). Low index (refractive index =
1.2-1.4). Therefore, an excellent antireflection effect can be obtained. In order for the antireflection layer to obtain such an excellent antireflection effect, it is necessary that the antireflection layer have a refractive index which is at least 0.02 lower than the refractive index of the substrate for optical materials. Such porous silica fine powder can be obtained, for example, by hydrolyzing an alkoxide of silicon in the presence of an alkali.
【００１０】多孔質シリカ微粉末の平均粒子径は、０．
３〜１００ｎｍのものが用いられる。この平均粒子径
が、１００ｎｍより大きくなると、得られる反射防止層
において、レイリー散乱によって光が散乱され、白っぽ
く見え、その透明性が低下することがある。また、前記
多孔質シリカ微粉末の平均粒子径が０．３ｎｍ未満であ
ると、微粉末が凝集しやすく、従って反射防止層を形成
するための塗布液中における多孔質シリカ微粉末の均一
分散が困難となり、塗布液の粘度が過大になるなどの問
題が生ずる。多孔質シリカについては、粉末状でも分散
されたゾル状で使用してもよい。The average particle size of the porous silica fine powder is 0.
Those having a thickness of 3 to 100 nm are used. When the average particle diameter is larger than 100 nm, in the obtained antireflection layer, light is scattered due to Rayleigh scattering, which looks whitish and its transparency may be deteriorated. Further, when the average particle size of the porous silica fine powder is less than 0.3 nm, the fine powder easily aggregates, and therefore the uniform dispersion of the porous silica fine powder in the coating liquid for forming the antireflection layer can be achieved. It becomes difficult, and problems such as an excessive viscosity of the coating liquid occur. The porous silica may be used in the form of powder or dispersed sol.
【００１１】反射防止層中の多孔質シリカ微粉末の含有
率に関しては、格別の制限はないが、光学材料用基体に
応じて適宜対応することができるが、一般には反射防止
層の全固形分に対して５〜６０％の範囲にあることが好
ましい。The content of the porous silica fine powder in the antireflection layer is not particularly limited, but it can be appropriately adjusted depending on the substrate for optical materials. Generally, the total solid content of the antireflection layer is not limited. It is preferably in the range of 5 to 60%.
【００１２】本発明において、反射防止層は次のように
形成される。即ち、上述の多孔質シリカ微粉末をバイン
ダーの材料及び必要な分散媒とともに混合して反射防止
層形成用塗布液を調製し、これをガラスあるいはプラス
チック基体の表面上またはこれら表面に形成された表面
層上に塗布し、更に加熱などの硬化処理により硬化させ
て反射防止層を形成する。In the present invention, the antireflection layer is formed as follows. That is, the above-mentioned porous silica fine powder is mixed with a binder material and a necessary dispersion medium to prepare a coating liquid for forming an antireflection layer, and the coating liquid is formed on the surface of a glass or plastic substrate or a surface formed on these surfaces. The antireflection layer is formed by coating on the layer and further curing by a curing treatment such as heating.
【００１３】上記バインダーとしては、膜形成能を有す
る樹脂を用いることができる。そのような樹脂として
は、アクリル樹脂、ポリウレタン樹脂、メラミン樹脂、
エポキシ樹脂、ポリエステル樹脂、ポリアミド樹脂、ア
ルキド樹脂、フッ素樹脂、シリコン樹脂などの熱可塑性
樹脂、ＵＶ硬化性樹脂、ＥＢ硬化性樹脂または熱硬化性
樹脂が用いられる。ＵＶ硬化性樹脂、ＥＢ硬化性樹脂ま
たは熱硬化性樹脂がバインダーとされる場合には、その
材料として当該樹脂の前駆体が用いられ、これによって
反射防止層形成用塗布液が調製される。As the binder, a resin capable of forming a film can be used. Such resins include acrylic resins, polyurethane resins, melamine resins,
A thermoplastic resin such as an epoxy resin, a polyester resin, a polyamide resin, an alkyd resin, a fluororesin, a silicon resin, a UV curable resin, an EB curable resin or a thermosetting resin is used. When a UV curable resin, an EB curable resin or a thermosetting resin is used as a binder, a precursor of the resin is used as the material, and the coating liquid for forming the antireflection layer is prepared by this.
