JPWO2015129129A1 - Optical member having broadband anti-reflection coating - Google Patents

Optical member having broadband anti-reflection coating Download PDF

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JPWO2015129129A1
JPWO2015129129A1 JP2016505005A JP2016505005A JPWO2015129129A1 JP WO2015129129 A1 JPWO2015129129 A1 JP WO2015129129A1 JP 2016505005 A JP2016505005 A JP 2016505005A JP 2016505005 A JP2016505005 A JP 2016505005A JP WO2015129129 A1 JPWO2015129129 A1 JP WO2015129129A1
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refractive index
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正章 能勢
正章 能勢
宗矩 川路
宗矩 川路
孔二 中村
孔二 中村
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Konica Minolta Inc
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G02B1/115—Multilayers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/418—Refractive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2551/00—Optical elements

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Abstract

光学部材は、樹脂基板と、前記樹脂基板上に形成され、ＴｉＯ２からなる高屈折率層と、ＳｉＯ２及びＡｌ２Ｏ３からなる低屈折率層と、の交互層を含む反射防止膜と、を有する。前記反射防止膜の総膜厚に占める前記低屈折率層の膜厚比率が６０％以上７２．５％以下であり、前記反射防止膜は、波長４２０ｎｍ〜９００ｎｍで入射角５°における平均反射率が１．５％以下の特性を有する。The optical member includes a resin substrate, and an antireflection film formed on the resin substrate and including an alternating layer of a high refractive index layer made of TiO 2 and a low refractive index layer made of SiO 2 and Al 2 O 3. The film thickness ratio of the low refractive index layer in the total film thickness of the antireflection film is 60% or more and 72.5% or less, and the antireflection film has an average reflectance at a wavelength of 420 nm to 900 nm and an incident angle of 5 °. Has a characteristic of 1.5% or less.

Description

本発明は、広帯域反射防止膜を有する光学部材に関するものであり、更に詳しくは、可視域〜赤外域（波長４２０ｎｍ〜９００ｎｍ）に対応した反射防止膜を有する光学部材（例えば、プラスチックレンズ，光学フィルター等）に関するものである。   The present invention relates to an optical member having a broadband antireflection film, and more specifically, an optical member (for example, a plastic lens or an optical filter) having an antireflection film corresponding to a visible region to an infrared region (wavelength 420 nm to 900 nm). Etc.).

デジタルカメラの軽量・小型化には、プラスチックレンズの使用が有効である。しかし、プラスチックレンズにはガラスレンズと比べてコーティングが難しいという問題がある。例えば、ガラス基板に対する成膜では高温加熱が可能であるが、樹脂基板に対する成膜では基板自体の耐熱性が低いため高温加熱は不可能である。このため、成膜性や耐久性が低く、剥離やクラックが発生しやすいという問題がある。また、可視域〜赤外域に対応した反射防止膜を樹脂基板に形成する場合、その反射防止膜には多層膜化と高膜厚化が必要になる。このため、反射防止膜の耐熱温度（１００℃以上）及び高温高湿（８５℃８５％）の保障が問題となる。この耐熱性（１００℃）・耐高温高湿性（８５℃８５％）の保障は、スマートフォン（高機能携帯電話）用撮像レンズや車載レンズではその使用環境から必須のものとなっている。   The use of plastic lenses is effective in reducing the weight and size of digital cameras. However, plastic lenses have a problem that they are difficult to coat compared to glass lenses. For example, high-temperature heating is possible in film formation on a glass substrate, but high-temperature heating is impossible in film formation on a resin substrate because the substrate itself has low heat resistance. For this reason, there exists a problem that film-forming property and durability are low and peeling and a crack are easy to generate | occur | produce. In addition, when an antireflection film corresponding to the visible region to the infrared region is formed on a resin substrate, the antireflection film needs to have a multilayer film and a thick film. For this reason, the guarantee of the heat-resistant temperature (100 degreeC or more) and high temperature, high humidity (85 degreeC85%) of an antireflection film becomes a problem. This guarantee of heat resistance (100 ° C.) and high temperature resistance and high humidity (85 ° C. and 85%) is indispensable for an imaging lens for a smartphone (high function mobile phone) and an in-vehicle lens because of its usage environment.

