【０００１】[0001]
【産業上の利用分野】本発明は反射防止膜を有する光学
部材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical member having an antireflection film.
【０００２】[0002]
【従来の技術】合成樹脂からなる光学部材の表面反射特
性を改善するために合成樹脂の表面上に反射防止膜を施
すこと、またその反射防止膜と合成樹脂の密着性を向上
させるために合成樹脂と反射防止膜との間に下地層を介
在させることがよく知られている。この下地層を介在さ
せている例として、例えば特開昭５６−１１６００３号
公報（以下単に、「公報１」という。）、特開平２−２
９１５０２号公報（以下単に、「公報２」という。）に
はＳｉＯ2のみからなる下地層が、また特開昭５６−６
６８０２号公報（以下単に、「公報３」という。）には
屈折率が１．５４でＳｉＯ2とＡｌ2Ｏ3を混合してな
る下地層を施した合成樹脂製光学部材が開示されてい
る。2. Description of the Related Art An antireflection film is provided on the surface of a synthetic resin in order to improve the surface reflection characteristics of an optical member made of a synthetic resin, and the adhesion between the antireflection film and the synthetic resin is improved. It is well known to interpose an underlayer between the resin and the antireflection film. Examples of interposing this underlayer include, for example, Japanese Patent Laid-Open No. 56-116003 (hereinafter simply referred to as "Gazette 1") and Japanese Patent Laid-Open No. 2-2.
Japanese Patent Laid-Open No. 91502 (hereinafter simply referred to as "publication 2") discloses an underlayer made of only SiO2 , and Japanese Patent Laid-Open No. 56-6.
Japanese Patent No. 6802 (hereinafter simply referred to as "publication 3") discloses a synthetic resin optical member having a base layer made of a mixture of SiO2 and Al2 O3 having a refractive index of 1.54. .
【０００３】[0003]
【発明が解決しようとする課題】公報１、２に開示され
ているＳｉＯ2のみからなる下地層を施した合成樹脂製
光学部材、公報３に開示されている屈折率が１．５４で
ＳｉＯ2とＡｌ2Ｏ3を混合してなる下地層を施した合
成樹脂製光学部材はガラス製基板のように蒸着時の基板
温度を高くして成膜することができないため、下地層の
耐熱性が不十分で、また経時的に耐熱温度の低下する程
度が大きいという特性を有する。その影響で下地層の上
に施される反射防止膜も耐熱性が不十分となりやすく、
また経時的に耐熱温度の低下する程度が大きくなるとい
う問題を有する。この問題は例えば、以下に記す不具合
が生じる。眼鏡装用者はサウナの中で眼鏡を装用した
り、また自動車の中に眼鏡を置いたまま自動車の外に出
ることがよくある。このような高温の条件下で公報１〜
３に開示されている下地層を施した光学部材を眼鏡用レ
ンズとして使用する場合において、耐熱性が良好でない
反射防止膜を施した場合にはひび割れ（クラック）が生
じやすい。また耐熱性が良好な反射防止膜を施した場合
でも施して４ケ月ぐらいで反射防止膜にひび割れが生じ
やすくなる。本発明は上述した不具合を解決するために
なされ、その目的は基板が合成樹脂のように、蒸着時の
基板温度を低くしなければならない場合でも、耐熱性が
良好で、且つ経時的に耐熱温度の低下する程度が小さく
なる反射防止膜を有する光学部材を提供することにあ
る。THE INVENTION to be solved problems were subjected to a base layer composed only of SiO2 which is disclosed in Japanese 1,2 plastic optical member, SiO2 in refractive index as disclosed in JP 3 1.54 Since a synthetic resin optical member having an underlayer formed by mixing Al2 O3 and Al2 O3 cannot be formed by raising the substrate temperature during vapor deposition like a glass substrate, the heat resistance of the underlayer is high. It has the characteristics that it is not sufficient and that the heat-resistant temperature decreases with time. Due to that effect, the heat resistance of the antireflection film applied on the underlayer tends to be insufficient,
Further, there is a problem that the degree of lowering of the heat resistant temperature increases with time. This problem causes the following problems, for example. A spectacle wearer often wears spectacles in a sauna or goes out of the car with the spectacles left in the car. Under such high temperature conditions,
When the optical member having the underlayer disclosed in No. 3 is used as an eyeglass lens, when an antireflection film having poor heat resistance is applied, cracks are likely to occur. Even when an antireflection film having good heat resistance is applied, the antireflection film is likely to crack in about 4 months after application. The present invention has been made to solve the above-described problems, and the object thereof is to provide good heat resistance even when the substrate temperature must be low during vapor deposition, such as a synthetic resin substrate, and the heat resistant temperature with time. Another object of the present invention is to provide an optical member having an antireflection film with which the degree of decrease of
【０００４】[0004]
【課題を解決するための手段】上述した目的は以下に記
す発明によって達成された。その発明は合成樹脂基板上
に反射防止膜を有する光学部材であって、前記合成樹脂
基板と前記反射防止膜との間に、下記に示すＡ層、Ｂ層
およびＣ層の順で前記合成樹脂基板側から積層されてな
る下地層を介在していることを特徴とする反射防止膜を
有する光学部材である。Ａ層；ＳｉＯ2からなる層で、その層の屈折率（ｎｄ）
の範囲が１．４５〜１．４７で、且つλ＝４５０〜５５
０ｎｍを設計波長とした場合の膜厚の範囲が０．０５〜
０．１５λである。Ｂ層；Ｔａ2Ｏ5からなる層で、その層の屈折率（ｎ
ｄ）の範囲が２．００〜２．１０で、且つλ＝４５０〜
５５０ｎｍを設計波長とした場合の膜厚の範囲が０．０
１〜０．１０λである。Ｃ層；ＳｉＯ2とＡｌ2Ｏ3との混合層で、その層の屈
折率（ｎｄ）の範囲が１．４８〜１．５２で、且つλ＝
４５０〜５５０ｎｍを設計波長とした場合の膜厚の範囲
が０．７５〜１．５０λである。The above-mentioned objects have been achieved by the invention described below. The invention is an optical member having an antireflection film on a synthetic resin substrate, wherein the synthetic resin is provided between the synthetic resin substrate and the antireflection film in the order of A layer, B layer and C layer shown below. An optical member having an antireflection film, characterized in that an underlying layer laminated from the substrate side is interposed. Layer A: a layer made of SiO2 and having a refractive index (nd)
Is 1.45 to 1.47, and λ = 450 to 55.
