JPH0461323B2 - - Google Patents
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- Publication number
- JPH0461323B2 JPH0461323B2 JP58238813A JP23881383A JPH0461323B2 JP H0461323 B2 JPH0461323 B2 JP H0461323B2 JP 58238813 A JP58238813 A JP 58238813A JP 23881383 A JP23881383 A JP 23881383A JP H0461323 B2 JPH0461323 B2 JP H0461323B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- layer
- thickness
- synthetic resin
- resin substrate
- 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 - Lifetime
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- 239000010408 film Substances 0.000 claims description 90
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 32
- 239000000758 substrate Substances 0.000 claims description 31
- 229920003002 synthetic resin Polymers 0.000 claims description 21
- 239000000057 synthetic resin Substances 0.000 claims description 21
- 235000012239 silicon dioxide Nutrition 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 230000003287 optical effect Effects 0.000 claims description 10
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 9
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 9
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 7
- KELHQGOVULCJSG-UHFFFAOYSA-N n,n-dimethyl-1-(5-methylfuran-2-yl)ethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=C(C)O1 KELHQGOVULCJSG-UHFFFAOYSA-N 0.000 claims description 7
- 239000012788 optical film Substances 0.000 claims description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 7
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 7
- 238000007740 vapor deposition Methods 0.000 claims description 7
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 6
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 239000006117 anti-reflective coating Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 7
- 229920000178 Acrylic resin Polymers 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000010894 electron beam technology Methods 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 230000005856 abnormality Effects 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- 229920000298 Cellophane Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- SYFOAKAXGNMQAX-UHFFFAOYSA-N bis(prop-2-enyl) carbonate;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.C=CCOC(=O)OCC=C SYFOAKAXGNMQAX-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Surface Treatment Of Optical Elements (AREA)
Description
【発明の詳細な説明】
本発明は合成樹脂レンズのような合成樹脂基板
の多層反射防止膜に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a multilayer antireflection coating for a synthetic resin substrate such as a synthetic resin lens.
近年、成形の容易さと軽量とによつて合成樹脂
製光学部品、特にレンズが用いられるようになつ
たが、これらの光学部品の反射防止膜には、なお
問題が残つている。 In recent years, synthetic resin optical parts, especially lenses, have come into use due to their ease of molding and light weight, but problems still remain with antireflection coatings for these optical parts.
従来、このような反射防止膜としては、例えば
次のものが知られている。すなわち、特開昭56−
18922号には、合成樹脂基板上に機械的強度を補
うに十分な、数μの膜厚の二酸化ケイ素（SiO2）
からなる第１層を形成し、その上に膜厚0.15λ〜
0.25λ〔λ（光の波長）＝450〜550nm〕の酸化イツ
トリウム（Y2O3）膜からなる第２層、その上に
膜厚0.35λ〜0.45λの酸化ジルコニウム（ZrO2）膜
からなる第３層、およびさらに第３層の上に膜厚
0.20λ〜0.30λの二酸化ケイ素膜からなる第４層を
順次積層した多層反射防止膜が開示されている。 Conventionally, the following are known as such antireflection films, for example. In other words, JP-A-56-
No. 18922 describes a silicon dioxide (SiO 2 ) film with a thickness of several μm, which is sufficient to supplement mechanical strength, on a synthetic resin substrate.
Form a first layer consisting of
The second layer consists of a yttrium oxide (Y 2 O 3 ) film with a thickness of 0.25λ [λ (wavelength of light) = 450 to 550 nm], and on top of that a zirconium oxide (ZrO 2 ) film with a thickness of 0.35λ to 0.45λ. The third layer, and the film thickness on top of the third layer
A multilayer antireflection coating is disclosed in which a fourth layer of silicon dioxide film having a thickness of 0.20λ to 0.30λ is sequentially laminated.
特開昭50−67147号には、合成樹脂基板上に、
例えば、第１層として一酸化ケイ素（SiO）を1/
４λまたは1/2λ（λ＝530nm）の厚さに蒸着し、
ついで第２層として二酸化ケイ素を1/4λの厚さ
に蒸着して多層反射防止膜を形成することが開示
されている。 JP-A No. 50-67147 discloses that on a synthetic resin substrate,
For example, silicon monoxide (SiO) is used as the first layer.