上記のような問題を解決するため、従来より様々なタイプの反射防止膜を有する光学部材が提案されている。例えば特許文献１には、可視域反射防止膜の硬度及び耐傷性を向上させるために、ＳｉＯ2とＡｌ2Ｏ3とからなる低屈折率材料にＩＡＤ（イオンアシストデポジション）処理を用いて成膜したプラスチック製の光学部材が提案されている。In order to solve the above problems, optical members having various types of antireflection films have been proposed. For example, Patent Document 1 discloses that a low refractive index material made of SiO 2 and Al 2 O 3 is subjected to an IAD (ion-assisted deposition) process in order to improve the hardness and scratch resistance of a visible antireflection film. A filmed plastic optical member has been proposed.

特開２００９−１９９０２２号公報JP 2009-199022 A

しかし、特許文献１に記載の光学部材には、耐熱性及び耐高温高湿性が十分でないという問題がある。   However, the optical member described in Patent Document 1 has a problem that heat resistance and high temperature and high humidity resistance are not sufficient.

本発明はこのような状況に鑑みてなされたものであって、その目的は、耐熱性及び耐高温高湿性の高い反射防止膜を有する光学部材を提供することにある。   The present invention has been made in view of such a situation, and an object thereof is to provide an optical member having an antireflection film having high heat resistance and high temperature and humidity resistance.

上記目的を達成するために、本発明の光学部材は、樹脂基板と、
前記樹脂基板上に形成され、ＴｉＯ2からなる高屈折率層と、ＳｉＯ2及びＡｌ2Ｏ3からなる低屈折率層と、の交互層を含む反射防止膜と、を有し、
前記反射防止膜の総膜厚に占める前記低屈折率層の膜厚比率が６０％以上７２．５％以下であり、
前記反射防止膜は、波長４２０ｎｍ〜９００ｎｍで入射角５°における平均反射率が１．５％以下の特性を有する。In order to achieve the above object, the optical member of the present invention comprises a resin substrate,
An antireflection film formed on the resin substrate and including an alternating layer of a high refractive index layer made of TiO 2 and a low refractive index layer made of SiO 2 and Al 2 O 3 ;
The film thickness ratio of the low refractive index layer in the total film thickness of the antireflection film is 60% or more and 72.5% or less,
The antireflection film has a characteristic in which an average reflectance at a wavelength of 420 nm to 900 nm and an incident angle of 5 ° is 1.5% or less.

本発明によれば、樹脂基板上の広帯域反射防止膜において低屈折率層をＳｉＯ2及びＡｌ2Ｏ3で構成し、かつ、総膜厚に占める低屈折率層の膜厚比率を適正に規定する構成になっているため、耐熱性及び耐高温高湿性の高い反射防止膜を有する光学部材を実現することができる。According to the present invention, in the broadband antireflection film on the resin substrate, the low refractive index layer is composed of SiO 2 and Al 2 O 3 and the film thickness ratio of the low refractive index layer in the total film thickness is appropriately specified. Therefore, an optical member having an antireflection film with high heat resistance and high temperature and humidity resistance can be realized.

広帯域反射防止膜を有する光学部材の実施の形態を示す多層膜構成図。The multilayer film block diagram which shows embodiment of the optical member which has a broadband antireflection film. ポリカーボネイト樹脂製基板からなる光学部材の実施例１〜１１及び比較例１〜７の設計分光特性を示すグラフ。The graph which shows the design spectral characteristics of Examples 1-11 and Comparative Examples 1-7 of the optical member which consists of a substrate made from polycarbonate resin. シクロオレフィン樹脂製基板からなる光学部材の実施例１２〜２２及び比較例８，９の設計分光特性を示すグラフ。The graph which shows the design spectral characteristic of Examples 12-22 and Comparative Examples 8 and 9 of the optical member which consists of a board | substrate made from cycloolefin resin.

