JP6724297B2 - Method for producing optical laminate, method for producing circularly polarizing plate, and method for producing organic electroluminescence display device - Google Patents
Method for producing optical laminate, method for producing circularly polarizing plate, and method for producing organic electroluminescence display device Download PDFInfo
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- JP6724297B2 JP6724297B2 JP2015107857A JP2015107857A JP6724297B2 JP 6724297 B2 JP6724297 B2 JP 6724297B2 JP 2015107857 A JP2015107857 A JP 2015107857A JP 2015107857 A JP2015107857 A JP 2015107857A JP 6724297 B2 JP6724297 B2 JP 6724297B2
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Description
本発明は、光学積層体の製造方法、当該製造方法により製造してなる光学積層体、光学異方性積層体、円偏光板、及び有機エレクトロルミネッセンス表示装置に関する。 The present invention relates to a method for producing an optical laminate, an optical laminate produced by the production method, an optically anisotropic laminate, a circularly polarizing plate, and an organic electroluminescence display device.
位相差板等の光学異方性を有するフィルムは、液晶表示装置及び有機エレクトロルミネッセンス（以下において「有機ＥＬ」と呼ぶことがある）表示装置等の表示装置の構成要素として、広く用いられている。特に、λ／４、λ／２等の所望の位相差を有する複数層の光学異方性層を備える光学積層体は、有機ＥＬ表示装置の反射防止フィルムとして用いられている（例えば特許文献１）。 A film having optical anisotropy such as a retardation plate is widely used as a constituent element of a display device such as a liquid crystal display device and an organic electroluminescence (hereinafter sometimes referred to as “organic EL”) display device. .. In particular, an optical laminate including a plurality of optically anisotropic layers having a desired retardation such as λ/4 and λ/2 is used as an antireflection film of an organic EL display device (for example, Patent Document 1). ).
光学異方性層を得るための方法の一つとして、液晶相を呈しうる化合物を、液晶相を呈した状態のまま固体のフィルムに成形する方法が知られている。そのような方法の例としては、重合性を有し且つ液晶相を呈しうる重合性液晶化合物を含む組成物を、適切な基材の表面に塗布して層とし、層内の重合性液晶化合物を配向させ、さらに配向させた状態を維持して重合させることにより、光学異方性を有するフィルムを形成する方法が挙げられる。このような液晶相を呈しうる化合物を配向させる方法としては、基材の表面に配向規制力を付与し、その上に液晶相を呈しうる化合物を含む組成物を塗布し、さらに配向に適した条件に置くことが一般的に行なわれる。基材の表面に配向規制力を付与する方法の例としては、光配向（例えば特許文献２〜４）およびラビング（例えば特許文献５〜７）による方法が挙げられる。また、基材として延伸処理を施されたフィルムを用いることにより、液晶化合物をフィルム上に配向させる方法も知られている（例えば特許文献８〜１０）。
As one of methods for obtaining an optically anisotropic layer, a method is known in which a compound capable of exhibiting a liquid crystal phase is molded into a solid film in the state of exhibiting the liquid crystal phase. As an example of such a method, a composition containing a polymerizable liquid crystal compound which is polymerizable and can exhibit a liquid crystal phase is applied to the surface of a suitable substrate to form a layer, and the polymerizable liquid crystal compound in the layer is formed. A method of forming a film having optical anisotropy by orienting and polymerizing while maintaining the oriented state. As a method for orienting a compound capable of exhibiting such a liquid crystal phase, an alignment regulating force is imparted to the surface of a substrate, a composition containing a compound capable of exhibiting a liquid crystal phase is applied thereon, and further suitable for orientation. Conditioning is generally done. Examples of the method for imparting the alignment regulating force to the surface of the base material include methods by photo-alignment (for example,
上に述べた従来技術により複数層の光学異方性層を有する光学積層体を製造する方法は、複数枚の基材の上にそれぞれの光学異方性層を形成しそれらを貼合する方法と、１層の基材の上に光学異方性層を順次形成する方法とに大別される。前者は、工程が煩雑であるという問題点がある。一方後者は、基材の直上に形成する１層目の光学異方性層には良好な品質を付与することが可能だが、２層目以上の光学異方層の形成においては、表面にスジが入る等の不具合が起きやすいという問題点がある。 The method for producing an optical laminate having a plurality of optically anisotropic layers by the above-mentioned conventional technique is a method of forming each optically anisotropic layer on a plurality of substrates and bonding them. And a method of sequentially forming an optically anisotropic layer on a single-layer substrate. The former has a problem that the process is complicated. On the other hand, the latter is capable of imparting good quality to the first optically anisotropic layer formed directly on the substrate, but when forming the second or more optically anisotropic layers, stripes are formed on the surface. There is a problem that troubles such as entering are likely to occur.
