JP3412302B2 - Method for manufacturing plastic optical component having antireflection film - Google Patents
Method for manufacturing plastic optical component having antireflection filmInfo
- Publication number
- JP3412302B2 JP3412302B2 JP31669294A JP31669294A JP3412302B2 JP 3412302 B2 JP3412302 B2 JP 3412302B2 JP 31669294 A JP31669294 A JP 31669294A JP 31669294 A JP31669294 A JP 31669294A JP 3412302 B2 JP3412302 B2 JP 3412302B2
- Authority
- JP
- Japan
- Prior art keywords
- antireflection film
- film
- cured
- optical component
- ion beam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Landscapes
- Surface Treatment Of Optical Elements (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Polarising Elements (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、反射防止フィルムや、
反射防止膜を有する偏光板等、反射防止膜を有するプラ
スチック製光学部品の製造方法に関する。The present invention relates to an antireflection film,
The present invention relates to a method for manufacturing a plastic optical component having an antireflection film, such as a polarizing plate having an antireflection film.
【０００２】[0002]
【従来の技術】レンズ等の光学部品には、従来、無機ガ
ラスが多く使用されてきたが、近年、軽量、耐衝撃性、
易加工性の長所を持ち、かつ量産性に優れているプラス
チックが用いられるようになってきた。しかし、プラス
チック製光学部品は、無機ガラス製光学部品に比べて表
面硬度が低く、傷が付きやすいうえに、無機ガラス製光
学部品と同様に表面での反射光が強いという欠点も有し
ている。このような問題に対しては、プラスチック基材
表面に硬化被膜を設けて耐擦傷性を向上させるととも
に、さらにその硬化被膜の表面に反射防止膜を付与し、
実用的な性能を確保している。2. Description of the Related Art Inorganic glass has been widely used for optical components such as lenses, but in recent years, it is lightweight, has high impact resistance,
Plastics, which have the advantage of easy workability and are excellent in mass productivity, have come into use. However, plastic optical parts have lower surface hardness than inorganic glass optical parts, are more likely to be scratched, and have the drawback that the light reflected from the surface is stronger, similar to inorganic glass optical parts. . For such a problem, a cured coating is provided on the surface of the plastic substrate to improve scratch resistance, and an antireflection film is further provided on the surface of the cured coating.
Secures practical performance.
【０００３】このようなレンズ等の光学部品において
は、反射率を１％以下に抑える必要があることから、反
射防止膜は、フッ化マグネシウム、二酸化珪素、二酸化
ジルコニウム、二酸化チタン、酸化アルミニウム等の屈
折率の異なる誘電体の多層構成となっている。しかし、
このような多層構成のものは、反射防止性能は優れてい
るものの、価格が高くなることから、レンズ等の比較的
高価な光学部品に限られていた。一方、ディスプレイ表
面に用いられる反射防止フィルムや偏光板等の光学部品
については、例えば、フッ化マグネシウム膜一層からな
る反射防止膜を有し、安価で、しかも量産化に適した反
射防止膜を有するプラスチック製光学部品が望まれてい
る。In such optical components as lenses, it is necessary to suppress the reflectance to 1% or less. Therefore, the antireflection film is made of magnesium fluoride, silicon dioxide, zirconium dioxide, titanium dioxide, aluminum oxide or the like. It has a multilayer structure of dielectrics having different refractive indexes. But,
Although such a multi-layered structure is excellent in antireflection performance, it is expensive and therefore limited to relatively expensive optical parts such as lenses. On the other hand, for optical components such as an antireflection film and a polarizing plate used for the display surface, for example, an antireflection film composed of a single layer of magnesium fluoride film is provided, and the antireflection film is inexpensive and suitable for mass production. Plastic optical components are desired.