以下、本発明を実施した光学部材等を、図面を参照しつつ説明する。図１に、広帯域反射防止膜を有する光学部材の一実施の形態について、その反射防止膜ＡＲの積層構造を光学断面で模式的に示す。なお、成膜材料の表記に関しては、必要に応じて（図１等）、ＴｉＯ2をＴｉＯ２とし、ＳｉＯ2をＳｉＯ２とし、Ａｌ2Ｏ3をＡＬ２Ｏ３とし、ＳｉＯ2とＡｌ2Ｏ3との混合物をＳｉＯ2＋Ａｌ2Ｏ3又はＳｉＯ２＋ＡＬ２Ｏ３とする。Hereinafter, an optical member and the like embodying the present invention will be described with reference to the drawings. FIG. 1 schematically shows a laminated structure of an antireflection film AR in an optical section of an embodiment of an optical member having a broadband antireflection film. Regarding the notation of the film forming material (FIG. 1 etc.), TiO 2 is TiO 2 , SiO 2 is SiO 2 , Al 2 O 3 is AL 2 O 3, and a mixture of SiO 2 and Al 2 O 3 as necessary. Is SiO 2 + Al 2 O 3 or SiO 2 + AL 2 O 3 .

図１に示す光学部材ＫＢは、波長４２０ｎｍ〜９００ｎｍで入射角５°における平均反射率が１．５％以下の反射防止膜ＡＲを、樹脂基板Ｓ上に有している。その反射防止膜ＡＲは、例えば真空蒸着法での成膜により、ＴｉＯ2(酸化チタン)からなる高屈折率層Ｈと、ＳｉＯ2(酸化ケイ素)及びＡｌ2Ｏ3(酸化アルミニウム)からなる低屈折率層Ｌと、の交互層で構成されている。樹脂基板Ｓとしては、プラスチックレンズ，プラスチック平板等の合成樹脂製光学部材が挙げられ、樹脂基板Ｓを構成する材料としては、ポリカーボネイト樹脂，シクロオレフィン樹脂等が挙げられる。低屈折率層Ｌを構成する成膜材料としては、Ａｌ2Ｏ3とＳｉＯ2との混合物が挙げられ、また、高屈折率層Ｈを構成する成膜材料としてはＴｉＯ2ベースの材料(蒸着材料としてＴｉ2Ｏ3，Ｔｉ3Ｏ5等)が挙げられる。The optical member KB shown in FIG. 1 has an antireflection film AR having a wavelength of 420 nm to 900 nm and an average reflectance of 1.5% or less at an incident angle of 5 ° on the resin substrate S. The antireflection film AR is formed by, for example, a vacuum deposition method, and a high refractive index layer H made of TiO 2 (titanium oxide), and a low refractive index film made of SiO 2 (silicon oxide) and Al 2 O 3 (aluminum oxide). It is composed of alternating layers of refractive index layers L. Examples of the resin substrate S include synthetic resin optical members such as plastic lenses and plastic flat plates. Examples of the material constituting the resin substrate S include polycarbonate resin and cycloolefin resin. The film forming material constituting the low refractive index layer L includes a mixture of Al 2 O 3 and SiO 2, and the film forming material constituting the high refractive index layer H is a TiO 2 based material (evaporation). Examples of the material include Ti 2 O 3 and Ti 3 O 5 .