When the design wavelength is 0 nm, the film thickness range is 0.05 to
It is 0.15λ. Layer B: a layer composed of Ta2 O5 and having a refractive index (n
The range of d) is 2.00 to 2.10, and λ = 450 to
When the design wavelength is 550 nm, the film thickness range is 0.0
It is 1 to 0.10λ. C layer: a mixed layer of SiO2 and Al2 O3 , the range of the refractive index (nd) of the layer is 1.48 to 1.52, and λ =
When the design wavelength is 450 to 550 nm, the film thickness range is 0.75 to 1.50λ.
【０００５】下地層を上述したＡ〜Ｃ層の構成にした理
由を説明する。下地層をＡ〜Ｃ層の多層下地層の構成に
すれば、ＳｉＯ2からなる単層下地層、ＳｉＯ2とＡｌ
2Ｏ3からなる単層下地層、Ｔａ2Ｏ5からなる単層下
地層などの従来の下地層の特性を損なわず、さらに前述
した従来の単層下地層と比べ耐熱温度が著しく向上し、
さらに経時的な耐熱温度の低下の程度が小さくなるとい
う予想しえない効果を本発明者は見い出した。これに伴
いさらに本発明者は、基板が合成樹脂のように蒸着時の
基板温度を低くしなければならない場合において、本発
明の下地層を施すことによって下地層の表面上に施され
た反射防止膜全体の耐熱温度が著しく向上し、さらに経
時的な耐熱温度の低下の程度が小さくなることを見い出
し本発明に至った。The reason why the above-mentioned layers A to C are used as the underlayer will be described. If an underlying layer structure of the multilayer underlayer A~C layer, a single layer underlying layer made of SiO2, SiO2 and Al
The characteristics of conventional underlayers such as a single-layer underlayer made of2 O3 and a single-layer underlayer made of Ta2 O5 are not impaired, and the heat resistance temperature is remarkably improved as compared with the above-mentioned conventional single-layer underlayer.
Further, the present inventor has found an unexpected effect that the degree of decrease in heat resistant temperature with time decreases. Along with this, the present inventor further applies the underlayer of the present invention to prevent the reflection on the surface of the underlayer when the substrate has to have a low substrate temperature during vapor deposition such as a synthetic resin. The inventors have found that the heat resistant temperature of the entire film is remarkably improved, and further, the degree of decrease in the heat resistant temperature with time is reduced, and the present invention has been completed.
【０００６】本発明の下地層におけるＡ〜Ｃ層は前述し
た素材、屈折率、膜厚に特定される。この範囲外では反
射防止膜全体の耐熱温度が向上せず、また経時的な耐熱
温度の低下の程度が大きくなり前述した効果が得られな
いので好ましくない。The layers A to C in the underlayer of the present invention are specified by the above-mentioned materials, refractive index and film thickness. Outside this range, the heat resistant temperature of the entire antireflection film is not improved, and the degree of decrease in the heat resistant temperature over time becomes large, so that the above-described effects cannot be obtained, which is not preferable.
【０００７】本発明における下地層のＡ〜Ｃ層には、上
述した効果を損なわない程度でＴａ2Ｏ5、Ｙ2Ｏ3、
ＴｉＯ2、ＺｒＯ2、ＭｇＦ2、ＳｉＯ2等の金属を混
合することが可能である。The layers A to C of the underlayer in the present invention include Ta2 O5 , Y2 O3 and
It is possible to mix metals such as TiO2 , ZrO2 , MgF2 and SiO2 .
【０００８】本発明における反射防止膜の膜構成は特に
限定されず、λ／４−λ／４の２層膜、λ／４−λ／４
−λ／４あるいはλ／４−λ／２−λ／４の３層膜、さ
らに４層以上の多層膜などを用いることができる。特に
好ましい膜構成は以下に記述する二つの反射防止膜が挙
げられる。その第１の反射防止膜（特許請求の範囲の欄
の請求項２に該当する。）は、下地層の表面から順にＴ
ａ2Ｏ5層と、Ｔａ2Ｏ5、Ｙ2Ｏ3およびＳｉＯ2を
含む混合層からなる第１の低屈折率層と；Ｔａ2Ｏ5層
と、Ｔａ2Ｏ5、Ｙ2Ｏ3およびＳｉＯ2を含む混合層
と、Ｔａ2Ｏ5層からなる高屈折率層と；ＳｉＯ2層か
らなる第２の低屈折率層とを積層して構成されるもので
ある。また第２の反射防止膜（特許請求の範囲の欄の請
求項３に該当する。）は、下地層の表面から順にＴａ2
Ｏ5、Ｙ2Ｏ3及びＳｉＯ2とを含む混合層と、Ｔａ2
Ｏ5層からなる第１の低屈折率層と；Ｔａ2Ｏ5、Ｙ2
Ｏ3およびＳｉＯ2とを含む混合層と、Ｔａ2Ｏ5層
と、Ｔａ2Ｏ5、Ｙ2Ｏ3、およびＳｉＯ2を含む混合
層からなる高屈折率層；ＳｉＯ2層からなる第２の低屈
折率層を積層して構成されるものである。The film constitution of the antireflection film in the present invention is not particularly limited, and it is a two-layer film of λ / 4-λ / 4, λ / 4-λ / 4.