従って、本発明の目的は、高品質な複数層の光学異方性層を有する光学積層体を簡便且つ効率的に製造することができる、光学積層体の製造方法、並びに、高品質で簡便且つ効率的に製造できる光学積層体、光学異方性積層体、円偏光板、及び有機エレクトロルミネッセンス表示装置を提供することにある。 Therefore, an object of the present invention is to provide a method for producing an optical layered body, which can easily and efficiently produce an optical layered body having a plurality of high-quality optically anisotropic layers, and a high-quality, simple and An object of the present invention is to provide an optical laminate, an optically anisotropic laminate, a circularly polarizing plate, and an organic electroluminescence display device that can be efficiently manufactured.
本発明者は前記の課題を解決するべく検討した結果、特定の基材の上に光学異方性層を順次形成する方法において、第２の光学異方性層を形成する際に光配向層により配向規制力を付与し、さらに、各層を形成する操作の条件を特定のものとすることにより、上記課題を解決しうることを見出し、本発明を完成した。
すなわち、本発明によれば、以下のものが提供される。
As a result of studies to solve the above-mentioned problems, the present inventor has found that in a method of sequentially forming an optically anisotropic layer on a specific substrate, a photo-alignment layer is formed when the second optically anisotropic layer is formed. It was found that the above-mentioned problems can be solved by imparting an orientation regulating force by the above and further by making the conditions of the operation for forming each layer specific, and completed the present invention.
That is, according to the present invention, the following is provided.
〔１〕 光学積層体の製造方法であって、
長尺状の基材上に、直接、第１の液晶化合物を含有する第１の液晶組成物を塗布し、第１の液晶組成物の層を得る工程（Ｉ）、
前記第１の液晶組成物の層中の前記第１の液晶化合物を配向させ、前記第１の液晶組成物の層に不活性ガス雰囲気下で活性エネルギー線を照射し前記第１の液晶組成物を硬化させ、第１光学異方性層を形成する工程（ＩＩ）、
前記第１光学異方性層上に、直接、光配向材料を含む液を塗布して光配向材料を含む液の層を得て、不活性ガス雰囲気下、前記基材の幅手方向と異なる方向の照射偏光方向を有する偏光紫外線を前記光配向材料を含む液の層に照射し、光配向層を形成する工程（ＩＩＩ）、及び
前記光配向層上に、直接、第２の液晶化合物を含有する第２の液晶組成物を塗布して第２の液晶組成物の層を得て、前記第２の液晶組成物の層中の前記第２の液晶化合物を配向させ、前記第２の液晶組成物の層に活性エネルギー線を照射し前記第２の液晶組成物を硬化させ、第２光学異方性層を形成する工程（ＩＶ）
を含む、製造方法。
〔２〕 〔１〕に記載の光学積層体の製造方法であって、
前記工程（ＩＩＩ）における前記照射偏光方向が、前記幅手方向となす角度が１０〜２０°又は７０〜８０°である、製造方法。
〔３〕 〔１〕又は〔２〕に記載の光学積層体の製造方法であって、
前記工程（ＩＩ）および前記工程（ＩＩＩ）における照射の積算光量が１０００ｍＪ／ｃｍ２以上である、製造方法。
〔４〕 〔１〕〜〔３〕のいずれか１項に記載の製造方法により製造してなる光学積層体であって、
前記基材が、配向規制力を有し、かつ、配向軸方向が前記幅手方向と異なる方向にあり、
前記第１光学異方性層の遅相軸が前記基材の配向軸方向と平行で、かつ、
前記第１光学異方性層の遅相軸と前記第２光学異方性層の遅相軸とがなす角が５５°〜６５°である、光学積層体。
〔５〕 〔４〕に記載の光学積層体であって、
前記第１光学異方性層の、前記光配向層側の表面の鉛筆硬度がＢ以上であり、かつ、
前記光配向層の、前記第２光学異方性層側の表面の鉛筆硬度がＢ以上である、光学積層体。
〔６〕 〔４〕又は〔５〕に記載の光学積層体であって、
前記基材が延伸フィルムである、光学積層体。
〔７〕 〔４〕〜〔６〕のいずれか１項に記載の光学積層体であって、
前記基材が、脂環式構造含有重合体を含む樹脂のフィルムである、光学積層体。
〔８〕 〔４〕〜〔７〕のいずれか１項に記載の光学積層体であって、
前記第１光学異方性層及び前記第２光学異方性層の一方がλ／４波長板であり、他方がλ／２波長板である、光学積層体。
〔９〕 第１光学異方性層、光配向膜、及び第２光学異方性層をこの順に備える光学異方性積層体であって、
〔４〕〜〔８〕のいずれか１項に記載の光学積層体より前記基材を剥離してなる、光学異方性積層体。
〔１０〕 〔９〕に記載の光学異方性積層体と、長尺状の直線偏光子とをロールツーロールで貼合してなる円偏光板であって、
前記光学異方性積層体の、前記直線偏光子と貼合する側の前記光学異方性層が、λ／２波長板であり、
前記直線偏光子の透過軸と、前記直線偏光子と貼合する側の前記光学異方性層の遅相軸とがなす角が１０〜２０°又は７０〜８０°である、円偏光板。
〔１１〕 〔１０〕に記載の円偏光板を備える、有機エレクトロルミネッセンス表示装置。
[1] A method for producing an optical layered body, comprising:
A step (I) of directly applying a first liquid crystal composition containing a first liquid crystal compound onto a long substrate to obtain a layer of the first liquid crystal composition,
The first liquid crystal composition is prepared by aligning the first liquid crystal compound in the layer of the first liquid crystal composition, and irradiating the layer of the first liquid crystal composition with an active energy ray under an inert gas atmosphere. Curing (II) to form a first optically anisotropic layer (II),
A liquid containing a photo-alignment material is directly applied onto the first optically anisotropic layer to obtain a layer of a liquid containing the photo-alignment material, which is different from the width direction of the substrate in an inert gas atmosphere. Irradiation of polarized light having a polarization direction to the layer of the liquid containing the photo-alignment material to form a photo-alignment layer (III), and a second liquid crystal compound directly on the photo-alignment layer. The second liquid crystal composition is applied to obtain a layer of the second liquid crystal composition, and the second liquid crystal compound in the layer of the second liquid crystal composition is aligned to form the second liquid crystal. Step (IV) of irradiating the composition layer with active energy rays to cure the second liquid crystal composition to form a second optically anisotropic layer.
