JPH0812902A - Coating fluid for forming antireflection film and substrate with antireflection film - Google Patents
Coating fluid for forming antireflection film and substrate with antireflection filmInfo
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- JPH0812902A JPH0812902A JP6150966A JP15096694A JPH0812902A JP H0812902 A JPH0812902 A JP H0812902A JP 6150966 A JP6150966 A JP 6150966A JP 15096694 A JP15096694 A JP 15096694A JP H0812902 A JPH0812902 A JP H0812902A
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- antireflection film
- substrate
- refractive index
- average particle
- forming
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Abstract
Description
【０００１】[0001]
【発明の技術分野】本発明は、反射防止膜形成用塗布液
および反射防止膜付基材に関し、さらに詳しくはガラ
ス、プラスチックなどからなる基材の表面反射を防止す
る反射防止膜形成用塗布液および反射防止膜付基材に関
する。TECHNICAL FIELD The present invention relates to a coating liquid for forming an antireflection film and a substrate with an antireflection film, and more specifically, a coating liquid for forming an antireflection film for preventing surface reflection of a substrate made of glass, plastic or the like. And a substrate with an antireflection film.
【０００２】[0002]
【発明の技術的背景】従来より、ガラス、プラスチック
などからなる基材表面に、高屈折率を有する透明被膜と
低屈折率を有する透明被膜とを交互に積層することによ
り、基材表面の反射率を効果的に低減した反射防止膜を
得ている。BACKGROUND OF THE INVENTION Conventionally, a transparent coating having a high refractive index and a transparent coating having a low refractive index are alternately laminated on the surface of a substrate made of glass, plastic or the like to reflect the surface of the substrate. An antireflection film having an effective reduction in the rate is obtained.
【０００３】従来、このような多層反射防止膜は、各層
毎に真空蒸着法、スパッタリング法などの乾式薄膜形成
法またはコーティング法、ディッピング法などの湿式薄
膜形成法で形成されていた。Conventionally, such a multilayer antireflection film has been formed for each layer by a dry thin film forming method such as a vacuum vapor deposition method and a sputtering method or a wet thin film forming method such as a coating method and a dipping method.
【０００４】しかしながら、このような従来の多層反射
防止膜の形成法では、各層毎に薄膜を形成する工程を繰
り返さなければならず、このため、反射防止膜の形成工
程が複雑になり、反射防止膜を形成する際に必要とされ
るコストが高くなるといった問題点があった。However, in such a conventional method for forming a multilayer antireflection film, the step of forming a thin film for each layer must be repeated, which complicates the step of forming the antireflection film and prevents the reflection. There is a problem that the cost required for forming the film becomes high.
【０００５】さらに、上記従来の乾式薄膜形成法で多層
反射防止膜を形成した場合には大面積の反射防止膜が得
難く、上記従来の湿式薄膜形成法で多層反射防止膜を形
成した場合には、高屈折率を有する透明被膜と低屈折率
を有する透明被膜との界面での密着性が不充分であるな
どの問題点があった。Further, when a multilayer antireflection film is formed by the above-mentioned conventional dry thin film forming method, it is difficult to obtain a large-area antireflection film, and when a multilayer antireflection film is formed by the above-mentioned conventional wet thin film forming method. Has problems such as insufficient adhesion at the interface between the transparent coating having a high refractive index and the transparent coating having a low refractive index.
【０００６】[0006]
【発明の目的】本発明は、上記事情に鑑みてなされたも
ので、反射防止性能に優れた反射防止膜が簡単な工程で
安価に基材表面に形成できるような反射防止膜形成用塗
布液、およびこのような塗布液から得られた反射防止膜
を有する反射防止膜付基材を提供することを目的として
いる。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is an antireflection film-forming coating liquid capable of inexpensively forming an antireflection film having excellent antireflection performance on a substrate surface in a simple process. , And an antireflection film-coated substrate having an antireflection film obtained from such a coating liquid.
【０００７】[0007]
【発明の概要】本発明に係る反射防止膜形成用塗布液
は、平均粒径Ｄ1 が大きく、屈折率ｎ1が大きな微粒子
Ｐ1 と、平均粒径Ｄ2 が小さく、屈折率ｎ2 が小さな微
粒子Ｐ2と、被膜形成成分Ｆとを含有してなり、 Ｄ1 ／Ｄ2 ≧３ ｎ1 ＞ｎ2 であることを特徴としている。Antireflection film-forming coating liquid according to the SUMMARY OF THE INVENTION The present invention has a large average particle diameter D 1, the refractive index n 1 is greater particles P 1, smaller average particle diameter D 2, the refractive index n 2 It is characterized in that it contains small particles P 2 and a film-forming component F and that D 1 / D 2 ≧ 3 n 1 > n 2 .