Deposited to a thickness of 4λ or 1/2λ (λ = 530nm),
It is disclosed that silicon dioxide is then deposited as a second layer to a thickness of 1/4λ to form a multilayer antireflection coating.
また、特開昭56−121001号には、合成樹脂基板
上に第１層として膜厚20nm以下の一酸化ケイ素
膜、その上に第２層として膜厚0.50λ未満のアル
ミナ膜、さらにその上に第３層として膜厚0.25λ
〜0.30λのフツ化マグネシウム（MgF2）膜を順次
積層したプラスチツク光学部品が開示されてい
る。 In addition, JP-A-56-121001 discloses a silicon monoxide film with a thickness of 20 nm or less as a first layer on a synthetic resin substrate, an alumina film with a thickness of less than 0.50λ as a second layer, and film thickness 0.25λ as the third layer
A plastic optical component in which magnesium fluoride (MgF 2 ) films of ~0.30λ are sequentially laminated is disclosed.
さらに、特開昭58−60701号には、複数の蒸着
条件を異にするため異つた屈折率を持つた一酸化
ケイ素の蒸着膜によつて構成される多層反射防止
膜が開示され、具体的には基板上に屈折率1.60〜
1.68光学的膜厚がλ／４の一酸化ケイ素からなる
第１層、その上に屈折率1.75〜1.83、光学的膜厚
がλ／４の一酸化ケイ素からなる第２層、さらに
その上に屈折率1.50〜1.55、光学的膜厚がλ／４
の一酸化ケイ素膜からなる第３層を、順次積層し
た多層反射防止膜が開示されている。この際、一
酸化ケイ素の屈折率は蒸着速度一定の条件下に酸
素ガス圧力を変化させたり、または酸素ガス圧力
一定の条件下に蒸着速度を変化させることによつ
て、変化させることが開示されている。 Furthermore, JP-A No. 58-60701 discloses a multilayer anti-reflection coating composed of vapor-deposited films of silicon monoxide having different refractive indexes under different vapor-deposition conditions. The refractive index on the substrate is 1.60~
1.68 A first layer made of silicon monoxide with an optical thickness of λ/4, on top of which a second layer made of silicon monoxide with a refractive index of 1.75 to 1.83 and an optical thickness of λ/4, and further on top of that a second layer made of silicon monoxide with an optical thickness of λ/4. Refractive index 1.50-1.55, optical film thickness λ/4
A multilayer antireflection coating is disclosed in which a third layer of silicon monoxide is sequentially laminated. In this case, it is disclosed that the refractive index of silicon monoxide can be changed by changing the oxygen gas pressure under conditions of a constant evaporation rate, or by changing the evaporation rate under conditions of a constant oxygen gas pressure. ing.
これらの多層反射防止膜のうち、特開昭56−
18922号に開示されたものは、合成樹脂基板とし
てジエチレングリコールビスアリルカーボネート
（CR−39）が使用され、メガネ用に開発された多
層反射防止膜であり、上記の構成膜をインジエク
シヨンおよびキヤスト成形された基板に適用する
と第１層の二酸化ケイ素膜に亀裂が発生する。ま
た、特開昭50−67147号および特開昭56−121001
号に開示されたものは、膜の亀裂の発生はない
が、可視光領域における反射防止効果が低く、密
着性に若干の不安がある。 Among these multilayer antireflection coatings, JP-A-56-
What was disclosed in No. 18922 is a multilayer anti-reflection film developed for eyeglasses, using diethylene glycol bisallyl carbonate (CR-39) as a synthetic resin substrate. When applied to a substrate, cracks occur in the first layer silicon dioxide film. Also, JP-A-50-67147 and JP-A-56-121001
Although the film disclosed in the above publication does not cause cracks in the film, it has a low antireflection effect in the visible light region, and there are some concerns about adhesion.