And a manufacturing method.
[2] The method for producing an optical laminate according to [1],
The manufacturing method, wherein the irradiation polarization direction in the step (III) forms an angle with the width direction of 10 to 20° or 70 to 80°.
[3] The method for producing an optical laminate according to [1] or [2],
The manufacturing method, wherein the integrated light amount of irradiation in the step (II) and the step (III) is 1000 mJ/cm 2 or more.
[4] An optical layered body manufactured by the manufacturing method according to any one of [1] to [3],
The base material has an alignment regulating force, and the alignment axis direction is in a direction different from the width direction,
The slow axis of the first optically anisotropic layer is parallel to the alignment axis direction of the substrate, and
An optical laminate, wherein an angle formed by the slow axis of the first optically anisotropic layer and the slow axis of the second optically anisotropic layer is 55° to 65°.
[5] The optical laminate according to [4],
The surface of the first optical anisotropic layer on the side of the photo-alignment layer has a pencil hardness of B or more, and
An optical laminate in which the pencil hardness of the surface of the photo-alignment layer on the side of the second optical anisotropic layer is B or more.
[6] The optical layered body according to [4] or [5],
An optical laminate in which the substrate is a stretched film.
[7] The optical layered body according to any one of [4] to [6],
An optical laminate, wherein the base material is a film of a resin containing an alicyclic structure-containing polymer.
[8] The optical laminate according to any one of [4] to [7],
An optical laminate, wherein one of the first optically anisotropic layer and the second optically anisotropic layer is a λ/4 wavelength plate, and the other is a λ/2 wavelength plate.
[9] An optically anisotropic laminate including a first optically anisotropic layer, a photo-alignment film, and a second optically anisotropic layer in this order,
An optically anisotropic laminate obtained by peeling the base material from the optical laminate according to any one of [4] to [8].
[10] A circularly polarizing plate obtained by laminating the optically anisotropic laminate according to [9] and a long linear polarizer by roll-to-roll,
The optically anisotropic layer on the side of the optically anisotropic laminate that is bonded to the linear polarizer is a λ/2 wavelength plate,
A circularly polarizing plate in which an angle formed by the transmission axis of the linear polarizer and the slow axis of the optically anisotropic layer on the side to be bonded to the linear polarizer is 10 to 20° or 70 to 80°.
[11] An organic electroluminescence display device including the circularly polarizing plate according to [10].
本発明の光学積層体の製造方法によれば、高品質な複数層の光学異方性層を有する光学積層体を簡便且つ効率的に製造することができる。また、本発明の光学積層体、光学異方性積層体、円偏光板、及び有機エレクトロルミネッセンス表示装置は、高品質で簡便且つ効率的に製造できる。 According to the method for producing an optical laminate of the present invention, it is possible to easily and efficiently produce an optical laminate having a plurality of high-quality optically anisotropic layers. Further, the optical layered body, the optically anisotropic layered body, the circularly polarizing plate and the organic electroluminescence display device of the present invention can be manufactured with high quality simply and efficiently.
以下、例示物及び実施形態を挙げて本発明について詳細に説明するが、本発明は以下に挙げる例示物及び実施形態に限定されるものではなく、本発明の請求の範囲及びその均等の範囲を逸脱しない範囲において任意に変更して実施してもよい。
本願において、「偏光板」、「λ／２波長板」、「λ／４波長板」及び「位相差板」といった板状の形状を有する部材は、剛直な部材に限られるものではなく、フィルム状の、可撓性を有するものとしうる。
本願において、構成要素の角度関係が「平行」「垂直」であるとは、別に断らない限り、本発明の効果を損ねない範囲での誤差を含みうる。例えば、５°以内、好ましくは３°以内、より好ましくは１°以内の誤差を含みうる。
また特に、本願において「略１５°」とは、１５°又はそれに近い角度であり、好ましくは１０〜２０°、より好ましくは１１〜１９°、さらにより好ましくは１２〜１８°である。一方、「略７５°」とは、７５°又はそれに近い角度であり、好ましくは７０〜８０°、より好ましくは７１〜７９°、さらにより好ましくは７２〜７８°である。
Hereinafter, the present invention will be described in detail with reference to examples and embodiments, but the present invention is not limited to the following examples and embodiments, and the scope of claims of the present invention and the equivalent range thereof. It may be arbitrarily modified and implemented within a range that does not deviate.
