JP2022001890A - Wire grid type polarizer - Google Patents

Wire grid type polarizer Download PDF

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JP2022001890A
JP2022001890A JP2018186781A JP2018186781A JP2022001890A JP 2022001890 A JP2022001890 A JP 2022001890A JP 2018186781 A JP2018186781 A JP 2018186781A JP 2018186781 A JP2018186781 A JP 2018186781A JP 2022001890 A JP2022001890 A JP 2022001890A
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wire grid
grid type
light
layer
absorption layer
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賢太 関川
Kenta Sekikawa
総 石戸
Satoshi Ishido
康宏 池田
Yasuhiro Ikeda
拓馬 西坂
Takuma NISHIZAKA
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AGC Inc
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Asahi Glass Co Ltd
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Priority to JP2018186781A priority Critical patent/JP2022001890A/en
Priority to PCT/JP2019/038051 priority patent/WO2020071256A1/en
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

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  • Optics & Photonics (AREA)
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Abstract

To provide a wire grid type polarizer capable of reducing the reflectance Rp of p polarized light while suppressing reduction in the reflectance Rs of s polarized light.SOLUTION: A wire grid type polarizer includes a light transmissive substrate 1 having a projection strip 11 and a recessed groove 12 parallel to each other and alternately formed at a the predetermined pitch on the surface; and a metal layer 2 provided on the surface of the projection strip 11 and consisting of metal or a metal compound. An absorber layer 3 including dye or pigment is provided on the bottom surface of the recessed groove 12; and a height f from the bottom surface of the recessed groove 12 to the upper surface of the absorber layer 3 is equal to or less than that g from the bottom surface of the recessed groove 12 to the upper end of the metal layer 2.SELECTED DRAWING: Figure 1

Description

本発明は、ワイヤグリッド型偏光子に関する。 The present invention relates to a wire grid type polarizing element.

ワイヤグリッド型偏光子は、光透過性基板上に複数の金属細線が互いに平行に配列した構造を有する。金属細線のピッチが入射光の波長よりも充分に短い場合、入射光のうち、金属細線に直交する電場ベクトルを有する成分（すなわちｐ偏光）は透過し、金属細線と平行な電場ベクトルを有する成分（すなわちｓ偏光）は反射する。
特許文献１には、基材表面に凸条と凹溝を交互に設け、凸条の倒れを防止するために、凹溝に低屈折材料からなる支持部を設けた偏光子が記載されている。 The wire grid type polarizing element has a structure in which a plurality of fine metal wires are arranged in parallel with each other on a light transmissive substrate. When the pitch of the thin metal wire is sufficiently shorter than the wavelength of the incident light, the component of the incident light having an electric field vector orthogonal to the thin metal wire (that is, p-polarized light) is transmitted, and the component having an electric field vector parallel to the thin metal wire is transmitted. (That is, s-polarized light) is reflected.
Patent Document 1 describes a polarizing element in which ridges and grooves are alternately provided on the surface of a base material, and a support portion made of a low refraction material is provided in the ridges in order to prevent the ridges from collapsing. ..

特開２０１６−１８９０１４号公報Japanese Unexamined Patent Publication No. 2016-189014

例えば偏光ビームスプリッタなど、ワイヤグリッド型偏光子の使い方によっては、（ｓ偏光の反射率Ｒｓ）／（ｐ偏光の反射率Ｒｐ）の比が高いことが求められる場合がある。
本発明は、ｓ偏光の反射率Ｒｓの低下を抑えつつ、ｐ偏光の反射率Ｒｐを低減できるワイヤグリッド型偏光子の提供を目的とする。 Depending on how the wire grid type splitter is used, for example, a polarizing beam splitter, it may be required that the ratio of (reflectance Rs of s-polarized light Rs) / (reflectance Rp of p-polarized light) is high.
An object of the present invention is to provide a wire grid type polarizing element capable of reducing the reflectance Rp of p-polarized light while suppressing the decrease of the reflectance Rs of s-polarized light.

本発明は、下記の態様を有する。
［１］表面に、互いに平行な凸条と凹溝が所定のピッチで交互に形成された光透過性基板と、前記凸条の表面上に設けられた、金属又は金属化合物からなる金属層とを有し、
前記凹溝の底面上に、色素又は顔料を含む吸収層が設けられており、
前記凹溝の底面から前記吸収層の上面までの高さが、前記凹溝の底面から前記金属層の上端までの高さ以下である、ワイヤグリッド型偏光子。
［２］前記光透過性基板、前記金属層及び前記吸収層を覆う樹脂層を有する、［１］のワイヤグリッド型偏光子。 The present invention has the following aspects.
[1] A light-transmitting substrate in which ridges and grooves parallel to each other are alternately formed at a predetermined pitch on the surface, and a metal layer made of a metal or a metal compound provided on the surface of the ridges. Have,
An absorption layer containing a dye or a pigment is provided on the bottom surface of the concave groove.
A wire grid type polarizing element in which the height from the bottom surface of the concave groove to the upper surface of the absorption layer is equal to or less than the height from the bottom surface of the concave groove to the upper end of the metal layer.
[2] The wire grid type polarizing element according to [1], which has a light-transmitting substrate, a metal layer, and a resin layer covering the absorption layer.

本発明によれば、ｓ偏光の反射率Ｒｓの低下を抑えつつ、ｐ偏光の反射率Ｒｐを低減できるワイヤグリッド型偏光子が得られる。 According to the present invention, a wire grid type splitter capable of reducing the reflectance Rp of p-polarized light while suppressing the decrease of the reflectance Rs of s-polarized light can be obtained.

ワイヤグリッド型偏光子の第１の実施形態を模式的に示す断面図である。It is sectional drawing which shows the 1st Embodiment of the wire grid type polarizing element schematically. ワイヤグリッド型偏光子の製造工程の一例を示す断面図である。It is sectional drawing which shows an example of the manufacturing process of a wire grid type polarizing element. ワイヤグリッド型偏光子の製造工程の他の例を示す断面図である。It is sectional drawing which shows the other example of the manufacturing process of a wire grid type polarizing element. ワイヤグリッド型偏光子の第２の実施形態を模式的に示す断面図である。It is sectional drawing which shows the 2nd Embodiment of the wire grid type polarizing element schematically. 実施例１で製造したワイヤグリッド型偏光子の断面の走査型電子顕微鏡像である。It is a scanning electron microscope image of the cross section of the wire grid type polarizing element manufactured in Example 1. FIG. 比較例１で製造したワイヤグリッド型偏光子の断面の走査型電子顕微鏡像である。It is a scanning electron microscope image of the cross section of the wire grid type polarizing element manufactured in the comparative example 1. FIG. 実施例１及び比較例１におけるＴｐの測定結果を示すスペクトルである。6 is a spectrum showing the measurement results of Tp in Example 1 and Comparative Example 1. 実施例１及び比較例１におけるＲｓの測定結果を示すスペクトルである。6 is a spectrum showing the measurement results of Rs in Example 1 and Comparative Example 1. 実施例１及び比較例１におけるＲｐの測定結果を示すスペクトルである。6 is a spectrum showing the measurement results of Rp in Example 1 and Comparative Example 1. 実施例２で製造したワイヤグリッド型偏光子の断面の走査型電子顕微鏡像である。It is a scanning electron microscope image of the cross section of the wire grid type polarizing element manufactured in Example 2. FIG. 比較例２で製造したワイヤグリッド型偏光子の断面の走査型電子顕微鏡像である。It is a scanning electron microscope image of the cross section of the wire grid type polarizing element manufactured in the comparative example 2.

以下の用語の定義は、本明細書及び特許請求の範囲にわたって適用される。
「〜」で表される数値範囲は、〜の前後の数値を下限値及び上限値とする数値範囲を意味する。
「屈折率」は、波長５８９．３ｎｍの光に対する屈折率を意味する。 The definitions of the following terms apply throughout the specification and claims.
The numerical range represented by "~" means a numerical range in which the numerical values before and after ~ are the lower limit value and the upper limit value.
"Refractive index" means the refractive index for light having a wavelength of 589.3 nm.

＜第１の実施形態＞
図１は、本発明のワイヤグリッド型偏光子の第１の実施形態を模式的に示す断面図である。図中符号１は光透過性基板、２は金属層、３は吸収層、１１は凸条、１２は凹溝である。以下、凸条１１の長さ方向をＺ方向、Ｚ方向に直交する面内における凸条１１の幅方向をＸ方向、Ｘ方向とＺ方向に直交する方向をＹ方向という。 <First Embodiment>
FIG. 1 is a cross-sectional view schematically showing a first embodiment of the wire grid type polarizing element of the present invention. In the figure, reference numeral 1 is a light transmissive substrate, 2 is a metal layer, 3 is an absorption layer, 11 is a ridge, and 12 is a concave groove. Hereinafter, the length direction of the ridge 11 is referred to as the Z direction, the width direction of the ridge 11 in the plane orthogonal to the Z direction is referred to as the X direction, and the direction orthogonal to the X direction and the Z direction is referred to as the Y direction.