さらに、特開昭58−60701号に開示されたもの
は、一酸化ケイ素のみで構成されているので、大
気中に放置すると酸素の影響を受け、二酸化ケイ
素に近ずくため、経時的に分光反射特性が変化す
るという欠点がある。 Furthermore, since the material disclosed in JP-A No. 58-60701 is composed only of silicon monoxide, if left in the atmosphere it will be affected by oxygen and will approach silicon dioxide, resulting in spectral reflection over time. The disadvantage is that the characteristics change.
本発明の目的は、合成樹脂基板の種類に関係な
く、基板の補強効果と可視光領域および近赤外領
域における反射防止効果を向上させた合成樹脂基
板の反射防止膜を提供することにある。 An object of the present invention is to provide an antireflection film for a synthetic resin substrate that improves the reinforcing effect of the substrate and the antireflection effect in the visible light region and near-infrared region, regardless of the type of synthetic resin substrate.
本発明のいま一つの目的は、カラーバランスが
良好で、基板に対する密着性が高く、かつ耐溶剤
性、耐磨耗性、耐環境性の良好な反射防止膜を提
供することにある。 Another object of the present invention is to provide an antireflection film that has good color balance, high adhesion to a substrate, and good solvent resistance, abrasion resistance, and environmental resistance.
本発明による合成樹脂基板の反射防止膜は、合
成樹脂基板上に形成された光学的膜厚0.13λ〜λ
〔λ（光の波長）＝450〜550nm〕の一酸化ケイ素膜
からなる第１層、該第１層上に形成された光学的
膜厚0.13λ〜λの二酸化ケイ素膜からなる第２層、
該第２層上に形成された光学的膜厚0.23λ〜0.29λ
の酸化ジルコニウム（ZrO2）、酸化セリウム
（CeO2）またはこれらの混合物の膜、或は酸化ジ
ルコニウムおよび酸化セリウムの多層膜からなる
第３層、該第３層上に形成された光学的膜厚
0.23λ〜0.29λの五酸化タンタル（Ta2O5）一酸化
チタン（TiO）二酸化チタン（TiO2）またはそ
れらの２以上の混合物の膜、或は五酸化タンタ
ル、一酸化チタンおよび二酸化チタンの２以上の
多層膜からなる第４層および該第４層上に形成さ
れた光学的膜厚0.23λ〜0.29λの二酸化ケイ素、フ
ツ化マグネシウムまたはこれらの混合物の膜、或
は二酸化ケイ素およびフツ化マグネシウムの多層
膜からなる第５層からなることを特徴とするもの
である。 The antireflection film for a synthetic resin substrate according to the present invention has an optical film thickness of 0.13λ to λ formed on a synthetic resin substrate.
[λ (wavelength of light) = 450 to 550 nm] A first layer made of a silicon monoxide film, a second layer made of a silicon dioxide film with an optical thickness of 0.13λ to λ formed on the first layer,
Optical film thickness formed on the second layer: 0.23λ to 0.29λ
A third layer consisting of a film of zirconium oxide (ZrO 2 ), cerium oxide (CeO 2 ), or a mixture thereof, or a multilayer film of zirconium oxide and cerium oxide, and an optical film thickness formed on the third layer.
A film of tantalum pentoxide (Ta 2 O 5 ), titanium monoxide (TiO), titanium dioxide (TiO 2 ) or a mixture of two or more thereof, or a film of tantalum pentoxide, titanium monoxide and titanium dioxide of 0.23λ to 0.29λ. A fourth layer consisting of two or more multilayer films, and a film of silicon dioxide, magnesium fluoride, or a mixture thereof having an optical thickness of 0.23λ to 0.29λ formed on the fourth layer, or a film of silicon dioxide and fluoride It is characterized in that it consists of a fifth layer made of a multilayer film of magnesium.
本発明において、前記第２層から第５層までは
活性化反応蒸着により形成されたものであること
が各層間の密着性を高める上で好ましい。こゝで
「活性化反応蒸着」とは、プラズマ化された活性
ガス、例えば酸素ガス中で蒸着を行なうことを意
味する。 In the present invention, it is preferable that the second to fifth layers are formed by activated reaction vapor deposition in order to improve the adhesion between each layer. The term "activated reactive vapor deposition" as used herein means that vapor deposition is performed in an active gas that has been turned into plasma, such as oxygen gas.
