JP5301766B2 - Transparent substrate with antireflection film - Google Patents
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- JP5301766B2 JP5301766B2 JP2006096669A JP2006096669A JP5301766B2 JP 5301766 B2 JP5301766 B2 JP 5301766B2 JP 2006096669 A JP2006096669 A JP 2006096669A JP 2006096669 A JP2006096669 A JP 2006096669A JP 5301766 B2 JP5301766 B2 JP 5301766B2
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- 239000000758 substrate Substances 0.000 title claims description 80
- 239000010408 film Substances 0.000 claims description 150
- 230000004888 barrier function Effects 0.000 claims description 13
- 239000010409 thin film Substances 0.000 claims description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 239000012788 optical film Substances 0.000 claims description 6
- 230000003373 anti-fouling effect Effects 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 4
- 239000003989 dielectric material Substances 0.000 claims description 2
- 150000002222 fluorine compounds Chemical class 0.000 claims description 2
- 238000011156 evaluation Methods 0.000 description 13
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
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Description
本発明は反射防止機能を有する反射防止膜付透明基板に関する。 The present invention relates to a transparent substrate with an antireflection film having an antireflection function.
従来より、ガラス板やプラスチック板（プラスチックフィルム）等の透明基板に屈折率の異なる薄膜層を多数積層させ、反射防止機能を得る反射防止膜付透明基板が知られている（特許文献１）。このような反射防止膜付透明基板はディスプレイの表面部材として用いられることが多い。
このような、反射防止膜付透明基板の用途は近年拡大しており、例えば自動車や船舶等の計器類のディスプレイにも用いられてきている。しかしながら、自動車や船舶は劣悪な環境下で使用されることも多く、従来の反射防止膜付透明基板を用いる場合、このような環境下では反射防止膜の膜ハゲや性能劣化が生じやすく充分な耐久性が得られない。
本発明では上記従来技術の問題点に鑑み、耐久性のよい反射防止膜付透明基板を提供することを技術課題とする。
The use of such a transparent substrate with an antireflection film has been expanding in recent years, and has been used for displays of instruments such as automobiles and ships. However, automobiles and ships are often used in a poor environment, and when using a conventional transparent substrate with an antireflection film, the antireflection film is likely to be bald or deteriorate in performance under such an environment. Durability cannot be obtained.
In the present invention, in view of the above-mentioned problems of the prior art, it is an object of the present invention to provide a transparent substrate with an antireflection film having good durability.
上記課題を解決するために、本発明は以下のような構成を備えることを特徴とする。
（１） 透明基板上に薄膜層を積層してなる反射防止膜付透明基板において、前記透明基板上に光学膜厚として１０nm以上４０nm以下であるＡｌ２Ｏ３からなる下地層と、該下地層の上に多層の誘電体層のみからなる反射防止膜とが形成されているとともに、該反射防止膜の耐候性の向上を得るために，該反射防止膜の最外層と該最外層の下に置かれる誘電体層との間に光学膜厚として２０nm以上５０nm以下であるＡｌ２Ｏ３の薄膜からなるバリア層と、が形成されていることを特徴とする。
（２） （１）の反射防止膜付透明基板において、前記反射防止膜は前記透明基板側から順に、前記透明基板の屈折率より高い屈折率である透明誘電体からなる第１誘電膜層と、前記透明基板の屈折率より低い屈折率である透明誘電体からなる第２誘電膜層と、前記透明基板の屈折率より高い屈折率である透明誘電体からなる第３誘電膜層と、最外層に前記透明基板の屈折率より低い屈折率である透明誘電体からなる第４誘電膜層と、との少なくとも４層を有し、前記バリア層は前記第３誘電膜層と第４誘電膜層との間に形成されていることを特徴とする。
（３） （２）の反射防止膜付透明基板において、前記第１及び第３誘電膜層はＴｉＯ2からなる薄膜層であり、前記第２及び第４誘電膜層はＳｉＯ２からなる薄膜層であることを特徴とする。
（４） （１）〜（３）の反射防止膜付透明基板において、前記反射防止膜の上にさらにフッ素系化合物からなる防汚層が形成されていることを特徴とする。
In order to solve the above problems, the present invention is characterized by having the following configuration.