【０００８】上記微粒子Ｐ1 は、ＴｉＯ2 、ＺｒＯ2 、
ＣｅＯ2 またはＳｎＯ2 からなることが好ましく、上記
微粒子Ｐ2 は、ＭｇＦ2 またはＳｉＯ2 からなることが
好ましい。The fine particles P 1 are composed of TiO 2 , ZrO 2 ,
CeO 2 or SnO 2 is preferable, and the fine particles P 2 are preferably made of MgF 2 or SiO 2 .
【０００９】本発明に係る反射防止膜付基材は、上記塗
布液から得られた反射防止膜を基材上に有することを特
徴としている。The base material with an antireflection film according to the present invention is characterized by having the antireflection film obtained from the above coating solution on the base material.
【００１０】[0010]
【発明の具体的説明】反射防止膜形成用塗布液 まず、本発明に係る反射防止膜形成用塗布液について具
体的に説明する。DETAILED DESCRIPTION OF THE INVENTION Coating Liquid for Forming Antireflection Film First, the coating liquid for forming antireflection film according to the present invention will be specifically described.
【００１１】本発明に係る反射防止膜形成用塗布液は、
平均粒径Ｄ1 が大きく、屈折率ｎ1が大きな微粒子Ｐ1
と、平均粒径Ｄ2 が小さく、屈折率ｎ2 が小さな微粒子
Ｐ2とを含有している。The coating liquid for forming an antireflection film according to the present invention is
Large average particle diameter D 1, the refractive index n 1 is greater particles P 1
And fine particles P 2 having a small average particle diameter D 2 and a small refractive index n 2 .
【００１２】上記平均粒径Ｄ1 は０．０８〜１．０μ
ｍ、好ましくは０．１〜０．５μｍであることが望まし
く、上記平均粒径Ｄ2 は０．００１〜０．１μｍ、好ま
しくは０．０１〜０．０５であることが望ましい。The average particle diameter D 1 is 0.08 to 1.0 μm.
m, preferably 0.1 to 0.5 μm, and the average particle diameter D 2 is 0.001 to 0.1 μm, preferably 0.01 to 0.05.
【００１３】本発明では、上記平均粒径Ｄ1 と上記平均
粒径Ｄ2 とが、下記式： Ｄ1 ／Ｄ2 ≧３ を満足することが必要である。In the present invention, it is necessary that the average particle diameter D 1 and the average particle diameter D 2 satisfy the following formula: D 1 / D 2 ≧ 3.
【００１４】Ｄ1 ／Ｄ2 ＜３の場合には、平均粒径がＤ
1 であり、屈折率がｎ1 である微粒子Ｐ1 と、平均粒径
がＤ2 であり、屈折率がｎ2 である微粒子Ｐ2 とを含む
塗布液から基材上に形成された反射防止膜により、充分
な反射防止性能を基材に付与できないことがある。When D 1 / D 2 <3, the average particle size is D
1, the fine particles P 1 having a refractive index of n 1, an average particle diameter of D 2, the coating liquid antireflective formed on a substrate from containing and fine particles P 2 having a refractive index of n 2 Depending on the film, sufficient antireflection performance may not be imparted to the substrate.
【００１５】屈折率ｎ1 が大きな材料としては、屈折率
が１．６０以上のものであれば良く、具体的にはＴｉＯ
2 、ＺｒＯ2 、ＳｎＯ2 、ＣｅＯ2 、Ｉｎ2 Ｏ3 あるい
はチタン酸バリウム、ダイアモンド、硫化亜鉛などが挙
げられ、ＴｉＯ2 、ＺｒＯ2、ＣｅＯ2 またはＳｎＯ2
が好ましい。As a material having a large refractive index n 1 , any material having a refractive index of 1.60 or more may be used.
2 , ZrO 2 , SnO 2 , CeO 2 , In 2 O 3 or barium titanate, diamond, zinc sulfide and the like, and TiO 2 , ZrO 2 , CeO 2 or SnO 2
Is preferred.
【００１６】屈折率ｎ2 が小さな材料としては、屈折率
が１．４５以下のものであれば良く、具体的にはＳｉＯ
2 、ＭｇＦ2 、ＣａＦ2 、ＬｉＦ、フッ素樹脂などが挙
げられ、ＭｇＦ2 、ＳｉＯ2 （多孔性シリカを含む）が
好ましい。As a material having a small refractive index n 2 , any material having a refractive index of 1.45 or less may be used.
