JP5227909B2 - Stamper and manufacturing method of antireflection film using the same - Google Patents

Stamper and manufacturing method of antireflection film using the same Download PDF

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JP5227909B2
JP5227909B2 JP2009164498A JP2009164498A JP5227909B2 JP 5227909 B2 JP5227909 B2 JP 5227909B2 JP 2009164498 A JP2009164498 A JP 2009164498A JP 2009164498 A JP2009164498 A JP 2009164498A JP 5227909 B2 JP5227909 B2 JP 5227909B2
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porous alumina
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秀樹 益田
賢志 安井
泰 川本
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本発明は、高分子膜(フィルム)の表面に形成され、可視光域における反射を低減させる反射防止層(反射防止膜)の形成等に好適なスタンパの製造方法およびそれを用いた反射防止膜の製造方法に関する。 The present invention relates to a method for producing a stamper which is formed on the surface of a polymer film (film) and is suitable for forming an antireflection layer (antireflection film) which reduces reflection in the visible light region, and an antireflection film using the same. It relates to the manufacturing method .

様々な情報機器用表示装置において、高分子フィルムが広く用いられているが、良好な視認性を確保するためには、反射光を抑制するための反射防止層の形成が必要とされる。通常,反射防止層としては,異なる屈折率からなる誘電体から構成される多層膜が用いられているが、誘電体層の形成には、真空蒸着法、あるいはスパッタ法が用いられており、反射層形成には、高価な装置と多大な作製時間を必要とするという問題点があった。   In various display devices for information equipment, polymer films are widely used. However, in order to ensure good visibility, it is necessary to form an antireflection layer for suppressing reflected light. Usually, a multilayer film composed of dielectrics having different refractive indexes is used as the antireflection layer. However, a vacuum deposition method or a sputtering method is used to form the dielectric layer, and the reflection layer The layer formation has a problem of requiring an expensive apparatus and a great production time.

一方、高分子フィルムの表面に突起状の形状を付与し、屈折率が連続的に変化する層を形成することにより反射率を低減する方式が知られている。高分子フィルムに突起形状を付与するためには、通常、突起形状に対応した窪み配列を有するスタンパを用意し、これをもとに高分子フィルムを加工する方法が用いられている。   On the other hand, a method is known in which the reflectance is reduced by providing a protrusion-like shape on the surface of the polymer film and forming a layer whose refractive index continuously changes. In order to impart a protrusion shape to the polymer film, a method is generally used in which a stamper having a depression array corresponding to the protrusion shape is prepared and the polymer film is processed based on the stamper.

高分子フィルムの表面に突起形状を形成するためのスタンパに形成する窪みは、光の波長に比較して微細な周期を有し、可視光域で反射率を十分減衰させるためには、波長の1/4程度の深さを有することが必要とされる(たとえば、特許文献1)。このとき、窪みは、屈折率を連続的に変化させる必要があることから、テーパー形状を有することが必要とされる。   The depression formed in the stamper for forming the protrusion shape on the surface of the polymer film has a fine period compared to the wavelength of light, and in order to sufficiently attenuate the reflectance in the visible light region, It is necessary to have a depth of about 1/4 (for example, Patent Document 1). At this time, the recess needs to have a tapered shape because it is necessary to continuously change the refractive index.

このような条件を満たす窪み配列の形成のため、電子ビームリソグラフィー、あるいは光露光法によるパターニングとSiに代表される半導体単結晶の異方性エッチングを組み合わせる手法が一般に用いられている。これは、所望の周期の開口を各種リソグラフィーで形成した後、湿式あるいは乾式エッチング法によりテーパー形状の孔を形成するものである。リソグラフィー法として、電子ビームリソグラフィーは十分に微細な周期のパターンニングが可能であるが、加工に多大な時間と高価な装置が必要とされる。光露光法では、レーザー光の干渉を用いることでパターンを形成する方法が用いられるが、十分に微細な周期の構造を形成することは困難である。   In order to form a hollow array that satisfies such conditions, a technique that combines electron beam lithography or patterning by light exposure and anisotropic etching of a semiconductor single crystal typified by Si is generally used. In this method, an opening having a desired period is formed by various lithography, and then a tapered hole is formed by a wet or dry etching method. As a lithography method, electron beam lithography is capable of patterning with a sufficiently fine period, but requires a great deal of time and an expensive apparatus for processing. In the light exposure method, a method of forming a pattern by using interference of laser light is used, but it is difficult to form a structure having a sufficiently fine period.