【００１４】またバインダーとしては、上述した樹脂の
ほかに、本発明においては、加熱により硬化する被膜を
形成する金属アルコキシドをバインダーとして用いるこ
とができ、特に低屈折率の反射防止層が形成されること
から、シリコンのアルコキシドを用いることが好まし
い。そして、シリコンのアルコキシドとしては、アルコ
キシシランまたはカーボンファンクショナルポリオルガ
ノシロキサンが用いられる。As the binder, in addition to the above-mentioned resins, in the present invention, a metal alkoxide which forms a coating film which is cured by heating can be used as a binder, and in particular, an antireflection layer having a low refractive index is formed. Therefore, it is preferable to use a silicon alkoxide. As the silicon alkoxide, alkoxysilane or carbon functional polyorganosiloxane is used.
【００１５】アルコキシシランの具体例としては、テト
ラメトキシシラン、テトラエトキシシラン、テトラプロ
ポキシシラン、テトラブトキシシラン、メチルトリメト
キシシラン、メチルトリエトキシシラン、メチルトリプ
ロポキシシラン、メチルトリブトシキシラン、エチルト
リメトキシシラン、エチルトリエトキシシラン、エチル
トリプロポキシシラン、エチルトリブトシキシラン、プ
ロピルトリメトキシシラン、プロピルトリエトキシシラ
ン、プロピルトリプロポキシシラン、プロピルトリブト
シキシラン、ジメチルジメトキシシラン、ジメチルジエ
トキシシラン、ジメチルジプロポキシシラン、ジメチル
ジブトシキシラン、ジエチルジメトキシシラン、ジエチ
ルジエトキシシラン、ジエチルジプロポキシシラン、ジ
エチルジブトシキシラン、メチルエチルジメトキシシラ
ン、メチルプロピルジエトキシシラン等がある。Specific examples of the alkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane and ethyltrimethoxy. Silane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane , Dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane Orchids, methyl ethyl dimethoxy silane, methyl propyl diethoxy silane.
【００１６】カーボンファンクショナルポリオルガノシ
ロキサンとしては、３，４−エポキシシクロヘキシルア
ルキルトリアルコキシシラン、メタクリロキシアルキル
トリアルコキシシラン、ビニルトリアルコキシシラン、
γ−グリシドキシアルキルトリアルコキシシラン、アミ
ノアルキルトリアルコキシシランなどがある。Examples of the carbon functional polyorganosiloxane include 3,4-epoxycyclohexylalkyltrialkoxysilane, methacryloxyalkyltrialkoxysilane, vinyltrialkoxysilane,
Examples include γ-glycidoxyalkyltrialkoxysilane and aminoalkyltrialkoxysilane.
【００１７】上述したバインダーは、反射防止層形成用
塗布液において、多孔質シリカ微粉末が分散された分散
媒中に分散もしくは溶解される。これらのバインダーに
ついては、単一種で用いてもよく、二種以上の混合物と
して用いても良い。特にバインダーがシランのアルコキ
シドであるときには、加水分解させて熟成させることに
より、好適な反射防止層形成用塗布液を得ることができ
る。反射防止層形成用塗布液は、光学材料用基体に対し
て容易に塗布することができるよう、上述の多孔質シリ
カ微粉末とバインダーとを水または有機溶剤よりなる分
散媒中に適当な濃度で均一に分散させたものとする。特
に、均一な塗布を達成するためには、分散媒として有機
溶剤を用いることが好ましい。この場合には、使用する
光学材料用基体を用いて、多孔質シリカ微粉末／バイン
ダーの重量比、濃度を変えた予備テストを行い、適宜検
討する必要がある。The above-mentioned binder is dispersed or dissolved in the dispersion medium in which the fine powder of porous silica is dispersed in the coating liquid for forming the antireflection layer. These binders may be used alone or as a mixture of two or more. Particularly when the binder is an alkoxide of silane, a suitable coating liquid for forming an antireflection layer can be obtained by hydrolyzing and aging. The coating liquid for forming an antireflection layer is a suitable concentration of the above-mentioned porous silica fine powder and a binder in a dispersion medium composed of water or an organic solvent so that it can be easily applied to a substrate for an optical material. It should be uniformly dispersed. Particularly, in order to achieve uniform coating, it is preferable to use an organic solvent as the dispersion medium. In this case, it is necessary to conduct a preliminary test using the substrate for an optical material to be used, in which the weight ratio and the concentration of the porous silica fine powder / binder are changed, and to examine it appropriately.