本発明における合成樹脂基板としては、特に小
型カメラ用レンズ、ビデオカメラ用レンズ、複写
機用レンズ等に利用される非球面レンズを目的と
したレンズ構成に用いられる合成樹脂レンズを挙
げることができる。これらの合成樹脂基板は、例
えばジエチレングリコールビスアリルカーボネー
ト、キヤステイング成形またはインジエクシヨン
成形されたアクリル樹脂、ポリカーボネート樹
脂、スチレン樹脂からなる。 Examples of the synthetic resin substrate in the present invention include synthetic resin lenses used in lens constructions intended for aspherical lenses used particularly in small camera lenses, video camera lenses, copier lenses, and the like. These synthetic resin substrates are made of, for example, diethylene glycol bisallyl carbonate, cast or injection molded acrylic resin, polycarbonate resin, or styrene resin.
合成樹脂基板上に各層を順次積層するには、真
空蒸着、エレクトロンビームなどの公知の手段を
用いることができるが、第２層から第５層までは
前述した活性化反応蒸着により積層するのが、各
層相互間の密着性が高くなるので好ましい。第１
層の一酸化ケイ素膜は合成樹脂との密着性がよい
ので、特に活性化反応蒸着によらなくてもよい。 In order to sequentially laminate each layer on a synthetic resin substrate, known means such as vacuum evaporation or electron beam can be used, but it is preferable to laminate the second to fifth layers by the activation reaction evaporation described above. , is preferable because the adhesion between each layer becomes high. 1st
Since the silicon monoxide film of the layer has good adhesion to the synthetic resin, activation reaction vapor deposition is not particularly necessary.
本発明による多層反射防止膜において、一酸化
ケイ素膜からなる第１層と二酸化ケイ素膜からな
る第２層とは反射防止の機能とともに、基板の補
強機能をも備えている。 In the multilayer antireflection film according to the present invention, the first layer made of a silicon monoxide film and the second layer made of a silicon dioxide film have not only an antireflection function but also a substrate reinforcing function.
以下に本発明を実施例を示して本発明をさらに
詳細に説明する。 EXAMPLES The present invention will be explained in more detail by showing examples below.
実施例 １
第１図を参照して本発明の実施例を説明する。
第１図は、この実施例の反射防止膜の一部の拡大
断面図である。インジエクシヨン成形されたアク
リル樹脂基板１の表面に、真空度１×10-5Torr
において一酸化ケイ素を抵抗加熱により、蒸着速
度２〓／秒（一定）で真空蒸着して膜厚0.5λ（λ
＝450〜550nm）の第１層２を形成する。このと
きの第１層の屈折率は1.60〜1.68である。Example 1 An example of the present invention will be described with reference to FIG.
FIG. 1 is an enlarged sectional view of a part of the antireflection film of this example. A vacuum of 1×10 -5 Torr is applied to the surface of the injection molded acrylic resin substrate 1.
, silicon monoxide was vacuum-deposited by resistance heating at a deposition rate of 2〓/sec (constant) to a film thickness of 0.5λ (λ
= 450 to 550 nm). The refractive index of the first layer at this time is 1.60 to 1.68.
第１層の上に二酸化ケイ素をエレクトロンビー
ムで蒸着して膜厚0.5λの第２層３を形成する。第
２層の屈折率は1.45〜1.46である。第１層と第２
層とは基板の補強効果をも有している。 Silicon dioxide is deposited on the first layer using an electron beam to form a second layer 3 having a thickness of 0.5λ. The second layer has a refractive index of 1.45 to 1.46. 1st layer and 2nd layer
The layer also has the effect of reinforcing the substrate.
第２層の上に、酸化ジルコニウムをエレクトロ
ンビームで蒸着して膜厚0.25λの第３層４を形成
する。第３層の屈折率は1.89〜1.91である。 On the second layer, zirconium oxide is deposited using an electron beam to form a third layer 4 having a thickness of 0.25λ. The third layer has a refractive index of 1.89 to 1.91.