微細なパターンを形成する手法として、規則的な細孔配列を有する陽極酸化ポーラスアルミナを用いる方法が提案されている(たとえば、非特許文献1)。この方法では,規則的な細孔配列を有する陽極酸化ポーラスアルミナをマスクとし、反応性イオンエッチングを施すことによりSi基板に窪みを形成する。このようにして形成された窪み配列を鋳型とし,高分子に同様の構造を形成する手法は容易に類推し得るが、この方法においては、無反射層形成に必須なテーパー形状の形成は困難であった。   As a method for forming a fine pattern, a method using anodized porous alumina having a regular pore arrangement has been proposed (for example, Non-Patent Document 1). In this method, a recess is formed in the Si substrate by performing reactive ion etching using anodized porous alumina having a regular pore arrangement as a mask. The method of forming a similar structure in a polymer using the hollow array formed in this way as a template can be easily analogized, but in this method, it is difficult to form a tapered shape that is essential for the formation of a non-reflective layer. there were.

これらの他、陽極酸化ポーラスアルミナの多孔質構造にエッチングを施し、これをもとにスタンパを作製する方法が提案されているが(たとえば、特許文献1)、陽極酸化ポーラスアルミナの細孔形状は円柱状であるので、単にこれをもとに反射防止膜に必要な制御されたテーパー形状を有する突起形状を高分子フィルムに形成することは困難である。   In addition to these, a method of etching a porous structure of anodized porous alumina and producing a stamper based on this is proposed (for example, Patent Document 1). Since it is cylindrical, it is difficult to form a protrusion shape having a controlled taper shape necessary for the antireflection film on the polymer film simply based on this.

特開2003―43203号公報JP 2003-43203 A

Kanamori et al., Appl. Phys. Lett., vol. 78, No.2, p.142 (2001)Kanamori et al., Appl. Phys. Lett., Vol. 78, No. 2, p. 142 (2001)

上記のように、リソグラフィーを用いる方法では、大面積を加工可能なスタンパを安価に製造することは困難であり、またテーパー形状を制御することは困難であった。また、陽極酸化ポーラスアルミナを用いる手法においても、無反射層形成に必須な最適なテーパー形状を形成するのが困難であるという問題点を有していた。   As described above, in the method using lithography, it is difficult to inexpensively manufacture a stamper capable of processing a large area, and it is difficult to control the taper shape. Also, the method using anodized porous alumina has a problem that it is difficult to form an optimum tapered shape essential for forming a non-reflective layer.

そこで本発明の課題は、とくに、例えば高分子フィルム面に所望の反射防止膜を効率的に形成すること等が可能なスタンパの製造方法およびそれを用いた反射防止膜の製造方法を提供することにある。 Accordingly, an object of the present invention is to provide, in particular, a stamper manufacturing method capable of efficiently forming a desired antireflection film on, for example, a polymer film surface, and a manufacturing method of an antireflection film using the stamper. It is in.

上記課題を解決するために、本発明に係るスタンパの製造方法は、以下の工程を含む方法からなる。
(1)陽極酸化と孔径拡大処理を交互に繰り返すことで、連続的に細孔径が変化するテーパー形状の細孔を形成した陽極酸化ポーラスアルミナを鋳型として用い、ネガ型材に転写する工程。
(2)前記陽極酸化ポーラスアルミナを除去し、作製されたネガ型にポジ型材を充填し、ネガ型を除去する工程。
In order to solve the above-described problems, a stamper manufacturing method according to the present invention includes a method including the following steps.
(1) A process in which anodized porous alumina in which tapered pores whose pore diameter continuously changes is repeatedly formed by alternately repeating anodization and pore diameter enlargement processing as a mold and transferred to a negative mold.
(2) A step of removing the anodized porous alumina, filling the produced negative mold with a positive mold material, and removing the negative mold.

このスタンパの製造方法においては、ネガ型材は例えばポリマー材料とすることができる。また、ポジ型材は例えば金属とすることができる。In this stamper manufacturing method, the negative mold material can be, for example, a polymer material. Further, the positive mold material can be a metal, for example.