なお、図１は設計値に基づく模式図であり、実際のワイヤグリッド型偏光子には、製造上不可避の形状の崩れや金属層の厚みの不均一が生じている。本明細書においてワイヤグリッド型偏光子の各部の寸法は、Ｚ方向に直交する断面の走査型電子顕微鏡像又は透過型電子顕微鏡像における、任意の５箇所の測定値の平均値とする。 Note that FIG. 1 is a schematic diagram based on the design values, and the actual wire grid type polarizing element has a shape collapse that is unavoidable in manufacturing and a non-uniform thickness of the metal layer. In the present specification, the dimensions of each part of the wire grid type extruder are taken as the average value of the measured values at any five points in the scanning electron microscope image or the transmission electron microscope image of the cross section orthogonal to the Z direction.

光透過性基板１は、ワイヤグリッド型偏光子の使用波長範囲において光透過性である。光透過性とは、透過率が８０％以上を意味する。
ワイヤグリッド型偏光子の使用波長範囲は、３００〜１０００ｎｍの範囲内が好ましく、４００〜８００ｎｍの範囲内がより好ましく、４２０〜６８０ｎｍがさらに好ましい。
光透過性基板１の屈折率は１．３５〜１．６が好ましく、１．４〜１．５８がより好ましく、１．４５〜１．５５がさらに好ましい。 The light transmissive substrate 1 is light transmissive in the wavelength range used by the wire grid type polarizing element. The light transmittance means that the transmittance is 80% or more.
The wavelength range of the wire grid type polarizing element is preferably in the range of 300 to 1000 nm, more preferably in the range of 400 to 800 nm, and even more preferably in the range of 420 to 680 nm.
The refractive index of the light transmissive substrate 1 is preferably 1.35 to 1.6, more preferably 1.4 to 1.58, and even more preferably 1.45 to 1.55.

光透過性基板１の材料としては、光硬化樹脂、熱硬化樹脂、熱可塑性樹脂、ガラスが例示できる。インプリント法で凸条１１及び凹溝１２を形成できる点から、光硬化樹脂又は熱硬化樹脂が好ましい。特に加工性、耐熱性及び耐久性に優れる点から光硬化樹脂が好ましい。 Examples of the material of the light transmissive substrate 1 include a photocurable resin, a thermosetting resin, a thermoplastic resin, and glass. A photo-curing resin or a thermosetting resin is preferable because the ridges 11 and the grooves 12 can be formed by the imprint method. In particular, a photocurable resin is preferable because it is excellent in processability, heat resistance and durability.

光硬化樹脂としては、生産性の点から、光ラジカル重合により光硬化しうる光硬化性組成物を光硬化した硬化物が好ましい。
光硬化性組成物は、例えば、単量体、光重合開始剤、溶剤、及び必要に応じた添加剤（例えば界面活性剤、重合禁止剤）を含む組成物である。例えば特許第５９７８７６１号公報の段落００２８〜００６０に記載されている光硬化性組成物を使用できる。 As the photocurable resin, a cured product obtained by photocuring a photocurable composition that can be photocured by photoradical polymerization is preferable from the viewpoint of productivity.
The photocurable composition is, for example, a composition containing a monomer, a photopolymerization initiator, a solvent, and an optional additive (for example, a surfactant, a polymerization inhibitor). For example, the photocurable composition described in paragraphs 0028 to 0060 of Japanese Patent No. 5978761 can be used.

金属層２の材料は、導電性の金属材料であればよく、耐蝕性の材料が好ましい。金属又は金属化合物が例示できる。
例えば、金属単体、合金、ドーパント又は不純物を含む金属が挙げられる。具体的には、アルミニウム、銀、クロム、マグネシウム、アルミニウム系合金、銀系合金が例示できる。
金属層２の材料は、可視光に対する反射率が高く、可視光の吸収が少なく、かつ導電率が高い点から、アルミニウム、アルミニウム系合金、銀、クロム、マグネシウム、銀系合金が好ましく、アルミニウム、アルミニウム系合金、銀系合金がより好ましい。 The material of the metal layer 2 may be a conductive metal material, and a corrosion-resistant material is preferable. A metal or a metal compound can be exemplified.
Examples include simple metals, alloys, dopants or metals containing impurities. Specifically, aluminum, silver, chromium, magnesium, aluminum alloys, and silver alloys can be exemplified.
The material of the metal layer 2 is preferably aluminum, an aluminum-based alloy, silver, chromium, magnesium, or a silver-based alloy because of its high reflectivity to visible light, low absorption of visible light, and high conductivity. Aluminum-based alloys and silver-based alloys are more preferable.

吸収層３は、光透過性樹脂中に色素又は顔料を含む材料で形成される。吸収層３を構成する前記光透過性樹脂の屈折率は、光透過性基板１の屈折率より高くてもよく、低くてもよい。両者の屈折率の差の絶対値は０．５以下が好ましく、０．３以下がより好ましい。前記光透過性樹脂の屈折率が光透過性基板１の屈折率より低いことがより好ましい。
吸収層３を構成する光透過性樹脂は、光硬化性樹脂、熱硬化性樹脂、又は熱可塑性樹脂が好ましく、凹溝へ充填しやすい点から、光硬化樹脂又は熱硬化性樹脂が好ましい。例えば特許第５９７８７６１号公報の段落００２８〜００６０に記載されている光硬化性樹脂を使用できる。 The absorbent layer 3 is formed of a material containing a dye or a pigment in a light-transmitting resin. The refractive index of the light-transmitting resin constituting the absorption layer 3 may be higher or lower than the refractive index of the light-transmitting substrate 1. The absolute value of the difference between the two refractive indexes is preferably 0.5 or less, more preferably 0.3 or less. It is more preferable that the refractive index of the light-transmitting resin is lower than the refractive index of the light-transmitting substrate 1.
The light-transmitting resin constituting the absorption layer 3 is preferably a photocurable resin, a thermosetting resin, or a thermoplastic resin, and a photocurable resin or a thermosetting resin is preferable because it is easy to fill the concave groove. For example, the photocurable resin described in paragraphs 0028 to 0060 of Japanese Patent No. 5978761 can be used.

吸収層３は光吸収材として色素又は顔料を含む。ワイヤグリッド型偏光子の使用波長の光の一部またはすべてを吸収する色素又は顔料を用いる。Ｒｐを下げたい波長帯に吸収をもつ光吸収材を適宜選択することが好ましい。色素又は顔料は１種でもよく、２種以上を併用してもよい。例えば、１種単独で黒色を呈する光吸収材が好適であるほか、２種以上を混合して黒色を呈する混合物も好適である。色素と顔料を併用してもよい。
色素の例としてはアゾ系、アントラキノン系、ペリノン系、メチン系、キノリン系、アジン系、オキサジン系、フタロシアニン系が挙げられる。
顔料の例としてはカーボンブラック、チタンブラック、ペリレン系顔料、金属酸化物が挙げられる。
吸収層３に対して、色素及び顔料の合計の含有量（以下、光吸収材濃度ともいう。）は１〜８０質量％が好ましく、５〜５０質量％がより好ましく、１０〜３０質量％がより好ましい。光吸収材濃度が上記範囲の下限値以上であると、Ｒｓの低下を抑えつつＲｐを低減させる効果が充分に得られやすく、上限値以下であるとワイヤグリッド型偏光子を折り曲げたり３次元形状に成型したときに吸収層３が変形しやすい。 The absorption layer 3 contains a dye or a pigment as a light absorber. A dye or pigment that absorbs part or all of the light of the wavelength used by the wire grid type transducer is used. It is preferable to appropriately select a light absorber having absorption in the wavelength band in which Rp is desired to be lowered. The dye or pigment may be used alone or in combination of two or more. For example, a light absorber that exhibits black color by itself is suitable, and a mixture that exhibits black color by mixing two or more types is also suitable. A dye and a pigment may be used in combination.
Examples of dyes include azo-based, anthraquinone-based, perinone-based, methine-based, quinoline-based, azine-based, oxazine-based, and phthalocyanine-based dyes.
Examples of pigments include carbon black, titanium black, perylene-based pigments, and metal oxides.
The total content of the dye and the pigment (hereinafter, also referred to as the light absorber concentration) is preferably 1 to 80% by mass, more preferably 5 to 50% by mass, and 10 to 30% by mass with respect to the absorption layer 3. More preferred. When the concentration of the light absorber is at least the lower limit of the above range, the effect of reducing Rp while suppressing the decrease of Rs can be sufficiently obtained, and when it is at least the upper limit, the wire grid type polarizing element is bent or the three-dimensional shape is formed. The absorbent layer 3 is easily deformed when molded into.