2 , MgF 2 , CaF 2 , LiF, fluororesin and the like can be mentioned, and MgF 2 and SiO 2 (including porous silica) are preferable.
【００１７】上記屈折率ｎ1 と上記屈折率ｎ2 とは、下
記式： ｎ1 ＞ｎ2 で表される。この屈折率差（ｎ1 −ｎ2 ）は、０．１以
上、特に０．２以上であることが好ましい。The refractive index n 1 and the refractive index n 2 are represented by the following formula: n 1 > n 2 . This refractive index difference (n 1 −n 2 ) is preferably 0.1 or more, and particularly preferably 0.2 or more.
【００１８】屈折率差（ｎ1 −ｎ2 ）が０．１未満の場
合には、平均粒径がＤ1 であり、屈折率がｎ1 である微
粒子Ｐ1 と、平均粒径がＤ2 であり、屈折率がｎ2 であ
る微粒子Ｐ2 とを含む塗布液から基材上に形成された反
射防止膜により、充分な反射防止性能を基材に付与でき
ないことがある。[0018] When the refractive index difference (n 1 -n 2) is less than 0.1, an average particle size of D 1, the fine particles P 1 having a refractive index of n 1, an average particle diameter D 2 Therefore, the antireflection film formed on the substrate from the coating liquid containing the fine particles P 2 having a refractive index of n 2 may not be able to impart sufficient antireflection performance to the substrate.
【００１９】本発明に係る塗布液は、上記のような平均
粒径がＤ1 であり、屈折率がｎ1 である微粒子Ｐ1 と、
平均粒径がＤ2 であり、屈折率がｎ2 である微粒子Ｐ2
とを含んでいればよく、さらに前記微粒子Ｐ1 と平均粒
径および屈折率がほぼ等しい他の材料からなる微粒子、
前記微粒子Ｐ2 と平均粒径および屈折率がほぼ等しい他
の材料からなる微粒子、平均粒径および屈折率が前記微
粒子Ｐ1 とＰ2 との中間の値を示す他の材料からなる微
粒子を含んでいてもよい。The coating solution according to the present invention comprises the fine particles P 1 having the average particle diameter D 1 and the refractive index n 1 as described above,
Average particle diameter of D 2, fine particles P 2 having a refractive index of n 2
And a fine particle made of another material having an average particle diameter and a refractive index substantially equal to those of the fine particle P 1 .
Including fine particles made of another material having an average particle diameter and refractive index substantially equal to those of the fine particles P 2, and fine particles made of another material having an average particle diameter and refractive index intermediate between those of the fine particles P 1 and P 2. You can leave.
【００２０】前記微粒子Ｐ1 と前記微粒子Ｐ2 との混合
比（Ｐ1 ／Ｐ2 ）は、平均粒径Ｄ1およびＤ2 、屈折率
がｎ1 およびｎ2 の値に応じて適宜調整され、８０／２
０〜２０／８０重量比、好ましくは７０／３０〜２０／
８０重量比に調整することが望ましい。The mixing ratio (P 1 / P 2 ) of the fine particles P 1 and the fine particles P 2 is appropriately adjusted according to the average particle diameters D 1 and D 2 and the refractive indices n 1 and n 2. , 80/2
0 to 20/80 weight ratio, preferably 70/30 to 20 /
It is desirable to adjust the weight ratio to 80.
【００２１】Ｐ1 ／Ｐ2 が８０／２０重量比を越える
と、これらの微粒子Ｐ1 およびＰ2 を含む塗布液から基
材上に形成された被膜は、高屈折率を有する単層被膜と
区別できなくなり、基材上に被膜が形成されていない場
合に比較して基材の反射率を高めることがある。逆にＰ
1 ／Ｐ2 が２０／８０重量比未満の場合には、これらの
微粒子Ｐ1 およびＰ2 を含む塗布液から基材上に形成さ
れた被膜は、低屈折率を有する単層被膜と区別できなく
なり、充分な反射防止性能を発揮しえないことがある。When P 1 / P 2 exceeds 80/20 weight ratio, the coating film formed on the substrate from the coating solution containing these fine particles P 1 and P 2 is a single layer coating having a high refractive index. It may become indistinguishable, and the reflectance of the substrate may be increased as compared with the case where the coating is not formed on the substrate. Conversely, P
When 1 / P 2 is less than 20/80 weight ratio, the coating formed on the substrate from the coating liquid containing these fine particles P 1 and P 2 can be distinguished from the single-layer coating having a low refractive index. In some cases, sufficient antireflection performance cannot be exhibited.