【００１８】上記分散媒として用いられる有機溶剤とし
ては、例えば、アルコール、ケトン、エステル、グリコ
ールエーテル等があり、特にメチルアルコール、エチル
アルコール、ブチルアルコール、ｎ−プロピルアルコー
ル、イソプロピルアルコールなどのアルコール類が好ま
しく用いられる。Examples of the organic solvent used as the dispersion medium include alcohols, ketones, esters, glycol ethers, etc., and particularly alcohols such as methyl alcohol, ethyl alcohol, butyl alcohol, n-propyl alcohol and isopropyl alcohol. It is preferably used.
【００１９】反射防止層形成用塗布液には、塗布膜の表
面の平滑性を向上させるためのフローコントロール剤や
濡れ改良を目的としたシリコーンオイルなどを添加する
ことが可能である。この場合には、目的とする反射防止
効果を得るために（添加剤）／（多孔質シリカ微粉末｜
バインダー）の重量比を変えた予備テストを行い、適宜
選定する必要がある。A flow control agent for improving the smoothness of the surface of the coating film and a silicone oil for improving wetting can be added to the coating liquid for forming the antireflection layer. In this case, in order to obtain the desired antireflection effect, (additive) / (porous silica fine powder)
It is necessary to carry out preliminary tests by changing the weight ratio of (binder) and select appropriately.
【００２０】このような反射防止層形成用塗布液は、上
述した光学材料用基体の表面に、通常のスピンコート
法、ディッピング法、バーコート法、グラビアコート
法、ロールコート法等の塗工法を利用して塗布され、形
成された塗布膜を硬化させることにより、反射防止層が
形成される。Such an antireflection layer-forming coating liquid is applied to the surface of the above-mentioned optical material substrate by a conventional coating method such as spin coating, dipping, bar coating, gravure coating, or roll coating. The antireflection layer is formed by curing the coating film that is applied and formed.
【００２１】本発明の反射防止層の膜厚については、そ
の厚さが小さいほど、位相の条件［（反射防止層の屈折
率）×（層厚）＝（設計波長）／４］を容易に実現する
ことができるので、反射防止効果の発現のために望まし
い。一方、反射防止層は実際上光学材料の最外表面を形
成するものとなるので、ある程度の硬度を有することが
実用上必須であり、これを達成するためには、反射防止
層は厚さが大きいものであることが望ましい。このよう
な観点から、本発明においては、反射防止層の厚さは５
０〜５０００ｎｍ、好ましくは１００〜３０００ｎｍの
範囲内とされる。Regarding the film thickness of the antireflection layer of the present invention, the smaller the thickness, the easier the phase condition [(refractive index of antireflection layer) × (layer thickness) = (design wavelength) / 4] becomes. Since it can be realized, it is desirable for exhibiting the antireflection effect. On the other hand, since the antireflection layer practically forms the outermost surface of the optical material, it is practically essential to have a certain degree of hardness, and in order to achieve this, the antireflection layer has a thickness of It is desirable to be large. From such a viewpoint, in the present invention, the thickness of the antireflection layer is 5
It is set in the range of 0 to 5000 nm, preferably 100 to 3000 nm.
【００２２】この反射防止層を有する光学材料は、光を
透過させる光学材料用基体と、この光学材料用基体を覆
う反射防止層とからなる光学材料であって、該反射防止
層がバインダー中に多孔質シリカ微粉末が分散したもの
からなり、しかもこの多孔質シリカ微粉末の屈折率が
１．２〜１．４と極めて低いために優れた反射防止効果
が得られ、また、多孔質シリカ微粉末の平均粒子径が
０．３〜１００ｎｍの非常に粒子径の小さいものである
ため、形成される反射防止層に十分な透明性を有するも
のとなる。The optical material having the antireflection layer is an optical material comprising an optical material substrate that transmits light and an antireflection layer that covers the optical material substrate, and the antireflection layer is contained in a binder. An excellent antireflection effect is obtained because the fine powder of porous silica is dispersed and the refractive index of the fine powder of porous silica is extremely low at 1.2 to 1.4. Since the average particle diameter of the powder is 0.3 to 100 nm and the particle diameter is very small, the antireflection layer to be formed has sufficient transparency.