このようなスタンパの製造方法は、例えば、無反射高分子フィルムの作製に適用できる。例えば、後述の図4に示すように、高分子膜の表面に凹凸を形成し、屈折率を連続的に変化させることで反射を低減させる反射防止膜の製造に際し、前記凹凸の形成に、表面に細孔を有し、該細孔に、陽極酸化と孔径拡大処理を交互に繰り返すことで、連続的に細孔径が変化するテーパー形状を付与した陽極酸化ポーラスアルミナを鋳型として、その構造をネガ型材に転写し、陽極酸化ポーラスアルミナを除去し、作製されたネガ型にポジ型材を充填し、ネガ型を除去してスタンパを製造し、作製したスタンパを鋳型として反射防止膜を製造する方法に適用できる。 Such a stamper manufacturing method can be applied to, for example, production of an antireflective polymer film. For example, as shown in FIG. 4 to be described later, when forming an unevenness on the surface of the polymer film and producing an antireflection film that reduces reflection by continuously changing the refractive index, The structure is negative using anodized porous alumina with a taper shape in which the pore diameter changes continuously by alternately repeating anodization and pore diameter enlargement treatment on the pore as a template. Transfer to mold material, remove anodized porous alumina, fill the produced negative mold with positive mold material, remove the negative mold to produce a stamper, and produce an antireflection film using the produced stamper as a mold Applicable.

このような反射防止膜の製造においては、細孔周期50nm〜300nm,細孔深さ100nm以上の陽極酸化ポーラスアルミナを鋳型として用いることで、より最適な無反射膜の作製を実現できる。また、定電圧で長時間陽極酸化を施したのち、一旦酸化皮膜を除去し、再び同一条件で陽極酸化を施すことで作製した陽極酸化ポーラスアルミナを用いることで、高い孔配列規則性を有する陽極酸化ポーラスアルミナを鋳型とすることが可能となる。In the production of such an antireflection film, the use of anodized porous alumina having a pore period of 50 nm to 300 nm and a pore depth of 100 nm or more as a template can realize the production of a more optimal antireflection film. In addition, an anode having high pore arrangement regularity is obtained by using anodized porous alumina prepared by anodizing at a constant voltage for a long time, once removing the oxide film, and again anodizing under the same conditions. It becomes possible to use oxidized porous alumina as a mold.

使用する陽極酸化ポーラスアルミナとしては、たとえば、シュウ酸を電解液として用い、化成電圧30V〜60Vにおいて作製した陽極酸化ポーラスアルミナを用いることもでき、硫酸を電解液として用い、化成電圧25V〜30Vにおいて作製した陽極酸化ポーラスアルミナを用いることもできる。このような陽極酸化ポーラスアルミナを用いることで、より高い規則性を有する窪み配列を鋳型とすることが可能となる。As the anodized porous alumina to be used, for example, anodized porous alumina prepared using an oxalic acid as an electrolytic solution at a chemical conversion voltage of 30 V to 60 V can be used, and sulfuric acid is used as an electrolytic solution at a chemical conversion voltage of 25 V to 30 V. The produced anodized porous alumina can also be used. By using such anodized porous alumina, it becomes possible to use a hollow array having higher regularity as a template.

さらに、陽極酸化ポーラスアルミナの作製において、陽極酸化に先立ちアルミニウム表面に微細な窪みを形成し、これを陽極酸化時の細孔発生点とすることもできる。これにより、任意の配列を有する窪み配列を有する鋳型とすることが可能となる。Further, in the production of anodized porous alumina, a fine depression can be formed on the aluminum surface prior to anodization, and this can be used as a pore generation point during anodization. Thereby, it becomes possible to set it as the casting_mold | template which has a hollow arrangement | sequence which has arbitrary arrangement | sequences.

本発明に係る方法により製造された反射防止膜は、所望形状に形成された表面凹凸により、優れた反射防止性能を有するものである。この反射防止膜は、とくに光透過性高分子膜の表面に形成することにより、各種用途において目標とする反射防止性能を発揮することができる。 The antireflection film produced by the method according to the present invention has excellent antireflection performance due to surface irregularities formed in a desired shape. By forming this antireflection film on the surface of the light-transmitting polymer film, the antireflection performance targeted in various applications can be exhibited.

本発明におけるスタンパ、例えば反射防止膜作製用スタンパは、例えば後述の図4に示されるような方法により製造されたものからなる。 Stamper definitive to the present invention, for example anti-reflection film manufactured stamper is made from that produced by the method as illustrated for example in FIG. 4 which will be described later.