(1) In a transparent substrate with an antireflection film formed by laminating a thin film layer on a transparent substrate, an underlayer made of Al 2 O 3 having an optical film thickness of 10 nm to 40 nm on the transparent substrate, and the underlayer And an antireflection film consisting of only a plurality of dielectric layers is formed on the substrate, and in order to improve the weather resistance of the antireflection film, an outermost layer of the antireflection film and below the outermost layer are formed. A barrier layer made of an Al 2 O 3 thin film having an optical film thickness of 20 nm or more and 50 nm or less is formed between the dielectric layer to be placed .
(2) In the transparent substrate with an antireflection film according to (1), the antireflection film includes, in order from the transparent substrate side, a first dielectric film layer made of a transparent dielectric having a refractive index higher than the refractive index of the transparent substrate; A second dielectric film layer made of a transparent dielectric having a refractive index lower than the refractive index of the transparent substrate, a third dielectric film layer made of a transparent dielectric having a refractive index higher than the refractive index of the transparent substrate, The outer layer has at least four layers of a fourth dielectric film layer made of a transparent dielectric having a refractive index lower than that of the transparent substrate, and the barrier layer includes the third dielectric film layer and the fourth dielectric film. It is formed between the layers.
(3) In the transparent substrate with an antireflection film according to (2), the first and third dielectric film layers are thin film layers made of TiO 2 , and the second and fourth dielectric film layers are thin film layers made of SiO 2. It is characterized by being.
(4) In the transparent substrate with an antireflection film of (1) to (3), an antifouling layer made of a fluorine compound is further formed on the antireflection film.
本発明によれば、使用環境が悪くても膜ハゲや性能劣化を抑制し、耐久性のよい反射防止膜付透明基板を得ることができる。 ADVANTAGE OF THE INVENTION According to this invention, even if a use environment is bad, a film baldness and performance degradation can be suppressed and a transparent substrate with an antireflection film with good durability can be obtained.
以下、本発明の実施の形態における反射防止膜付透明基板について、図面を参照しながら説明する。図１は本発明の実施の形態における反射防止膜付透明基板の積層構成を示す概略図である。 Hereinafter, a transparent substrate with an antireflection film in an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a schematic view showing a laminated structure of a transparent substrate with an antireflection film in an embodiment of the present invention.
１は透明の基板である。基板１は通常に入手できるものであればよく、屈折率は１．４８以上１．７以下程度のものを使用する。具体的に、基板材料としてはガラス類（屈折率１．４８〜１．７０）、プラスチック類（アクリル基板（屈折率１．５２）、ポリカーボネイト（屈折率１．５９）、ポリエチレンテレフタレート（屈折率１．６３）等）が用いられ、光学的に透明であれば特に限定されない。また、本実施形態で述べる基板とは板状に限らず、フィルム基板を含むものとしている。 Reference numeral 1 denotes a transparent substrate. The substrate 1 may be any substrate that is normally available and has a refractive index of about 1.48 or more and 1.7 or less. Specifically, the substrate material is glass (refractive index 1.48 to 1.70), plastics (acrylic substrate (refractive index 1.52), polycarbonate (refractive index 1.59), polyethylene terephthalate (refractive index 1). .63) and the like are used and are not particularly limited as long as they are optically transparent. The substrate described in the present embodiment is not limited to a plate shape, and includes a film substrate.