また吸収層３を構成する材料からなる厚さ１００ｎｍの硬化膜の透過率をＡ％、光吸収材を加えないほかは同じ材料からなる厚さ１００ｎｍの硬化膜の透過率をＢ％とするとき、（Ｂ−Ａ）／Ｂ×１００で算出される透過光低減率は、１〜２０％が好ましく、３〜１５％がより好ましい。なお、前記透過率Ａ、Ｂは４００〜７００ｎｍにおける平均透過率である。
透過光低減率が上記範囲の下限値以上であるとＲｓの低下を抑えつつＲｐを低減させる効果が充分に得られやすく、上限値以下であるとＴｐの低減が充分に抑えられる。 When the transmittance of the cured film having a thickness of 100 nm made of the material constituting the absorption layer 3 is A%, and the transmittance of the cured film having a thickness of 100 nm made of the same material except that the light absorber is not added is B%. , (BA) / B × 100, the transmitted light reduction rate is preferably 1 to 20%, more preferably 3 to 15%. The transmittances A and B are average transmittances at 400 to 700 nm.
When the transmitted light reduction rate is not less than the lower limit of the above range, the effect of reducing Rp while suppressing the decrease of Rs can be sufficiently obtained, and when it is not more than the upper limit, the reduction of Tp can be sufficiently suppressed.

本実施形態において、光透過性基板１の表面には、複数の凸条１１と複数の凹溝１２が交互に形成されている。複数の凸条１１はＺ方向に延在し互いに平行である。複数の凹溝１２はＺ方向に延在し互いに平行である。 In the present embodiment, a plurality of ridges 11 and a plurality of concave grooves 12 are alternately formed on the surface of the light transmissive substrate 1. The plurality of ridges 11 extend in the Z direction and are parallel to each other. The plurality of concave grooves 12 extend in the Z direction and are parallel to each other.

本実施形態において、凸条１１の、Ｚ方向に直交する断面における形状（断面形状）は、頂部１１ａに向かって幅が漸次縮小する略三角形である。
凸条１１の頂部１１ａは、Ｙ方向の高さが最も高い部分であり、Ｚ方向に連なって線をなしている。頂部１１ａを含む頂角は鋭角でもよく、丸みのある角でもよい。 In the present embodiment, the shape (cross-sectional shape) of the ridge 11 in the cross section orthogonal to the Z direction is a substantially triangle whose width gradually decreases toward the top 11a.
The top portion 11a of the ridge 11 is the portion having the highest height in the Y direction, and forms a continuous line in the Z direction. The apex angle including the apex 11a may be an acute angle or a rounded angle.

前記凸条１１は、断面形状において接線の傾きが一定である主側面１１ｂを有する。主側面１１ｂの下端を凸条１１の下端１１ｃとする。
複数の凸条１１の断面形状は均一である。前記凸条１１の下端１１ｃを通りＹ方向に直交する面を基準面とする。前記基準面における凸条１１のＸ方向の幅ａ、前記基準面における凸条１１のＸ方向のピッチｂ、及び基準面から凸条１１の頂部１１ａまでのＹ方向の高さｃはそれぞれ均一である。 The ridge 11 has a main side surface 11b in which the inclination of the tangent line is constant in the cross-sectional shape. The lower end of the main side surface 11b is the lower end 11c of the ridge 11.
The cross-sectional shape of the plurality of ridges 11 is uniform. A plane that passes through the lower end 11c of the ridge 11 and is orthogonal to the Y direction is used as a reference plane. The width a of the ridges 11 in the X direction on the reference plane, the pitch b of the ridges 11 in the X direction on the reference plane, and the height c in the Y direction from the reference plane to the top 11a of the ridges 11 are uniform. be.

凸条１１の下端１１ｃより下の部分が凹溝１２である。
本実施形態において、凹溝１２のＺ方向に直交する断面における形状（断面形状）は、底部１２ａに向かって溝幅が漸次縮小するテーパ面１２ｂを有する。Ｙ方向における位置が最も低い部分が底部１２ａである。凹溝１２の底部１２ａから前記基準面までのＹ方向の高さを、凹溝の深さｄとする。
本実施形態において、凹溝１２の前記断面形状は、テーパ面１２ｂの接線の傾きが一定であるＶ字状である。底部１２ａは鋭角でもよく、丸みを有する角でもよい。本実施形態において底部１２ａはＺ方向に連なって線をなしている。
複数の凹溝１２の断面形状は均一であり凹溝１２の深さｄは均一である。 The portion below the lower end 11c of the ridge 11 is the concave groove 12.
In the present embodiment, the shape (cross-sectional shape) of the concave groove 12 in the cross section orthogonal to the Z direction has a tapered surface 12b whose groove width gradually decreases toward the bottom portion 12a. The portion having the lowest position in the Y direction is the bottom portion 12a. The height in the Y direction from the bottom portion 12a of the concave groove 12 to the reference surface is defined as the depth d of the concave groove.
In the present embodiment, the cross-sectional shape of the concave groove 12 is a V shape in which the inclination of the tangent line of the tapered surface 12b is constant. The bottom portion 12a may have an acute angle or a rounded corner. In the present embodiment, the bottom portion 12a is continuous in the Z direction to form a line.
The cross-sectional shape of the plurality of concave grooves 12 is uniform, and the depth d of the concave grooves 12 is uniform.

凸条１１の下端１１ｃから凸条１１の頂部１１ａまでの面を、凸条１１の側面とする。凸条１１の頂部１１ａを挟む２つの側面を、第１の側面及び第２の側面とする。
金属層２は、凸条１１の第１の側面及び第２の側面のうち、少なくとも第１の側面の全面を被覆するように設けられる。第２の側面の一部、及び凹溝１２の底面の一部が金属層２で被覆されてもよい。
凸条１１の第２の側面は、全面が金属層２で被覆されることはなく、光透過性基板１が露出している露出面が存在する。 The surface from the lower end 11c of the ridge 11 to the top 11a of the ridge 11 is defined as the side surface of the ridge 11. The two side surfaces sandwiching the top portion 11a of the ridge 11 are referred to as a first side surface and a second side surface.
The metal layer 2 is provided so as to cover at least the entire surface of the first side surface and the second side surface of the ridge 11. A part of the second side surface and a part of the bottom surface of the groove 12 may be covered with the metal layer 2.
The entire surface of the second side surface of the ridge 11 is not covered with the metal layer 2, and there is an exposed surface on which the light transmissive substrate 1 is exposed.

凹溝１２の底面（テーパ面１２ｂ）上に吸収層３が設けられている。凹溝１２の底面から吸収層３の上面までの高さｆは、凹溝１２の底面から金属層２の上端までの高さｇ以下である。
また、前記高さｆは、凹溝１２の底面から凸条１１の頂部１１ａまでの高さ（ｃ＋ｄ）以下である。
本実施形態において、前記吸収層３の高さｆは、凹溝１２の最も深い底部１２ａから吸収層３の上面までの高さとする。 The absorption layer 3 is provided on the bottom surface (tapered surface 12b) of the concave groove 12. The height f from the bottom surface of the concave groove 12 to the upper surface of the absorption layer 3 is the height g or less from the bottom surface of the concave groove 12 to the upper end of the metal layer 2.
Further, the height f is equal to or less than the height (c + d) from the bottom surface of the concave groove 12 to the top portion 11a of the ridge 11.
In the present embodiment, the height f of the absorption layer 3 is the height from the deepest bottom portion 12a of the concave groove 12 to the upper surface of the absorption layer 3.

本実施形態のワイヤグリッド型偏光子は以下の方法で製造できる。
まず、光透過性の基材の表面に光硬化性組成物を塗布し、光インプリント法を用いて、前記光硬化性組成物の層に凸条及び凹溝を形成して光透過性基板を作製する。光インプリント法の後に、必要に応じてエッチングを行ってもよい。
光インプリント法は、例えば、電子線描画とエッチングとの組み合わせにより、複数の溝が互いに平行にかつ所定のピッチで形成されたモールドを作製し、前記モールドの溝を、基材の表面に塗布された光硬化性組成物に転写し、同時に前記光硬化性組成物を光硬化させる方法である。
例えば電子線描画及びエッチングにより作製したモールドを親モールド（マスターモールド）として、光インプリント法で複製した子モールドや孫モールドを、前記光硬化性組成物への転写に使用してもよい。 The wire grid type polarizing element of the present embodiment can be manufactured by the following method.
First, a photocurable composition is applied to the surface of a light-transmitting substrate, and ridges and grooves are formed in the layer of the photo-curable composition by using a photoimprint method to form a light-transmitting substrate. To make. Etching may be performed after the optical imprint method, if necessary.
In the optical imprint method, for example, a mold in which a plurality of grooves are formed in parallel with each other and at a predetermined pitch is produced by a combination of electron beam drawing and etching, and the grooves of the mold are applied to the surface of the base material. It is a method of transferring to the obtained photocurable composition and at the same time photocuring the photocurable composition.
For example, a mold produced by electron beam drawing and etching may be used as a parent mold (master mold), and a child mold or a grandchild mold duplicated by an optical imprint method may be used for transfer to the photocurable composition.

光透過性の基材としては、ガラス板（例えば、石英ガラス板、無アルカリガラス板）、樹脂（環状オレフィン樹脂、トリアセチルセルロース樹脂、アクリル樹脂、ポリイミド樹脂、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリジメチルシロキサン、透明フッ素樹脂）からなるフィルムが例示できる。 Examples of the light-transmitting base material include glass plates (for example, quartz glass plates and non-alkali glass plates), resins (cyclic olefin resin, triacetyl cellulose resin, acrylic resin, polyimide resin, polyethylene terephthalate, polybutylene terephthalate, and polyethylene na). A film made of phthalate, polydimethylsiloxane, transparent fluororesin) can be exemplified.