本発明によれば、簡便に、テーパー形状の孔を有する陽極酸化ポーラスアルミナに基づく鋳型の形成が可能となり、この結果、例えば、可視光域における反射を低減した反射防止層を形成するのに好適なスタンパの製造が可能となる。このスタンパを用いることにより、上記の如く、優れた反射防止性能を有する反射防止膜の製造が可能となる。 According to the present invention, it is possible to easily form a template based on anodized porous alumina having tapered holes, and as a result, for example, suitable for forming an antireflection layer with reduced reflection in the visible light region. Can be manufactured. By using this stamper, as described above, it is possible to produce an antireflection film having excellent antireflection performance.

表面突起配列を形成した高分子無反射膜の例を示す概断面図である。It is a schematic sectional drawing which shows the example of the polymer non-reflective film in which the surface protrusion arrangement | sequence was formed. 本発明において、陽極酸化とエッチングを組み合わせることでテーパー状細孔を有する陽極酸化ポーラスアルミナを形成する過程を示す図である。In this invention, it is a figure which shows the process in which the anodic oxidation porous alumina which has a taper-shaped pore is formed by combining an anodic oxidation and an etching. テーパー状細孔を有する陽極酸化ポーラスアルミナを鋳型として突起形状を有する高分子無反射膜の形成過程を示す図である。It is a figure which shows the formation process of the polymeric non-reflective film which has a protrusion shape using the anodized porous alumina which has a taper-shaped pore as a casting_mold | template. 本発明により、テーパー状細孔を有する陽極酸化ポーラスアルミナを鋳型にして金属からなるスタンパの形成過程を示す図である。It is a figure which shows the formation process of the stamper which consists of a metal using the anodized porous alumina which has a taper-shaped pore as a casting_mold | template by this invention . 陽極酸化を施した後、一旦酸化層を溶解除去し、再び陽極酸化を行うことで、規則性の高いテーパー形状細孔を有する陽極酸化ポーラスアルミナを作製する過程を示す図である。It is a figure which shows the process of producing the anodic oxidation porous alumina which has a taper-shaped pore with a high regularity by once dissolving and removing an oxidation layer after anodizing and performing anodization again. 規則突起配列を有するモールドを用い、アルミニウム表面に窪み配列を形成し、陽極酸化を行うことで細孔配列が制御されたテーパー状細孔を有する陽極酸化ポーラスアルミナを作製する過程を示す図である。It is a figure which shows the process of producing the anodic oxidation porous alumina which has the taper-shaped pore by which the pore arrangement | sequence was controlled by forming the hollow arrangement | sequence on the aluminum surface using the mold which has a regular projection arrangement | sequence, and performing anodization .

以下に、本発明の望ましい実施の形態について、図面を参照して説明する。
図1は,高分子からなる反射防止膜(無反射膜)の構造例を示している。高分子膜1の表面にテーパー状の突起配列、つまり凹凸を有することで,屈折率が連続的に変化し、反射率の低減が可能となる。
Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings.
Figure 1 shows an example of the structure of the antireflection film (antireflection coating) made of a high molecule. Since the surface of the polymer film 1 has a tapered protrusion arrangement, that is, unevenness, the refractive index changes continuously, and the reflectance can be reduced.