【００２２】本発明に係る反射防止膜形成用塗布液は、
上記微粒子Ｐ1 およびＰ2 に加え、さらに被膜形成成分
Ｆを含有している。この被膜形成成分Ｆは、この成分か
ら基材上に形成された被膜に必要とされる基材との密着
性、硬度、機械的強度、透明性などに応じて適宜選択さ
れる。The coating liquid for forming an antireflection film according to the present invention is
In addition to the fine particles P 1 and P 2 described above, a film-forming component F is further contained. The film-forming component F is appropriately selected according to the adhesion to the substrate, hardness, mechanical strength, transparency, etc. required for the film formed on the substrate from this component.
【００２３】この被膜形成成分Ｆを具体的に例示する
と、ポリエステル樹脂、アクリル樹脂、ウレタン樹脂、
エポキシ樹脂、メラミン樹脂、シリコーン樹脂、フッ素
樹脂、塩化ビニル樹脂、酢酸ビニル樹脂、紫外線硬化樹
脂などの重合体またはこれらの重合体を形成する際に用
いられるモノマーおよび／またはオリゴマー、あるいは
アルコキシシランなどのような加水分解重縮合性化合
物、さらにはポリシラザン、ポリシラン等の無機ポリマ
ーなどが挙げられる。Specific examples of the film-forming component F include polyester resin, acrylic resin, urethane resin,
Polymers such as epoxy resins, melamine resins, silicone resins, fluororesins, vinyl chloride resins, vinyl acetate resins, and ultraviolet curing resins, or monomers and / or oligomers used in forming these polymers, or alkoxysilanes, etc. Such hydrolytic polycondensable compounds, and further inorganic polymers such as polysilazane and polysilane can be mentioned.
【００２４】これらの被膜形成成分は、単独で、あるい
は２種以上を混合して用いられる。本発明に係る反射防
止膜形成用塗布液では、微粒子Ｐ1 およびＰ2 と被膜形
成成分Ｆとの混合比〔（Ｐ1 ＋Ｐ2 ）／Ｆ〕が２０／８
０〜９０／１０重量比、好ましくは３０／７０〜８０／
２０重量比に調整されていることが望ましい。These film-forming components may be used alone or in admixture of two or more. In the coating liquid for forming an antireflection film according to the present invention, the mixing ratio [(P 1 + P 2 ) / F] of the fine particles P 1 and P 2 and the film-forming component F is 20/8.
0-90 / 10 weight ratio, preferably 30 / 70-80 /
It is desirable that the weight ratio is adjusted to 20.
【００２５】本発明に係る反射防止膜形成用塗布液は、
希釈剤としてさらに必要に応じて有機溶媒を含んでい
る。この有機溶媒としては、メタノール、エタノール、
イソプロパノール、ブタノールなどのアルコール類、ア
セトン、ＭＥＫ、ＭＩＢＫなどのケトン類、酢酸エチ
ル、酢酸ブチルなどのエステル類、トルエン、キシレン
などの芳香族類、メチルセロソルブ、エチルセロソルブ
などのエーテル類などが挙げられる。The coating liquid for forming an antireflection film according to the present invention is
If necessary, an organic solvent is further contained as a diluent. As the organic solvent, methanol, ethanol,
Examples include alcohols such as isopropanol and butanol, ketones such as acetone, MEK and MIBK, esters such as ethyl acetate and butyl acetate, aromatics such as toluene and xylene, and ethers such as methyl cellosolve and ethyl cellosolve. .
【００２６】これらの有機溶媒は、単独で、あるいは２
種以上を混合して用いられる。本発明に係る反射防止膜
形成用塗布液は、本発明の目的を損なわない範囲で、た
とえば、染料、顔料などの着色剤を加えても良い。These organic solvents may be used alone or in a mixture of 2
It is used as a mixture of two or more species. The coating liquid for forming an antireflection film according to the present invention may contain a colorant such as a dye or a pigment within a range not impairing the object of the present invention.
【００２７】また、得られる被膜の耐擦傷性を付与する
目的で平均粒径Ｄ1 よりも大きい粒径の粒子を、被膜の
反射防止性能を損なわない程度に混合しても良い。For the purpose of imparting scratch resistance to the obtained coating, particles having a particle diameter larger than the average particle diameter D 1 may be mixed to the extent that the antireflection performance of the coating is not impaired.