A three-layer film of -λ / 4 or λ / 4-λ / 2-λ / 4, and a multilayer film of four or more layers can be used. Particularly preferable film configurations include the two antireflection films described below. The first antireflection film (corresponding to claim 2 in the scope of the claims) has a T layer in order from the surface of the underlayer.
an a2 O5 layer and a first low refractive index layer comprising a mixed layer containing Ta2 O5 , Y2 O3 and SiO2 ; Ta2 O5 layer, Ta2 O5 , Y2 O3 And a mixed layer containing SiO2 ; a high refractive index layer made of a Ta2 O5 layer; and a second low refractive index layer made of a SiO2 layer. The second antireflection film (corresponding to claim 3 in the scope of claims) is provided with Ta2 in order from the surface of the underlayer.
A mixed layer containing O5 , Y2 O3 and SiO2, and Ta2
A first low refractive index layer consisting of an O5 layer; Ta2 O5 , Y2
O3 and a mixed layer containing a SiO2, and Ta2 O5layer, Ta 2 O 5, Y 2 O 3, and a high refractive index layer composed of a mixed layer including SiO2; second consisting of SiO2 layer The low refractive index layer is laminated.
【０００９】これらの反射防止膜が特に好ましい理由
は、これらの反射防止膜自体が良好な耐熱性を有し、さ
らに経時的な耐熱温度の低下の程度が小さいという特性
を有しているためである。本発明における下地層の上に
これらの反射防止膜を施すことによってさらに耐熱性に
優れ、経時的な耐熱温度の低下が極めて小さい反射防止
膜を有する光学部材を得ることができる。本発明の光学
部材に用いる合成樹脂としては、メチルメタクリレート
単独重合体、メチルメタクリレートと１種以上の他のモ
ノマーとをモノマー成分とする共重合体、ジエチレング
リコールビスアリルカーボネート単独重合体、ジエチレ
ングリコールビスアリルカーボネートと１種以上の他の
モノマーとをモノマー成分とする共重合体、イオウ含有
共重合体、ハロゲン含有共重合体、ポリカーボネート、
ポリスチレン、ポリ塩化ビニル、不飽和ポリエステル、
ポリエチレンテレフタレート、ポリウレタンなどの重合
体が挙げられる。The reason why these antireflection films are particularly preferable is that these antireflection films themselves have good heat resistance and further have a characteristic that the degree of decrease in heat resistant temperature with time is small. is there. By providing these antireflection films on the underlayer in the present invention, it is possible to obtain an optical member having an antireflection film that is more excellent in heat resistance and has an extremely small decrease in heat resistant temperature with time. Examples of the synthetic resin used for the optical member of the present invention include a methyl methacrylate homopolymer, a copolymer containing methyl methacrylate and one or more other monomers as a monomer component, diethylene glycol bisallyl carbonate homopolymer, diethylene glycol bisallyl carbonate. And a copolymer containing at least one other monomer as a monomer component, a sulfur-containing copolymer, a halogen-containing copolymer, a polycarbonate,
Polystyrene, polyvinyl chloride, unsaturated polyester,
Examples thereof include polymers such as polyethylene terephthalate and polyurethane.
【００１０】合成樹脂の上に下地層、反射防止膜を設け
る場合には、合成樹脂表面に有機ケイ素重合体を含むハ
ードコート層をディッピング法、スピンコート法等の塗
布法により成膜し、このハードコート層上に下地層およ
び反射防止膜を設けることが好ましい。なお、本発明の
反射防止膜を成膜するにあたっては、真空蒸着法の他、
焼結体をターゲット材料とするスパッタリング法や、イ
オンプレーティング法等の方法を用いることもできる。When a base layer and an antireflection film are provided on a synthetic resin, a hard coat layer containing an organic silicon polymer is formed on the surface of the synthetic resin by a coating method such as a dipping method or a spin coating method. It is preferable to provide a base layer and an antireflection film on the hard coat layer. In forming the antireflection film of the present invention, in addition to the vacuum vapor deposition method,
A sputtering method using a sintered body as a target material, an ion plating method, or the like can also be used.
【００１１】本発明の反射防止膜を有する光学部材は、
眼鏡レンズのほか、カメラ用レンズ、自動車の窓ガラ
ス、ワードプロセッサーのディスプレイに付設する光学
フィルターなどに使用することが可能である。The optical member having the antireflection film of the present invention comprises
In addition to eyeglass lenses, it can be used for camera lenses, automobile window glass, and optical filters attached to word processor displays.
【００１２】[0012]
【実施例】以下、実施例により本発明を詳細に説明する
が、本発明はこれらの実施例に限定されるものではな
い。なお、実施例及び比較例で得られた反射防止膜を有
する光学部材は、以下に示す試験方法により、諸物性を
測定した。EXAMPLES The present invention is described in detail below with reference to examples, but the present invention is not limited to these examples. The physical properties of the optical members having the antireflection film obtained in Examples and Comparative Examples were measured by the following test methods.
【００１３】（ａ）耐擦傷性試験＃００００のスチールウールにより表面を往復回数で１
０回こすって耐擦傷性を次のように判定した。Ａ：わずかに傷がつくＢ：多く傷がつくＣ：膜のはがれが生じる(A) Scratch resistance test # 0000 The steel wool of the number of times of reciprocating 1
The scratch resistance was evaluated by rubbing 0 times as follows. A: Slightly scratched B: Many scratches C: Film peeling occurs
【００１４】（ｂ）密着性試験ＪＩＳ−Ｚ−１５２２に従いゴバン目を１０×１０個作
りセロファン粘着テープにより剥離試験を３回行い、残
ったゴバン目の数を数えた。(B) Adhesion test In accordance with JIS-Z-1522, 10 × 10 goggles were made and a peeling test was conducted three times with a cellophane adhesive tape, and the number of gobangs remaining was counted.
【００１５】（ｃ）視感反射率（片面）日立製作所製Ｕ３４１０型自記分光光度計を用い、視感
反射率を求めた。（ｄ）耐熱性試験蒸着膜形成直後の反射防止膜を有する光学部材をオーブ
ンに１時間入れて加熱し、クラックの発生の有無を調べ
た。加熱温度は５０℃より始め、５℃ずつ上げてクラッ
クが発生する温度を調べた。(C) Luminous reflectance (single-sided) Luminous reflectance was determined using a U3410 type self-recording spectrophotometer manufactured by Hitachi Ltd. (D) Heat resistance test An optical member having an antireflection film immediately after formation of a vapor deposition film was placed in an oven for 1 hour to be heated and examined for the occurrence of cracks. The heating temperature was started from 50 ° C. and was increased by 5 ° C., and the temperature at which cracks were generated was examined.