図2は,本発明において,テーパー形状を有する陽極酸化ポーラスアルミナの作製方法の例を示したものである。陽極酸化ポーラスアルミナ3は、アルミニウム基材2の表面に形成されるが、陽極酸化ポーラスアルミナ3の細孔4の形状は、円筒形状をしており、そのままでは、無反射膜を形成するための鋳型としての利用は困難である。本発明においては、陽極酸化と、エッチングによる孔の拡大処理を組み合わせることにより、所望のテーパー形状の孔を有する陽極酸化ポーラスアルミナの作製を実現する。所定の時間陽極酸化を施して所望の深さの細孔を形成したのち、適当な酸溶液中に浸漬することにより孔径の拡大処理を施す。この後、再び陽極酸化を施すことにより、1段階目に比較して孔径の小さな孔を形成する。この操作を繰り返すことにより、テーパー形状を有する陽極酸化ポーラスアルミナを得ることができる。このとき,繰り返し段数を増大することにより、より滑らかなテーパー形状を得ることが可能となる。陽極酸化時間と孔径拡大処理時間とを調整することで、様々なテーパー形状を有する孔の形成が可能であり、周期、孔深さに合わせて、最適な屈折率変化を設計することが可能となる。 FIG. 2 shows an example of a method for producing an anodized porous alumina having a tapered shape in the present invention. The anodized porous alumina 3 is formed on the surface of the aluminum substrate 2, but the pores 4 of the anodized porous alumina 3 have a cylindrical shape, and as it is, for forming a non-reflective film. Use as a mold is difficult. In the present invention, anodized porous alumina having a desired taper-shaped hole is realized by combining anodization and hole enlargement processing by etching. After anodizing for a predetermined time to form pores having a desired depth, the pores are enlarged by being immersed in an appropriate acid solution. Thereafter, anodization is performed again to form a hole having a smaller hole diameter compared to the first stage. By repeating this operation, anodized porous alumina having a tapered shape can be obtained. At this time, a smoother taper shape can be obtained by increasing the number of steps. By adjusting the anodizing time and the hole diameter expansion processing time, it is possible to form holes with various taper shapes, and it is possible to design an optimal refractive index change according to the period and hole depth Become.

このようにして形成されたテーパー形状を有する陽極酸化ポーラスアルミナを鋳型とし、図3に示すように、高分子フィルム(高分子膜)1に構造を直接転写し(たとえば、ポリマーを鋳型に充填することにより転写し)、鋳型を除去することで表面に突起を有する無反射構造得ることができる。高分子フィルム1としては,良好な光透過性と加工性を有するものが利用できるが、代表的なものとして、アクリル樹脂、ポリカーボネート樹脂、ポリスチレン樹脂等が挙げられる。また、高分子への転写には、モノマーを充填した後重合させる方法、適当な溶媒に溶解した高分子をキャストする方法のほか、加温あるいは溶媒を加えることで可塑化した状態の高分子フィルムへ鋳型を押し付けることにより達成することができる。 As shown in FIG. 3, the structure is directly transferred to the polymer film (polymer film) 1 as shown in FIG. 3 (for example, the polymer is filled in the template). it was transcribed by), non-reflective structure having projections on the surface by removing the mold can be obtained. As the polymer film 1, a film having good light transmittance and processability can be used, and representative examples include acrylic resin, polycarbonate resin, polystyrene resin and the like. For transfer to polymer, polymer film filled with monomer, polymer film dissolved in an appropriate solvent, cast polymer, heated or polymerized polymer film by adding solvent This can be achieved by pressing the mold into the mold.

本発明に係るスタンパの製造方法は、例えば図4に示すように行われる。テーパー形状の孔を有する陽極酸化ポーラスアルミナを鋳型として用いる場合、上述の如き陽極酸化ポーラスアルミナを直接用いる方法に加え、図4に示すように、陽極酸化ポーラスアルミナを鋳型とし、金属等の材料により同一の形状を有する新たな鋳型、つまり反射防止膜作製用スタンパを得ること可能であり、耐久性、耐摩耗性、あるいは剥離特性の向上に有効である。本発明に係るスタンパの製造方法を例示した図4に示す方法では、先ず陽極酸化ポーラスアルミナ3を鋳型としてネガ型材としてのポリマー1に構造を転写した後陽極酸化ポーラスアルミナ3を除去し、作製されたネガ型にポジ型材としての金属等を充填し、ネガ型を除去して金属等からなるスタンパを得る。 The stamper manufacturing method according to the present invention is performed, for example, as shown in FIG. When anodized porous alumina having tapered holes is used as a mold, in addition to the method of directly using anodized porous alumina as described above , as shown in FIG. It is possible to obtain a new mold having the same shape, that is, a stamper for producing an antireflection film, which is effective in improving durability, wear resistance, or peeling characteristics. In method 4 illustrating the method of manufacturing a stamper according to the present invention, first, an anodized porous alumina 3 to remove the anodized porous alumina 3 after transferring the structure to a polymer 1 as a negative type material as a template, the produced The negative mold is filled with metal or the like as a positive mold material, and the negative mold is removed to obtain a stamper made of metal or the like.