【００２８】反射防止膜付基材 次いで本発明に係る反射防止膜付基材について説明す
る。本発明に係る反射防止膜付基材は、上記塗布液から
得られた反射防止膜をアクリル樹脂、ポリカーボネート
樹脂、ＰＥＴなどのプラスチックまたはガラスなどから
なる基材上に有している。 Substrate with Antireflection Film Next, the substrate with antireflection film according to the present invention will be described. The base material with an antireflection film according to the present invention has the antireflection film obtained from the coating solution on a base material made of acrylic resin, polycarbonate resin, plastic such as PET, or glass.
【００２９】反射防止を必要とする基材としては、カメ
ラ、メガネなどのレンズ、ＣＲＴ、液晶表示装置などの
ような表示装置、複写機において原稿を載置するコンタ
クトガラスなどが挙げられ、これらは、通常、透明であ
る。Examples of the base material requiring antireflection include a camera, a lens such as glasses, a CRT, a display device such as a liquid crystal display device, a contact glass for placing an original in a copying machine, and the like. , Usually transparent.
【００３０】本発明では、これらの反射防止を必要とす
る基材上に、通常、０．１〜０．４μｍ、好ましくは
０．１〜０．２μｍの反射防止膜が形成されている。こ
の反射防止膜は、上記塗布液をバーコート法、スピンコ
ート法、ロールコート法、スプレー法などの方法で基材
上に塗布した後、基材、塗布液中に含まれる被膜形成成
分Ｆの性質などに応じて乾燥・被膜形成成分Ｆの硬化が
行われる。In the present invention, an antireflection film having a thickness of usually 0.1 to 0.4 .mu.m, preferably 0.1 to 0.2 .mu.m is formed on the substrate which requires antireflection. This antireflection film is obtained by applying the above coating solution onto a base material by a method such as a bar coating method, a spin coating method, a roll coating method, or a spraying method, and then applying the coating film forming component F contained in the base material and the coating solution. Drying and film-forming component F are cured depending on their properties.
【００３１】たとえば被膜形成成分Ｆが紫外線硬化樹脂
である場合、塗布液を塗布・乾燥した後の基材に紫外線
を照射して被膜形成成分Ｆを硬化させることにより反射
防止膜付基材が得られる。被膜形成成分Ｆが熱硬化性樹
脂である場合、あるいは塗布液が有機溶媒を含む場合に
は、塗布液を塗布・乾燥した後の基材に熱処理を施すこ
とにより反射防止膜付基材が得られる。For example, when the film-forming component F is an ultraviolet curable resin, the substrate after coating and drying the coating solution is irradiated with ultraviolet rays to cure the film-forming component F to obtain a substrate with an antireflection film. To be When the film-forming component F is a thermosetting resin, or when the coating liquid contains an organic solvent, the substrate after coating and drying the coating liquid is heat-treated to obtain a substrate with an antireflection film. To be
【００３２】このようにして得られる本発明に係る反射
防止膜付基材が反射防止性能に優れる理由は、上記乾燥
・被膜形成成分Ｆの硬化の過程、例えば有機溶媒が蒸発
する過程で、高屈折率の大粒径粒子が主として基材と反
射防止膜との界面近くに集まり、高屈折率の大粒径粒子
上に低屈折率の小粒径粒子が形成された反射防止膜が得
られる。この結果、高屈折率の大粒径粒子を含む層と低
屈折率の小粒径粒子を含む層とがこの順序で基材上に形
成された従来の反射防止膜より広い領域で反射防止性能
が発揮されるものと推定される。The reason why the substrate with an antireflection film according to the present invention thus obtained is excellent in the antireflection performance is that the substrate is high in the process of curing the drying / film forming component F, for example, the process of evaporating the organic solvent. Large particles with a large refractive index gather mainly near the interface between the substrate and the antireflection film, and an antireflection film in which small particles with a small refractive index are formed on large particles with a high refractive index is obtained. . As a result, the layer containing the large particle size particles having a high refractive index and the layer containing the small particle size particles having a low refractive index are provided in this order in a wider area than the conventional anti-reflection film. Is estimated to be exhibited.
【００３３】[0033]
【発明の効果】本発明によれば、単層でありながら可視
光の全領域で１％以下の反射率を有する反射防止性能に
優れた反射防止膜が基材上に形成された反射防止膜付基
材が得られる。EFFECTS OF THE INVENTION According to the present invention, an antireflection film having a single layer and a reflectance of 1% or less in the entire visible light region and having an excellent antireflection performance is formed on a substrate. A coated substrate is obtained.