【００１６】（ｅ）経時的な耐熱性試験蒸着形成直後の反射防止膜を有する光学部材を４ヶ月間
屋外暴露を行い、その後前記した耐熱性試験と同じ方法
により評価を行った。(E) Temporal heat resistance test An optical member having an antireflection film immediately after vapor deposition was exposed outdoors for 4 months, and then evaluated by the same method as the heat resistance test.
【００１７】（ｆ）耐酸性試験２０℃、１０％塩酸水溶液に１時間浸漬した後、耐酸性
を次のように判定した。○：浸漬前と変化せず×：反射防止膜にはがれが生じる(F) Acid resistance test After being immersed in a 10% hydrochloric acid aqueous solution at 20 ° C. for 1 hour, the acid resistance was evaluated as follows. ○: No change from before immersion ×: Peeling occurs on the antireflection film
【００１８】（ｇ）耐アルカリ性試験２０℃、１０％水酸化ナトリウム水溶液に１時間浸漬し
た後、耐アルカリ性を次のように判定した。○：浸漬前と変化せず×：反射防止膜にはがれが生じる(G) Alkali resistance test After immersion in a 10% aqueous sodium hydroxide solution at 20 ° C. for 1 hour, the alkali resistance was evaluated as follows. ○: No change from before immersion ×: Peeling occurs on the antireflection film
【００１９】実施例１−１まず反射防止膜を設ける合成樹脂として、ジエチレング
リコールビスアリルカーボネートを主成分とし、紫外線
吸収剤として２−ヒドロキシ−４−ｎ−オプトキシベン
ゾフェノンを、前者／後者の重量比が９９．９７／０．
０３となるように含有する、屈折率が１．４９９のプラ
スチックレンズを用意した。Example 1-1 First, as a synthetic resin for providing an antireflection film, diethylene glycol bisallyl carbonate was used as a main component, and 2-hydroxy-4-n-optoxybenzophenone was used as an ultraviolet absorber, the former / the latter weight ratio. Is 99.97 / 0.
A plastic lens having a refractive index of 1.499, which is contained so as to have a value of 03, was prepared.
【００２０】（ｉ）ハードコート層（ｎｄ１．５０）の
形成前記プラスチックレンズを、８０モル％のコロイダルシ
リカと２０モル％のγ−グリシドキシプロピルトリメト
キシシランを含有するコーティング液に浸漬し、その後
硬化してハードコート層を設けた。(I) Formation of Hard Coat Layer (nd 1.50) The above plastic lens was dipped in a coating solution containing 80 mol% of colloidal silica and 20 mol% of γ-glycidoxypropyltrimethoxysilane, Then, it was cured to form a hard coat layer.
【００２１】（ｉｉ）下地層および反射防止膜の形成前記ハードコート層を有するプラスチックレンズを８０
℃に加熱し、前記ハードコート層の上に真空蒸着法（真
空度２×１０-5Ｔｏｒｒ）によりＳｉＯ2層（屈折率
１．４６、膜厚０．０７λ（λ＝５００ｎｍ））と、Ｔ
ａ2Ｏ5層（屈折率２．０５、膜厚０．０３λ）と、Ｓ
ｉＯ2とＡｌ2Ｏ3との混合層（屈折率１．５２、膜厚
１．２５λ）からなる下地層を形成した。次に、前記下
地層の上にＴａ2Ｏ5層（屈折率２．０５、膜厚０．０
６λ）と、Ｔａ2Ｏ5、Ｙ2Ｏ3およびＳｉＯ2を混合
した混合層（屈折率１．６１、膜厚０．１１λ）からな
る第１の低屈折率層を形成した。この第１の低屈折率層
の上にＴａ2Ｏ5層（屈折率２．０５、膜厚０．０５
λ）と、Ｔａ2Ｏ5、Ｙ2Ｏ3およびＳｉＯ2からなる
混合層（屈折率１．６１、膜厚０．０５λ）と、Ｔａ2
Ｏ5層（屈折率２．０５、膜厚０．１５λ）よりなる高
屈折率層を形成し、さらに高屈折率層の上にＳｉＯ2か
らなる第２の低屈折率層（屈折率１．４６、膜厚０．２
５λ）を形成して、反射防止膜付きプラスチックレンズ
を得た。尚、前記第１の低屈折率層から第２の低屈折率
層は前記下地層を形成した同様の真空蒸着法により形成
した。得られた反射防止膜付きプラスチックレンズの評
価結果を表２に示す。表２に示されるように実施例１の
反射防止膜付きプラスチックレンズは耐擦傷性、密着
性、耐酸性、耐アルカリ性に優れ、さらにクラック発生
温度が１２０℃と高く、また４ヶ月間屋外暴露を行った
後のクラック発生温度が１１０℃と経時的な耐熱温度の
低下の程度が小さいものであった。尚、実施例１は特許
請求の範囲の欄の請求項２に該当するものである。(Ii) Formation of underlayer and antireflection filmThe plastic lens having the hard coat layer is made of 80
It is heated to ℃, vacuum deposition method (true
Vacancy 2 × 10-FiveTorr) by SiO2Layer (refractive index
1.46, film thickness 0.07λ (λ = 500 nm)) and T
a2OFiveLayer (refractive index 2.05, film thickness 0.03λ) and S
iO2And Al2O3And mixed layer (refractive index 1.52, film thickness
An underlayer made of 1.25λ) was formed. Next, above
Ta on the stratum2OFiveLayer (refractive index 2.05, film thickness 0.0
6λ) and Ta2OFive, Y2O3And SiO2Mixed
Mixed layer (refractive index 1.61, film thickness 0.11λ)
To form a first low refractive index layer. This first low refractive index layer
On top of2OFiveLayer (refractive index 2.05, film thickness 0.05
λ) and Ta2OFive, Y2O3And SiO2Consists of
Mixed layer (refractive index 1.61, film thickness 0.05λ) and Ta2
OFiveLayer (refractive index 2.05, film thickness 0.15λ)
A refractive index layer is formed, and SiO is formed on the high refractive index layer.2Or
Second low-refractive index layer (refractive index 1.46, film thickness 0.2
5λ) to form a plastic lens with antireflection film
Got The first low refractive index layer to the second low refractive index layer
The layer is formed by the same vacuum evaporation method as the above-mentioned underlayer.