２は基板１上に形成される多層膜からなる反射防止膜の成膜前に事前に形成される下地層である。この下地層２は、反射防止膜を成膜する前に基板１にコーティングすることにより、基板１と反射防止膜との間の密着力を上げるために形成される層である。この下地層２を形成するための材料にはＡｌ2Ｏ3（屈折率１．６）が用いられる。このような下地層２の膜厚（光学的膜厚ｎｄ）は、５ｎｍ以上８０ｎｍ以下が好ましく、より好ましくは１０ｎｍ以上４０ｎｍ以下である。膜厚が５ｎｍ未満であると密着力が弱くなり、反射防止膜が剥がれやすくなる。また、膜厚が８０ｎｍを超えると、反射防止効果が得られにくくなる。なお、基板１と下地層２との間に基板１の表面を保護するためのハードコート層を設けるようにすることもできる。このようなハードコート層は一般的にアクリル系ハードコートを用いることができる。何れの場合においても、ハードコート（アンダーコート）の膜厚は、光学的な阻害が起こらないように基板の屈折率と同程度の屈折率を有するようにしておくことが好ましい。 Reference numeral 2 denotes an underlayer formed in advance before the formation of a multi-layer antireflection film formed on the substrate 1. The underlayer 2 is a layer formed to increase the adhesion between the substrate 1 and the antireflection film by coating the substrate 1 before forming the antireflection film. Al 2 O 3 (refractive index 1.6) is used as a material for forming the underlayer 2. The film thickness (optical film thickness nd) of such an underlayer 2 is preferably 5 nm or more and 80 nm or less, and more preferably 10 nm or more and 40 nm or less. When the film thickness is less than 5 nm, the adhesion is weakened and the antireflection film is easily peeled off. On the other hand, when the film thickness exceeds 80 nm, it is difficult to obtain the antireflection effect. Note that a hard coat layer for protecting the surface of the substrate 1 may be provided between the substrate 1 and the base layer 2. In general, an acrylic hard coat can be used for such a hard coat layer. In any case, it is preferable that the film thickness of the hard coat (undercoat) has a refractive index comparable to the refractive index of the substrate so that optical inhibition does not occur.
３は下地層２上に屈折率の異なる透明誘電体からなる誘電膜層（薄膜層）を複数積層することにより反射防止効果をもたせるための反射防止層帯（反射防止膜）である。本実施形態における反射防止層帯３は４つの誘電膜層３ａ〜３ｄにより形成されている。
３ａは基板１の屈折率よりも高い屈折率をもつ透明誘電体からなる第１誘電膜層である。第１誘電膜層３ａに使用される透明誘電体は、使用する基板１に応じて適宜選択されるが、基板１及び下地層２の屈折率よりも高い屈折率の必要がある。また同時に、安価に入手可能でかつ安定した成膜が確認されているものが好ましいため、それらを考慮して屈折率が１．９０以上２．５０以下程度の範囲のものが使用される。具体的には、第１誘電膜層３ａの主成分にはＺｒＯ2（屈折率１．９５）や、ＴｉＯ2（屈折率２．２０）、等が挙げられる。第１誘電膜層３の光学的膜厚ｎｄ（以後、単に膜厚と記す）は１０ｎｍ以上６００ｎｍ以下が好ましく、より好ましくは５０ｎｍ以上５５０ｎｍ以下である。膜厚がこれ以上薄くても厚くても、反射防止効果が得られにくい。
Reference numeral 3 denotes an antireflection layer band (antireflection film) for providing an antireflection effect by laminating a plurality of dielectric film layers (thin film layers) made of transparent dielectric materials having different refractive indexes on the base layer 2. The antireflection layer band 3 in this embodiment is formed by four dielectric film layers 3a to 3d.
Reference numeral 3 a denotes a first dielectric film layer made of a transparent dielectric having a refractive index higher than that of the substrate 1. The transparent dielectric used for the first dielectric film layer 3a is appropriately selected according to the substrate 1 to be used, but it needs to have a refractive index higher than that of the substrate 1 and the underlying layer 2. At the same time, it is preferable that the film is available at a low cost and has been confirmed to have a stable film formation. Therefore, a film having a refractive index in the range of about 1.90 or more and 2.50 or less is used. Specifically, ZrO 2 (refractive index 1.95), TiO 2 (refractive index 2.20), and the like are listed as main components of the first dielectric film layer 3a. The optical film thickness nd (hereinafter simply referred to as film thickness) of the first dielectric film layer 3 is preferably 10 nm or more and 600 nm or less, and more preferably 50 nm or more and 550 nm or less. Even if the film thickness is thinner or thicker than this, it is difficult to obtain the antireflection effect.