ついで、第３層の上に五酸化タンタルをエレク
トロンビームで蒸着して膜厚0.25λの第４層５を
形成する。第４層の屈折率は2.0〜2.1である。 Next, tantalum pentoxide is deposited on the third layer using an electron beam to form a fourth layer 5 having a thickness of 0.25λ. The fourth layer has a refractive index of 2.0 to 2.1.
さらに、第４層の上に二酸化ケイ素を蒸着して
膜厚が0.25λ、屈折率が1.45〜1.46の第５層６を形
成する。 Further, silicon dioxide is deposited on the fourth layer to form a fifth layer 6 having a thickness of 0.25λ and a refractive index of 1.45 to 1.46.
このようにして得られた反射防止膜の分光反射
率特性は第２図から明らかなように、近赤外領域
まで良好な特性を示し、波長500〜540nmの光の
反射率が、わずかに山形に高くなつているので反
射光が鮮やかな緑色となる。したがつて、眼鏡用
レンズに対しても適用することができる。 As is clear from Figure 2, the spectral reflectance characteristics of the antireflection film obtained in this way show good characteristics up to the near-infrared region, and the reflectance for light in the wavelength range of 500 to 540 nm is slightly mountain-shaped. Because the sky is so high, the reflected light becomes a bright green color. Therefore, it can also be applied to spectacle lenses.
次に、得られた反射防止膜について以下の試験
を行つた。 Next, the following tests were conducted on the obtained antireflection film.
(1) 密着性テスト：上記のようにして得られた反
射防止膜の表面にセロハンテープ（ニチバン）
を接着させた後、この表面にほゞ垂直な角度
で、すばやくとりのぞくテストを15回繰返した
が、蒸着膜の剥離を生ずることがなかつた。(1) Adhesion test: Cellophane tape (Nichiban) was applied to the surface of the anti-reflection film obtained as above.
After adhering, the test was repeated 15 times by quickly removing the film at an angle almost perpendicular to the surface, but no peeling of the deposited film occurred.
(2) 耐溶剤性テスト：反射防止膜表面をエーテ
ル、アルコール混合液をつけたレンズ拭き紙
（シルボン紙）で拭いたが、異常が認められな
かつた。(2) Solvent resistance test: The surface of the antireflection film was wiped with lens wiping paper (Silbon paper) moistened with a mixture of ether and alcohol, but no abnormalities were observed.
(3) 耐摩耗テスト：反射防止膜表面の１ケ所をレ
ンズ拭き紙（シルボン紙）を用いて３〜４Kg／
cm2の圧で50往復こすつたが、異常が認められな
かつた。(3) Abrasion resistance test: One place on the surface of the anti-reflection film was coated with 3-4 kg of lens wiping paper (Silbon paper).
I rubbed it back and forth 50 times with a pressure of cm2 , but no abnormalities were observed.
(4) 耐環境テスト：反射防止膜を45℃、相対湿度
95％の恒温恒湿槽中に1000時間放置し、ついで
熱衝撃テスト（60℃−30℃）を５回繰返した
が、異常が認められなかつた。(4) Environmental resistance test: anti-reflection coating at 45℃, relative humidity
It was left in a constant temperature and humidity chamber at 95% for 1000 hours, and then the thermal shock test (60°C - 30°C) was repeated 5 times, but no abnormality was observed.
実施例 ２
実施例１における第２層３、第３層４、第４層
５および第５層６を真空度７×10-5〜１×10-4
Torrにおいて高周波（13.56MHz）酸素プラズマ
中において活性化蒸着する。Example 2 The second layer 3, third layer 4, fourth layer 5, and fifth layer 6 in Example 1 were vacuumed to a degree of vacuum of 7×10 -5 to 1×10 -4
Activated deposition in high frequency (13.56 MHz) oxygen plasma at Torr.
この実施例により得られた反射防止膜は、実施
例１により得られた反射防止膜と実質的に同じ分
光反射特性を示し、密着性テストにおける20回の
繰返しでも膜の剥離は認められず、また耐溶剤性
も実施例１の反射防止膜のそれと同等またはそれ
以上であつた。 The antireflection film obtained in this example showed substantially the same spectral reflection characteristics as the antireflection film obtained in Example 1, and no peeling of the film was observed even after 20 repetitions of the adhesion test. Further, the solvent resistance was equal to or higher than that of the antireflection film of Example 1.