例えば、まず、図２（Ａ）に示すように、基材２１の表面に、未硬化の光硬化性組成物２２を塗布し、得ようとする凸条１１及び凹溝１２に対応する形状の凹凸が形成されたモールド２３を、光硬化性組成物２２に押しつける。この状態で放射線（例えば紫外線、電子線）を照射して光硬化性組成物を硬化させた後、図２（Ｂ）に示すように、モールド２３を離型して、光透過性基板１を得る。
光透過性基板１は基材２１と一体のまま金属層を形成できる。基材２１を後述の支持体としてもよい。必要により金属層の形成前又は形成後に、光透過性基板１と基材２１を分離してもよい。 For example, first, as shown in FIG. 2A, the surface of the base material 21 is coated with the uncured photocurable composition 22, and has a shape corresponding to the ridges 11 and the grooves 12 to be obtained. The uneven mold 23 is pressed against the photocurable composition 22. In this state, the photocurable composition is cured by irradiating it with radiation (for example, ultraviolet rays or electron beams), and then, as shown in FIG. 2B, the mold 23 is released to form the light transmissive substrate 1. obtain.
The light transmissive substrate 1 can form a metal layer while being integrated with the base material 21. The base material 21 may be used as a support described later. If necessary, the light transmissive substrate 1 and the base material 21 may be separated before or after the formation of the metal layer.

又は、図３（Ａ）、（Ｂ）に示すように、前記モールド２３とは形状が異なるモールド２４を用いる方法でも光透過性基板１を製造できる。具体的には、まず、基材２１上の光硬化性組成物２２にモールド２４を押し付けて光硬化させることにより、得ようとする凸条１１よりも大きい矩形の凸条２５が形成された硬化物を得る。この後、図３（Ｃ）に示すように、硬化物の凸条２５をエッチングして、目的の形状の凸条１１に加工して光透過性基板１を得る。 Alternatively, as shown in FIGS. 3A and 3B, the light transmissive substrate 1 can be manufactured by a method using a mold 24 having a shape different from that of the mold 23. Specifically, first, the mold 24 is pressed against the photocurable composition 22 on the base material 21 and photocured to form a rectangular ridge 25 larger than the ridge 11 to be obtained. Get things. After that, as shown in FIG. 3C, the ridges 25 of the cured product are etched and processed into ridges 11 having a desired shape to obtain a light-transmitting substrate 1.

このようにして作製した光透過性基板１に金属層２を設け、さらに凹溝１２内に吸収層３を設けることにより、本実施形態のワイヤグリッド型偏光子が得られる。
金属層２の形成方法は蒸着法が好ましい。蒸着法としては、物理蒸着法（ＰＶＤ）又は化学蒸着法（ＣＶＤ）が挙げられる。真空蒸着法、スパッタ法、又はイオンプレーティング法が好ましい。特に、付着させる微粒子の光透過性基板に対する入射方向の制御が容易である点で、真空蒸着法が好ましい。 By providing the metal layer 2 on the light transmissive substrate 1 thus produced and further providing the absorption layer 3 in the concave groove 12, the wire grid type polarizing element of the present embodiment can be obtained.
A thin-film deposition method is preferable as the method for forming the metal layer 2. Examples of the vapor deposition method include physical vapor deposition (PVD) and chemical vapor deposition (CVD). A vacuum deposition method, a sputtering method, or an ion plating method is preferable. In particular, the vacuum vapor deposition method is preferable because it is easy to control the incident direction of the fine particles to be adhered to the light-transmitting substrate.

本実施形態では、真空蒸着法による斜方蒸着法を用いて、凸条１１の第１の側面の全面とその近傍に、金属層２を蒸着させることが好ましい。
具体的には、図１に示すように、Ｚ方向に対して略直交し、かつＹ方向に対して第１の側面の側にθ（単位は「°」）の角度（蒸着角度）をなす方向（蒸着方向）から金属又は金属化合物を蒸着して金属層２を形成する。
蒸着量は、所定の金属層２の厚みが得られるように制御する。具体的には、光透過性基板１と同じ成膜環境下にテストピースを置き、テストピース上に成膜される金属層の厚みが目標値となるように蒸着量を制御する。テストピースとしては例えばガラス基板を使用する。膜厚は例えば触針式接触膜厚計で測定する。 In the present embodiment, it is preferable to deposit the metal layer 2 on the entire surface of the first side surface of the ridge 11 and in the vicinity thereof by using an orthorhombic vapor deposition method by a vacuum vapor deposition method.
Specifically, as shown in FIG. 1, it is substantially orthogonal to the Z direction and forms an angle (deposited angle) of θ (unit is “°”) on the side of the first side surface with respect to the Y direction. A metal or a metal compound is vapor-deposited from the direction (deposited direction) to form the metal layer 2.
The amount of thin-film deposition is controlled so that a predetermined thickness of the metal layer 2 can be obtained. Specifically, the test piece is placed in the same film formation environment as the light transmissive substrate 1, and the vapor deposition amount is controlled so that the thickness of the metal layer formed on the test piece becomes a target value. For example, a glass substrate is used as the test piece. The film thickness is measured, for example, with a stylus type contact film thickness meter.

吸収層３は、光透過性樹脂、色素又は顔料、及び溶剤を含む未硬化の樹脂組成物を凹溝１２内に塗布した後、硬化させる方法で形成できる。樹脂組成物は界面活性剤等の任意成分を含んでもよい。硬化前に、加熱乾燥して溶剤の一部又は全部を除去してもよい。
光透過性樹脂が、光硬化性樹脂である場合、樹脂組成物に光硬化開始剤を添加し、放射線（例えば紫外線、電子線）を照射して硬化させる。
樹脂組成物の塗布は、例えばバーコーター、ダイコーター、スピンコーター、グラビアコーター、スプレーコーター、インクジェットコーターを用いて行うことができる。樹脂組成物の塗布量によって、凹溝の底面から吸収層の上面までの高さｆを調整できる。 The absorption layer 3 can be formed by a method in which an uncured resin composition containing a light-transmitting resin, a dye or a pigment, and a solvent is applied into the groove 12 and then cured. The resin composition may contain an arbitrary component such as a surfactant. Prior to curing, it may be heat-dried to remove some or all of the solvent.
When the light-transmitting resin is a photo-curable resin, a photo-curing initiator is added to the resin composition, and the resin is cured by irradiating it with radiation (for example, ultraviolet rays or electron beams).
The resin composition can be applied using, for example, a bar coater, a die coater, a spin coater, a gravure coater, a spray coater, or an inkjet coater. The height f from the bottom surface of the concave groove to the top surface of the absorption layer can be adjusted by the amount of the resin composition applied.

本実施形態において、凸条１１のＸ方向の幅ａは１０〜１５０ｎｍが好ましく、２０〜１００ｎｍがより好ましく、３０〜６０ｎｍがさらに好ましい。
Ｘ方向における凸条１１のピッチｂは３０〜２００ｎｍが好ましく、５０〜１５０ｎｍがより好ましく、８０〜１００ｎｍがさらに好ましい。
前記ピッチｂに対する前記幅ａの比を表すａ／ｂは、０．２〜０．８が好ましく、０．３〜０．７がより好ましく、０．４〜０．６がさらに好ましい。
凸条１１のＹ方向の高さｃは５０〜２５０ｎｍが好ましく、７０〜２００ｎｍがより好ましく、９０〜１５０ｎｍがさらに好ましい。
前記幅ａに対する前記高さｃの比（アスペクト比）を表すｃ／ａは、１〜１０が好ましく、１．５〜５がより好ましく、２〜４がさらに好ましい。
凹溝１２の深さｄは１〜５０ｎｍが好ましく、３〜３０ｎｍがより好ましく、５〜１０ｎｍがさらに好ましい。
斜方蒸着法で金属層２を形成する際の、蒸着角度θは５〜６５°が好ましく、１０〜５０°がより好ましく、２０〜４０°がさらに好ましい。
前記高さ（ｃ＋ｄ）の１／２の位置における、金属層２のＸ方向の厚みｅは１５〜１００ｎｍが好ましく、２０〜８０ｎｍがより好ましく、２５〜５０ｎｍがさらに好ましい。 In the present embodiment, the width a of the ridge 11 in the X direction is preferably 10 to 150 nm, more preferably 20 to 100 nm, and even more preferably 30 to 60 nm.
The pitch b of the ridges 11 in the X direction is preferably 30 to 200 nm, more preferably 50 to 150 nm, and even more preferably 80 to 100 nm.
The a / b representing the ratio of the width a to the pitch b is preferably 0.2 to 0.8, more preferably 0.3 to 0.7, and even more preferably 0.4 to 0.6.
The height c of the ridge 11 in the Y direction is preferably 50 to 250 nm, more preferably 70 to 200 nm, and even more preferably 90 to 150 nm.
The c / a representing the ratio (aspect ratio) of the height c to the width a is preferably 1 to 10, more preferably 1.5 to 5, and even more preferably 2 to 4.
The depth d of the groove 12 is preferably 1 to 50 nm, more preferably 3 to 30 nm, and even more preferably 5 to 10 nm.
When the metal layer 2 is formed by the oblique vapor deposition method, the vapor deposition angle θ is preferably 5 to 65 °, more preferably 10 to 50 °, still more preferably 20 to 40 °.
The thickness e of the metal layer 2 in the X direction at the position of 1/2 of the height (c + d) is preferably 15 to 100 nm, more preferably 20 to 80 nm, and even more preferably 25 to 50 nm.