In the present application, the member having a plate shape such as a “polarizing plate”, a “λ/2 wavelength plate”, a “λ/4 wavelength plate” and a “retardation plate” is not limited to a rigid member, but a film. The shape may be flexible.
In the present application, the angular relationship of the constituent elements being “parallel” or “vertical” may include an error within a range that does not impair the effects of the present invention, unless otherwise specified. For example, it may include an error within 5°, preferably within 3°, and more preferably within 1°.
Further, in particular, in the present application, “approximately 15°” is 15° or an angle close thereto, preferably 10 to 20°, more preferably 11 to 19°, still more preferably 12 to 18°. On the other hand, “approximately 75°” is 75° or an angle close thereto, preferably 70 to 80°, more preferably 71 to 79°, and even more preferably 72 to 78°.
〔１．光学積層体の製造方法の概要〕
本発明の光学積層体の製造方法は、
長尺状の基材上に、直接、第１の液晶化合物を含有する第１の液晶組成物を塗布し、第１の液晶組成物の層を得る工程（Ｉ）、
第１の液晶組成物の層中の第１の液晶化合物を配向させ、第１の液晶組成物の層に不活性ガス雰囲気下で活性エネルギー線を照射し第１の液晶組成物を硬化させ、第１光学異方性層を形成する工程（ＩＩ）、
第１光学異方性層上に、直接、光配向材料を含む液を塗布して光配向材料を含む液の層を得て、不活性ガス雰囲気下、基材の幅手方向と異なる方向の照射偏光方向を有する偏光紫外線を光配向材料を含む液の層に照射し、光配向層を形成する工程（ＩＩＩ）、及び
光配向層上に、直接、第２の液晶化合物を含有する第２の液晶組成物を塗布して第２の液晶組成物の層を得て、第２の液晶組成物の層中の第２の液晶化合物を配向させ、第２の液晶組成物の層に活性エネルギー線を照射し第２の液晶組成物を硬化させ、第２光学異方性層を形成する工程（ＩＶ）
を含む。
[1. Outline of manufacturing method of optical laminate]
The manufacturing method of the optical layered body of the present invention,
A step (I) of directly applying a first liquid crystal composition containing a first liquid crystal compound onto a long substrate to obtain a layer of the first liquid crystal composition,
Aligning the first liquid crystal compound in the layer of the first liquid crystal composition, and irradiating the layer of the first liquid crystal composition with an active energy ray in an inert gas atmosphere to cure the first liquid crystal composition; A step (II) of forming a first optically anisotropic layer,
The liquid containing the photo-alignment material is directly applied onto the first optically anisotropic layer to obtain a layer of the liquid containing the photo-alignment material, and the layer in a direction different from the width direction of the substrate is provided in an inert gas atmosphere. A step (III) of forming a photo-alignment layer by irradiating a layer of a liquid containing a photo-alignment material with polarized ultraviolet light having an irradiation polarization direction, and a second step of directly containing the second liquid crystal compound on the photo-alignment layer. Is applied to obtain a layer of the second liquid crystal composition, the second liquid crystal compound in the layer of the second liquid crystal composition is aligned, and active energy is applied to the layer of the second liquid crystal composition. Step (IV) of irradiating a ray to cure the second liquid crystal composition to form a second optically anisotropic layer.
including.
〔２．工程（Ｉ）：基材〕
本発明において用いる基材は、長尺状の基材である。本願において「長尺状」の形状とは、幅に対して、少なくとも５倍以上の長さを有する形状をいい、好ましくは１０倍若しくはそれ以上の長さを有し、具体的にはロール状に巻き取られて保管又は運搬される程度の長さを有するフィルムの形状をいう。
[2. Step (I): Substrate]
The base material used in the present invention is a long base material. In the present application, the “long shape” means a shape having a length of at least 5 times or more the width, preferably having a length of 10 times or more, specifically a roll shape. The shape of a film that has a length such that it can be wound up and stored or transported.