高屈折率層Ｈ（成膜材料：Ｔｉ酸化物，例えばＴｉＯ2）と、低屈折率層Ｌ（成膜材料：ＳｉＯ2＋Ａｌ2Ｏ3）と、の積層構造を有する薄膜の設計においては、Ｈ／Ｌの膜厚比率を変更しても、同じ分光特性を得ることが可能である。そこで、４２０ｎｍ〜９００ｎｍの波長領域において入射角５°での平均反射率が１．５％以下となるように、Ｈ／Ｌの膜厚比率を変更する反射防止膜ＡＲの設計を行った結果、耐熱性と耐高温高湿性との両立が可能な高い信頼性と、Ｈ／Ｌの膜厚比率と、の関係を見出し本発明に至った。In designing a thin film having a laminated structure of a high refractive index layer H (film forming material: Ti oxide, for example, TiO 2 ) and a low refractive index layer L (film forming material: SiO 2 + Al 2 O 3 ), Even if the film thickness ratio of H / L is changed, the same spectral characteristics can be obtained. Therefore, as a result of designing the antireflection film AR that changes the film thickness ratio of H / L so that the average reflectance at an incident angle of 5 ° in the wavelength region of 420 nm to 900 nm is 1.5% or less, The present inventors have found a relationship between high reliability capable of achieving both heat resistance and high temperature and high humidity resistance, and a film thickness ratio of H / L.

つまり、本発明に係る光学部材ＫＢは、反射防止膜ＡＲの総膜厚に占める低屈折率層Ｌの膜厚比率が６０％以上７２．５％以下であることを特徴としている。この構成によって、耐熱性及び耐高温高湿性の高い反射防止膜を有する光学部材ＫＢを実現することが可能となる。膜厚比率が６０％を下回ると、耐熱性が低下し（後述する比較例１〜５）、膜厚比率が７２．５％を上回ると、耐高温高湿性が低下する（後述する比較例６〜９）。したがって、膜厚比率は６０％〜７２．５％であれば、耐熱性と耐高温高湿性との両立が可能となる。また、複数の光学面を有する光学系において反射防止膜が複数存在すると、面間反射が生じて透過率が低下してしまうので、前記平均反射率を１．５％以下に抑えることによって、透過率の維持も可能となる。   That is, the optical member KB according to the present invention is characterized in that the film thickness ratio of the low refractive index layer L to the total film thickness of the antireflection film AR is 60% or more and 72.5% or less. With this configuration, it is possible to realize an optical member KB having an antireflection film with high heat resistance and high temperature and humidity resistance. When the film thickness ratio falls below 60%, the heat resistance decreases (Comparative Examples 1 to 5 described later), and when the film thickness ratio exceeds 72.5%, the high temperature and high humidity resistance decreases (Comparative Example 6 described later). ~ 9). Therefore, if the film thickness ratio is 60% to 72.5%, both heat resistance and high temperature and high humidity resistance can be achieved. In addition, when there are a plurality of antireflection films in an optical system having a plurality of optical surfaces, inter-surface reflection occurs and the transmittance is lowered. Therefore, by suppressing the average reflectance to 1.5% or less, transmission is achieved. The rate can also be maintained.

図１に示す反射防止膜ＡＲは１５層の積層構造を有しているが、層数はこれに限らない。透過率は層数に応じて変化させることができるので、例えば、反射防止膜ＡＲの層数が１０層以上２０層以下ならば、反射防止膜ＡＲの総膜厚は３２０ｎｍ以上８００ｎｍ以下であることが好ましい。総膜厚が３２０ｎｍを下回ると、波長域４２０ｎｍ〜９００ｎｍの平均反射率１．５％以下の反射防止膜ＡＲの設計が困難になり、総膜厚が８００ｎｍを上回ると、総膜厚が大きすぎて信頼性，生産性等が低下し、コストアップを招くおそれがある。   The antireflection film AR shown in FIG. 1 has a laminated structure of 15 layers, but the number of layers is not limited to this. Since the transmittance can be changed according to the number of layers, for example, if the number of layers of the antireflection film AR is 10 or more and 20 or less, the total thickness of the antireflection film AR is 320 nm or more and 800 nm or less. Is preferred. If the total film thickness is less than 320 nm, it becomes difficult to design the antireflection film AR having an average reflectance of 1.5% or less in the wavelength range of 420 nm to 900 nm. If the total film thickness exceeds 800 nm, the total film thickness is too large. As a result, reliability, productivity, etc. may be reduced, leading to an increase in cost.