【００３４】[0034]
【実施例】以下、本発明を実施例により説明するが、本
発明はこれら実施例に限定されるものではない。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
【００３５】[0035]
【実施例１】平均粒径０．１４μｍの酸化スズ微粒子
（ｎ1 ＝２．１０）がエタノールに分散したゾル（酸化
スズ濃度：１５ｗｔ％）と、平均粒径０．０２μｍのシ
リカ微粒子（ｎ2 ＝１．４５）がエタノールに分散した
ゾル（シリカ濃度：２０ｗｔ％）とを酸化スズ／シリカ
＝３５／６５重量比となるように混合した。Example 1 A sol in which tin oxide fine particles (n 1 = 2.10) having an average particle diameter of 0.14 μm are dispersed in ethanol (tin oxide concentration: 15 wt%) and silica fine particles (n having an average particle diameter of 0.02 μm (n 2 = 1.45) was mixed with sol (silica concentration: 20 wt%) dispersed in ethanol so that tin oxide / silica = 35/65 weight ratio was obtained.
【００３６】被膜形成成分として紫外線硬化樹脂（大日
本インキ社製ユニデック １７−８２４）を２％含むイ
ソプロパノール／ブタノール混合溶液（イソプロパノー
ル／ブタノール混合比＝１／１（ｗｔ／ｗｔ））に上記
混合ゾルを加え、固形分濃度４重量％の反射防止膜形成
用塗布液を調製した。An isopropanol / butanol mixed solution (isopropanol / butanol mixing ratio = 1/1 (wt / wt)) containing 2% of an ultraviolet curable resin (Unidec 17-824 manufactured by Dainippon Ink and Chemicals Inc.) as a film-forming component was added to the above mixed sol. Was added to prepare a coating liquid for forming an antireflection film having a solid content concentration of 4% by weight.
【００３７】この塗布液をＮｏ．５のバーコーターで偏
光フィルム（日東電工社製ＮＰＦ１０５ＤＵ）に塗布
し、乾燥後、８０Ｗ／ｃｍの紫外線（高圧水銀ランプ）
を照射して反射防止膜付基材を得た。This coating solution was Polarizing film (NPF105DU manufactured by Nitto Denko Corporation) is coated with a bar coater No. 5 and dried, and then 80 W / cm ultraviolet ray (high pressure mercury lamp)
Was irradiated to obtain a base material with an antireflection film.
【００３８】得られた反射防止膜付基材の波長５５０ｎ
ｍにおける反射率を分光光度計（日本分光社製）で測定
したところ、反射率は０．６％であった。The wavelength of the obtained antireflection film-coated substrate is 550 n.
When the reflectance at m was measured with a spectrophotometer (manufactured by JASCO Corporation), the reflectance was 0.6%.
【００３９】[0039]
【実施例２】平均粒径０．１２μｍの酸化チタン微粒子
（ｎ1 ＝２．５０）がエタノールに分散したゾル（酸化
チタン濃度：１０ｗｔ％）と、平均粒径０．０３μｍの
多孔質シリカ微粒子（ｎ2 ＝１．４３）がエタノールに
分散したゾル（シリカ濃度：２０ｗｔ％）とを酸化チタ
ン／シリカ＝４０／６０重量比となるように混合した。Example 2 A sol (titanium oxide concentration: 10 wt%) in which titanium oxide fine particles (n 1 = 2.50) having an average particle diameter of 0.12 μm are dispersed in ethanol, and porous silica fine particles having an average particle diameter of 0.03 μm A sol in which (n 2 = 1.43) was dispersed in ethanol (silica concentration: 20 wt%) was mixed in a titanium oxide / silica = 40/60 weight ratio.
【００４０】被膜形成成分としてアクリル樹脂（大日本
インキ社製アクリディック Ａ−１９０）を３％含むメ
チルエチルケトン／トルエン混合溶液（メチルエチルケ
トン／トルエン混合比＝１／１（ｗｔ／ｗｔ））に上記
混合ゾルを加え、固形分濃度５重量％の反射防止膜形成
用塗布液を調製した。The above mixed sol was added to a methylethylketone / toluene mixed solution (methylethylketone / toluene mixing ratio = 1/1 (wt / wt)) containing 3% of an acrylic resin (Acridic A-190 manufactured by Dainippon Ink and Chemicals) as a film forming component. Was added to prepare a coating liquid for forming an antireflection film having a solid content concentration of 5% by weight.