did. Evaluation of the obtained anti-reflection coating plastic lens
Valency results are shown in Table 2. As shown in Table 2,
Plastic lens with anti-reflection film is scratch resistant and adheres well
Excellent in resistance, acid resistance, alkali resistance, and cracks
The temperature was as high as 120 ° C, and the outdoor exposure was performed for 4 months.
The subsequent cracking temperature is 110 ° C,
The degree of decrease was small. In addition, Example 1 is a patent
This corresponds to claim 2 in the scope of claims.
【００２２】実施例１−２、実施例１−３下地層におけるＳｉＯ2とＡｌ2Ｏ3との混合層の屈折
率を１．５１（実施例１−２）、１．４８（実施例１−
３）に代えた以外は実施例１−１と同様にして反射防止
膜付きプラスチックレンズを得た。評価結果は表２に示
すようにクラック発生温度が１２０℃と優れ、さらに４
ヶ月間屋外暴露を行った後のクラック発生温度が１１０
℃と経時的なクラック発生温度の低下の程度が小さいも
のであった。尚、実施例１−１〜実施例１−３の下地層
および反射防止膜の膜構成を表１に示す。Examples 1-2 and 1-3 The refractive index of the mixed layer of SiO2 and Al2 O3 in the underlayer is 1.51 (Example 1-2) and 1.48 (Example 1). −
A plastic lens with an antireflection film was obtained in the same manner as in Example 1-1, except that 3) was replaced. As shown in Table 2, the evaluation result shows that the crack generation temperature is excellent at 120 ° C.
Cracking temperature is 110 after outdoor exposure for months
The degree of decrease in the crack generation temperature with temperature was low. Table 1 shows the film configurations of the underlayer and the antireflection film of Examples 1-1 to 1-3.
【００２３】比較例１−１〜比較例１−３実施例１−１〜実施例１−３の比較例として比較例１−
１〜比較例１−３を挙げる。下地層におけるＳｉＯ2か
らなる層の膜厚を本発明の範囲外である０．２０λに
し、さらに下地層におけるＳｉＯ2とＡｌ2Ｏ3との混
合層の屈折率を１．５２（比較例１−１）、１．５１
（比較例１−２）、１．４８（比較例１−３）にした以
外はすべて実施例１−１と同様にして反射防止膜付きプ
ラスチックレンズを得た。評価結果は表２に示されるよ
うに実施例１−１〜実施例１−３の反射防止膜付きプラ
スチックレンズと比べクラック発生温度が低く、また経
時的なクラック発生温度の低下の程度が大きいものであ
った。Comparative Example 1-1 to Comparative Example 1-3 Comparative Example 1 as a comparative example of Example 1-1 to Example 1-3
1 to Comparative Example 1-3 will be given. The thickness of the layer made of SiO2 in the base layer to outside the scope of 0.20λ of the present invention, the refractive index of the mixed layer of SiO2 and Al2 O3 1.52 in yet underlayer (Comparative Example 1 -1), 1.51
A plastic lens with an antireflection film was obtained in the same manner as in Example 1-1, except that Comparative Examples 1-2 and 1.48 (Comparative Example 1-3) were used. As shown in Table 2, the evaluation results show that the crack generation temperature is lower than that of the plastic lenses with the antireflection film of Examples 1-1 to 1-3, and the degree of decrease in the crack generation temperature with time is large. Met.
【００２４】実施例２−１〜実施例２−３特許請求の範囲の欄の請求項２に該当する実施例として
実施例２−１〜実施例２−３を挙げる。表３に示すよう
に下地層におけるＴａ2Ｏ5層の膜厚を上限の０．１０
λに、ＳｉＯ2層の膜厚を下限の０．０５λに、ＳｉＯ
2とＡｌ2Ｏ3との混合層の屈折率を１．５２（実施例
２−１）、１．５１（実施例２−２）、１．４８（実施
例２−３）に、反射防止膜の膜構成を表３に示したよう
にした以外はすべて実施例１−１と同様にして反射防止
膜付きプラスチックレンズを得た。評価結果は表４に示
すように実施例１−１の反射防止膜付きプラスチックレ
ンズ同様、クラック発生温度が高く、経時的なクラック
発生温度の低下の程度が小さいものであった。Examples 2-1 to 2-3 Examples 2-1 to 2-3 are given as examples corresponding to claim 2 in the scope of claims. As shown in Table 3, the film thickness of the Ta2 O5 layer in the underlayer is set to the upper limit of 0.10.
to λ, the lower limit of the thickness of the SiO2 layer is 0.05λ, and
The refractive index of the mixed layer of2 and Al2 O3 is set to 1.52 (Example 2-1), 1.51 (Example 2-2), and 1.48 (Example 2-3) to prevent reflection. A plastic lens with an antireflection film was obtained in the same manner as in Example 1-1, except that the film structure of the film was as shown in Table 3. As shown in Table 4, as shown in Table 4, similarly to the plastic lens with the antireflection film of Example 1-1, the crack generation temperature was high and the degree of decrease in the crack generation temperature with time was small.