凹溝１２の底面から金属層２の上端までの高さｇに対する凹溝１２の底面から吸収層３の上面までの高さｆの比を表すｆ／ｇは、１以下であり、１未満が好ましく、０．８以下がより好ましく、０．５以下がさらに好ましい。ｆ／ｇが前記範囲であると、ｓ偏光の反射率Ｒｓの低下を抑制しやすく、ｐ偏光の反射率Ｒｐを下げやすい。
吸収層３は、凹溝１２の底面の全面を覆うことが好ましい。凹溝１２の底面から吸収層３の上面までの高さｆは、凹溝１２の深さｄ以上が好ましい。（ｆ−ｄ）は０ｎｍ以上が好ましく、１０ｎｍ以上がより好ましく、３０ｎｍ以上がさらに好ましい。凹溝１２の底面の全面を吸収層３で覆うと、ｐ偏光の反射率Ｒｐを低減しやすい。 F / g representing the ratio of the height f from the bottom surface of the concave groove 12 to the upper surface of the absorption layer 3 to the height g from the bottom surface of the concave groove 12 to the upper end of the metal layer 2 is 1 or less, and less than 1 is It is preferably 0.8 or less, more preferably 0.5 or less. When f / g is in the above range, it is easy to suppress a decrease in the reflectance Rs of s-polarized light, and it is easy to decrease the reflectance Rp of p-polarized light.
The absorption layer 3 preferably covers the entire bottom surface of the concave groove 12. The height f from the bottom surface of the concave groove 12 to the upper surface of the absorption layer 3 is preferably the depth d or more of the concave groove 12. (Fd) is preferably 0 nm or more, more preferably 10 nm or more, still more preferably 30 nm or more. When the entire bottom surface of the concave groove 12 is covered with the absorption layer 3, it is easy to reduce the reflectance Rp of p-polarized light.

また、吸収層３を構成する材料からなり、厚さが前記吸収層３の高さｆと同じである硬化膜の吸光度は０．００２〜０．３が好ましく、０．００５〜０．０５がより好ましく、０．００８〜０．０２５がさらに好ましい。前記範囲の下限値以上であるとＲｓの低下を抑えつつＲｐを低減させる効果が充分に得られやすく、上限値以下であるとＴｐの低減が充分に抑えられる。
本明細書において、吸光度は波長４００〜７００ｎｍにおける値であり、分光光度計を用いて測定できる。 Further, the absorbance of the cured film made of the material constituting the absorption layer 3 and having the same thickness as the height f of the absorption layer 3 is preferably 0.002 to 0.3, preferably 0.005 to 0.05. More preferably, 0.008 to 0.025 is even more preferable. When it is at least the lower limit of the above range, the effect of reducing Rp while suppressing the decrease of Rs can be sufficiently obtained, and when it is at least the upper limit, the decrease of Tp is sufficiently suppressed.
In the present specification, the absorbance is a value at a wavelength of 400 to 700 nm and can be measured using a spectrophotometer.

＜第２の実施形態＞
図４は、ワイヤグリッド型偏光子の第２の実施形態を模式的に示す断面図である。図１と同じ構成要素には同じ符号を付して説明を省略する。
第２の実施形態が第１の実施形態と異なる点は、光透過性基板１、金属層２、及び吸収層３を一括的に覆う樹脂層４を設けた点である。
樹脂層４を設けると入射光側（透過性基板１の凸条及び凹溝が設けられている表面側））に機能層を積層する際に、形状を維持しやすい。 <Second embodiment>
FIG. 4 is a cross-sectional view schematically showing a second embodiment of the wire grid type polarizing element. The same components as those in FIG. 1 are designated by the same reference numerals, and the description thereof will be omitted.
The second embodiment differs from the first embodiment in that the resin layer 4 that collectively covers the light-transmitting substrate 1, the metal layer 2, and the absorption layer 3 is provided.
When the resin layer 4 is provided, it is easy to maintain the shape when laminating the functional layer on the incident light side (the surface side where the ridges and grooves of the transmissive substrate 1 are provided).

樹脂層４は光透過性である。樹脂層４は、色素及び顔料をいずれも含まない。樹脂層４の屈折率は１．１０〜１．５０が好ましく、１．１５〜１．４０がより好ましく、１．１８〜１．３６がさらに好ましい。樹脂層４の屈折率は、光透過性基板１の屈折率より低いことが好ましい。その差は０．０５以上が好ましく、０．１〜０．４がより好ましく、０．１２〜０．３５がさらに好ましい。また、樹脂層４の屈折率は、吸収層３の屈折率より低いことが好ましい。その差は０．０５以上が好ましく、０．１〜０．４がより好ましく、０．１２〜０．３５がさらに好ましい。
金属層２の上端から樹脂層４の上面までの高さｈは、５ｎｍ以上が好ましく、５０ｎｍ以上がより好ましい。前記高さｈの上限は可撓性の点からは、５０μｍ以下が好ましく、１０μｍ以下がより好ましい。
本実施形態のワイヤグリッド型偏光子は、光透過性基板１を作製し、金属層２及び吸収層３を設けた後、これらを覆うように樹脂層４の材料を塗布し、硬化させる方法で製造できる。 The resin layer 4 is light transmissive. The resin layer 4 does not contain any dye or pigment. The refractive index of the resin layer 4 is preferably 1.10 to 1.50, more preferably 1.15 to 1.40, and even more preferably 1.18 to 1.36. The refractive index of the resin layer 4 is preferably lower than that of the light transmissive substrate 1. The difference is preferably 0.05 or more, more preferably 0.1 to 0.4, still more preferably 0.12 to 0.35. Further, the refractive index of the resin layer 4 is preferably lower than that of the absorption layer 3. The difference is preferably 0.05 or more, more preferably 0.1 to 0.4, still more preferably 0.12 to 0.35.
The height h from the upper end of the metal layer 2 to the upper surface of the resin layer 4 is preferably 5 nm or more, more preferably 50 nm or more. The upper limit of the height h is preferably 50 μm or less, more preferably 10 μm or less, from the viewpoint of flexibility.
The wire grid type polarizing element of the present embodiment is a method in which a light transmissive substrate 1 is prepared, a metal layer 2 and an absorption layer 3 are provided, and then the material of the resin layer 4 is applied and cured so as to cover them. Can be manufactured.

＜変形例＞
第１、２の実施形態において、凸条１１の断面形状は略三角形であるが、頂部１１ａがＹ方向に直交する平坦面である台形でもよい。
第１、２の実施形態において、凹溝１２の底面の断面形状はＶ字状であるが、テーパ面１２ｂとテーパ面１２ｂの間の底部にＹ方向に直交する平坦面が存在してもよい。また、テーパ面１２ｂが無い平坦面（ｄ＝０）であってもよい。
第１、２の実施形態において、金属層２の下端が吸収層３の上面より下方にあり、金属層２の一部が吸収層３で覆われているが、金属層２の下端が吸収層３の上面より上方にあってもよい。
第１、２の実施形態において、光透過性基板１の裏面（凸条及び凹溝が設けられている表面とは反対側の面）に、熱可塑性樹脂、ガラス等からなる支持体（図示略）を有していてもよい。ワイヤグリッド型偏光子の光学特性の点から、光透過性基板１の裏面上に支持体（以下、第１の支持体ともいう。）を有することが好ましい。支持体と光透過性基板１との屈折率の差（絶対値）は、０．１以下が好ましく、０．０５以下がより好ましい。支持体と光透過性基板１との屈折率の差が０．１以下であれば、ｐ偏光透過率の低下、ｓ偏光反射率の低下が抑えられる。さらに樹脂層４を設ける場合には、樹脂層の表面（光透過性基板１側とは反対側の面）上に支持体（以下、第２の支持体ともいう。）を設けてもよい。樹脂層と支持体（第２の支持体）は粘着剤で一体化されていることが好ましい。第１の支持体と第２の支持体は、材質が同じであってもよく、異なってもよい。 <Modification example>
In the first and second embodiments, the cross-sectional shape of the ridge 11 is substantially triangular, but it may be a trapezoid in which the top portion 11a is a flat surface orthogonal to the Y direction.
In the first and second embodiments, the cross-sectional shape of the bottom surface of the concave groove 12 is V-shaped, but a flat surface orthogonal to the Y direction may exist at the bottom portion between the tapered surface 12b and the tapered surface 12b. .. Further, it may be a flat surface (d = 0) without the tapered surface 12b.
In the first and second embodiments, the lower end of the metal layer 2 is below the upper surface of the absorption layer 3, and a part of the metal layer 2 is covered with the absorption layer 3, but the lower end of the metal layer 2 is the absorption layer. It may be above the upper surface of 3.
In the first and second embodiments, a support made of a thermoplastic resin, glass, or the like is formed on the back surface of the light transmissive substrate 1 (the surface opposite to the surface on which the ridges and grooves are provided) (not shown). ) May have. From the viewpoint of the optical characteristics of the wire grid type polarizing element, it is preferable to have a support (hereinafter, also referred to as a first support) on the back surface of the light transmissive substrate 1. The difference (absolute value) in the refractive index between the support and the light transmissive substrate 1 is preferably 0.1 or less, more preferably 0.05 or less. When the difference in the refractive index between the support and the light transmissive substrate 1 is 0.1 or less, the decrease in the p-polarized light transmittance and the decrease in the s polarized light reflectance can be suppressed. Further, when the resin layer 4 is provided, a support (hereinafter, also referred to as a second support) may be provided on the surface of the resin layer (the surface opposite to the light transmissive substrate 1 side). It is preferable that the resin layer and the support (second support) are integrated with an adhesive. The first support and the second support may be made of the same material or may be different.