【０００４】一般的に使われている硬化被膜の屈折率
は、１.５ 付近であるため、屈折率が１.３８ であるフ
ッ化マグネシウム一層からなる反射防止膜では、基準波
長での反射率を１.４％ まで低減させるのにとどまり、
反射防止性能は十分に満足されるものではなかった。硬
化被膜と反射防止膜の屈折率の差を大きくすることによ
って、反射防止性能を向上させることができ、このよう
な問題を解決する試みとして、例えば、特開昭 62-1180
1 号公報には、高屈折率のプラスチック基材に、ほぼ同
等の屈折率を持つ硬化被膜を形成し、さらにその上に反
射防止膜を設けることにより、反射防止性能を向上させ
ることが示されている。しかし、この方法では、その素
材自体として使用できる物質が少ないうえに、耐衝撃性
や密着性の面から、高屈折率のプラスチック基材上に形
成できる硬化被膜の種類が限られてしまうので、実用化
できるものがさらに少ない。また、これらのプラスチッ
ク基材と硬化被膜はともに高価なものが多いことも、問
題となっている。Since the refractive index of a generally used hardened film is around 1.5, an antireflection film consisting of a single layer of magnesium fluoride having a refractive index of 1.38 has a reflectance at a reference wavelength. To 1.4%,
Antireflection performance was not fully satisfactory. By increasing the difference in refractive index between the cured film and the antireflection film, the antireflection performance can be improved. As an attempt to solve such a problem, for example, JP-A-62-1180.
Japanese Patent Publication No. 1 discloses that a high-refractive-index plastic substrate is coated with a cured film having an almost equal refractive index, and an antireflection film is provided on the cured film to improve antireflection performance. ing. However, in this method, there are few substances that can be used as the material itself, and in terms of impact resistance and adhesion, the types of cured coatings that can be formed on a plastic substrate having a high refractive index are limited, There are even fewer things that can be put to practical use. Another problem is that many of these plastic substrates and cured coatings are expensive.
【０００５】[0005]
【発明が解決しようとする課題】屈折率の差が大きい硬
化被膜とプラスチック基材とを組み合わせて使用する場
合には、屈折率の差に起因する干渉が起き、分光光学特
性が低下してしまう。このように、反射防止性能に優
れ、かつ安価に量産できる一層からなる反射防止膜を有
するプラスチック製光学部品に関して、様々な検討が行
われてきたにも関わらず、未だに充分なものは得られて
いない。When a cured film having a large difference in refractive index and a plastic substrate are used in combination, interference due to the difference in refractive index occurs and the spectroscopic optical characteristics deteriorate. . As described above, in spite of various studies being conducted on the plastic optical component having the antireflection film which is excellent in antireflection performance and can be mass-produced at low cost, the plastic optical component is still sufficient. Absent.
【０００６】本発明は、このような状況に鑑みてなされ
たものであり、一層からなる反射防止膜でも良好な反射
防止性能を有するプラスチック製光学部品を、量産性良
く製造する方法を提供しようとするものである。The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a method for manufacturing a plastic optical component having a good antireflection property even with a single-layer antireflection film with good mass productivity. To do.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、プラスチ
ック基材表面に順次、硬化被膜および反射防止膜を形成
してなる反射防止膜を有するプラスチック製光学部品に
ついて、良好な反射防止性能を持ち、干渉による分光光
学特性が低下することなく、かつ工業的量産性にも優れ
る製造方法を開発すべく、鋭意検討した結果、反射防止
膜形成の前処理として、プラスチック基材に形成された
硬化被膜表面に酸素イオンビーム照射を行うことによ
り、硬化被膜表面の屈折率が上昇することを見出し、こ
のことにより、容易に硬化被膜と反射防止膜の屈折率の
差を大きくすることができ、反射防止性能と量産性を両
立させて製造する方法を完成するに至った。The present inventors have found that a plastic optical component having an antireflection film formed by sequentially forming a cured film and an antireflection film on the surface of a plastic substrate has good antireflection performance. In order to develop a manufacturing method that does not deteriorate the spectroscopic optical characteristics due to interference and is excellent in industrial mass productivity, as a result of diligent study, as a pretreatment for forming an antireflection film, curing formed on a plastic substrate It was found that the refractive index of the surface of the cured film is increased by irradiating the surface of the film with oxygen ion beam, which makes it possible to easily increase the difference in the refractive index between the cured film and the antireflection film. We have completed a manufacturing method that achieves both prevention performance and mass productivity.