【００２５】比較例２−１〜比較例２−３実施例２−１〜実施例２−３の比較例として比較例２−
１〜比較例２−３を挙げる。表３に示すように下地層に
おけるＳｉＯ2からなる層の膜厚を本発明の範囲外であ
る０．０３λにし、さらに下地層におけるＳｉＯ2とＡ
ｌ2Ｏ3との混合層の屈折率を１．５２（比較例２−
１）、１．５１（比較例２−２）、１．４８（比較例２
−３）にした以外はすべて実施例２−１と同様にして反
射防止膜付きプラスチックレンズを得た。評価結果は表
４に示されるように実施例２−１〜実施例２−３の反射
防止膜付きプラスチックレンズと比べクラック発生温度
が低く、また経時的なクラック発生温度の低下の程度が
大きいものであった。Comparative Example 2-1 to Comparative Example 2-3 Comparative Example 2-as a comparative example of Example 2-1 to Example 2-3
1 to Comparative Example 2-3 will be given. The thickness of the layer made of SiO2 in the base layer as shown in Table 3 to 0.03λ outside the scope of the present invention, further SiO2 and A in the underlying layer
The refractive index of the mixed layer with l2 O3 was 1.52 (Comparative Example 2-
1), 1.51 (Comparative Example 2-2), 1.48 (Comparative Example 2)
A plastic lens with an antireflection film was obtained in the same manner as in Example 2-1, except that the procedure (3) was performed. As shown in Table 4, the evaluation results show that the crack generation temperature is lower than that of the plastic lenses with antireflection film of Examples 2-1 to 2-3, and the degree of decrease in crack generation temperature with time is large. Met.
【００２６】実施例３−１〜実施例３−３特許請求の範囲の欄の請求項２に該当する他の実施例と
して実施例３−１〜実施例３−３を挙げる。表５に示す
ように下地層におけるＳｉＯ2層の膜厚を０．０５λ
（実施例３−１）、０．１０λ（実施例３−２）、０．
１５λ（実施例３−３）に、またＴａ2Ｏ5層の膜厚を
０．１０λ（実施例３−１）、０．０１λ（実施例３−
２）、０．０２λ（実施例３−３）に、反射防止膜の膜
構成を表５に示したようにした以外はすべて実施例３−
１と同様にして反射防止膜付きプラスチックレンズを得
た。評価結果は表６に示すように実施例１−１同様、ク
ラック発生温度が高く、経時的なクラック発生温度の低
下の程度が小さいものであった。Examples 3-1 to 3-3 Examples 3-1 to 3-3 will be given as other examples corresponding to claim 2 in the scope of claims. As shown in Table 5, the thickness of the SiO2 layer in the underlayer is set to 0.05λ.
(Example 3-1), 0.10λ (Example 3-2), 0.
15λ (Example 3-3), and the film thickness of the Ta2 O5 layer was 0.10λ (Example 3-1) and 0.01λ (Example 3-).
2) and 0.02λ (Example 3-3) except that the film constitution of the antireflection film is as shown in Table 5.
A plastic lens with an antireflection film was obtained in the same manner as in 1. As shown in Table 6, as shown in Table 6, the crack generation temperature was high and the degree of decrease in the crack generation temperature with time was small as in Example 1-1.
【００２７】比較例３−１〜比較例３−３実施例３−１〜実施例３−３の比較例として比較例３−
１〜比較例３−３を挙げる。表５に示すように下地層に
おけるＳｉＯ2層の膜厚を本発明の範囲外である０．２
０λ（比較例３−１）、０．０３λ（比較例３−２）、
０．０１λ（比較例３−３）に、またＴａ2Ｏ5層の膜
厚を本発明の範囲外である０．１５λ（比較例３−
１）、０．００５λ（比較例３−２）、０．２０λ（比
較例３−３）にした以外はすべて実施例３−１と同様に
して反射防止膜付きプラスチックレンズを得た。評価結
果は表６に示されるように実施例３−１〜実施例３−３
の反射防止膜付きプラスチックレンズと比べクラック発
生温度が低く、また経時的なクラック発生温度の低下の
程度が大きいものであった。Comparative Example 3-1 to Comparative Example 3-3 Comparative Example 3 as a comparative example of Example 3-1 to Example 3-3
1 to Comparative Example 3-3 will be given. As shown in Table 5, the thickness of the SiO2 layer in the underlayer is outside the range of the present invention.
0λ (Comparative Example 3-1), 0.03λ (Comparative Example 3-2),
0.01λ (Comparative Example 3-3), and the film thickness of the Ta2 O5 layer was out of the range of the present invention of 0.15λ (Comparative Example 3-3).
1), 0.005λ (Comparative Example 3-2) and 0.20λ (Comparative Example 3-3) were used, and a plastic lens with an antireflection film was obtained in the same manner as in Example 3-1. The evaluation results are shown in Table 6 as Example 3-1 to Example 3-3.
The crack generation temperature was lower than that of the plastic lens with the antireflection film, and the degree of decrease in the crack generation temperature with time was large.
【００２８】実施例４−１〜実施例４−３特許請求の範囲の欄の請求項３に該当する実施例として
実施例４−１〜実施例４−３を挙げる。下地層および反
射防止膜の膜構成を表７に示すようにした以外は実施例
１−１〜実施例１−３に準じて反射防止膜付きプラスチ
ックレンズを得た。評価結果は表８に示すように実施例
１−１同様クラック発生温度が高く、経時的なクラック
発生温度の低下の程度が小さいものであった。Examples 4-1 to 4-3 Examples 4-1 to 4-3 will be given as examples corresponding to claim 3 in the scope of claims. A plastic lens with an antireflection film was obtained according to Examples 1-1 to 1-3 except that the underlayer and the antireflection film had the film configurations shown in Table 7. As shown in Table 8, the evaluation results showed that the crack generation temperature was high as in Example 1-1, and the degree of decrease in the crack generation temperature with time was small.