前記実施形態によれば、吸収層３で凹溝１２の底面を覆い、金属層２の上端を覆わない構成により、後述の例に示されるように、Ｒｓの低下を抑えつつＲｐを低減できる。例えば、吸収層３を設けない場合と比べて、Ｒｓの低下の幅が使用波長範囲の平均で５％以下、かつＲｐの低下の幅が使用波長範囲の平均で０．１％以上を実現できる。
また吸収層３は、色素又は顔料を含む樹脂層であるため曲げ変形への追従性に優れる。特に、凹溝の幅が狭い場合にも、吸収層３の材料を凹溝内へ充填しやすい点、及びワイヤグリッド型偏光子を折り曲げたり３次元形状に成型したときに吸収層３が変形しやすい点で、吸収層３が色素を含有することがより好ましい。 According to the above embodiment, the absorption layer 3 covers the bottom surface of the concave groove 12 and does not cover the upper end of the metal layer 2, so that Rp can be reduced while suppressing a decrease in Rs, as shown in an example described later. For example, as compared with the case where the absorption layer 3 is not provided, the range of decrease in Rs can be 5% or less on average in the wavelength range used, and the range of decrease in Rp can be 0.1% or more on average in the wavelength range used. ..
Further, since the absorption layer 3 is a resin layer containing a dye or a pigment, it is excellent in followability to bending deformation. In particular, even when the width of the concave groove is narrow, the material of the absorption layer 3 can be easily filled in the concave groove, and the absorption layer 3 is deformed when the wire grid type polarizing element is bent or molded into a three-dimensional shape. It is more preferable that the absorption layer 3 contains a dye in terms of ease.

前記実施形態のワイヤグリッド型偏光子の用途の例としては、偏光ビームスプリッター、ディスプレイ用偏光板、偏光レンズ、ミラーディスプレイが挙げられる。 Examples of applications of the wire grid type polarizing element of the above embodiment include a polarizing beam splitter, a polarizing plate for a display, a polarizing lens, and a mirror display.

以下に実施例を用いて本発明をさらに詳しく説明するが、本発明はこれら実施例に限定されない。
＜測定方法＞
以下の測定方法を用いた。
［ｐ偏光透過率（Ｔｐ）の測定方法］
ｐ偏光透過率は、紫外可視分光光度計（日立分光社製、ＵＨ−４１５０）を用いて測定した。具体的には、測定対象のワイヤグリッド型偏光子と光源との間に、付属の偏光子を、ワイヤグリッド型偏光子の金属細線の長軸方向（Ｚ方向）と、付属の偏光子の吸収軸が並行となる向きにセットした。ワイヤグリッド型偏光子の表面側（凸条が形成された側）から、入射角度０°で偏光を入射して、ｐ偏光透過率を測定した。測定波長は、４２０ｎｍ〜６８０ｎｍとした。
［ｓ偏光反射率（Ｒｓ）の測定方法］
前記ｐ偏光透過率の測定方法において、付属の偏光子の向きを、ワイヤグリッド型偏光子の金属細線の長軸方向（Ｚ方向）と、付属の偏光子の吸収軸が直交する向きに変更した。ワイヤグリッド型偏光子の表面側（凸条が形成された側）から、入射角度５°で偏光を入射して、ｓ偏光反射率を測定した。測定波長は、４２０ｎｍ〜６８０ｎｍとした。
［ｐ偏光反射率（Ｒｐ）の測定方法］
前記ｐ偏光透過率の測定方法において、偏光の入射方向を、入射角度５°に変えてｐ偏光反射率を測定した。測定波長は４２０ｎｍ〜６８０ｎｍとした。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
<Measurement method>
The following measurement method was used.
[Measurement method of p-polarized light transmittance (Tp)]
The p-polarized light transmittance was measured using an ultraviolet-visible spectrophotometer (UH-4150, manufactured by Hitachi Spectroscopy Co., Ltd.). Specifically, the attached polarizing element is inserted between the wire grid type polarizing element to be measured and the light source in the long axis direction (Z direction) of the metal wire of the wire grid type polarizing element and the absorption of the attached polarizing element. The axes were set so that they were parallel to each other. Polarized light was incident at an incident angle of 0 ° from the surface side (the side where the ridges were formed) of the wire grid type polarizing element, and the p-polarized light transmittance was measured. The measurement wavelength was 420 nm to 680 nm.
[Measurement method of s polarization reflectance (Rs)]
In the method for measuring the p-polarization transmittance, the direction of the attached polarizing element is changed to the direction in which the long axis direction (Z direction) of the metal wire of the wire grid type polarizing element and the absorption axis of the attached polarizing element are orthogonal to each other. .. Polarized light was incident at an incident angle of 5 ° from the surface side (the side where the ridges were formed) of the wire grid type polarizing element, and the s polarization reflectance was measured. The measurement wavelength was 420 nm to 680 nm.
[Measurement method of p-polarized reflectance (Rp)]
In the method for measuring the p-polarized light transmittance, the incident direction of polarized light was changed to an incident angle of 5 °, and the p-polarized light reflectance was measured. The measurement wavelength was 420 nm to 680 nm.

＜材料＞
単量体１：新中村化学工業社製品名「ＮＫエステル Ａ−ＤＰＨ」、ジペンタエリスリトールヘキサアクリレート。
単量体２：新中村化学工業社製品名「ＮＫエステル Ａ−ＨＤ−Ｎ」、１，６−ヘキサンジオールジアクリレート。
単量体３：新中村化学工業社製品名「ＮＫエステル Ａ−ＴＭＭ−３ＬＭ−Ｎ」。
単量体４：ソルベイスペシャルティポリマーズジャパン株式会社製品名「ＭＤ７００」、フッ素系ジメタクリレート。
アゾ系色素１：オリエント化学工業社製品名「Ｏｌｉｂｌａｃｋ８６０」。
アジン系色素２：オリエント化学工業社製品名「ＶＡＬＩＦＡＳＴ１８２１」。
光重合開始剤１：チバスペシャリティーケミカルズ社製品名「ＩＲＧＡＣＵＲＥ９０７」。
光重合開始剤２：チバスペシャリティーケミカルズ社製品名「ＤＲ１１７３」。
含フッ素界面活性剤１：旭硝子社製、フルオロアクリレート（ＣＨ２＝ＣＨＣＯＯ（ＣＨ２）２（ＣＦ２）８Ｆ）とブチルアクリレートとのコオリゴマー、フッ素含有量約３０質量％、質量平均分子量約３０００。
溶剤１：イソプロピルアルコール。 <Material>
Monomer 1: Shin-Nakamura Chemical Industry Co., Ltd. Product name "NK ester A-DPH", dipentaerythritol hexaacrylate.
Monomer 2: Shin-Nakamura Chemical Industry Co., Ltd. Product name "NK ester A-HD-N", 1,6-hexanediol diacrylate.
Monomer 3: Shin Nakamura Chemical Industry Co., Ltd. Product name "NK Ester A-TMM-3LM-N".
Monomer 4: Solvay Specialty Polymers Japan Co., Ltd. Product name "MD700", Fluorine-based dimethacrylate.
Azo dye 1: Orient Chemical Industry Co., Ltd. Product name "Oliblack 860".
Adin-based dye 2: Orient Chemical Industry Co., Ltd. Product name "VALUESTAT 1821".
Photopolymerization Initiator 1: Chivas Specialty Chemicals Co., Ltd. Product name "IRGACURE907".
Photopolymerization Initiator 2: Product name "DR1173" manufactured by Ciba Specialty Chemicals.
Fluorine-containing surfactant 1: Co-oligomer of fluoroacrylate (CH 2 = CHCOO (CH 2 ) 2 (CF 2 ) 8 F) manufactured by Asahi Glass Co., Ltd., fluorine content of about 30% by mass, mass average molecular weight of about 3000.
Solvent 1: Isopropyl alcohol.

＜調製例１：光硬化性組成物の調製＞
単量体１の４０ｇ、単量体２の６０ｇ、光重合開始剤１の４．０ｇ、及び含フッ素界面活性剤１の０．１ｇを混合して光硬化性組成物を調製した。 <Preparation Example 1: Preparation of photocurable composition>
A photocurable composition was prepared by mixing 40 g of the monomer 1, 60 g of the monomer 2, 4.0 g of the photopolymerization initiator 1, and 0.1 g of the fluorine-containing surfactant 1.