なお、この実施例において第３層４の酸化ジル
コニウム膜を酸化セリウム膜、酸化ジルコニウム
と酸化セリウムの混合物の膜または酸化ジルコニ
ウムと酸化セリウムの多層膜に代えた反射防止
膜、第４層５の五酸化タンタル膜を一酸化チタン
膜、二酸化チタン膜、または一酸化チタン、二酸
化チタンおよび五酸化タンタルの２以上の混合物
の膜若しくはこれらの２以上の多層膜に代えた反
射防止膜、および／または第５層６の二酸化ケイ
素膜に代えて弗化マグネシウム膜または二酸化ケ
イ素とフツ化マグネシウムの混合物の膜若しくは
これらの多層膜を用いた反射防止膜は、いずれも
密着性、耐溶剤性、耐摩耗性、耐環境性に優れた
ものであつた。 In this example, the zirconium oxide film of the third layer 4 is replaced with a cerium oxide film, a film of a mixture of zirconium oxide and cerium oxide, or a multilayer film of zirconium oxide and cerium oxide; An antireflection film in which the tantalum oxide film is replaced with a titanium monoxide film, a titanium dioxide film, a film of a mixture of two or more of titanium monoxide, titanium dioxide, and tantalum pentoxide, or a multilayer film of two or more of these, and/or a third film. In place of the 5-layer 6 silicon dioxide film, a magnesium fluoride film, a film of a mixture of silicon dioxide and magnesium fluoride, or an antireflection film using a multilayer film of these films have excellent adhesion, solvent resistance, and abrasion resistance. , and had excellent environmental resistance.
比較例 １
実施例１と同じインジエクシヨン成形されたア
クリル樹脂基板１を用い、このアクリル樹脂基板
１の表面に真空度１×10-5Torrにおいて一酸化
ケイ素を抵抗加熱により、蒸着速度２〓／秒（一
定）で真空蒸着して膜厚3λ（λ＝450〜550nm）
の第１層２を形成する。このときの第１層の屈折
率は1.60〜1.68である。Comparative Example 1 Using the same injection molded acrylic resin substrate 1 as in Example 1, silicon monoxide was deposited on the surface of the acrylic resin substrate 1 by resistance heating at a vacuum degree of 1×10 -5 Torr at a vapor deposition rate of 2〓/sec. Film thickness: 3λ (λ = 450-550nm)
A first layer 2 is formed. The refractive index of the first layer at this time is 1.60 to 1.68.
第１層の上には、実施例１と同様の操作により
第２層から第５層を形成した。ただし、この様に
して得られた膜は本発明が目的とする良好なカラ
ーバランスを得ていなかつた。この比較例により
得られた反射防止膜について実施例１と同様に試
験を行つた。その結果は次の通りであつた。 On the first layer, the second to fifth layers were formed by the same operation as in Example 1. However, the film thus obtained did not have the good color balance aimed at by the present invention. The antireflection film obtained in this comparative example was tested in the same manner as in Example 1. The results were as follows.
(1) 密着性テスト：実施例１と同じ。(1) Adhesion test: Same as Example 1.
(2) 耐溶剤性テスト：実施例１と同じ。(2) Solvent resistance test: Same as Example 1.
(3) 耐摩耗テスト：実施例１と同じ。(3) Wear resistance test: Same as Example 1.
(4) 耐環境テスト：熱衝撃テストの５回繰返し
で、透過目視観察にて樹脂基板中央に微小な膜
ワレの発生が認められた。(4) Environmental resistance test: After repeating the thermal shock test five times, small film cracks were observed in the center of the resin substrate through transparent visual observation.
比較例 ２
第１層の膜厚を6λ（λ＝450〜550nm）にした
ことを除いて比較例１と同様にして反射防止膜を
形成し、実施例１と同様に試験を行つた。その結
果は次の通りであつた。Comparative Example 2 An antireflection film was formed in the same manner as in Comparative Example 1, except that the thickness of the first layer was 6λ (λ = 450 to 550 nm), and the test was conducted in the same manner as in Example 1. The results were as follows.