【０００８】すなわち本発明は、プラスチック基材表面
に順次、硬化被膜および反射防止膜を形成して、反射防
止膜を有するプラスチック製光学部品を製造する方法で
あって、反射防止膜を形成する前に予め硬化被膜を酸素
イオンビームで照射し、かつ酸素イオンビームが照射さ
れた硬化被膜の表面に反射防止膜を一層で形成すること
を特徴とする、反射防止膜を有するプラスチック製光学
部品の製造方法を提供するものである。That is, the present invention is a method for producing a plastic optical component having an antireflection film by sequentially forming a cured film and an antireflection film on the surface of a plastic substrate, and before forming the antireflection film. Of a plastic optical component having an antireflection film, characterized by irradiating a cured film with an oxygen ion beam in advance and forming a single layer of an antireflection film on the surface of the cured film irradiated with the oxygen ion beam. It provides a method.
【０００９】以下にその内容を詳細に述べる。本発明で
対象とする反射防止膜を有するプラスチック製光学部品
としては、反射防止フィルム、反射防止膜を有する偏光
板などが挙げられる。プラスチック基材としては、光学
用途に適した透明性のある材料であればどのようなもの
でもよく、例えば、アクリル系樹脂、ポリカーボネート
系樹脂、セルロース系樹脂、ポリビニルアルコール系樹
脂、ポリプロピレン系樹脂等のフィルム、シートなどを
挙げることができる。The details will be described below. Examples of the plastic optical component having an antireflection film, which is a target of the present invention, include an antireflection film and a polarizing plate having an antireflection film. As the plastic substrate, any material may be used as long as it is a transparent material suitable for optical applications, for example, acrylic resin, polycarbonate resin, cellulose resin, polyvinyl alcohol resin, polypropylene resin, etc. Examples thereof include films and sheets.
【００１０】本発明におけるプラスチック基材の好適な
例としては、ポリビニルアルコール系樹脂フィルムから
なる偏光膜や、これにセルロース系樹脂の保護層等が形
成された偏光板を例示することができる。A preferred example of the plastic substrate in the present invention is a polarizing film made of a polyvinyl alcohol resin film, and a polarizing plate having a cellulose resin protective layer formed thereon.
【００１１】プラスチック基材上に形成される硬化被膜
としては、アクリル系硬化被膜を挙げることができる。
アクリル系硬化被膜を形成するための硬化被膜剤とし
て、具体的には例えば、広栄化学工業（株）から販売さ
れている「コーエーハード」、三菱レイヨン（株）から
販売されている「ダイヤナール」などが挙げられる。The cured coating formed on the plastic substrate may be an acrylic cured coating.
As a cured coating agent for forming an acrylic cured coating, specifically, for example, "Koei Hard" sold by Koei Chemical Industry Co., Ltd., "Dianal" sold by Mitsubishi Rayon Co., Ltd. And so on.
【００１２】本発明における反射防止膜に用いる物質と
しては、一般の光学用途に使われ、硬化被膜よりも低い
屈折率を有するものであれば特に限定されず、フッ化マ
グネシウム、二酸化珪素等の無機化合物や、含フッ素重
合体などの低屈折率物質が例示できる。また、反射防止
膜の形成方法についても特に限定されず、ディップコー
ト法、スピンコート法、イオンプレーティング法、スパ
ッタリング法など、どのような方法でもよいが、酸素イ
オンビーム照射後、同一チャンバー内で連続して反射防
止膜を形成できる、電子ビーム加熱蒸着法や抵抗加熱蒸
着法などが好ましい。The substance used for the antireflection film in the present invention is not particularly limited as long as it is used for general optical applications and has a refractive index lower than that of the cured film, and inorganic substances such as magnesium fluoride and silicon dioxide. Examples thereof include compounds and low refractive index substances such as fluoropolymers. Further, the method for forming the antireflection film is not particularly limited, and any method such as a dip coating method, a spin coating method, an ion plating method, a sputtering method may be used. An electron beam heating vapor deposition method, a resistance heating vapor deposition method, and the like, which can continuously form an antireflection film, are preferable.