低屈折率層Ｌが、ＳｉＯ2：９０〜９９重量％と、Ａｌ2Ｏ3：１〜１０重量％と、を含むことが好ましい。Ａｌ2Ｏ3の混合割合の増大に伴って、耐熱性や耐傷性が向上する。このため、ＳｉＯ2とＡｌ2Ｏ3との混合割合として、Ａｌ2Ｏ3が１重量％を下回るとＡｌ2Ｏ3による耐熱性や耐傷性の効果が得られなくなり、Ａｌ2Ｏ3が１０重量％を上回ると成膜速度が安定せず、かつ、成膜外観（スプラッシュ）に著しく不利になる。したがって、Ａｌ2Ｏ3の混合割合は１〜１０重量％が好ましい。The low refractive index layer L preferably contains SiO 2 : 90 to 99% by weight and Al 2 O 3 : 1 to 10% by weight. As the mixing ratio of Al 2 O 3 increases, heat resistance and scratch resistance are improved. For this reason, if Al 2 O 3 is less than 1% by weight as a mixing ratio of SiO 2 and Al 2 O 3 , the heat resistance and scratch resistance effects due to Al 2 O 3 cannot be obtained, and Al 2 O 3 is 10%. If it exceeds wt%, the film forming speed is not stable, and the film forming appearance (splash) is extremely disadvantageous. Therefore, the mixing ratio of Al 2 O 3 is preferably 1 to 10% by weight.

樹脂基板Ｓがシクロオレフィン樹脂又はポリカーボネイト樹脂からなることが好ましい。撮像レンズを構成する場合、高屈折率材料と低屈折率材料との組み合わせが必要となるので、低屈折率材料としてシクロオレフィン樹脂、高屈折率材料としてポリカーボネイト樹脂を、それぞれ樹脂基板Ｓとして用いることが好ましい。そのような樹脂基板Ｓとしてのプラスチックレンズ上に、前述した構成を有する反射防止膜ＡＲを設ければ、反射防止膜ＡＲに高い信頼性を有するプラスチックレンズを得ることができる。そして、そのようなプラスチックレンズを撮像レンズに用いれば、それを搭載するデジタルカメラの軽量・小型化が可能になるとともに、高い反射防止効果を安定かつ高い信頼性で得ることが可能となる。   The resin substrate S is preferably made of a cycloolefin resin or a polycarbonate resin. When an imaging lens is configured, a combination of a high refractive index material and a low refractive index material is required. Therefore, a cycloolefin resin is used as the low refractive index material, and a polycarbonate resin is used as the resin substrate S as the high refractive index material. Is preferred. If the antireflection film AR having the above-described configuration is provided on the plastic lens as the resin substrate S, a plastic lens having high reliability can be obtained for the antireflection film AR. If such a plastic lens is used as an imaging lens, a digital camera equipped with the plastic lens can be reduced in weight and size, and a high antireflection effect can be obtained stably and with high reliability.

以下、本発明に係る光学部材の構成等を、実施例１〜２２及び比較例１〜９を挙げて更に具体的に説明する。   Hereinafter, the structure of the optical member according to the present invention will be described more specifically with reference to Examples 1 to 22 and Comparative Examples 1 to 9.