＜調製例２：吸収層の樹脂組成物の調製＞
単量体２の１ｇ、アゾ系色素１の０．２５ｇ、光重合開始剤１の０．０４ｇ、及び含フッ素界面活性剤１の０．０１ｇを混合し、得られた混合物を、固形分濃度１質量％となるように、溶剤１で希釈して、吸収層の樹脂組成物１を得た。
本例で用いる単量体２の単独重合体の屈折率は１．５１である。
樹脂組成物１の、光吸収材濃度（色素の濃度）は１９質量％、厚さ１００ｎｍの硬化膜における透過光低減率は１０％、厚さ３０ｎｍの硬化膜の吸光度は０．０１であった。 <Preparation Example 2: Preparation of Resin Composition for Absorption Layer>
1 g of the monomer 2, 0.25 g of the azo dye 1, 0.04 g of the photopolymerization initiator 1, and 0.01 g of the fluorine-containing surfactant 1 were mixed, and the obtained mixture was obtained by mixing the solid content concentration. The resin composition 1 of the absorption layer was obtained by diluting with the solvent 1 so as to have a concentration of 1% by mass.
The refractive index of the homopolymer of the monomer 2 used in this example is 1.51.
The concentration of the light absorber (concentration of the dye) of the resin composition 1 was 19% by mass, the reduction rate of transmitted light in the cured film having a thickness of 100 nm was 10%, and the absorbance of the cured film having a thickness of 30 nm was 0.01. ..

＜調製例３：吸収層の樹脂組成物調製＞
単量体３の１ｇ、アジン系色素２の０．２ｇ、及び光重合開始剤１の０．０４ｇを混合し、得られた混合物を、固形分濃度１質量％となるように、溶剤１で希釈して、吸収層の樹脂組成物２を得た。
本例で用いる単量体３の単独重合体の屈折率は１．５２である。
樹脂組成物２の、光吸収材濃度は１７質量％、厚さ１００ｎｍの硬化膜における透過光低減率は７％、厚さ８０ｎｍの硬化膜の吸光度は０．０２であった。 <Preparation Example 3: Preparation of resin composition for absorption layer>
1 g of the monomer 3 and 0.2 g of the azine dye 2 and 0.04 g of the photopolymerization initiator 1 were mixed, and the obtained mixture was mixed with the solvent 1 so as to have a solid content concentration of 1% by mass. The mixture was diluted to obtain the resin composition 2 of the absorption layer.
The refractive index of the homopolymer of the monomer 3 used in this example is 1.52.
The concentration of the light absorber of the resin composition 2 was 17% by mass, the reduction rate of transmitted light in the cured film having a thickness of 100 nm was 7%, and the absorbance of the cured film having a thickness of 80 nm was 0.02.

＜調製例４：吸収層の樹脂組成物の調製＞
調製例３において、色素の配合量および固形分濃度を変更した。
単量体３の１ｇ、アジン系色素２の０．１ｇ、及び光重合開始剤１の０．０４ｇを混合し、得られた混合物を、固形分濃度２質量％となるように、溶剤１で希釈して、吸収層の樹脂組成物３を得た。
樹脂組成物３の、光吸収材濃度は９質量％、厚さ１００ｎｍの硬化膜における透過光低減率は１％、厚さ１６０ｎｍの硬化膜の吸光度は０．０２であった。 <Preparation Example 4: Preparation of Resin Composition for Absorption Layer>
In Preparation Example 3, the blending amount of the dye and the solid content concentration were changed.
1 g of the monomer 3 and 0.1 g of the azine dye 2 and 0.04 g of the photopolymerization initiator 1 were mixed, and the obtained mixture was mixed with the solvent 1 so as to have a solid content concentration of 2% by mass. The mixture was diluted to obtain the resin composition 3 of the absorption layer.
The concentration of the light absorber of the resin composition 3 was 9% by mass, the reduction rate of transmitted light in the cured film having a thickness of 100 nm was 1%, and the absorbance of the cured film having a thickness of 160 nm was 0.02.

＜調製例５：樹脂層の樹脂組成物の調製＞
単量体４の１ｇ、光重合開始剤２の０．０４ｇ、及び光重合開始剤１の０．００５ｇを混合して樹脂層の樹脂組成物を得た。 <Preparation Example 5: Preparation of Resin Composition of Resin Layer>
A resin composition of a resin layer was obtained by mixing 1 g of the monomer 4, 0.04 g of the photopolymerization initiator 2, and 0.005 g of the photopolymerization initiator 1.

＜製造例１：ワイヤグリッド型偏光子の製造＞
本例では、図２に示す製造方法で光透過性基板を作製し、金属層を形成した。
［光透過性基板の作製］
基材２１として、厚さ１００μｍの環状ポリオレフィンフィルム（日本ゼオン社製、ゼオノアフィルム、１００ｍｍ×１００ｍｍ）を用いた。
基材２１の表面に、調製例１で得た光硬化性組成物２２をスピンコート法により塗布し、厚さ５μｍの塗膜を形成した。
図２に示す形状の凹凸が形成されたシリコン製モールド２３を、凹部の全面が光硬化性組成物２２に接するように、２５℃にて０．５ＭＰａ（ゲージ圧）の押圧力で、光硬化性組成物２２の塗膜に押しつけた。
この状態を保持したまま、基材２１側から高圧水銀灯（周波数：１．５ｋＨｚ〜２．０ｋＨｚ、主波長光：２５５ｎｍ、３１５ｎｍ及び３６５ｎｍ、３６５ｎｍにおける照射エネルギー：１０００ｍＪ。）の光を１５秒間照射し、光硬化性組成物２２を硬化させた後、シリコン製モールドをゆっくり分離して、基材２１上に光透過性基板１を作製した。
光透過性基板１の屈折率は１．５２である。
［金属層の形成］
前記で得た光透過性基板１に下記の方法で金属層を形成した。
蒸着源に対向する光透過性基板１の傾きを変更可能な真空蒸着装置（昭和真空社製、ＳＥＣ−１６ＣＭ）を用い、光透過性基板１の凸条に斜方蒸着法にてアルミニウムを蒸着させ、金属層を形成した。蒸着角度θは２７°とした。 <Manufacturing Example 1: Manufacture of Wire Grid Type Polarizer>
In this example, a light-transmitting substrate was produced by the manufacturing method shown in FIG. 2 to form a metal layer.
[Manufacturing of light transmissive substrate]
As the base material 21, a cyclic polyolefin film having a thickness of 100 μm (Zeon Corporation, Zeonoa film, 100 mm × 100 mm) was used.
The photocurable composition 22 obtained in Preparation Example 1 was applied to the surface of the base material 21 by a spin coating method to form a coating film having a thickness of 5 μm.
The silicon mold 23 having the irregularities of the shape shown in FIG. 2 is photocured at 25 ° C. with a pressing force of 0.5 MPa (gauge pressure) so that the entire surface of the recesses is in contact with the photocurable composition 22. It was pressed against the coating film of the sex composition 22.
While maintaining this state, the light of a high-pressure mercury lamp (frequency: 1.5 kHz to 2.0 kHz, main wavelength light: 255 nm, 315 nm and 365 nm, irradiation energy at 365 nm: 1000 mJ) is irradiated from the base material 21 side for 15 seconds. After the photocurable composition 22 was cured, the silicon mold was slowly separated to prepare a light transmissive substrate 1 on the base material 21.
The refractive index of the light transmissive substrate 1 is 1.52.
[Formation of metal layer]
A metal layer was formed on the light transmissive substrate 1 obtained above by the following method.
Using a vacuum vapor deposition device (SEC-16CM, manufactured by Showa Vacuum Co., Ltd.) that can change the inclination of the light transmissive substrate 1 facing the vapor deposition source, aluminum is vapor-deposited on the ridges of the light transmissive substrate 1 by the oblique vapor deposition method. And formed a metal layer. The vapor deposition angle θ was 27 °.