３ｂは第１誘電膜層３ａ上に積層され、基板１の屈折率よりも低い屈折率をもつ透明誘電体からなる第２誘電膜層である。第２誘電膜層３ｂに使用される透明誘電体は、使用する基板１に応じて適宜選択されるが、基板１及び下地層２の屈折率よりも低い屈折率の必要がある。また同時に、安価に入手可能でかつ安定した成膜が確認されているものが好ましいため、それらを考慮して屈折率が１．３５以上１．５０以下程度の範囲のものが使用される。具体的には、第２誘電膜層３ｂの主成分にはＳｉＯ2（屈折率１．４６）やＭｇＦ2（屈折率１．３８）が挙げられる。また、第２誘電膜層３ｂの膜厚は１０ｎｍ以上６００ｎｍ以下が好ましく、より好ましくは５０ｎｍ以上５５０ｎｍ以下である。膜厚がこれ以上薄くても厚くても、反射防止効果が得られにくい。 Reference numeral 3 b denotes a second dielectric film layer which is laminated on the first dielectric film layer 3 a and is made of a transparent dielectric having a refractive index lower than that of the substrate 1. The transparent dielectric used for the second dielectric film layer 3b is appropriately selected according to the substrate 1 to be used, but it needs to have a refractive index lower than that of the substrate 1 and the underlying layer 2. At the same time, it is preferable that the film is available at a low cost and has been confirmed to have a stable film formation. Therefore, a film having a refractive index in the range of 1.35 to 1.50 is used in consideration of these. Specifically, SiO 2 (refractive index 1.46) and MgF 2 (refractive index 1.38) are listed as main components of the second dielectric film layer 3b. The film thickness of the second dielectric film layer 3b is preferably 10 nm or more and 600 nm or less, more preferably 50 nm or more and 550 nm or less. Even if the film thickness is thinner or thicker than this, it is difficult to obtain the antireflection effect.
３ｃは第２誘電膜層３ｂ上に積層され、基板１の屈折率よりも高い屈折率をもつ透明誘電体からなる第３誘電膜層である。第３誘電膜層３ｃに使用される透明誘電体は、第１誘電膜層３ａと基本的に同じ材料のものが使用可能であるが、反射防止効果を向上させるためには第１誘電膜層３ａにて用いられる材料の屈折率と同じか、それより高い屈折率を有する材料を用いることが好ましい。第３誘電膜層３ｃの膜厚は１０ｎｍ以上６００ｎｍ以下が好ましく、より好ましくは５０ｎｍ以上５５０ｎｍ以下である。膜厚がこれ以上薄くても厚くても、反射防止効果が得られにくい。 Reference numeral 3 c denotes a third dielectric film layer which is laminated on the second dielectric film layer 3 b and is made of a transparent dielectric having a refractive index higher than that of the substrate 1. The transparent dielectric used for the third dielectric film layer 3c can be basically made of the same material as that of the first dielectric film layer 3a. To improve the antireflection effect, the first dielectric film layer is used. It is preferable to use a material having the same or higher refractive index than that of the material used in 3a. The film thickness of the third dielectric film layer 3c is preferably 10 nm or more and 600 nm or less, more preferably 50 nm or more and 550 nm or less. Even if the film thickness is thinner or thicker than this, it is difficult to obtain the antireflection effect.
３ｄは第３誘電膜層３ｃの上方（本実施形態では最外層）に積層され、基板１の屈折率よりも低い屈折率をもつ透明誘電体からなる第４誘電膜層である。第４誘電膜層３ｄに使用される透明誘電体は、第２誘電膜層３ｂと基本的に同じ材料のものが使用可能である。また、第４誘電膜層３ｄの膜厚は１０ｎｍ以上６００ｎｍ以下が好ましく、より好ましくは５０ｎｍ以上５５０ｎｍ以下である。膜厚がこれ以上薄くても厚くても、反射防止効果が得られにくい。 Reference numeral 3d denotes a fourth dielectric film layer which is laminated above the third dielectric film layer 3c (in this embodiment, the outermost layer) and is made of a transparent dielectric having a refractive index lower than that of the substrate 1. The transparent dielectric used for the fourth dielectric film layer 3d can be made of basically the same material as the second dielectric film layer 3b. The thickness of the fourth dielectric film layer 3d is preferably 10 nm or more and 600 nm or less, more preferably 50 nm or more and 550 nm or less. Even if the film thickness is thinner or thicker than this, it is difficult to obtain the antireflection effect.