【００４１】この塗布液をＮｏ．４のバーコーターで実
施例１と同様の偏光フィルムに塗布し、乾燥後、７０℃
で加熱して反射防止膜付基材を得た。得られた反射防止
膜付基材の反射率を実施例１と同様にして測定したとこ
ろ、反射率は０．８％であった。This coating solution was The same polarizing film as in Example 1 was coated with a bar coater No. 4 and dried at 70 ° C.
The substrate with an antireflection film was obtained by heating at. When the reflectance of the obtained substrate with antireflection film was measured in the same manner as in Example 1, the reflectance was 0.8%.
【００４２】[0042]
【実施例３】平均粒径０．３μｍの酸化スズ微粒子（ｎ
1 ＝２．１０）がエタノールに分散したゾル（酸化スズ
濃度：２０ｗｔ％）と、平均粒径０．０３μｍのフッ化
マグネシウム微粒子（ｎ2 ＝１．３８）がエタノールに
分散したゾル（フッ化マグネシウム濃度：１０ｗｔ％）
とを酸化スズ／フッ化マグネシウム＝５０／５０重量比
となるように混合した。Example 3 Tin oxide fine particles having an average particle size of 0.3 μm (n
1 = 2.10) dispersed in ethanol (tin oxide concentration: 20 wt%) and sol in which magnesium fluoride fine particles (n 2 = 1.38) having an average particle diameter of 0.03 μm are dispersed in ethanol (fluorinated). Magnesium concentration: 10 wt%)
And were mixed so that tin oxide / magnesium fluoride = 50/50 weight ratio.
【００４３】被膜形成成分としてフッ素樹脂（旭硝子社
製ルミフロン）を１％含むメチルエチルケトン／トルエ
ン混合溶液（メチルエチルケトン／トルエン混合比＝１
／１（ｗｔ／ｗｔ））に上記混合ゾルを加え、固形分濃
度２重量％の反射防止膜形成用塗布液を調製した。A methyl ethyl ketone / toluene mixed solution containing 1% of a fluororesin (Lumiflon manufactured by Asahi Glass Co., Ltd.) as a film forming component (methyl ethyl ketone / toluene mixing ratio = 1).
/ (Wt / wt)) to prepare a coating liquid for forming an antireflection film having a solid content concentration of 2% by weight.
【００４４】この塗布液をＮｏ．５のバーコーターでア
クリル板に塗布し、乾燥後、８０℃で加熱して反射防止
膜付基材を得た。得られた反射防止膜付基材の反射率を
実施例１と同様にして測定したところ、反射率は１．１
％であった。This coating solution was It was coated on an acrylic plate with a bar coater of No. 5, dried, and then heated at 80 ° C. to obtain a substrate with an antireflection film. When the reflectance of the obtained substrate with antireflection film was measured in the same manner as in Example 1, the reflectance was 1.1.
%Met.
【００４５】[0045]
【実施例４】平均粒径０．１μｍの酸化セリウム微粒子
（ｎ1 ＝２．５０）がエタノールに分散したゾル（酸化
セリウム濃度：１０ｗｔ％）と、平均粒径０．００２μ
ｍのシリカ微粒子（ｎ2 ＝１．４５）がエタノールに分
散したゾル（シリカ濃度：２０ｗｔ％）とを酸化セリウ
ム／シリカ＝３０／７０重量比となるように混合した。Example 4 A sol (cerium oxide concentration: 10 wt%) in which cerium oxide fine particles (n 1 = 2.50) having an average particle size of 0.1 μm are dispersed in ethanol, and an average particle size of 0.002 μ
A sol (silica concentration: 20 wt%) in which silica fine particles of m (n 2 = 1.45) were dispersed in ethanol was mixed so as to have a cerium oxide / silica = 30/70 weight ratio.
【００４６】被膜形成成分として紫外線硬化樹脂（大日
本インキ社製ユニデック Ｖ−５５００）を５％含むエ
タノール／イソプロパノール混合溶液（エタノール／イ
ソプロパノール混合比＝２／１（ｗｔ／ｗｔ））に上記
混合ゾルを加え、固形分濃度３重量％の反射防止膜形成
用塗布液を調製した。The above mixed sol was added to an ethanol / isopropanol mixed solution (ethanol / isopropanol mixing ratio = 2/1 (wt / wt)) containing 5% of an ultraviolet curable resin (Unidec V-5500 manufactured by Dainippon Ink and Chemicals) as a film forming component. Was added to prepare a coating liquid for forming an antireflection film having a solid content concentration of 3% by weight.