【００２３】また、このような反射防止層を光学材料用
基体の表面に形成するには、反射防止層形成用塗布液を
光学材料用基体の表面に塗布して硬化させればよいの
で、製造が極めて容易で、生産性が高いことより、低コ
ストで光学材料を提供できる。このようにして反射防止
層を形成すると、蒸着法を用いていないことから、光学
材料用基体の耐衝撃性などの特性が損なわれることな
く、かつ反射防止層の密着性が十分であり、また、多孔
質シリカ微粉末の平均粒子径が０．３〜１００ｎｍの非
常に粒子径の小さいものであるため、画像の解像度が低
下することがない反射防止層を有する光学材料を提供で
きる。Further, in order to form such an antireflection layer on the surface of the substrate for optical materials, it is sufficient to apply a coating liquid for forming an antireflection layer on the surface of the substrate for optical materials and cure it. Since it is extremely easy and the productivity is high, an optical material can be provided at low cost. When the antireflection layer is formed in this manner, since the vapor deposition method is not used, the properties such as impact resistance of the optical material substrate are not impaired, and the adhesion of the antireflection layer is sufficient. Since the porous silica fine powder has an average particle size of 0.3 to 100 nm and a very small particle size, it is possible to provide an optical material having an antireflection layer that does not reduce image resolution.
【００２４】従って、本発明により得られる反射防止層
を有する光学材料は、ディスプレー装置の表示面、その
表示カバー材料、タッチパネル、窓ガラス、ショーウィ
ンド用ガラス、ＴＶブラウン管の表示面、液晶表示装置
の表示面、計器のカバーガラス、時計のカバーガラス、
偏光用フィルム、眼鏡用レンズ、カメラ用レンズ、陰極
線管の前面映像面などに好適に用いられるものとなる。Therefore, the optical material having an antireflection layer obtained by the present invention is used as a display surface of a display device, a display cover material thereof, a touch panel, a window glass, a glass for show windows, a display surface of a TV CRT, and a liquid crystal display device. Display surface, instrument cover glass, watch cover glass,
It can be suitably used for a polarizing film, a lens for glasses, a lens for cameras, a front image plane of a cathode ray tube, and the like.
【００２５】[0025]
【実施例】以下、発明の実施例について説明するが、本
発明がこれらに限定されるものではない。 ［実施例１］ （１）ガラス基体 厚さ２ｍｍの板状のソーダガラス板を用いた。この屈折
率は１．５１であった。 （２）反射防止層形成用塗布液 テトラメトキシシラン１００ｇとメタノール５３０ｇを
混合し、この混合液に室温において、アンモニア水（３
０％アンモニア含有）を滴下し、２４時間攪拌後、２４
時間還流してアンモニアを除去し、さらに濃縮して多孔
質シリカゾル（固形分２０重量％）を得た。得られた多
孔質シリカの平均粒子径は約１０ｎｍであり、その屈折
率は、反射防止層を種々の多孔質シリカ／バインダー比
を変化させて形成して、反射防止層の屈折率と多孔質シ
リカ固形分の関係を求め、多孔質シリカ１００％の時の
値をその直線値から求めた。その結果、多孔質シリカの
屈折率は１．２５であった。上記多孔質シリカゾル１４
５重量部とテトラエトキシシラン１００重量部と０．１
Ｎ塩酸１７重量部とをエチルアルコール中に混合分散さ
せて固形分１．０重量％の反射防止層形成用塗布液Ａを
調整した。 （３）反射防止層 上記ソーダガラス板の表面に上記反射防止層形成用塗布
液Ａをスピンコート法により塗布し、１００℃で９０分
加熱して硬化させ、平均厚さ１００ｎｍ、屈折率１．３
９の反射防止層を形成して、光学材料を得た。この光学
材料の評価結果を下記表１に示す。EXAMPLES Examples of the present invention will be described below, but the present invention is not limited thereto. Example 1 (1) Glass Substrate A plate-shaped soda glass plate having a thickness of 2 mm was used. This refractive index was 1.51. (2) Coating liquid for forming antireflection layer Tetramethoxysilane (100 g) and methanol (530 g) were mixed, and an aqueous ammonia solution (3:
(0% ammonia content) was added dropwise, and after stirring for 24 hours, 24
The mixture was refluxed for hours to remove ammonia, and further concentrated to obtain a porous silica sol (solid content 20% by weight). The average particle size of the obtained porous silica was about 10 nm, and the refractive index of the obtained anti-reflection layer was varied by changing various porous silica / binder ratios. The relationship of the silica solid content was obtained, and the value when the porous silica was 100% was obtained from the linear value. As a result, the refractive index of the porous silica was 1.25. The porous silica sol 14
5 parts by weight and tetraethoxysilane 100 parts by weight and 0.1
17 parts by weight of N hydrochloric acid was mixed and dispersed in ethyl alcohol to prepare a coating liquid A for forming an antireflection layer having a solid content of 1.0% by weight. (3) Antireflection Layer The coating liquid A for forming an antireflection layer was applied to the surface of the soda glass plate by a spin coating method, and heated at 100 ° C. for 90 minutes to be cured to have an average thickness of 100 nm and a refractive index of 1. Three
The antireflection layer 9 was formed to obtain an optical material. The evaluation results of this optical material are shown in Table 1 below.