４は反射防止層帯を形成する膜の最外層の下に形成され、反射防止層帯３の耐候性を向上させるためのバリア層である。本実施形態のバリア層４は、第３誘電膜層３ｃと第４誘電膜層３ｄとの間に形成される。このバリア層４を形成するための材料にはＡｌ2Ｏ3（屈折率１．６）が用いられる。このようなバリア層４の膜厚は、１０ｎｍ以上６０ｎｍ以下が好ましく、より好ましくは２０ｎｍ以上５０ｎｍ以下である。膜厚が１０ｎｍ未満であると所望する効果が得られ難い。また、膜厚が６０ｎｍを超えると、反射防止膜による反射防止効果が得られにくくなる。 Reference numeral 4 denotes a barrier layer formed under the outermost layer of the film forming the antireflection layer zone and improving the weather resistance of the antireflection layer zone 3. The barrier layer 4 of the present embodiment is formed between the third dielectric film layer 3c and the fourth dielectric film layer 3d. Al 2 O 3 (refractive index 1.6) is used as a material for forming the barrier layer 4. The film thickness of such a barrier layer 4 is preferably 10 nm or more and 60 nm or less, more preferably 20 nm or more and 50 nm or less. If the film thickness is less than 10 nm, it is difficult to obtain a desired effect. On the other hand, when the film thickness exceeds 60 nm, it is difficult to obtain the antireflection effect by the antireflection film.
また、反射防止層帯３を形成する各層の最適な膜厚は以下の方法により決定される。
初めに、用途に応じて必要とされる下地層２及びバリア層４の膜厚を決定させておく。また、用途に応じて反射防止層帯３に使用する材料の屈折率を固定値とし、最適化アルゴリズムを用いながら反射防止層帯３の各層の膜厚を変化させていく。このような手法により、視野２°、標準光ＣにおけるＬ*ａ*ｂ*表色系のクロマティクネス指数ａ*、ｂ*を−２〜＋２の範囲以内としつつ、このようなクロマティクネス指数ａ*、ｂ*の範囲内において最も高い透過率若しくは最も低い反射率が得られるような誘電体層膜厚を求める。最適化アルゴリズムは例えば、Adaptive Random SearchやModified Gardient、Monte Carilo method、Simurated Annealing等、メリット関数を使用した様々な最適化手法を基に与えられる。
The optimum film thickness of each layer forming the antireflection layer band 3 is determined by the following method.
First, the required film thicknesses of the underlayer 2 and the barrier layer 4 are determined according to the application. Further, the refractive index of the material used for the antireflection layer band 3 is set to a fixed value according to the application, and the film thickness of each layer of the antireflection layer band 3 is changed using an optimization algorithm. By such a method, the chromaticness index a is set such that the chromaticness index a * and b * of the L * a * b * color system in the field of view 2 ° and the standard light C is within the range of −2 to +2. The dielectric layer thickness is determined so as to obtain the highest transmittance or the lowest reflectance within the range of * and b *. The optimization algorithm is given based on various optimization methods using merit functions such as Adaptive Random Search, Modified Gardient, Monte Carilo method, and Simulated Rated Annealing.
上記で示した各薄膜層を基板１上に形成する方法としては、物理的気層成長方法（ＰＶＤ）では真空蒸着方法やスパッタ方法、イオンプレーティング方法等が挙げられる。また、化学的気層成長方法（ＣＶＤ）では、めっき方法や化学的気層成長方法等が挙げられる。これらの成膜方法は、本実施の形態としてすべて使用可能であるが、成膜に際して高温を伴うような方法では熱によるプラスチック基板の変形等が考えられるため、プラスチック基板での多層膜の成膜は高熱を必要としない真空蒸着方法やスパッタ方法が好適に用いられる。 Examples of a method for forming each thin film layer on the substrate 1 include a vacuum vapor deposition method, a sputtering method, an ion plating method, and the like in the physical vapor deposition method (PVD). In addition, examples of the chemical vapor deposition method (CVD) include a plating method and a chemical vapor deposition method. Any of these film forming methods can be used as this embodiment mode. However, since a method involving a high temperature during film formation may cause deformation of the plastic substrate due to heat, the multilayer film is formed on the plastic substrate. A vacuum deposition method or sputtering method that does not require high heat is preferably used.
なお、前述の実施形態では反射防止層帯を４層の誘電体層から形成するものとしているが、これに限るものではなく、所望する透過率（反射率）が得られるような多層構造（例えば2層〜６層等）を形成すればよい。また、反射防止層帯の上（最表面）に撥水性を高めて防汚効果を持たせるためのフッ素系化合物からなる薄膜層を形成することもできる。このような防汚層は膜厚5ｎｍ以上20ｎｍ程度（反射防止効果を損なわない程度）にて形成させる。 In the above-described embodiment, the antireflection layer band is formed from four dielectric layers. However, the present invention is not limited to this, and a multilayer structure (for example, a desired transmittance (reflectance)) can be obtained. (2 to 6 layers, etc.) may be formed. Further, a thin film layer made of a fluorine-based compound for enhancing the water repellency and providing an antifouling effect can be formed on the antireflection layer band (outermost surface). Such an antifouling layer is formed with a film thickness of about 5 nm to about 20 nm (a level that does not impair the antireflection effect).