【００１３】硬化被膜に酸素イオンビームを照射するこ
とにより、硬化被膜の屈折率が上昇する。用いられる酸
素イオンビームの加速電圧は、３００〜１５００Ｖの範
囲が好ましく、８００〜１０００Ｖの範囲がさらに好ま
しい。加速電圧が低すぎる場合には、硬化被膜の屈折率
の上昇が僅かであって、反射防止性能向上の効果が乏し
く、一方、加速電圧が高すぎる場合には、酸素イオンビ
ームの照射によりプラスチック基材の温度が上昇し、プ
ラスチック基材自体が変形したり着色したりするので、
好ましくない。酸素イオンビームの照射時間は、１〜５
分の範囲が好ましく、照射時間が１分未満の場合には、
反射防止性能向上の効果が乏しく、５分より長時間にわ
たる照射は、プラスチック基材の温度上昇により基材自
体が変形化するので、好ましくない。By irradiating the cured coating with an oxygen ion beam, the refractive index of the cured coating rises. The acceleration voltage of the oxygen ion beam used is preferably in the range of 300 to 1500V, more preferably in the range of 800 to 1000V. If the accelerating voltage is too low, the increase in the refractive index of the cured coating is slight, and the effect of improving the antireflection performance is poor. On the other hand, if the accelerating voltage is too high, the plastic substrate is irradiated with an oxygen ion beam. As the temperature of the material rises and the plastic substrate itself deforms and colors,
Not preferable. The irradiation time of the oxygen ion beam is 1 to 5
The range of minutes is preferable, and when the irradiation time is less than 1 minute,
Irradiation for more than 5 minutes is not very effective in improving the antireflection performance, and the base material itself is deformed by the temperature rise of the plastic base material, which is not preferable.
【００１４】[0014]
【実施例】以下、実施例で本発明を詳細に説明するが、
本発明はこれらに限定されるものではない。The present invention will be described in detail below with reference to Examples.
The present invention is not limited to these.
【００１５】実施例１
プラスチック基材として、片側表面にアクリル系硬化被
膜が形成された偏光板（住友化学工業（株）製、商品
名：スミカラン）を用い、これを真空蒸着機にセット
し、チャンバー内部を３×１０-5Torrまで排気した後、
カウフマン型のイオン銃を用いて、加速電圧１.０kV、
加速電流８０mA の条件で、酸素イオンビームをこの硬
化被膜表面に２分間照射した。反射率から見積もった硬
化被膜の屈折率は、処理前の１.５０から処理後は１.５
９に上昇していた。照射時の真空度は５×１０-5Torrで
あった。その後、この硬化被膜上に、電子ビーム加熱蒸
着法により光学膜厚０.２５λ（λ＝５５０nm） のフッ
化マグネシウムを蒸着し、反射防止層を形成した。この
分光反射率特性を図１の１ａに示す。可視光領域（３０
０〜８００nm）での最低反射率は０.８％であった。Example 1 As a plastic substrate, a polarizing plate (Sumitomo Chemical Co., Ltd., trade name: Sumikaran) having an acrylic cured coating formed on one surface was used, which was set in a vacuum vapor deposition machine. After exhausting the inside of the chamber to 3 × 10 -5 Torr,
Using a Kauffman type ion gun, acceleration voltage 1.0kV,
The surface of the cured coating was irradiated with an oxygen ion beam for 2 minutes under the condition of an accelerating current of 80 mA. The refractive index of the cured film estimated from the reflectance is 1.50 before the treatment and 1.5 after the treatment.