各数値例（実施例１〜２２，比較例１〜９）に対応する反射防止膜について、そのコンストラクションデータを表１〜表６に示し、設計分光特性を図２，図３のグラフに示す。なお、表１〜表６において膜厚ゼロと表記されている場合は、その層が存在しないことを意味する。したがって、比較例５，実施例１１，実施例２２は層数１０層、実施例９，１０，２０，２１は層数１４層、その他は層数１５層である。   For the antireflection films corresponding to the numerical examples (Examples 1 to 22 and Comparative Examples 1 to 9), construction data are shown in Tables 1 to 6, and design spectral characteristics are shown in the graphs of FIGS. In Tables 1 to 6, when the film thickness is expressed as zero, it means that the layer does not exist. Therefore, Comparative Example 5, Example 11, and Example 22 have 10 layers, Examples 9, 10, 20, and 21 have 14 layers, and others have 15 layers.

また、各数値例を構成する樹脂基板と成膜材料について、ｄ線（波長５８７．６ｎｍ）に対する屈折率Ｎｄを以下に示す。
樹脂基板：
ポリカーボネイト樹脂基板（ＥＰ５０００） …Ｎｄ＝１．６３５
シクロオレフィン樹脂基板（ＡＰＥＬ） …Ｎｄ＝１．５４５
成膜材料：
ＴｉＯ2 …Ｎｄ＝２．２２８
ＳｉＯ2＋Ａｌ2Ｏ3 …Ｎｄ＝１．４７５Moreover, the refractive index Nd with respect to d line | wire (wavelength 587.6nm) is shown below about the resin substrate and film-forming material which comprise each numerical example.
Resin substrate:
Polycarbonate resin substrate (EP5000) ... Nd = 1.635
Cycloolefin resin substrate (APEL) ... Nd = 1.545
Film forming material:
TiO 2 ... Nd = 2.228
SiO 2 + Al 2 O 3 ... Nd = 1.475

各数値例（実施例１〜２２，比較例１〜９）のサンプルを作製し、その性能評価を行った。成膜を行うに際し、まず樹脂基板（EP-5000/APL 5514ML）を真空蒸着装置に配置し、１．３×１０-3Ｐａまで排気した。そして、各数値例の層番号（表１〜表６）の材料で所定の膜厚の層を形成した。実験内容（成膜材料，成膜条件，樹脂基板）を以下に示し、評価結果を表７，表８に示す。また表９に、反射防止膜ＡＲの総膜厚の良好範囲と、低屈折率層Ｌ（ＳｉＯ2＋Ａｌ2Ｏ3）の膜厚比率の良好範囲を示す。Samples of numerical examples (Examples 1 to 22 and Comparative Examples 1 to 9) were prepared and performance evaluation was performed. When film formation was performed, first, a resin substrate (EP-5000 / APL 5514ML) was placed in a vacuum deposition apparatus and evacuated to 1.3 × 10 −3 Pa. And the layer of the predetermined | prescribed film thickness was formed with the material of the layer number (Table 1-Table 6) of each numerical example. The contents of the experiment (film formation material, film formation conditions, resin substrate) are shown below, and the evaluation results are shown in Tables 7 and 8. Table 9 shows a good range of the total film thickness of the antireflection film AR and a good range of the film thickness ratio of the low refractive index layer L (SiO 2 + Al 2 O 3 ).

各数値例の設計反射率は、図２，図３に示すように、４２０ｎｍ〜９００ｎｍで１．５％以下であった。耐熱温度が１００℃以上で、かつ、８５℃８５％１０００ｈの外観が良好（○）である領域は、実施例１〜２２に示す範囲（表９）であった。総膜厚に占める低屈折率層Ｌの膜厚比率は６０％以上７２．５％以下であった。   The design reflectivity of each numerical example was 1.5% or less from 420 nm to 900 nm as shown in FIGS. The region where the heat resistant temperature was 100 ° C. or higher and the appearance at 85 ° C. and 85% 1000 h was good (◯) was the range shown in Examples 1 to 22 (Table 9). The film thickness ratio of the low refractive index layer L in the total film thickness was 60% or more and 72.5% or less.