以下に実施例、及び比較例を挙げる。
＜実施例１＞
アクリル系ハードコート（屈折率１．５２）付きアクリル基板（屈折率１．５２）を用意し、真空蒸着法により、各層の形成を行った。始めにＡｌ2Ｏ3（屈折率１．６）からなる下地層を膜厚１０ｎｍにて基板上（ハードコート上）に形成した。次に下地層の上にＴｉＯ2（２．２０）からなる第１誘電膜層を膜厚３０ｎｍにて形成し、さらに第１誘電膜層の上に、ＳｉＯ2（１．４６）からなる第２誘電膜層を膜厚４３ｎｍで、ＴｉＯ2からなる第３誘電膜層を膜厚２３０ｎｍで順次積層した。第３誘電膜層を形成後、その上にＡｌ2Ｏ3からなるバリア層を膜厚４０ｎｍにて形成し、バリア層の上にＳｉＯ2からなる第４誘電膜層（最外層）を膜厚９５ｎｍで形成して、合計６層からなる反射防止膜付透明基板を作成した。このようにして得られた反射防止膜付透明基板の視感度透過率を測定した。測定装置は朝日分光社製 視感度透過率計ＭＯＤＥＬ３０４を用いた。得られた視感度透過率は９５．9％であった。
このようにして得られた反射防止膜付透明基板の密着性及び耐候性を評価するために、以下の評価を行った。
Examples and comparative examples are given below.
<Example 1>
An acrylic substrate (refractive index 1.52) with an acrylic hard coat (refractive index 1.52) was prepared, and each layer was formed by vacuum deposition. First, an underlayer made of Al 2 O 3 (refractive index 1.6) was formed on a substrate (on a hard coat) with a film thickness of 10 nm. Next, a first dielectric film layer made of TiO 2 (2.20) is formed to a thickness of 30 nm on the underlayer, and a first dielectric film layer made of SiO 2 (1.46) is formed on the first dielectric film layer. A second dielectric film layer having a thickness of 43 nm and a third dielectric film layer made of TiO 2 having a thickness of 230 nm were sequentially stacked. After the third dielectric film layer is formed, a barrier layer made of Al 2 O 3 is formed thereon with a thickness of 40 nm, and a fourth dielectric film layer (outermost layer) made of SiO 2 is formed on the barrier layer. A transparent substrate with an antireflective film having a total thickness of 6 layers was formed. The visibility transmittance of the thus obtained transparent substrate with an antireflection film was measured. As a measuring apparatus, Asahi Spectroscopic Visibility Transmittance Model MODEL304 was used. The visibility transmission obtained was 95.9%.
In order to evaluate the adhesion and weather resistance of the thus obtained transparent substrate with an antireflection film, the following evaluation was performed.
（評価１）
評価１ではJIS B 7754の規格に準じてキセノンランプを用いた耐候性試験、及び密着性試験を行った。キセノンランプはスガ試験器(株)製の「キセノンロングライフウェザーメーター」（WEL-25AX-HC.B.EC）を用い、キセノンランプから３０ｃｍほど離れた位置に上記の反射膜付透明基板とブラックパネル（ＢＰ）を置き、ＢＰ温度６３℃となるようにキセノンランプの出力を調整し、反射膜付透明基板に向けて長時間キセノン光を照射した。
照射開始から２４時間毎に蒸留水にて湿らせたワイピングクロスにより、反射膜付透明基板の成膜面側を３Kg荷重で５０往復させ反射防止膜の膜ハゲの有無を確認した。
変化がなければ○、軽く擦り痕が残れば△、膜ハゲが確認された場合には×とした。また、外観検査ではクラック等がなければ○、クラックが入れば×とした。
以上の結果を表１に示す。
(Evaluation 1)
In Evaluation 1, a weather resistance test and an adhesion test using a xenon lamp were performed according to the standard of JIS B 7754. The xenon lamp uses “Xenon Long Life Weather Meter” (WEL-25AX-HC.B.EC) manufactured by Suga Test Instruments Co., Ltd. The panel (BP) was placed, the output of the xenon lamp was adjusted so that the BP temperature was 63 ° C., and the xenon light was irradiated for a long time toward the transparent substrate with a reflective film.