【００２６】［実施例２］ （１）ガラス基体 厚さ５ｍｍの板状の無アルカリガラス板を用いた。この
屈折率は１．５３であった。 （２）反射防止層形成用塗布液 実施例１で調整した多孔質シリカゾル６５重量部とγ−
グリシドキシプロピルトリメトキシシラン１０重量部と
テトラメトキシシラン１５重量部と０．１Ｎ塩酸５重量
部とをエチルアルコール中に混合分散させて固形分５．
０重量％の反射防止層形成用塗布液Ｂを調整した。 （３）反射防止層 上記無アルカリガラスの表面に上記反射防止層形成用塗
布液Ｂをディッピング法により塗布し、１５０℃で３０
分加熱して硬化させ、平均厚さ２００ｎｍ、屈折率１．
４０の反射防止層を形成して、光学材料を得た。この光
学材料の評価結果を下記表１に示す。Example 2 (1) Glass Substrate A plate-shaped non-alkali glass plate having a thickness of 5 mm was used. This refractive index was 1.53. (2) Coating liquid for forming antireflection layer 65 parts by weight of porous silica sol prepared in Example 1 and γ-
A solid content of 5 parts by weight of 10 parts by weight of glycidoxypropyltrimethoxysilane, 15 parts by weight of tetramethoxysilane, and 5 parts by weight of 0.1N hydrochloric acid was mixed and dispersed in ethyl alcohol.
A coating liquid B for forming an antireflection layer of 0% by weight was prepared. (3) Antireflection Layer The coating liquid B for forming an antireflection layer is applied to the surface of the alkali-free glass by a dipping method, and the coating liquid B is applied at 150 ° C.
It is heated for a minute to be cured, and has an average thickness of 200 nm and a refractive index of 1.
40 antireflection layers were formed to obtain an optical material. The evaluation results of this optical material are shown in Table 1 below.
【００２７】［実施例３］ （１）プラスチック基体 厚さ２ｍｍの板状のアクリル板を用いた。この屈折率は
１．４８であった。一方、γ−グリシドキシプロピルト
リメトキシシラン３５重量部とメチルトリメトキシシラ
ン２０重量部と０．１Ｎ塩酸８重量との混合物６３重量
部に、五酸化アンチモンゾル（３０重量％）５０重量部
とエチルアルコール５２重量部を添加して、表面層形成
用塗布液Ｆを調整した。そして、上記アクリル板の表面
にこの表面層形成用塗布液Ｆをディッピング法により塗
布し、９０℃で１時間加熱して硬化させ、平均厚さ３０
００ｎｍ、屈折率１．５５の表面層を形成して、プラス
チック基体を得た。 （２）反射防止層形成用塗布液 実施例２において調整した反射防止層形成用塗布液Ｂを
用いた。 （３）反射防止層 上記表面層を形成したプラスチック基体の表面層上に実
施例２において調整した反射防止層形成用塗布液Ｂをデ
ィッピング用により塗布し、９０℃２時間加熱して硬化
させ、平均厚さ１００ｎｍ、屈折率１．４０の反射防止
層を形成して、光学材料を得た。この光学材料の評価結
果を下記表１に示す。Example 3 (1) Plastic Substrate A plate-shaped acrylic plate having a thickness of 2 mm was used. This refractive index was 1.48. On the other hand, 63 parts by weight of a mixture of 35 parts by weight of γ-glycidoxypropyltrimethoxysilane, 20 parts by weight of methyltrimethoxysilane and 8 parts by weight of 0.1N hydrochloric acid was added to 50 parts by weight of antimony pentoxide sol (30% by weight). 52 parts by weight of ethyl alcohol was added to prepare a coating liquid F for forming a surface layer. Then, the surface layer-forming coating liquid F is applied to the surface of the acrylic plate by a dipping method, and is heated at 90 ° C. for 1 hour to be cured to have an average thickness of 30.