基材の材料は、特に限定されず、種々の樹脂を用いうる。樹脂の例としては、各種の重合体を含む樹脂が挙げられる。当該重合体としては、脂環式構造含有重合体、セルロースエステル、ポリビニルアルコール、ポリイミド、ＵＶ透過アクリル、ポリカーボネート、ポリスルホン、ポリエーテルスルホン、エポキシ重合体、ポリスチレン、及びこれらの組み合わせが挙げられる。これらの中でも、透明性、低吸湿性、寸法安定性、軽量性等の観点から、脂環式構造含有重合体及びセルロースエステルが好ましく、脂環式構造含有重合体がより好ましい。 The material of the base material is not particularly limited, and various resins can be used. Examples of the resin include resins containing various polymers. Examples of the polymer include alicyclic structure-containing polymer, cellulose ester, polyvinyl alcohol, polyimide, UV transparent acrylic, polycarbonate, polysulfone, polyether sulfone, epoxy polymer, polystyrene, and combinations thereof. Among these, the alicyclic structure-containing polymer and the cellulose ester are preferable, and the alicyclic structure-containing polymer is more preferable, from the viewpoints of transparency, low hygroscopicity, dimensional stability, lightness, and the like.
基材は正の固有複屈折性を有する樹脂のフィルムであることが好ましい。正の固有複屈折性を有する樹脂を材料として用いた場合、配向規制力の高さ、強度の高さ、コストの低さ等の良好な特性を備えた基材を、容易に得ることができる。 The substrate is preferably a resin film having a positive intrinsic birefringence. When a resin having a positive intrinsic birefringence is used as a material, it is possible to easily obtain a base material having good properties such as high alignment regulation force, high strength, and low cost. ..
脂環式構造含有重合体は、繰り返し単位中に脂環式構造を有する非晶性の重合体であり、主鎖中に脂環式構造を含有する重合体及び側鎖に脂環式構造を含有する重合体のいずれも用いることができる。
脂環式構造としては、例えば、シクロアルカン構造、シクロアルケン構造等が挙げられるが、熱安定性等の観点からシクロアルカン構造が好ましい。
１つの脂環式構造の繰り返し単位を構成する炭素数に特に制限はないが、通常４〜３０個、好ましくは５〜２０個、より好ましくは６〜１５個である。
The alicyclic structure-containing polymer is an amorphous polymer having an alicyclic structure in the repeating unit, and a polymer having an alicyclic structure in the main chain and an alicyclic structure in the side chain. Any of the polymers contained can be used.
Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure, and the cycloalkane structure is preferable from the viewpoint of thermal stability and the like.
The number of carbon atoms constituting one repeating unit of the alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, and more preferably 6 to 15.
脂環式構造含有重合体中の脂環式構造を有する繰り返し単位の割合は使用目的に応じて適宜選択されるが、通常５０重量％以上、好ましくは７０重量％以上、より好ましくは９０重量％以上である。
脂環式構造を有する繰り返し単位が過度に少ないと、フィルムの耐熱性が低下するおそれがある。
The proportion of repeating units having an alicyclic structure in the alicyclic structure-containing polymer is appropriately selected according to the purpose of use, but is usually 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight. That is all.
When the repeating unit having an alicyclic structure is excessively small, the heat resistance of the film may be reduced.
脂環式構造含有重合体は、具体的には、（１）ノルボルネン重合体、（２）単環の環状オレフィン重合体、（３）環状共役ジエン重合体、（４）ビニル脂環式炭化水素重合体、及びこれらの水素添加物などが挙げられる。
これらの中でも、透明性や成形性の観点から、ノルボルネン重合体及びこれらの水素添加物がより好ましい。
Specific examples of the alicyclic structure-containing polymer include (1) norbornene polymer, (2) monocyclic cycloolefin polymer, (3) cyclic conjugated diene polymer, (4) vinyl alicyclic hydrocarbon. Examples thereof include polymers and hydrogenated products thereof.
Among these, norbornene polymers and hydrogenated products thereof are more preferable from the viewpoint of transparency and moldability.
ノルボルネン重合体としては、例えば、ノルボルネンモノマーの開環重合体、ノルボルネンモノマーと開環共重合可能なその他のモノマーとの開環共重合体、及びそれらの水素添加物；ノルボルネンモノマーの付加重合体、ノルボルネンモノマーと共重合可能なその他のモノマーとの付加共重合体などが挙げられる。
これらの中でも、透明性の観点から、ノルボルネンモノマーの開環重合体水素添加物が最も好ましい。
上記の脂環式構造含有重合体は、例えば特開２００２−３２１３０２号公報等に開示されている公知の重合体から選ばれる。
Examples of the norbornene polymer include ring-opening polymers of norbornene monomers, ring-opening copolymers of norbornene monomers with other monomers capable of ring-opening copolymerization, and hydrogenated products thereof; addition polymers of norbornene monomers, Examples thereof include addition copolymers of norbornene monomers and other copolymerizable monomers.
Among these, the hydrogenated product of a ring-opening polymer of a norbornene monomer is most preferable from the viewpoint of transparency.
The alicyclic structure-containing polymer is selected from the known polymers disclosed in, for example, JP-A-2002-321302.
脂環式構造含有重合体は、そのガラス転移温度が、好ましくは８０℃以上、より好ましくは１００〜２５０℃の範囲である。
ガラス転移温度がこのような範囲にある脂環式構造含有重合体は、高温下での使用における変形や応力が生じることがなく耐久性に優れる。
The glass transition temperature of the alicyclic structure-containing polymer is preferably 80° C. or higher, more preferably 100 to 250° C.