With a wiping cloth moistened with distilled water every 24 hours from the start of irradiation, the film-forming surface side of the transparent substrate with a reflective film was reciprocated 50 times with a 3 kg load to confirm the presence or absence of film baldness on the antireflection film.
If there was no change, it was rated as “◯”, a light scratch mark was left as “Δ”, and a film baldness was confirmed as “x”. In addition, in the appearance inspection, “O” was given if there were no cracks, and “X” was given if there were cracks.
The results are shown in Table 1.
（評価２）
評価２では、冷熱サイクル試験を行って反射膜付透明基板の耐候性を検査した。冷熱サイクル用試験機は楠本化成（株）製の「気槽式 熱衝撃試験器」（WINTECH NT-1020A）を用いて、反射膜付透明基板に対して−３０℃の冷風と８５℃の温風を３０分間隔で交互に当て、これを１サイクルとし、５サイクル毎に反射膜付透明基板の外観を確認した。外観検査ではクラック等がなければ○、クラックが入れば×とした。
以上の結果を表２に示す。
(Evaluation 2)
In Evaluation 2, a cold cycle test was performed to inspect the weather resistance of the transparent substrate with a reflective film. The test equipment for the thermal cycle uses “Air tank type thermal shock tester” (WINTECH NT-1020A) manufactured by Enomoto Kasei Co., Ltd., with -30 ° C cold air and 85 ° C temperature on the transparent substrate with a reflective film. Wind was applied alternately at intervals of 30 minutes, and this was defined as one cycle, and the appearance of the transparent substrate with a reflective film was confirmed every five cycles. In the appearance inspection, if there was no crack or the like, it was marked as ◯, and if there was a crack, it was marked as x.
The results are shown in Table 2.
＜実施例２＞
実施例２では、下地層の膜厚を２０nmに変えた以外は、すべて実施例１と同じ条件にて成膜を行い反射防止膜付透明基板を得た。得られた視感度透過率は９５．５％であった。
また、実施例１と同様に評価１及び評価２の試験を行った。その結果を表１、表２に示す。
<Example 2>
In Example 2, a film was formed under the same conditions as in Example 1 except that the film thickness of the underlayer was changed to 20 nm to obtain a transparent substrate with an antireflection film. The visibility transmission obtained was 95.5%.
Moreover, the test of evaluation 1 and evaluation 2 was done like Example 1. FIG. The results are shown in Tables 1 and 2.
＜実施例３＞
実施例３では、下地層の膜厚を４０nmに変えた以外は、すべて実施例１と同じ条件にて成膜を行い反射防止膜付透明基板を得た。得られた視感度透過率は９５．６％であった。
また、実施例１と同様に評価１及び評価２の試験を行った。その結果を表１、表２に示す。
<Example 3>
In Example 3, a film was formed under the same conditions as in Example 1 except that the film thickness of the underlayer was changed to 40 nm to obtain a transparent substrate with an antireflection film. The visibility transmission obtained was 95.6%.
Moreover, the test of evaluation 1 and evaluation 2 was done like Example 1. FIG. The results are shown in Tables 1 and 2.
＜比較例１＞
比較例１では、下地層をなくした以外は、すべて実施例１と同じ条件にて成膜を行い反射防止膜付透明基板を得た。得られた視感度透過率は９５．９％であった。
また、実施例１と同様に評価１及び評価２の試験を行った。その結果を表１、表２に示す。
<Comparative Example 1>
In Comparative Example 1, a film was formed under the same conditions as in Example 1 except that the base layer was eliminated, and a transparent substrate with an antireflection film was obtained. The resulting luminous transmittance was 95.9%.
Moreover, the test of evaluation 1 and evaluation 2 was done like Example 1. FIG. The results are shown in Tables 1 and 2.