【００２９】比較例４−１〜比較例４−３実施例４−１〜実施例４−３の比較例として比較例４−
１〜比較例４−３を挙げる。下地層におけるＳｉＯ2と
Ａｌ2Ｏ3との混合層の膜厚を本発明の範囲外である
０．７０λ（比較例４−１）、１．５５λ（比較例４−
２）、１．６０λ（比較例４−３）にした以外はすべて
実施例４−１と同様にして反射防止膜付きプラスチック
レンズを得た。評価結果は表８に示されるように実施例
４−１〜実施例４−３の反射防止膜付きプラスチックレ
ンズと比べクラック発生温度が低く、また経時的なクラ
ック発生温度の低下の程度が大きいものであった。Comparative Example 4-1 to Comparative Example 4-3 Comparative Example 4 as a comparative example of Example 4-1 to Example 4-3
1 to Comparative Example 4-3 will be given. The film thickness of the mixed layer of SiO2 and Al2 O3 in the underlayer is 0.70λ (Comparative Example 4-1) and 1.55λ (Comparative Example 4-) outside the scope of the present invention.
A plastic lens with an antireflection film was obtained in the same manner as in Example 4-1, except for 2) and 1.60λ (Comparative Example 4-3). As shown in Table 8, the evaluation results are such that the crack generation temperature is lower than that of the plastic lenses with antireflection film of Examples 4-1 to 4-3, and the degree of decrease in crack generation temperature with time is large. Met.
【００３０】実施例５−１〜実施例６−３特許請求の範囲の欄の請求項１に該当する実施例として
実施例５−１〜実施例６−３を挙げる。実施例５−１〜
実施例５−３では表９に示すように下地層におけるＴａ
2Ｏ5層にＹ2Ｏ3とＺｒＯ2とを混合し、またＳｉＯ
2とＡｌ2Ｏ3との混合層の屈折率を１．５２（実施例
５−１）、１．５１（実施例５−２）、１．４８（実施
例５−３）にし、反射防止膜を表９に示す膜構成にして
反射防止膜付きプラスチックレンズを得た。実施例６−
１〜実施例６−３では下地層におけるＳｉＯ2とＡｌ2
Ｏ3との混合層の膜厚を０．７５λ（実施例６−１）、
１．０λ（実施例６−２）、１．５０λ（実施例６−
３）に、反射防止膜の膜構成を表１１に示したようにし
た以外はすべて実施例１−１と同様にして反射防止膜付
きプラスチックレンズを得た。評価結果は表１０、表１
２に示すようにクラック発生温度が高く、さらに経時的
なクラック発生温度の低下の程度が小さいものであっ
た。Examples 5-1 to 6-3 Examples 5-1 to 6-3 will be given as examples corresponding to claim 1 in the scope of claims. Example 5-1
In Example 5-3, Ta in the underlayer as shown in Table 9 was used.
In the 2 O5 layer, Y2 O3 and ZrO2 are mixed, and
The mixed layers of2 and Al2 O3 have a refractive index of 1.52 (Example 5-1), 1.51 (Example 5-2) and 1.48 (Example 5-3) to prevent reflection. The film was formed into the film configuration shown in Table 9 to obtain a plastic lens with an antireflection film. Example 6-
In Examples 1 to 3-3, SiO2 and Al2 in the underlayer are used.
The thickness of the mixed layer with O3 is 0.75λ (Example 6-1),
1.0λ (Example 6-2), 1.50λ (Example 6-)
In 3), a plastic lens with an antireflection film was obtained in the same manner as in Example 1-1, except that the film structure of the antireflection film was as shown in Table 11. The evaluation results are shown in Table 10 and Table 1.
As shown in 2, the crack generation temperature was high, and the decrease in the crack generation temperature with time was small.
【００３１】比較例５−１〜比較例６−２実施例５−１〜実施例５−３の比較例として比較例５−
１〜比較例５−３を、実施例６−１〜実施例６−３の比
較例として比較例６−１、比較例６−２を挙げる。下地
層におけるＳｉＯ2をＡｌ2Ｏ3との混合層の屈折率を
本発明の範囲外である１．４７（比較例５−１）、１．
５８（比較例５−２）、１．５３（比較例５−３）にし
た以外は実施例５−１と同様にして反射防止膜付きプラ
スチックレンズを得た。評価結果は表１０に示すように
実施例５−１〜実施例５−３で得られた反射防止膜付き
プラスチックレンズと比べ、クラック発生温度が低く、
経時的なクラック発生温度の低下の程度が大きいもので
あった。また比較例６−１、比較例６−２では、下地層
をＳｉＯ2からなる単層（比較例６−１）、Ａｌ2Ｏ3
からなる単層（比較例６−２）にした以外は実施例６−
１と同様にして反射防止膜付きプラスチックレンズを得
た。評価結果は表１２に示すように実施例６−１〜実施
例６−３で得られた反射防止膜付きプラスチックレンズ
と比べクラック発生温度が低く、また経時的なクラック
発生温度の低下の程度が大きいものであった。Comparative Example 5-1 to Comparative Example 6-2 Comparative Example 5 as a comparative example of Examples 5-1 to 5-3
Comparative Examples 6-1 and 6-2 will be given as Comparative Examples 6-1 to 6-3, respectively, as Comparative Examples of Example 6-1 to Example 6-3. The refractive index of the mixed layer of SiO2 and Al2 O3 in the underlayer is 1.47 (Comparative Example 5-1), which is outside the range of the present invention.
A plastic lens with an antireflection film was obtained in the same manner as in Example 5-1 except that the values were 58 (Comparative Example 5-2) and 1.53 (Comparative Example 5-3). As shown in Table 10, the evaluation results show that the crack generation temperature is lower than those of the plastic lenses with antireflection film obtained in Examples 5-1 to 5-3.
The degree of decrease in crack generation temperature with time was large. Further, in Comparative Examples 6-1 and 6-2, the base layer was a single layer made of SiO2 (Comparative Example 6-1), and Al2 O3 was used.
Example 6-except that the single layer (Comparative Example 6-2)
A plastic lens with an antireflection film was obtained in the same manner as in 1. As shown in Table 12, the evaluation results show that the crack generation temperature is lower than that of the plastic lens with the antireflection film obtained in each of Examples 6-1 to 6-3, and the degree of decrease in the crack generation temperature over time is small. It was a big one.