(1) 密着性テスト：実施例１と同じ。(1) Adhesion test: Same as Example 1.
(2) 耐溶剤性テスト：実施例１と同じ。(2) Solvent resistance test: Same as Example 1.
(3) 耐摩耗テスト：実施例１と同じ。(3) Wear resistance test: Same as Example 1.
(4) 耐環境テスト：熱衝撃テストの５回の繰返し
で、透過目視観察にて樹脂基板全面に微小な蒸
着膜の膜ワレの発生が認められた。(4) Environmental resistance test: After repeating the thermal shock test five times, microscopic cracking of the deposited film was observed on the entire surface of the resin substrate through transparent visual observation.
比較例 ３
実施例１と同じインジエクシヨン成形されたア
クリル樹脂基板１を用い、このアクリル樹脂基板
１の表面に真空度１×10-5Torrにおいて二酸化
ケイ素をエレクトロンビームにより真空蒸着して
膜厚0.5λ（λ＝450〜550nm）の第１層２を形成す
る。このときの第１層の屈折率は1.45〜1.46であ
る。Comparative Example 3 Using the same injection molded acrylic resin substrate 1 as in Example 1, silicon dioxide was vacuum-deposited on the surface of the acrylic resin substrate 1 using an electron beam at a vacuum degree of 1×10 -5 Torr to a film thickness of 0.5λ. (λ=450 to 550 nm). The refractive index of the first layer at this time is 1.45 to 1.46.
第１層の上には実施例１と同様の操作により第
２層から第４層を形成した。すなわち、この比較
例においては、第１層目と第２層目とが同じ二酸
化ケイ素膜から形成されるため、見かけ１層少な
い４層構成となる。 The second to fourth layers were formed on the first layer by the same operation as in Example 1. That is, in this comparative example, since the first layer and the second layer are formed from the same silicon dioxide film, the structure has four layers, which is apparently one layer less.
このようにして得られた膜は本発明が目的とす
る良好なカラーバランスを得ていなかつた。この
比較例により得られた反射防止膜について実施例
１と同様に試験を行つた。その結果は次の通りで
あつた。 The film thus obtained did not have the good color balance aimed at by the present invention. The antireflection film obtained in this comparative example was tested in the same manner as in Example 1. The results were as follows.
(1) 密着性テスト：セロハンテープを接着し取り
除く操作の５回の繰返しで、蒸着膜が樹脂基板
の面から剥離した。(1) Adhesion test: After repeating the procedure of attaching and removing cellophane tape five times, the deposited film was peeled off from the surface of the resin substrate.
(2) 耐溶剤性テスト：蒸着膜の膜うきと線状の膜
はがれが発生した。(2) Solvent resistance test: Thickness and linear peeling of the deposited film occurred.
(3) 耐摩耗テスト：50往復のこすりで線状の蒸着
膜の膜はがれが発生した。(3) Abrasion resistance test: Linear deposited film peeled off after 50 repeated rubbings.
(4) 耐環境テスト：熱衝撃の５回の繰返しで、透
過目視観察にて蒸着膜の一部に膜うきが認めら
れた。(4) Environmental resistance test: After 5 repetitions of thermal shock, film fraying was observed in some parts of the deposited film through transparent visual observation.
本発明によれば、合成樹脂の種類、成形方法に
無関係に、合成樹脂基板の補強効果と可視光領域
および近赤外領域における良好な反射防止効果と
を兼ね備え、しかも密着性、耐溶剤性、耐摩耗性
および耐環境性に優れた合成樹脂基板の反射防止
膜をうることができる。 According to the present invention, regardless of the type of synthetic resin or the molding method, it has both the reinforcing effect of the synthetic resin substrate and the good antireflection effect in the visible light region and the near-infrared region, and also has good adhesion, solvent resistance, It is possible to obtain an antireflection film for a synthetic resin substrate that has excellent wear resistance and environmental resistance.