＜比較例２＞
比較例２では、下地層及びバリア層を無くし、基板上から順にＴｉＯ2からなる第１誘電膜層を膜厚３３ｎｍ、ＳｉＯ2からなる第２誘電膜層を膜厚４５ｎｍ、ＴｉＯ2からなる第３誘電膜層を膜厚２３６ｎｍ、ＳｉＯ2からなる第４誘電膜層（最外層）を膜厚１２８ｎｍで形成して、合計４層からなる反射防止膜付透明基板を作成した。得られた視感度透過率は９５．８％であった。
また、実施例１と同様に評価１及び評価２の試験を行った。その結果を表１、表２に示す。
<Comparative example 2>
In Comparative Example 2, the base layer and the barrier layer are eliminated, the first dielectric film layer made of TiO 2 is formed in a thickness of 33 nm, and the second dielectric film layer made of SiO 2 is formed in a thickness of 45 nm and made of TiO 2 in order from the substrate. A three-dielectric film layer was formed with a film thickness of 236 nm, and a fourth dielectric film layer (outermost layer) made of SiO 2 was formed with a film thickness of 128 nm to produce a transparent substrate with an antireflection film consisting of a total of four layers. The visibility transmission obtained was 95.8%.
Moreover, the test of evaluation 1 and evaluation 2 was done like Example 1. FIG. The results are shown in Tables 1 and 2.
＜結果＞
表１に示すように、実施例１〜３の反射防止膜付透明基板においては、何れも視感度透過率が９０％以上と高透過率を示すとともに、比較例１及び２と比べ、耐候性、密着性ともに良好な結果が得られた。特に実施例３ではキセノンランプを用いた耐候性試験、及び密着性試験において２１６Ｈを超えても膜ハゲが見られない結果となった。また、図２に実施例３と比較例２における反射率特性のグラフを示す。これに示すように、本発明の実施形態である実施例３の膜構成であっても、比較例２に示す一般的な反射防止膜の反射率特性と大きく異なっていない。このため、本発明によれば、反射防止性能を従来と大きく変化させることなく、耐候性、密着性を向上させることが可能である。
<Result>
As shown in Table 1, in the transparent substrates with antireflection films of Examples 1 to 3, the luminous transmittance is 90% or more and high transmittance, and weather resistance is higher than those of Comparative Examples 1 and 2. Good results were obtained in both adhesion. In particular, in Example 3, film baldness was not observed even when exceeding 216H in a weather resistance test and an adhesion test using a xenon lamp. FIG. 2 shows a graph of reflectance characteristics in Example 3 and Comparative Example 2. As shown in this figure, even the film configuration of Example 3, which is an embodiment of the present invention, is not significantly different from the reflectance characteristics of a general antireflection film shown in Comparative Example 2. For this reason, according to this invention, it is possible to improve a weather resistance and adhesiveness, without changing an antireflection performance large conventionally.
１ 基板
２ 下地層
３ 反射防止層帯
３ａ 第１誘電膜層
３ｂ 第２誘電膜層
３ｃ 第３誘電膜層
３ｄ 第４誘電膜層
４ バリア層
DESCRIPTION OF SYMBOLS 1 Board | substrate 2 Underlayer 3 Antireflection layer 3a 1st dielectric film layer 3b 2nd dielectric film layer 3c 3rd dielectric film layer 3d 4th dielectric film layer 4 Barrier layer
Claims (4)
前記透明基板上に光学膜厚として１０nm以上４０nm以下であるＡｌ２Ｏ３からなる下地層と、該下地層の上に多層の誘電体層のみからなる反射防止膜とが形成されているとともに、該反射防止膜の耐候性の向上を得るために，該反射防止膜の最外層と該最外層の下に置かれる誘電体層との間に光学膜厚として２０nm以上５０nm以下であるＡｌ２Ｏ３の薄膜からなるバリア層と、が形成されていることを特徴とする反射防止膜付透明基板。 In a transparent substrate with an antireflection film formed by laminating a thin film layer on a transparent substrate,
On the transparent substrate, an underlayer made of Al 2 O 3 having an optical film thickness of 10 nm to 40 nm and an antireflection film made of only a multilayer dielectric layer are formed on the underlayer, In order to improve the weather resistance of the antireflection film, an Al 2 O film having an optical film thickness of 20 nm or more and 50 nm or less between the outermost layer of the antireflection film and the dielectric layer placed under the outermost layer. A transparent substrate with an antireflection film, wherein a barrier layer comprising a thin film 3 is formed.
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