A surface layer having a thickness of 00 nm and a refractive index of 1.55 was formed to obtain a plastic substrate. (2) Antireflection Layer-Forming Coating Liquid The antireflection layer-forming coating liquid B prepared in Example 2 was used. (3) Antireflection Layer The antireflection layer-forming coating liquid B prepared in Example 2 was applied by dipping on the surface layer of the plastic substrate on which the above surface layer was formed, and heated at 90 ° C. for 2 hours for curing. An antireflection layer having an average thickness of 100 nm and a refractive index of 1.40 was formed to obtain an optical material. The evaluation results of this optical material are shown in Table 1 below.
【００２８】［実施例４］ （１）プラスチック基体 厚さ１８０μｍのポリエチレンテレフタレートフィルム
を用いた。この屈折率は１．６５であった。一方、この
ポリエチレンテレフタレートフィルムの表面に実施例３
で調整した表面層形成用塗布液Ｆをバーコート法により
塗布して、１１０℃で２０分間加熱して硬化させ、平均
厚さ４０００ｎｍ、屈折率１．５５の表面層を形成し、
プラスチック基体を得た。 （２）反射防止層形成用塗布液 実施例１調整した多孔質シリカゾル７５重量部とビニル
トリメトキシシラン１０重量部とγ−グリシドキシプロ
ピルトリメトキシシラン２０重量部と０．１Ｎ塩酸５重
量部とをエチルアルコール中に混合分散させて固形分
５．０重量％の反射防止層形成用塗布液Ｃを調整した。 （３）反射防止層 上記表面層を形成したプラスチック基体の表面に上記反
射防止層形成用塗布液Ｃをバーコート法により塗布し
て、１１０℃で２０分加熱して硬化させ、平均厚さ１０
０ｎｍ、屈折率１．４０の反射防止層を形成して、光学
材料を得た。この光学材料の評価結果を下記表１に示
す。Example 4 (1) Plastic Substrate A polyethylene terephthalate film having a thickness of 180 μm was used. This refractive index was 1.65. On the other hand, Example 3 was formed on the surface of this polyethylene terephthalate film.
The coating solution F for forming a surface layer prepared in 1. is applied by a bar coating method and heated at 110 ° C. for 20 minutes to be cured to form a surface layer having an average thickness of 4000 nm and a refractive index of 1.55.
A plastic substrate was obtained. (2) Coating liquid for forming antireflection layer Example 1 75 parts by weight of the prepared porous silica sol, 10 parts by weight of vinyltrimethoxysilane, 20 parts by weight of γ-glycidoxypropyltrimethoxysilane and 5 parts by weight of 0.1N hydrochloric acid. And were mixed and dispersed in ethyl alcohol to prepare a coating liquid C for forming an antireflection layer having a solid content of 5.0% by weight. (3) Antireflection Layer The coating liquid C for forming an antireflection layer is applied to the surface of the plastic substrate on which the surface layer is formed by a bar coating method, and heated at 110 ° C. for 20 minutes to be cured, and the average thickness is
An antireflection layer having a thickness of 0 nm and a refractive index of 1.40 was formed to obtain an optical material. The evaluation results of this optical material are shown in Table 1 below.