第１図は本発明の一実施例の反射防止膜の一部
の拡大断面図であり、第２図は上記反射防止膜の
分光反射率特性を示すグラフである。
１……基板、２……第１層、３……第２層、４
……第３層、５……第４層、６……第５層。
FIG. 1 is an enlarged cross-sectional view of a part of an antireflection film according to an embodiment of the present invention, and FIG. 2 is a graph showing the spectral reflectance characteristics of the antireflection film. 1... Substrate, 2... First layer, 3... Second layer, 4
...3rd layer, 5...4th layer, 6...5th layer.
Claims (1)
0.13λ〜λ〔λ（光の波長）＝450〜550nm〕の一酸
化ケイ素膜からなる第１層、該第１層上に形成さ
れた光学的膜厚0.13λ〜λの二酸化ケイ素膜から
なる第２層、該第２層上に形成された光学的膜厚
0.23λ〜0.29λの酸化ジルコニウム、酸化セリウム
またはこれらの混合物の膜、或は酸化ジルコニウ
ムおよび酸化セリウムの多層膜からなる第３層、
該第３層上に形成された光学的膜厚0.23λ〜0.29λ
の五酸化タンタル、一酸化チタン、二酸化チタン
またはそれらの２以上の混合物の膜、或は五酸化
タンタル、一酸化チタンおよび二酸化チタンの２
以上の多層膜からなる第４層、および該第４層上
に形成された光学的膜厚0.23λ〜0.29λの二酸化ケ
イ素、フツ化マグネシウムまたはこれらの混合物
の膜、或は二酸化ケイ素およびフツ化マグネシウ
ムの多層膜からなる第５層からなることを特徴と
する合成樹脂基板の反射防止膜。 ２ 前記第２層から第５層までが活性化反応蒸着
により形成されたものである特許請求の範囲第１
項記載の反射防止膜。[Claims] 1. Optical film thickness formed on a synthetic resin substrate
A first layer consisting of a silicon monoxide film of 0.13λ to λ [λ (wavelength of light) = 450 to 550 nm], and a silicon dioxide film with an optical thickness of 0.13λ to λ formed on the first layer. Second layer, optical film thickness formed on the second layer
A third layer consisting of a film of zirconium oxide, cerium oxide or a mixture thereof, or a multilayer film of zirconium oxide and cerium oxide, with a thickness of 0.23λ to 0.29λ,
Optical film thickness formed on the third layer: 0.23λ to 0.29λ
film of tantalum pentoxide, titanium monoxide, titanium dioxide or a mixture of two or more thereof, or two or more of tantalum pentoxide, titanium monoxide and titanium dioxide
A fourth layer consisting of the above multilayer film, and a film of silicon dioxide, magnesium fluoride, or a mixture thereof having an optical thickness of 0.23λ to 0.29λ formed on the fourth layer, or a film of silicon dioxide and fluoride. An antireflection film for a synthetic resin substrate, characterized by comprising a fifth layer made of a multilayer film of magnesium. 2. Claim 1, wherein the second to fifth layers are formed by activated reaction vapor deposition.
Anti-reflective coating as described in section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58238813A JPS60130703A (en) | 1983-12-20 | 1983-12-20 | Antireflection film for plastic substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58238813A JPS60130703A (en) | 1983-12-20 | 1983-12-20 | Antireflection film for plastic substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60130703A JPS60130703A (en) | 1985-07-12 |
| JPH0461323B2 true JPH0461323B2 (en) | 1992-09-30 |
Family
ID=17035665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58238813A Granted JPS60130703A (en) | 1983-12-20 | 1983-12-20 | Antireflection film for plastic substrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60130703A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5105310A (en) * | 1990-10-11 | 1992-04-14 | Viratec Thin Films, Inc. | Dc reactively sputtered antireflection coatings |
| DE4128547A1 (en) * | 1991-08-28 | 1993-03-04 | Leybold Ag | METHOD AND DEVICE FOR THE PRODUCTION OF A RE-MIRRORING LAYER ON LENSES |
-
1983
- 1983-12-20 JP JP58238813A patent/JPS60130703A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60130703A (en) | 1985-07-12 |
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