The alicyclic structure-containing polymer having a glass transition temperature in such a range has excellent durability without causing deformation or stress during use at high temperature.
脂環式構造含有重合体の分子量は、溶媒としてシクロヘキサン（樹脂が溶解しない場合にはトルエン）を用いたゲル・パーミエーション・クロマトグラフィー（以下、「ＧＰＣ」と略す。）で測定したポリイソプレン換算（溶媒がトルエンのときは、ポリスチレン換算）の重量平均分子量（Ｍｗ）で、通常１０，０００〜１００，０００、好ましくは２５，０００〜８０，０００、より好ましくは２５，０００〜５０，０００である。
重量平均分子量がこのような範囲にあるときに、フィルムの機械的強度及び成形加工性が高度にバランスされ好適である。
The molecular weight of the alicyclic structure-containing polymer is the polyisoprene conversion measured by gel permeation chromatography (hereinafter, abbreviated as "GPC") using cyclohexane (toluene when the resin does not dissolve) as a solvent. The weight average molecular weight (Mw) in terms of polystyrene (when the solvent is toluene) is usually 10,000 to 100,000, preferably 25,000 to 80,000, and more preferably 25,000 to 50,000. is there.
When the weight average molecular weight is in such a range, the mechanical strength and the moldability of the film are highly balanced, which is preferable.
脂環式構造含有重合体の分子量分布（重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ））は特に制限されないが、通常１〜１０、好ましくは１〜４、より好ましくは１．２〜３．５の範囲である。 The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the alicyclic structure-containing polymer is not particularly limited, but is usually 1 to 10, preferably 1 to 4, and more preferably 1.2 to 3 The range is 0.5.
脂環式構造含有重合体を含む樹脂は、その分子量２，０００以下の樹脂成分（すなわち、オリゴマー成分）の含有量が、好ましくは５重量％以下、より好ましくは３重量％以下、さらに好ましくは２重量％以下である。
オリゴマー成分の量が前記範囲内にあると、表面における微細な凸部の発生が減少し、厚みむらが小さくなり面精度が向上する。
オリゴマー成分の量を低減するためには、重合触媒や水素化触媒の選択、重合、水素化等の反応条件、樹脂を成形用材料としてペレット化する工程における温度条件、等を最適化すればよい。
オリゴマーの成分量は、前述のＧＰＣによって測定することができる。
The resin containing the alicyclic structure-containing polymer has a content of a resin component (that is, an oligomer component) having a molecular weight of 2,000 or less, preferably 5% by weight or less, more preferably 3% by weight or less, and further preferably It is 2% by weight or less.
When the amount of the oligomer component is within the above range, the generation of fine projections on the surface is reduced, the thickness unevenness is reduced, and the surface accuracy is improved.
In order to reduce the amount of the oligomer component, the selection of the polymerization catalyst or hydrogenation catalyst, the reaction conditions such as polymerization and hydrogenation, the temperature condition in the step of pelletizing the resin as a molding material, etc. may be optimized. ..
The component amount of the oligomer can be measured by the above-mentioned GPC.
基材の厚みは特に制限されないが、生産性の向上、薄型化及び軽量化を容易にする観点から、その厚みは、通常１〜１０００μｍ、好ましくは５〜３００μｍ、より好ましくは３０〜１００μｍである。 The thickness of the base material is not particularly limited, but the thickness is usually 1 to 1000 μm, preferably 5 to 300 μm, and more preferably 30 to 100 μm from the viewpoint of facilitating productivity improvement, thinning, and weight reduction. ..
脂環式構造含有重合体を含む樹脂は、脂環式構造含有重合体のみからなってもよいが、本発明の効果を著しく損なわない限り、任意の配合剤を含んでもよい。脂環式構造含有重合体を含む樹脂中の、脂環式構造含有重合体の割合は、好ましくは７０重量％以上、より好ましくは８０重量％以上である。
脂環式構造含有重合体を含む樹脂の好適な具体例としては、日本ゼオン社製「ゼオノア１４２０、ゼオノア１４２０Ｒ」を挙げうる。
The resin containing the alicyclic structure-containing polymer may be composed of only the alicyclic structure-containing polymer, but may contain any compounding agent as long as the effects of the present invention are not significantly impaired. The proportion of the alicyclic structure-containing polymer in the resin containing the alicyclic structure-containing polymer is preferably 70% by weight or more, more preferably 80% by weight or more.
Preferable specific examples of the resin containing the alicyclic structure-containing polymer include “Zeonor 1420 and Zeonor 1420R” manufactured by Nippon Zeon Co., Ltd.
セルロースエステルとしては、セルロースの低級脂肪酸エステル（例：セルロースアセテート、セルロースアセテートブチレートおよびセルロースアセテートプロピオネート）が代表的である。低級脂肪酸は、１分子あたりの炭素原子数６以下の脂肪酸を意味する。セルロースアセテートには、トリアセチルセルロース（ＴＡＣ）やセルロースジアセテート（ＤＡＣ）が含まれる。 As the cellulose ester, a lower fatty acid ester of cellulose (eg, cellulose acetate, cellulose acetate butyrate and cellulose acetate propionate) is representative. The lower fatty acid means a fatty acid having 6 or less carbon atoms per molecule. Cellulose acetate includes triacetyl cellulose (TAC) and cellulose diacetate (DAC).