【００２９】［実施例５］ （１）プラスチック基体 板状の眼鏡用ジエチレングリコールビスアリルカーボン
コートボネート板を用いた。この屈折率は１．４９であ
った。一方、この板の表面に実施例３で調整した表面層
形成用塗布液Ｆをディッピング法により塗布して、１２
０℃で１時間加熱して硬化させ、平均厚さ２５００ｎ
ｍ、屈折率１．５５の表面層を形成し、プラスチック基
体を得た。 （２）反射防止層形成用塗布液 上記実施例１で調整した多孔質シリカゾル９０重量部と
メチルトリメトキシシラン２０重量部とテトラエトキシ
シラン３０重量部と０．１Ｎ塩酸９重量部とをエチルア
ルコール中に混合分散させて固形分５．０重量％の反射
防止層形成用塗布液Ｄを調整した。 （３）反射防止層 上記表面層を形成したプラスチック基体の表面に上記反
射防止層形成用塗布液Ｄをディッピング法により塗布し
て、１２０℃で２時間加熱して硬化させ、平均厚さ１２
０ｎｍ、屈折率１．３９の反射防止層を形成して、光学
材料を得た。この光学材料の評価結果を下記表１に示
す。Example 5 (1) Plastic Substrate A plate-shaped eyeglass-use diethylene glycol bisallyl carbon coated bonate plate was used. This refractive index was 1.49. On the other hand, the surface layer-forming coating liquid F prepared in Example 3 was applied to the surface of this plate by a dipping method to give 12
Heated at 0 ° C for 1 hour to cure, average thickness 2500n
A surface layer having m and a refractive index of 1.55 was formed to obtain a plastic substrate. (2) Coating liquid for forming antireflection layer 90 parts by weight of the porous silica sol prepared in Example 1 above, 20 parts by weight of methyltrimethoxysilane, 30 parts by weight of tetraethoxysilane and 9 parts by weight of 0.1N hydrochloric acid were mixed with ethyl alcohol. A coating liquid D for forming an antireflection layer having a solid content of 5.0% by weight was prepared by mixing and dispersing therein. (3) Antireflection Layer The antireflection layer-forming coating liquid D is applied to the surface of the plastic substrate having the surface layer formed thereon by a dipping method, and heated at 120 ° C. for 2 hours to be cured to have an average thickness of 12
An antireflection layer having a thickness of 0 nm and a refractive index of 1.39 was formed to obtain an optical material. The evaluation results of this optical material are shown in Table 1 below.
【００３０】[0030]
【表１】 [Table 1]
【００３１】表１中の評価項目の密着性テストは、プラ
スチック基体表面に１ｃｍ角を１ｍｍ間隔で１００個に
クロスカットし、メンディングテープで剥離テストを行
った。耐摩耗テストは、光学材料用基体がガラス基体で
あるものついてはＬｉｏｎ５０の消しゴムに１ｋｇの荷
重をかけ２０回往復させることにより行い、一方光学材
料用基体がプラスチック基体であるものついては＃００
００のスチールウールに５００ｇの荷重をかけ１０回往
復させることにより行った。In the adhesion test of the evaluation items in Table 1, 100 cm 1 cm square was cross-cut at intervals of 1 mm on the surface of the plastic substrate, and a peeling test was performed with a mending tape. The abrasion resistance test was conducted by applying a load of 1 kg to the eraser of Lion 50 and reciprocating 20 times for the glass substrate as the optical material substrate, while using # 00 for the plastic substrate as the optical material substrate.
It was carried out by applying a load of 500 g to steel wool of No. 00 and reciprocating 10 times.
【００３２】[0032]
【発明の効果】以上説明したように本発明の反射防止層
を有する光学材料は、光を透過させる光学材料用基体
と、この光学材料用基体を覆う反射防止層とからなる光
学材料であって、該反射防止層がバインダー中に多孔質
シリカ微粉末が分散したものからなり、しかもこの多孔
質シリカ微粉末の屈折率が１．２〜１．４と極めて低い
ために優れた反射防止効果が得られ、また、多孔質シリ
カ微粉末の平均粒子径が０．３〜１００ｎｍの非常に粒
子径の小さいものであるため、形成される反射防止層に
十分な透明性を有するものとなる。As described above, the optical material having the antireflection layer of the present invention is an optical material comprising an optical material substrate that transmits light and an antireflection layer that covers the optical material substrate. The antireflection layer is composed of a dispersion of finely divided porous silica powder in a binder, and the refractive index of the finely divided porous silica powder is as extremely low as 1.2 to 1.4, resulting in an excellent antireflection effect. Since the obtained porous silica fine powder has a very small average particle diameter of 0.3 to 100 nm, the antireflection layer to be formed has sufficient transparency.