It was rising to 9. The degree of vacuum at the time of irradiation was 5 × 10 −5 Torr. Thereafter, magnesium fluoride having an optical film thickness of 0.25λ (λ = 550 nm) was vapor-deposited on the cured coating by an electron beam heating vapor deposition method to form an antireflection layer. This spectral reflectance characteristic is shown in 1a of FIG. Visible light region (30
The minimum reflectance at 0 to 800 nm) was 0.8%.
【００１６】実施例２
実施例１と同一の基材を用い、チャンバー内部を３×１
０-5Torrまで排気した後、カウフマン型のイオン銃を用
いて、加速電圧１.５kV、加速電流１２０mA の条件で酸
素イオンビームを硬化被膜表面に１分間照射した。反射
率から見積もった硬化被膜の屈折率は、処理前の１.５
０から処理後は１.６７に上昇していた。照射時の真空
度は５×１０-5Torrであった。その後、この硬化被膜上
に、電子ビーム加熱蒸着法により光学膜厚０.２５λ
（λ＝５５０nm） の二酸化珪素を蒸着し、反射防止層
を形成した。この分光反射率特性を図２の２ａに示す。
可視光領域（３００〜８００nm）での最低反射率は１.
２％であった。Example 2 The same base material as in Example 1 was used, and the inside of the chamber was 3 × 1.
After evacuation to 0 -5 Torr, an oxygen ion beam was applied to the surface of the cured coating for 1 minute under the conditions of an accelerating voltage of 1.5 kV and an accelerating current of 120 mA using a Kauffman type ion gun. The refractive index of the cured film estimated from the reflectance is 1.5 before the treatment.
It increased from 0 to 1.67 after treatment. The degree of vacuum at the time of irradiation was 5 × 10 −5 Torr. Then, an optical film thickness of 0.25λ was formed on the cured film by electron beam heating vapor deposition.
(Λ = 550 nm) silicon dioxide was vapor-deposited to form an antireflection layer. This spectral reflectance characteristic is shown in 2a of FIG.
The minimum reflectance in the visible light range (300-800 nm) is 1.
It was 2%.
【００１７】比較例１
酸素イオンビームを照射することなく、実施例１と同一
のプラスチック基材に同一の蒸着方法でフッ化マグネシ
ウム一層からなる反射防止膜を形成した。この分光反射
率特性を図１の１ｂに示す。可視光領域（３００〜８０
０nm）での最低反射率は１.４％であった。Comparative Example 1 An antireflection film consisting of one layer of magnesium fluoride was formed on the same plastic substrate as in Example 1 by the same vapor deposition method without irradiating with an oxygen ion beam. This spectral reflectance characteristic is shown in 1b of FIG. Visible light region (300-80
The minimum reflectance at 0 nm) was 1.4%.
【００１８】比較例２
酸素イオンビームを照射することなく、実施例１と同一
のプラスチック基材に同一の蒸着方法で二酸化珪素一層
からなる反射防止膜を形成した。この分光反射率特性を
図２の２ｂに示す。可視光領域（３００〜８００nm）で
の最低反射率は２.６％であった。Comparative Example 2 An antireflection film consisting of one layer of silicon dioxide was formed on the same plastic substrate as in Example 1 by the same vapor deposition method without irradiating with oxygen ion beam. This spectral reflectance characteristic is shown in 2b of FIG. The minimum reflectance in the visible light region (300 to 800 nm) was 2.6%.
【００１９】[0019]
【発明の効果】本発明の方法によれば、得られる反射防
止膜を有するプラスチック製光学部品は、一層からなる
反射防止膜でも良好な反射防止性能を示し、干渉による
分光光学特性の低下がなく、酸素イオンビーム照射後、
同一チャンバー内で連続して反射防止膜を形成できる。
したがって本発明の方法は、安価でかつ量産性に優れた
製造方法である。According to the method of the present invention, the obtained plastic optical component having an antireflection film exhibits good antireflection performance even with an antireflection film consisting of one layer, and there is no deterioration in spectral optical characteristics due to interference. , After the oxygen ion beam irradiation,
The antireflection film can be continuously formed in the same chamber.
Therefore, the method of the present invention is a manufacturing method that is inexpensive and excellent in mass productivity.