セルロースアセテートの酢化度は、５０〜７０％が好ましく、特に５５〜６５％が好ましい。重量平均分子量７００００〜１２００００が好ましく、特に８００００〜１０００００が好ましい。また、上記セルロースアセテートは、酢酸だけでなく上記酢化度を満足する限り、一部プロピオン酸、酪酸等の脂肪酸でエステル化されていても良い。また、基材を構成する樹脂は、セルロースアセテートと、セルロースアセテート以外のセルロースエステル（セルロースプロピオネート及びセルロースブチレート等）とを組み合わせて含んでも良い。その場合、これらのセルロースエステルの全体が、上記酢化度を満足することが好ましい。 The acetylation degree of cellulose acetate is preferably 50 to 70%, and particularly preferably 55 to 65%. The weight average molecular weight is preferably 70,000 to 120,000, particularly preferably 80,000 to 100,000. The cellulose acetate may be partially esterified with a fatty acid such as propionic acid and butyric acid as long as it satisfies the acetic acid degree as well as acetic acid. Further, the resin constituting the base material may include a combination of cellulose acetate and a cellulose ester other than cellulose acetate (eg, cellulose propionate and cellulose butyrate). In that case, it is preferable that all of these cellulose esters satisfy the above acetylation degree.
基材として、トリアセチルセルロースのフィルムを用いる場合、かかるフィルムとしては、トリアセチルセルロースを低温溶解法あるいは高温溶解法によってジクロロメタンを実質的に含まない溶剤に溶解することで調製されたトリアセチルセルロースドープを用いて作成されたトリアセチルセルロースフィルムが、環境保全の観点から特に好ましい。トリアセチルセルロースのフィルムは、共流延法により作製しうる。共流延法は、トリアセチルセルロースの原料フレークを溶媒に溶解し、これに必要に応じて任意の添加剤を添加し溶液（ドープ）を調製し、当該ドープをドープ供給手段（ダイ）から支持体の上に流延し、流延物をある程度乾燥して剛性が付与された時点でフィルムとして支持体から剥離し、当該フィルムをさらに乾燥して溶媒を除去することにより行いうる。原料フレークを溶解する溶媒の例としては、ハロゲン化炭化水素類（ジクロロメタン等）、アルコール類（メタノール、エタノール、ブタノール等）、エステル類（蟻酸メチル、酢酸メチル等）、エーテル類（ジオキサン、ジオキソラン、ジエチルエーテル等）等が挙げられる。ドープに添加する添加剤の例としては、レターデーション上昇剤、可塑剤、紫外線吸収剤、劣化防止剤、滑り剤、剥離促進剤等が挙げられる。ドープを流延する支持体の例としては、水平式のエンドレスの金属ベルト、及び回転するドラムが挙げられる。流延に際しては、単一のドープを単層流延することもできるが、複数の層を共流延することもできる。複数の層を共流延する場合、例えば、低濃度のセルロースエステルドープの層と、そのおもて面及び裏面に接して設けられた高濃度のセルロースエステルドープの層が形成されるよう、複数のドープを順次流延しうる。フィルムを乾燥して溶媒を除去する手段の例としては、フィルムを搬送して、内部を乾燥に適した条件に設定した乾燥部を通過させる手段が挙げられる。 When a film of triacetyl cellulose is used as a substrate, such a film may be a triacetyl cellulose dope prepared by dissolving triacetyl cellulose in a solvent substantially free of dichloromethane by a low temperature dissolution method or a high temperature dissolution method. A triacetyl cellulose film produced by using is particularly preferable from the viewpoint of environmental protection. A film of triacetyl cellulose can be produced by a co-casting method. In the co-casting method, raw material flakes of triacetyl cellulose are dissolved in a solvent, and if necessary, any additive is added to prepare a solution (dope), and the dope is supported from a dope supply means (die). It can be carried out by casting on a body, peeling the cast product as a film from the support at a time when the cast product is dried to some extent to give rigidity, and further drying the film to remove the solvent. Examples of the solvent for dissolving the raw material flakes include halogenated hydrocarbons (dichloromethane etc.), alcohols (methanol, ethanol, butanol etc.), esters (methyl formate, methyl acetate etc.), ethers (dioxane, dioxolane, etc.). Diethyl ether, etc.) and the like. Examples of the additive added to the dope include a retardation increasing agent, a plasticizer, an ultraviolet absorber, a deterioration preventing agent, a slip agent, and a peeling accelerator. Examples of the support on which the dope is cast include a horizontal endless metal belt and a rotating drum. Upon casting, a single dope can be cast as a single layer, or a plurality of layers can be cast as a co-cast. When co-casting a plurality of layers, for example, a low-concentration cellulose ester dope layer and a high-concentration cellulose ester dope layer provided in contact with the front surface and the back surface thereof to form a plurality of layers. Can be sequentially cast. Examples of means for drying the film to remove the solvent include means for transporting the film and passing it through a drying section in which conditions suitable for drying are passed.