【００３３】また、本発明の反射防止層を有する光学材
料の製造方法は、反射防止層形成用塗布液を光学材料用
基体の表面に塗布して硬化させればよいので、製造が極
めて容易で、生産性が高いことより、低コストで光学材
料を提供できる。このようにして反射防止層を形成する
と、蒸着法を用いていないことから、光学材料用基体の
耐衝撃性などの特性が損なわれることなく、かつ反射防
止層の密着性が十分であり、また、多孔質シリカ微粉末
の平均粒子径が０．３〜１００ｎｍの非常に粒子径の小
さいものであるため、画像の解像度が低下することがな
い反射防止層を有する光学材料を提供できる。Further, in the method for producing an optical material having an antireflection layer of the present invention, since the coating liquid for forming an antireflection layer may be applied to the surface of the substrate for optical material and cured, the production is extremely easy. Since the productivity is high, the optical material can be provided at low cost. When the antireflection layer is formed in this manner, since the vapor deposition method is not used, the properties such as impact resistance of the optical material substrate are not impaired, and the adhesion of the antireflection layer is sufficient. Since the porous silica fine powder has an average particle size of 0.3 to 100 nm and a very small particle size, it is possible to provide an optical material having an antireflection layer that does not reduce image resolution.
【００３４】従って、本発明により得られる反射防止層
を有する光学材料は、ディスプレー装置の表示面、その
表示カバー材料、タッチパネル、窓ガラス、ショーウィ
ンド用ガラス、ＴＶブラウン管の表示面、液晶表示装置
の表示面、計器のカバーガラス、時計のカバーガラス、
偏光用フィルム、眼鏡用レンズ、カメラ用レンズ、陰極
線管の前面映像面などに好適に用いられるものとなる。Therefore, the optical material having an antireflection layer obtained by the present invention is used as a display surface of a display device, a display cover material thereof, a touch panel, a window glass, a glass for show windows, a display surface of a TV cathode ray tube and a liquid crystal display device. Display surface, instrument cover glass, watch cover glass,
It can be suitably used for a polarizing film, a lens for glasses, a lens for cameras, a front image plane of a cathode ray tube, and the like.
Claims (3)
学材料用基体と、この光学材料用基体の表面を覆う反射
防止層とからなる光学材料であって、前記反射防止層は
平均粒径０．３〜１００ｎｍの多孔質シリカよりなる無
機微粉末がバインダー中に分散したものからなり、前記
光学材料用基体よりも０．０２以上低い屈折率を有し、
かつ厚さが５０〜５０００ｎｍであることを特徴とする
反射防止層を有する光学材料。1. An optical material comprising a substrate for optical material which transmits light having a refractive index of 1.46 or more, and an antireflection layer covering the surface of the substrate for optical material, wherein the antireflection layer is an average. An inorganic fine powder made of porous silica having a particle diameter of 0.3 to 100 nm is dispersed in a binder, and has a refractive index of 0.02 or more lower than that of the optical material substrate,
An optical material having an antireflection layer having a thickness of 50 to 5000 nm.
であることを特徴とする請求項１記載の反射防止層を有
する光学材料。2. The optical material having an antireflection layer according to claim 1, wherein the refractive index of the substrate for optical material is 1.46 or more.
学材料用基体の表面に平均粒径０．３〜１００ｎｍの多
孔質シリカよりなる無機微粉末とバインダーとを含有す
る反射防止層形成用塗布液を塗布し、前記無機微粉末が
バインダー中に分散したものからなり、前記光学材料用
基体よりも０．０２以上低い屈折率を有し、かつ厚さが
５０〜５０００ｎｍの反射防止層を形成することを特徴
とする反射防止層を有する光学材料の製造方法。3. An antireflection layer containing an inorganic fine powder of porous silica having an average particle diameter of 0.3 to 100 nm and a binder on the surface of a substrate for an optical material which transmits light having a refractive index of 1.46 or more. A coating liquid for forming is applied, and the inorganic fine powder is dispersed in a binder, and has a refractive index of 0.02 or more lower than that of the substrate for optical materials, and has an antireflection property of 50 to 5000 nm in thickness. A method for producing an optical material having an antireflection layer, which comprises forming a layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5196533A JPH0748527A (en) | 1993-08-06 | 1993-08-06 | Optical meterial having antireflection layer and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5196533A JPH0748527A (en) | 1993-08-06 | 1993-08-06 | Optical meterial having antireflection layer and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0748527A true JPH0748527A (en) | 1995-02-21 |
Family
ID=16359326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5196533A Pending JPH0748527A (en) | 1993-08-06 | 1993-08-06 | Optical meterial having antireflection layer and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0748527A (en) |
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