［成膜材料］
高屈折率材料としてＴｉ3Ｏ5を用い、低屈折率材料としてＳｉＯ2＋Ａｌ2Ｏ3を用いた。Ｔｉ3Ｏ5は、富士チタン工業社製のＴＯＰ（商品名）であり、ＳｉＯ2＋Ａｌ2Ｏ3は、Merck社製のSubstance L5（商品名）である。[Film material]
Ti 3 O 5 was used as the high refractive index material, and SiO 2 + Al 2 O 3 was used as the low refractive index material. Ti 3 O 5 is TOP (trade name) manufactured by Fuji Titanium Industry Co., and SiO 2 + Al 2 O 3 is Substance L5 (trade name) manufactured by Merck.

［成膜条件］
真空蒸着装置としてBMC-1100（シンクロン社製）を用い、到達真空度を１．３×１０-3Ｐａとした。イオン銃としてRIS-120（シンクロン社製）を用いてＩＡＤを行った。成膜材としてＴＯＰ（商品名）を用いた際には、真空度を２×１０-2Ｐａとし、蒸着速度を３．５Å／Ｓｅｃとし、ＩＡＤ条件として、酸素ガスを導入し、加速電圧５００Ｖ、加速電流を２５０ｍＡとした。また、成膜材としてSubstance L5（商品名）を用いた際には、真空度を８×１０-3Ｐａとし、蒸着速度を５．０Å／Ｓｅｃとし、ＩＡＤを行わなかった。なお、低屈折率材料（ＳｉＯ2＋Ａｌ2Ｏ3）として用いたSubstance L5の組成は、ＳｉＯ2：９７重量％、Ａｌ2Ｏ3：３重量％である。[Film formation conditions]
BMC-1100 (manufactured by SYNCHRON Co., Ltd.) was used as a vacuum vapor deposition apparatus, and the ultimate vacuum was 1.3 × 10 −3 Pa. IAD was performed using RIS-120 (manufactured by SYNCHRON) as an ion gun. When TOP (trade name) is used as the film forming material, the degree of vacuum is 2 × 10 −2 Pa, the vapor deposition rate is 3.5 Å / Sec, oxygen gas is introduced as the IAD conditions, and the acceleration voltage is 500 V. The acceleration current was 250 mA. When Substance L5 (trade name) was used as the film forming material, the degree of vacuum was 8 × 10 −3 Pa, the deposition rate was 5.0 Å / Sec, and IAD was not performed. The composition of Substance L5 used as the low refractive index material (SiO 2 + Al 2 O 3 ) is SiO 2 : 97 wt% and Al 2 O 3 : 3 wt%.

［樹脂基板］
樹脂基板として、ポリカーボネイト樹脂とシクロオレフィン樹脂を用いた。ポリカーボネイト樹脂は、三菱ガス化学（株）製のユピゼーダ EP-5000（商品名）であり、シクロオレフィン樹脂は、三井化学（株）製のAPL 5514ML（商品名）である。[Resin substrate]
A polycarbonate resin and a cycloolefin resin were used as the resin substrate. The polycarbonate resin is Iupiseda EP-5000 (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd., and the cycloolefin resin is APL 5514ML (trade name) manufactured by Mitsui Chemicals.

性能評価は、成膜後半年常温常湿で放置した後、下記試験（耐熱温度試験，高温高湿試験）をそれぞれ実施することにより行った。   The performance evaluation was performed by leaving the sample at room temperature and humidity in the latter half of the film formation, and then performing the following tests (heat-resistant temperature test and high-temperature and high-humidity test).