本発明においては、更に、図5に示すように、テーパー状の孔を形成するのに先立ち、あらかじめ比較的長時間陽極酸化を施し、陽極酸化ポーラスアルミナ層の孔配列を規則化させ、その後、アルミナ層を除去することで、アルミニウム表面にポーラスアルミナの底部(バリア層と呼ばれる)に対応する規則的な窪み配列を得、再び同一の電圧での陽極酸化、および孔径拡大処理を組み合わせることで、最表面から細孔が規則配列したテーパー状ポーラスアルミナを形成することができる。つまり、好ましい形状のテーパー状細孔がより高い規則性をもって配列された再陽極酸化層6を形成する。一般に、陽極酸化ポーラスアルミナにおいて、陽極酸化初期に形成される最表面部分の細孔配列の規則性は低く、このような陽極酸化ポーラスアルミナをもとに形成された無反射膜では、光散乱が増大し良好な無反射膜としては利用が困難になる可能性があるが、上記手法に基づけば、細孔が高い規則性をもって配列した陽極酸化ポーラスアルミナを得ることが可能となり、良好な無反射膜の形成に寄与する。このとき、シュウ酸を電解液として用いる場合には、30〜60Vの化成電圧で、より好ましくは、40Vで、また、硫酸を電解液として用いる場合には、25〜30Vの化成電圧で高い規則性を有する陽極酸化ポーラスアルミナが得られることが知られている(たとえば、益田,応用物理,vol.69, No.5, p.558 (2000))。このようにして形成された高い規則性の孔配列を有する陽極酸化ポーラスアルミナは、直接、あるいは更に金属等の鋳型作製に有効に用いることが可能である。 In the present invention, as shown in FIG. 5, prior to forming the tapered holes, anodization is performed for a relatively long time in advance to regularize the hole arrangement of the anodized porous alumina layer. By removing the alumina layer, a regular array of depressions corresponding to the bottom of the porous alumina (called the barrier layer) is obtained on the aluminum surface, and again by combining anodization at the same voltage and pore size expansion treatment, Tapered porous alumina in which pores are regularly arranged from the outermost surface can be formed . That is, the reanodized layer 6 in which tapered pores having a preferable shape are arranged with higher regularity is formed. In general, in anodized porous alumina, the regularity of the pore arrangement of the outermost surface portion formed at the initial stage of anodization is low, and the light-reflective film formed based on such anodized porous alumina does not scatter light. Although it may be difficult to use as a good non-reflective film, it becomes possible to obtain anodized porous alumina with pores arranged with high regularity based on the above method, and good non-reflective film Contributes to film formation. At this time, when oxalic acid is used as the electrolytic solution, a high voltage is formed at a conversion voltage of 30 to 60 V, more preferably at 40 V, and when sulfuric acid is used as the electrolytic solution, a high voltage is formed at a conversion voltage of 25 to 30 V. It is known that anodized porous alumina having properties can be obtained (for example, Masuda, Applied Physics, vol. 69, No. 5, p. 558 (2000)). The anodized porous alumina having a highly ordered hole array formed in this way can be used directly or more effectively for the production of a metal mold or the like.

本発明においては、更に、図6に示すように、所望の配列の突起を有するモールド7を用いることでアルミニウム2の表面に窪み配列を形成し、その後、窪み間隔に適合した化成電圧での陽極酸化と孔径拡大処理を交互に繰り返すことで、窪みが孔発生の開始点となり、モールドの突起配列に対応した孔配列を有するテーパー状の孔を有する陽極酸化ポーラスアルミナを得ることが可能となる。この方法によれば、任意の周期、配列を有する陽極酸化ポーラスアルミナの形成が可能となり良好な無反射膜を得るのに寄与する。この方法では、高い規則性の細孔配列を有するポーラスアルミナを得るのみならず、表示材料として用いる際に問題となる光干渉にもとづく干渉色の発生等の抑制にも寄与する。このようにして形成された高い規則性の孔配列を有する陽極酸化ポーラスアルミナは、直接、あるいは更に金属等の鋳型作製に有効に用いることが可能である。 Further, in the present invention, as shown in FIG. 6, a mold 7 having projections in a desired arrangement is used to form a depression array on the surface of the aluminum 2, and thereafter an anode with a conversion voltage suitable for the depression spacing. By repeating the oxidation and the hole diameter enlargement process alternately, the depression becomes a starting point of hole generation, and it becomes possible to obtain anodized porous alumina having tapered holes having a hole arrangement corresponding to the protrusion arrangement of the mold. According to this method, anodized porous alumina having an arbitrary period and arrangement can be formed, which contributes to obtaining a good antireflection film. This method not only obtains porous alumina having a highly regular pore array, but also contributes to suppression of the generation of interference colors due to light interference, which is a problem when used as a display material. The anodized porous alumina having a highly ordered hole array formed in this way can be used directly or more effectively for the production of a metal mold or the like.