【図１】本発明の実施例１、比較例１の偏光板の分光反
射率特性図である。FIG. 1 is a spectral reflectance characteristic diagram of polarizing plates of Example 1 and Comparative Example 1 of the present invention.
【図２】本発明の実施例２、比較例２の偏光板の分光反
射率特性図である。FIG. 2 is a spectral reflectance characteristic diagram of polarizing plates of Example 2 and Comparative Example 2 of the present invention.
１ａ：実施例１ １ｂ：比較例１ ２ａ：実施例２ ２ｂ：比較例２ 1a: Example 1 1b: Comparative example 1 2a: Example 2 2b: Comparative example 2
───────────────────────────────────────────────────── フロントページの続き (72)発明者 波岡 誠 大阪府高槻市塚原２丁目10番１号 住友 化学工業株式会社内 (56)参考文献 特開 昭63−113401（ＪＰ，Ａ) 特開 平７−76048（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08J 7/00 - 7/18 G02B 1/11,5/30 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Makoto Namioka 2-10-1 Tsukahara, Takatsuki City, Osaka Sumitomo Chemical Co., Ltd. (56) Reference JP-A-63-113401 (JP, A) JP-A 7-76048 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C08J 7 /00-7/18 G02B 1 / 11,5 / 30
Claims (6)
よび反射防止膜を形成して、反射防止膜を有するプラス
チック製光学部品を製造する方法であって、反射防止膜
を形成する前に予め硬化被膜を酸素イオンビームで照射
し、かつ該酸素イオンビームが照射された硬化被膜の表
面に反射防止膜を一層で形成することを特徴とする、反
射防止膜を有するプラスチック製光学部品の製造方法。1. A sequential plastic substrate surface, to form a cured film and the antireflection film, a method for producing a plastic optical component having an antireflection film, pre-cured before forming the antireflection film Irradiate the coating with an oxygen ion beam
And the surface of the cured film irradiated with the oxygen ion beam.
And forming a reflection preventing film with more on the surface, the manufacturing method of the plastic optical component having an antireflection film.
求項１記載の製造方法。2. The method according to claim 1, wherein the plastic optical component is a polarizing plate.
項１または２記載の製造方法。 3. The cured coating is an acrylic cured coating.
Item 3. The manufacturing method according to Item 1 or 2.
二酸化珪素から選ばれる無機化合物の膜である請求項１
〜３のいずれかに記載の製造方法。 4. The antireflection film comprises magnesium fluoride and
A film of an inorganic compound selected from silicon dioxide.
The manufacturing method according to any one of to 3.
内で連続的に、電子ビーム加熱蒸着法または抵抗加熱蒸
着法により反射防止膜を形成する請求項１〜４のいずれ
かに記載の製造方法。 5. The same chamber after irradiation with oxygen ion beam
Continuously in the electron beam heating vapor deposition method or resistance heating vaporization
The antireflection film is formed by a deposition method.
The production method described in Crab.
００Ｖの加速電圧で１〜５分間行われる請求項１〜５の
いずれかに記載の製造方法。 6. Irradiation with an oxygen ion beam is carried out in the range of 300 to 15
The accelerating voltage of 00V is performed for 1 to 5 minutes.
The manufacturing method according to any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31669294A JP3412302B2 (en) | 1994-12-20 | 1994-12-20 | Method for manufacturing plastic optical component having antireflection film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31669294A JP3412302B2 (en) | 1994-12-20 | 1994-12-20 | Method for manufacturing plastic optical component having antireflection film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08169969A JPH08169969A (en) | 1996-07-02 |
| JP3412302B2 true JP3412302B2 (en) | 2003-06-03 |
Family
ID=18079844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31669294A Expired - Fee Related JP3412302B2 (en) | 1994-12-20 | 1994-12-20 | Method for manufacturing plastic optical component having antireflection film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3412302B2 (en) |
-
1994
- 1994-12-20 JP JP31669294A patent/JP3412302B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08169969A (en) | 1996-07-02 |
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