＜実施例１＞
［吸収層の形成］
製造例１の方法で光透過性基板を作製し金属層を形成した後、調製例２で得た樹脂組成物を、バーコーターを用いて凹溝１２内に塗布し、８０℃で３分間乾燥させた。樹脂組成物の塗布量は乾燥膜厚（吸収層の高さｆ）が３０ｎｍとなるように設定した。
窒素雰囲気中で高圧水銀灯から紫外線を２０００ｍＪ／ｃｍ２で照射し、樹脂組成物を硬化させてワイヤグリッド型偏光子を作製した。得られたワイヤグリッド型偏光子の断面の走査型電子顕微鏡像を図５に示す。
本例において凸条の幅ａは４５ｎｍ、ピッチｂは９０ｎｍ、凸条の高さｃは１１０ｎｍ、凹溝の深さｄは１０ｎｍ、金属層の厚みｅは４０ｎｍ、吸収層の高さｆは３０ｎｍ、ｆ／ｇは０．１９である。
得られたワイヤグリッド型偏光子の、Ｔｐ、Ｒｓ及びＲｐの測定結果（波長４２０〜６８０ｎｍの平均値）、Ｒｓ／Ｒｐの算出結果、及び主な製造条件を表１に示す（以下、同様）。
また、Ｔｐ、Ｒｓ及びＲｐのスペクトルを、図７、図８、図９にそれぞれ実線で示す。
＜比較例１＞
本例は、吸収層を設けないほかは、実施例１と同じである。得られたワイヤグリッド型偏光子の断面の走査型電子顕微鏡像を図６に示す。
Ｔｐ、Ｒｓ及びＲｐのスペクトルを、図７、図８、図９にそれぞれ破線で示す。 <Example 1>
[Formation of absorption layer]
After preparing a light-transmitting substrate by the method of Production Example 1 and forming a metal layer, the resin composition obtained in Preparation Example 2 is applied into the groove 12 using a bar coater and dried at 80 ° C. for 3 minutes. I let you. The coating amount of the resin composition was set so that the dry film thickness (height f of the absorption layer) was 30 nm.
The resin composition was cured by irradiating ultraviolet rays at 2000 mJ / cm 2 from a high-pressure mercury lamp in a nitrogen atmosphere to prepare a wire grid type polarizing element. A scanning electron microscope image of a cross section of the obtained wire grid type polarizing element is shown in FIG.
In this example, the width a of the ridges a is 45 nm, the pitch b is 90 nm, the height c of the ridges is 110 nm, the depth d of the concave groove is 10 nm, the thickness e of the metal layer is 40 nm, and the height f of the absorption layer is 30 nm. , F / g is 0.19.
Table 1 shows the measurement results of Tp, Rs and Rp (average value at wavelengths of 420 to 680 nm), the calculation results of Rs / Rp, and the main manufacturing conditions of the obtained wire grid type polarizing element (hereinafter, the same applies). ..
The spectra of Tp, Rs and Rp are shown by solid lines in FIGS. 7, 8 and 9, respectively.
<Comparative Example 1>
This example is the same as that of the first embodiment except that the absorption layer is not provided. A scanning electron microscope image of a cross section of the obtained wire grid type polarizing element is shown in FIG.
The spectra of Tp, Rs and Rp are shown by broken lines in FIGS. 7, 8 and 9, respectively.

＜実施例２＞
本例では、調製例３で得た樹脂組成物を用いて吸収層を形成した。また、吸収層の高さｆが８０ｎｍとなるように設定した。ｆ／ｇは０．５であった。その他は実施例１と同じである。得られたワイヤグリッド型偏光子の断面の走査型電子顕微鏡像を図１０に示す。 <Example 2>
In this example, an absorption layer was formed using the resin composition obtained in Preparation Example 3. Further, the height f of the absorption layer was set to be 80 nm. f / g was 0.5. Others are the same as in Example 1. A scanning electron microscope image of a cross section of the obtained wire grid type polarizing element is shown in FIG.

＜比較例２＞
本例では、調製例４で得た樹脂組成物を用いて吸収層を形成した。また、吸収層の高さｆが１６０ｎｍとなるように設定した。ｆ／ｇは１．０１であった。その他は実施例１と同じである。得られたワイヤグリッド型偏光子の断面の走査型電子顕微鏡像を図１１に示す。 <Comparative Example 2>
In this example, an absorption layer was formed using the resin composition obtained in Preparation Example 4. Further, the height f of the absorption layer was set to be 160 nm. f / g was 1.01. Others are the same as in Example 1. A scanning electron microscope image of a cross section of the obtained wire grid type polarizing element is shown in FIG.

＜実施例３＞
本例では、図４に示す構成のワイヤグリッド型偏光子を作製した。
製造例１の方法で光透過性基板を作製し金属層を形成した後、実施例２と同様にして吸収層を形成した。
本例において凸条の幅ａは４５ｎｍ、ピッチｂは９０ｎｍ、凸条の高さｃは１１５ｎｍ、凹溝の深さｄは１０ｎｍ、金属層の厚みｅは４０ｎｍ、吸収層の高さｆは８０ｎｍ、ｆ／ｇは０．５である。
［樹脂層の形成］
吸収層を形成した後、調製例５で得た樹脂組成物を、バーコーターを用いて光透過性基板１の表面側の全面に塗布した。樹脂組成物の塗布量は、金属層の上端から樹脂層の上面までの高さｈが１０μｍとなるように設定した。窒素雰囲気中で高圧水銀灯から紫外線を４０００ｍＪ／ｃｍ２で照射し、樹脂組成物を硬化させて樹脂層を形成し、ワイヤグリッド型偏光子を得た。樹脂層の屈折率は１．３６である。 <Example 3>
In this example, a wire grid type polarizing element having the configuration shown in FIG. 4 was produced.
A light-transmitting substrate was produced by the method of Production Example 1 to form a metal layer, and then an absorption layer was formed in the same manner as in Example 2.
In this example, the width a of the ridges a is 45 nm, the pitch b is 90 nm, the height c of the ridges is 115 nm, the depth d of the concave groove is 10 nm, the thickness e of the metal layer is 40 nm, and the height f of the absorption layer is 80 nm. , F / g is 0.5.
[Formation of resin layer]
After forming the absorption layer, the resin composition obtained in Preparation Example 5 was applied to the entire surface side of the light transmissive substrate 1 using a bar coater. The coating amount of the resin composition was set so that the height h from the upper end of the metal layer to the upper surface of the resin layer was 10 μm. Ultraviolet rays were irradiated from a high-pressure mercury lamp at 4000 mJ / cm 2 in a nitrogen atmosphere to cure the resin composition to form a resin layer, and a wire grid type splitter was obtained. The refractive index of the resin layer is 1.36.

＜比較例３＞
本例は、吸収層を設けないほかは、実施例３と同じである。すなわち隣り合う凸条１１間の空間の全部に樹脂層（ｈ＝１０μｍ）が充填されている。 <Comparative Example 3>
This example is the same as that of the third embodiment except that the absorption layer is not provided. That is, the entire space between the adjacent ridges 11 is filled with the resin layer (h = 10 μm).

Figure 2022001890
Figure 2022001890

表１の結果に示されるように、ｆ／ｇが１以下となるように、凹溝の底面上に吸収層を設けた実施例１、２は、比較例１と比べて、Ｒｓをほぼ同等に維持しつつＲｐを低くでき、Ｒｓ／Ｒｐが向上した。一方、ｆ／ｇが１を超えた比較例２は、比較例１と比べてＲｓ／Ｒｐが低下した。
樹脂層を設けた場合も同様の効果が得られた。すなわち、ｆ／ｇが１以下となるように、凹溝の底面上に吸収層を設けた実施例３は、比較例３と比べて、Ｒｓをほぼ同等に維持しつつＲｐを低くでき、Ｒｓ／Ｒｐが向上した。 As shown in the results of Table 1, Examples 1 and 2 in which the absorption layer is provided on the bottom surface of the concave groove so that f / g is 1 or less have substantially the same Rs as those of Comparative Example 1. Rp could be lowered while maintaining the value, and Rs / Rp was improved. On the other hand, in Comparative Example 2 in which f / g exceeded 1, Rs / Rp was lower than that in Comparative Example 1.
The same effect was obtained when the resin layer was provided. That is, in Example 3 in which the absorption layer is provided on the bottom surface of the concave groove so that f / g is 1 or less, Rs can be lowered while maintaining almost the same Rs as in Comparative Example 3, and Rs. / Rp improved.

１ 光透過性基板
２ 金属層
３ 吸収層
４ 樹脂層
１１ 凸条
１１ａ 頂部
１１ｂ 主側面
１１ｃ 凸条の下端
１２ 凹溝
１２ａ 底部
１２ｂ テーパ面（底面） 1 Light-transmitting substrate 2 Metal layer 3 Absorbent layer 4 Resin layer 11 Convex 11a Top 11b Main side surface 11c Bottom of the convex 12 Concave groove 12a Bottom 12b Tapered surface (bottom surface)

Claims (2)

表面に、互いに平行な凸条と凹溝が所定のピッチで交互に形成された光透過性基板と、前記凸条の表面上に設けられた、金属又は金属化合物からなる金属層とを有し、
前記凹溝の底面上に、色素又は顔料を含む吸収層が設けられており、
前記凹溝の底面から前記吸収層の上面までの高さが、前記凹溝の底面から前記金属層の上端までの高さ以下である、ワイヤグリッド型偏光子。 It has a light-transmitting substrate in which ridges and grooves parallel to each other are alternately formed at a predetermined pitch on the surface, and a metal layer made of a metal or a metal compound provided on the surface of the ridges. ,
An absorption layer containing a dye or a pigment is provided on the bottom surface of the concave groove.
A wire grid type polarizing element in which the height from the bottom surface of the concave groove to the upper surface of the absorption layer is equal to or less than the height from the bottom surface of the concave groove to the upper end of the metal layer. 前記光透過性基板、前記金属層及び前記吸収層を覆う樹脂層を有する、請求項１に記載のワイヤグリッド型偏光子。 The wire grid type polarizing element according to claim 1, further comprising the light transmissive substrate, the metal layer, and the resin layer covering the absorption layer.
JP2018186781A 2018-10-01 2018-10-01 Wire grid type polarizer Pending JP2022001890A (en)

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