次に、実施例に基づいて、本発明を更に具体的に説明する。
参考実施例1
純度99.99%のアルミニウム板を0.3Mシュウ酸を電解液とし、化成電圧40Vとし、50秒間陽極酸化を行った。その後、2重量%リン酸30℃中に5分間浸漬し、孔径拡大処理を施した。この操作を5回繰り返すことで、周期100nm、細孔径開口部80nm、底部25nm、孔深さ300nmのテーパー状細孔を有する陽極酸化ポーラスアルミナを得た。
Next, based on an Example, this invention is demonstrated further more concretely.
Reference Example 1
An aluminum plate having a purity of 99.99% was subjected to anodization for 50 seconds with 0.3M oxalic acid as an electrolytic solution and a formation voltage of 40V. Then, it was immersed in 2% by weight phosphoric acid at 30 ° C. for 5 minutes and subjected to a pore size expansion treatment. By repeating this operation five times, an anodized porous alumina having tapered pores having a period of 100 nm, a pore diameter opening portion of 80 nm, a bottom portion of 25 nm, and a pore depth of 300 nm was obtained.

重合開始剤として5重量%の過酸化ベンゾイルを含むメタクリル酸メチルモノマーを細孔内に充填した後、紫外線を照射することで重合させた。重合後、高分子層を鋳型から剥離することで、表面に突起配列を有するポリメチルメタクリレート樹脂を得た。得られた高分子膜の反射率を測定した結果、反射率の低減が確認された。   A methyl methacrylate monomer containing 5% by weight of benzoyl peroxide as a polymerization initiator was filled in the pores, and then polymerized by irradiation with ultraviolet rays. After the polymerization, the polymer layer was peeled from the mold to obtain a polymethyl methacrylate resin having a protrusion arrangement on the surface. As a result of measuring the reflectance of the obtained polymer film, it was confirmed that the reflectance was reduced.

参考実施例2
実施例1と同様のアルミニウム板に対して、0.3M硫酸を電解液とし、化成電圧25Vとし、陽極酸化、孔径拡大処理を繰り返した。その後、同様にポリメタクリル酸メチル樹脂に構造を転写することにより、反射率の低減が確認された。
Reference Example 2
With respect to the same aluminum plate as in Example 1, 0.3M sulfuric acid was used as the electrolytic solution, the formation voltage was 25V, and the anodic oxidation and the pore diameter expansion treatment were repeated. Thereafter, the structure was transferred to a polymethyl methacrylate resin in the same manner, thereby confirming a reduction in reflectance.

参考実施例3
実施例1と同様の条件で、2時間陽極酸化を施したのち、ポーラスアルミナ層をリン酸/クロム酸混合液により選択的に溶解除去した。この後、同一の条件で陽極酸化、孔径拡大処理を組み合わせることで、細孔が高度に配列したテーパー状孔を有する陽極酸化ポーラスアルミナを得た。その後、実施例1と同様の手法によりポリメタクリル酸メチル樹脂に構造を転写することにより、反射率の低減が確認された。
Reference Example 3
After anodizing for 2 hours under the same conditions as in Example 1, the porous alumina layer was selectively dissolved and removed with a phosphoric acid / chromic acid mixture. Thereafter, anodized porous alumina having tapered pores with highly arranged pores was obtained by combining anodization and pore diameter expansion treatment under the same conditions. Thereafter, the structure was transferred to a polymethyl methacrylate resin by the same method as in Example 1, and it was confirmed that the reflectance was reduced.

参考実施例4
実施例1と同様の方法でテーパー形状孔を有する陽極酸化ポーラスアルミナを形成後、これを鋳型として、ポリカーボネート樹脂に転写を行うことで、低反射率特性を示すことが確認された。
Reference Example 4
After forming anodized porous alumina having tapered holes by the same method as in Example 1, it was confirmed that low-reflectivity characteristics were exhibited by performing transfer to a polycarbonate resin using this as a template.