【００４７】この塗布液をガラス板にディッピング法
（引上げ速度 １００ｍｍ／分）で塗布し、乾燥後、８
０Ｗ／ｃｍの紫外線を照射して反射防止膜付基材を得
た。得られた反射防止膜付基材の反射率を実施例１と同
様にして測定したところ、反射率は０．６％であった。This coating solution was applied to a glass plate by a dipping method (pulling speed 100 mm / min), dried and then 8
The substrate with an antireflection film was obtained by irradiating with 0 W / cm of ultraviolet rays. When the reflectance of the obtained substrate with antireflection film was measured in the same manner as in Example 1, the reflectance was 0.6%.
Claims (3)
きな微粒子Ｐ1 と、平均粒径Ｄ2 が小さく、屈折率ｎ2
が小さな微粒子Ｐ2 と、被膜形成成分Ｆとを含有してな
り、 Ｄ1 ／Ｄ2 ≧３ ｎ1 ＞ｎ2 であることを特徴とする反射防止膜形成用塗布液。1. A large average particle diameter D 1, the refractive index n 1 is greater particles P 1, smaller average particle diameter D 2, the refractive index n 2
Containing small particles P 2 and a film-forming component F, wherein D 1 / D 2 ≧ 3 n 1 > n 2 is satisfied.
ＣｅＯ2 またはＳｎＯ2 からなり、前記微粒子Ｐ2 がＭ
ｇＦ2 またはＳｉＯ2 からなることを特徴とする請求項
１に記載の反射防止膜付基材。2. The fine particles P 1 are TiO 2 , ZrO 2 ,
CeO 2 or SnO 2 , and the fine particles P 2 are M
The base material with an antireflection film according to claim 1, which is made of gF 2 or SiO 2 .
反射防止膜を基材上に有することを特徴とする反射防止
膜付基材。3. A base material with an antireflection film, comprising an antireflection film formed from the coating liquid according to claim 1 on a base material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15096694A JP3186437B2 (en) | 1994-07-01 | 1994-07-01 | Coating solution for forming anti-reflective film and substrate with anti-reflective film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15096694A JP3186437B2 (en) | 1994-07-01 | 1994-07-01 | Coating solution for forming anti-reflective film and substrate with anti-reflective film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0812902A true JPH0812902A (en) | 1996-01-16 |
| JP3186437B2 JP3186437B2 (en) | 2001-07-11 |
Family
ID=15508335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15096694A Expired - Lifetime JP3186437B2 (en) | 1994-07-01 | 1994-07-01 | Coating solution for forming anti-reflective film and substrate with anti-reflective film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3186437B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003049092A (en) * | 2001-08-03 | 2003-02-21 | Hitachi Chem Co Ltd | Filler, resin composition, and application thereof |
| WO2003080718A1 (en) * | 2002-03-22 | 2003-10-02 | Institut für Neue Materialien Gemeinnützige GmbH | Plastic film with a multilayered interference coating |
| JP2006161021A (en) * | 2004-11-15 | 2006-06-22 | Jsr Corp | Curable liquid resin composition, cured film and laminate |
| JP2008007680A (en) * | 2006-06-30 | 2008-01-17 | Jsr Corp | Curable resin composition and anti-reflection film |
| CN103052651A (en) * | 2010-08-05 | 2013-04-17 | 日本曹达株式会社 | Organic-inorganic complex and composition for forming same |
-
1994
- 1994-07-01 JP JP15096694A patent/JP3186437B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003049092A (en) * | 2001-08-03 | 2003-02-21 | Hitachi Chem Co Ltd | Filler, resin composition, and application thereof |
| WO2003080718A1 (en) * | 2002-03-22 | 2003-10-02 | Institut für Neue Materialien Gemeinnützige GmbH | Plastic film with a multilayered interference coating |
| JP2006161021A (en) * | 2004-11-15 | 2006-06-22 | Jsr Corp | Curable liquid resin composition, cured film and laminate |
| JP2008007680A (en) * | 2006-06-30 | 2008-01-17 | Jsr Corp | Curable resin composition and anti-reflection film |
| CN103052651A (en) * | 2010-08-05 | 2013-04-17 | 日本曹达株式会社 | Organic-inorganic complex and composition for forming same |
| US20130131245A1 (en) * | 2010-08-05 | 2013-05-23 | Nippon Soda Co., Ltd. | Organic-inorganic complex and composition for forming same |
| US9234117B2 (en) * | 2010-08-05 | 2016-01-12 | Nippon Soda Co., Ltd. | Organic-inorganic complex and composition for forming same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3186437B2 (en) | 2001-07-11 |
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