［耐熱温度試験］
熱風乾燥炉を８０℃に設定して３０分放置し、取り出し１０分後に顕微鏡で薄膜のクラックを観察し、クラックが発生した温度を記録した。その際、同じサンプルを５℃毎に温度を上げてクラックが発生するまで試験、観察を繰り返した。薄膜の耐熱温度は経時変化の影響を埋めるため、成膜後１８０日経過したサンプルにて評価した。表７及び表８に、クラックが発生した直前の試験温度を示す。[Heat-resistant temperature test]
The hot-air drying oven was set at 80 ° C. and left for 30 minutes, and after 10 minutes of removal, the thin film was observed for cracks with a microscope, and the temperature at which the crack occurred was recorded. At that time, the test and observation were repeated until the same sample was heated at every 5 ° C. and cracks occurred. The heat-resistant temperature of the thin film was evaluated using a sample that had passed 180 days after film formation in order to compensate for the influence of changes over time. Tables 7 and 8 show the test temperatures immediately before the occurrence of cracks.

［高温高湿試験（８５℃８５％）］
高温高湿槽を８５℃８５％に設定して１０００時間放置した後取り出し、２４時間常温常湿に放置し顕微鏡にてクラック，膜浮き等の欠陥を観察した（観察倍率＝２００倍）。耐高温高湿性の評価は、クラック，膜浮き等の欠陥が観察されなかった場合を○：良好とし、クラック，膜浮き等の欠陥が観察された場合を×：不良とした。[High temperature and high humidity test (85 ℃ 85%)]
The high-temperature and high-humidity tank was set at 85 ° C. and 85% and allowed to stand for 1000 hours and then taken out, and left for 24 hours at room temperature and normal humidity. In the evaluation of the high temperature and high humidity resistance, a case where no defect such as a crack or a film floating was observed was evaluated as “Good”, and a case where a defect such as a crack or a film floating was observed was evaluated as “X”.

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ＫＢ 光学部材
ＡＲ 反射防止膜
Ｈ 高屈折率層
Ｌ 低屈折率層
Ｓ 樹脂基板KB Optical member AR Antireflection film H High refractive index layer L Low refractive index layer S Resin substrate

Claims (4)

樹脂基板と、
前記樹脂基板上に形成され、ＴｉＯ2からなる高屈折率層と、ＳｉＯ2及びＡｌ2Ｏ3からなる低屈折率層と、の交互層を含む反射防止膜と、を有し、
前記反射防止膜の総膜厚に占める前記低屈折率層の膜厚比率が６０％以上７２．５％以下であり、
前記反射防止膜は、波長４２０ｎｍ〜９００ｎｍで入射角５°における平均反射率が１．５％以下の特性を有する、光学部材。A resin substrate;
An antireflection film formed on the resin substrate and including an alternating layer of a high refractive index layer made of TiO 2 and a low refractive index layer made of SiO 2 and Al 2 O 3 ;
The film thickness ratio of the low refractive index layer in the total film thickness of the antireflection film is 60% or more and 72.5% or less,
The antireflection film is an optical member having a wavelength of 420 nm to 900 nm and an average reflectance at an incident angle of 5 ° of 1.5% or less. 前記反射防止膜の総膜厚が３２０ｎｍ以上８００ｎｍ以下、層数が１０層以上２０層以下である請求項１記載の光学部材。   The optical member according to claim 1, wherein the total thickness of the antireflection film is from 320 nm to 800 nm, and the number of layers is from 10 layers to 20 layers. 前記低屈折率層が、ＳｉＯ2：９０〜９９重量％と、Ａｌ2Ｏ3：１〜１０重量％と、を含む請求項１又は２記載の光学部材。The low refractive index layer, SiO 2: 90 to 99 and percent by weight, Al 2 O 3: 1 to 10 wt% and, according to claim 1 or 2, wherein the optical element includes a. 前記樹脂基板がシクロオレフィン樹脂又はポリカーボネイト樹脂からなる請求項１〜３のいずれか１項に記載の光学部材。   The optical member according to claim 1, wherein the resin substrate is made of a cycloolefin resin or a polycarbonate resin.
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