【００３２】[0032]
【表１】[Table 1]
【００３３】[0033]
【表２】[Table 2]
【００３４】[0034]
【表３】[Table 3]
【００３５】[0035]
【表４】[Table 4]
【００３６】[0036]
【表５】[Table 5]
【００３７】[0037]
【表６】[Table 6]
【００３８】[0038]
【表７】[Table 7]
【００３９】[0039]
【表８】[Table 8]
【００４０】[0040]
【表９】[Table 9]
【００４１】[0041]
【表１０】[Table 10]
【００４２】[0042]
【表１１】[Table 11]
【００４３】[0043]
【表１２】[Table 12]
【００４４】[0044]
【発明の効果】本発明によって耐熱性が良好で、且つ経
時的な耐熱温度の低下の程度が小さい反射防止膜を有す
る光学部材を提供することができた。また、本発明にお
ける下地層を用いることによって反射防止膜の耐熱温度
を向上させ、経時的な耐熱温度の低下の程度を小さくす
ることができる。According to the present invention, it is possible to provide an optical member having an antireflection film having good heat resistance and having a small decrease in heat resistant temperature with time. Further, by using the underlayer in the present invention, the heat resistant temperature of the antireflection film can be improved and the degree of decrease in the heat resistant temperature with time can be reduced.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3214467AJP3012712B2 (en) | 1991-07-31 | 1991-07-31 | Optical member having antireflection film |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3214467AJP3012712B2 (en) | 1991-07-31 | 1991-07-31 | Optical member having antireflection film |
| Publication Number | Publication Date |
|---|---|
| JPH0534502Atrue JPH0534502A (en) | 1993-02-12 |
| JP3012712B2 JP3012712B2 (en) | 2000-02-28 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3214467AExpired - Fee RelatedJP3012712B2 (en) | 1991-07-31 | 1991-07-31 | Optical member having antireflection film |
| Country | Link |
|---|---|
| JP (1) | JP3012712B2 (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6606196B2 (en)* | 2000-08-29 | 2003-08-12 | Hoya Corporation | Optical element having antireflection film |
| FR2903197A1 (en)* | 2006-06-28 | 2008-01-04 | Essilor Int | OPTICAL ARTICLE COATED WITH A TEMPERATURE-RESISTANT MULTILAYER COATED ANTI-REFLECTING COATING AND COATING, AND METHOD OF MANUFACTURING THE SAME |
| JP2011512553A (en)* | 2008-02-14 | 2011-04-21 | インド インテルナシオナル， エス．エー． | Cured layer, coherent multilayer and polymer-based lens comprising a hard layer sandwiched between the two layers and corresponding manufacturing method |
| US8318245B2 (en)* | 2007-02-23 | 2012-11-27 | Essilor International (Compagnie Generale D'optique) | Method for producing an optical article coated with an antireflection or a reflective coating having improved adhesion and abrasion resistance properties |
| AU2007264948B2 (en)* | 2006-06-28 | 2013-01-31 | Essilor International (Compagnie Generale D'optique) | Optical article having a temperature-resistant anti-reflection coating with optimized thickness ratio of low index and high index layers |
| US10962687B2 (en) | 2007-06-13 | 2021-03-30 | Essilor International | Optical article coated with an antireflection coating comprising a sub-layer partially formed under ion assistance and its manufacturing process |
| WO2024224672A1 (en)* | 2023-04-28 | 2024-10-31 | Ｔｏｗａ株式会社 | Reflectance adjustment film, multilayer body, and method for producing reflectance adjustment film |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6606196B2 (en)* | 2000-08-29 | 2003-08-12 | Hoya Corporation | Optical element having antireflection film |
| FR2903197A1 (en)* | 2006-06-28 | 2008-01-04 | Essilor Int | OPTICAL ARTICLE COATED WITH A TEMPERATURE-RESISTANT MULTILAYER COATED ANTI-REFLECTING COATING AND COATING, AND METHOD OF MANUFACTURING THE SAME |
| WO2008001011A3 (en)* | 2006-06-28 | 2008-03-06 | Essilor Int | Optical article coated with an underlayer and with a temperature-resistant multi-layer anti-reflection coating, and manufacturing method |
| AU2007264948B2 (en)* | 2006-06-28 | 2013-01-31 | Essilor International (Compagnie Generale D'optique) | Optical article having a temperature-resistant anti-reflection coating with optimized thickness ratio of low index and high index layers |
| US9625620B2 (en) | 2006-06-28 | 2017-04-18 | Essilor International (Compagnie Generale D'optique) | Optical article coated with a sub-layer and with a heat-resistant, multilayered antireflection coating, and method for producing same |
| US8318245B2 (en)* | 2007-02-23 | 2012-11-27 | Essilor International (Compagnie Generale D'optique) | Method for producing an optical article coated with an antireflection or a reflective coating having improved adhesion and abrasion resistance properties |
| US8846140B2 (en)* | 2007-02-23 | 2014-09-30 | Essilor International (Compagnie Generale D'optique) | Method for producing an optical article coated with an antireflection or a reflective coating having improved adhesion and abrasion resistance properties |
| US10962687B2 (en) | 2007-06-13 | 2021-03-30 | Essilor International | Optical article coated with an antireflection coating comprising a sub-layer partially formed under ion assistance and its manufacturing process |
| JP2011512553A (en)* | 2008-02-14 | 2011-04-21 | インド インテルナシオナル， エス．エー． | Cured layer, coherent multilayer and polymer-based lens comprising a hard layer sandwiched between the two layers and corresponding manufacturing method |
| WO2024224672A1 (en)* | 2023-04-28 | 2024-10-31 | Ｔｏｗａ株式会社 | Reflectance adjustment film, multilayer body, and method for producing reflectance adjustment film |
| TWI880648B (en)* | 2023-04-28 | 2025-04-11 | 日商Ｔｏｗａ股份有限公司 | Reflectivity adjustment film, laminate, and method for manufacturing reflectivity adjustment film |
| Publication number | Publication date |
|---|---|
| JP3012712B2 (en) | 2000-02-28 |
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