実施例5
実施例1と同様の方法でテーパー状孔を有する陽極酸化ポーラスアルミナを形成後、陽極酸化ポーラスアルミナにポリメチルメタクリレートを充填し、ポーラスアルミナのネガ鋳型を得た。その後、ポリメチルメタクリレート表面に導電化処理を施し、めっき法によりニッケルを充填した。ポリメタクリレートネガ鋳型を溶解除去することで、母型である陽極酸化ポーラスアルミナと同一の構造を有するニッケルポジ鋳型を得た。これを加温したポリメチルメタクリレートに押し付けることにより表面に突起配列を有する低反射膜を得た。
Example 5
After anodized porous alumina having tapered holes was formed by the same method as in Example 1, the anodized porous alumina was filled with polymethyl methacrylate to obtain a negative mold of porous alumina. Thereafter, the polymethyl methacrylate surface was subjected to a conductive treatment, and nickel was filled by a plating method. By dissolving and removing the polymethacrylate negative mold, a nickel positive mold having the same structure as the base anodized porous alumina was obtained. This was pressed against heated polymethylmethacrylate to obtain a low reflection film having a protrusion arrangement on the surface.

参考実施例6
周期200nmの突起配列を有するモールドをアルミニウム板に押し付けることにより、アルミニウム表面に突起に対応した窪み配列を得た。その後、0.05Mシュウ酸を用い、80Vの化成電圧での陽極酸化と孔径拡大処理を5回繰り返すことで、周期200nm、細孔径開口部160nm、底部50nm、孔深さ500nmのテーパー状細孔を有する陽極酸化ポーラスアルミナを得た。その後、実施例1と同様の手法によりポリメタクリル酸メチル樹脂に構造を転写することにより、反射率の低減が確認された。
Reference Example 6
By pressing a mold having a projection arrangement with a period of 200 nm against an aluminum plate, a depression arrangement corresponding to the projection was obtained on the aluminum surface. Subsequently, 0.05M oxalic acid was used, and the anodization at a conversion voltage of 80V and the pore size expansion treatment were repeated five times, so that tapered pores having a period of 200 nm, a pore size opening portion of 160 nm, a bottom portion of 50 nm, and a pore depth of 500 nm An anodized porous alumina having Thereafter, the structure was transferred to a polymethyl methacrylate resin by the same method as in Example 1, and it was confirmed that the reflectance was reduced.

本発明に係る方法は、該方法により製造されるスタンパを使用可能なあらゆる用途に有効に利用でき、例えば、反射防止膜の形成が要求され用途に適用でき、とくに、視認性の向上が要求される各種情報機器用表示装置等の製造に利用できる。 The method according to the present invention, a stamper manufactured by the method can be effectively used in all applications available, for example, applied can in applications forming the antireflection film Ru is required, in particular, improve the visibility requirements It can be used for manufacturing display devices for various information devices .

1 高分子フィルム(高分子膜、ポリマー)
2 アルミニウム
3 陽極酸化ポーラスアルミナ
4 細孔
5 金属(スタンパ)
6 再陽極酸化層
7 モールド
1 Polymer film (polymer film, polymer)
2 Aluminum 3 Anodized porous alumina 4 Pore 5 Metal (stamper)
6 Re-anodized layer 7 Mold

Claims (4)

以下の工程を含む、スタンパの製造方法。
(1)陽極酸化と孔径拡大処理を交互に繰り返すことで、連続的に細孔径が変化するテーパー形状の細孔を形成した陽極酸化ポーラスアルミナを鋳型として用い、ネガ型材に転写する工程。
(2)前記陽極酸化ポーラスアルミナを除去し、作製されたネガ型にポジ型材を充填し、ネガ型を除去する工程。
A stamper manufacturing method including the following steps.
(1) A process in which anodized porous alumina in which tapered pores whose pore diameter continuously changes is repeatedly formed by alternately repeating anodization and pore diameter enlargement processing as a mold and transferred to a negative mold.
(2) A step of removing the anodized porous alumina, filling the produced negative mold with a positive mold material, and removing the negative mold.
ネガ型材がポリマー材料である、請求項1に記載の製造方法。   The manufacturing method according to claim 1, wherein the negative mold material is a polymer material. ポジ型材が金属である、請求項1または2に記載の製造方法。   The manufacturing method according to claim 1, wherein the positive mold material is a metal. 請求項1に記載のスタンパを用いて反射防止膜を製造する方法。   A method for producing an antireflection film using the stamper according to claim 1.
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