トリアセチルセルロースのフィルムの好ましい例としては、ＴＡＣ−ＴＤ８０Ｕ（富士写真フィルム（株）製）等の公知のもの、及び発明協会公開技報公技番号２００１−１７４５号にて公開されたものが挙げられる。トリアセチルセルロースのフィルムの厚みは特に限定されないが、３０〜１５０μｍが好ましく、４０〜１３０μｍがより好ましく、７０〜１２０μｍが更に好ましい。 Preferable examples of the triacetyl cellulose film include known ones such as TAC-TD80U (manufactured by Fuji Photo Film Co., Ltd.) and those disclosed in JIII Journal of Technical Disclosure No. 2001-1745. To be The thickness of the triacetyl cellulose film is not particularly limited, but is preferably 30 to 150 μm, more preferably 40 to 130 μm, and further preferably 70 to 120 μm.
基材は、透明性に優れることが、製造工程の自由度を高める上で好ましい。具体的には、基材の全光線透過率は、好ましくは８０％以上、より好ましくは８５％以上、特に好ましくは８８％以上である。基材の全光線透過率は、紫外・可視分光計を用いて、波長４００ｎｍ〜７００ｎｍの範囲で測定しうる。 It is preferable that the base material has excellent transparency in order to increase the degree of freedom in the manufacturing process. Specifically, the total light transmittance of the base material is preferably 80% or more, more preferably 85% or more, and particularly preferably 88% or more. The total light transmittance of the substrate can be measured using a UV-visible spectrometer in the wavelength range of 400 nm to 700 nm.
長尺状の基材は、好ましくは、ロール状の形状として調製し、これを使用時に繰り出すことにより、本発明の製造方法に供しうる。 The long base material is preferably prepared in the shape of a roll and can be fed to the production method of the present invention by feeding it out at the time of use.
好ましい態様において、基材は、配向規制力を有する。配向規制力は、この上に形成される液晶組成物の層における液晶化合物の配向を規制する能力である。基材への配向規制力の付与は、延伸前の基材を延伸し、延伸基材とすることにより、好ましく行いうる。延伸基材においては、基材を構成する分子が配向し、当該配向軸方向に配向規制力が発現しうる。このように延伸により配向規制力を付与することにより、高品質な光学異方性層の配向を達成しうる基材を簡便に製造することができる。 In a preferred embodiment, the base material has an orientation regulating force. The alignment control force is the ability to control the alignment of the liquid crystal compound in the layer of the liquid crystal composition formed thereon. The orientation regulating force may be applied to the base material by stretching the base material before stretching to obtain a stretched base material. In the stretched base material, the molecules constituting the base material are oriented, and an orientation regulating force can be expressed in the orientation axis direction. By thus imparting the orientation regulating force by stretching, it is possible to easily manufacture a substrate capable of achieving orientation of a high-quality optically anisotropic layer.
好ましい態様において、基材の配向軸方向は、基材の幅手方向と異なる方向にある。基材の配向軸と基材の幅手方向とがなす角度は、具体的には０°超９０°未満としうる。このような範囲の角度において配向軸を有することにより、本発明の光学積層体を、円偏光板等の効率的な製造を可能にする材料とすることができる。
より具体的には、基材の配向軸と基材の幅手方向とがなす角度を、略７５°又は略１５°といった特定の範囲とすることにより、広帯域反射防止フィルムの材料として有用に用いうる光学積層体を、効率的に製造することができる。
In a preferred embodiment, the orientation axis direction of the substrate is different from the width direction of the substrate. The angle formed by the orientation axis of the base material and the width direction of the base material may be specifically more than 0° and less than 90°. By having the orientation axis at an angle in such a range, the optical layered body of the present invention can be used as a material that enables efficient production of a circularly polarizing plate or the like.
More specifically, the angle formed by the orientation axis of the base material and the width direction of the base material is set to a specific range such as about 75° or about 15°, so that it can be effectively used as a material for a broadband antireflection film. The optical layered product which can be obtained can be manufactured efficiently.
延伸前基材の延伸は、斜め延伸のみでもよく、横延伸（基材の幅手方向への延伸）のみでもよく、縦延伸（基材の長手方向への延伸）のみでもよく、又はこれらの延伸を組み合わせて行ってもよい。延伸倍率は、基材表面に配向規制力が生じる範囲で適宜設定しうる。基材が正の固有複屈折性を有する樹脂を材料として用いた場合、延伸方向に分子が配向して延伸方向に配向軸が発現する。延伸は、テンター延伸機などの既知の延伸機を用いて行いうる。 The stretching of the base material before stretching may be only diagonal stretching, transverse stretching (stretching in the width direction of the substrate), longitudinal stretching (stretching in the longitudinal direction of the substrate), or these. The stretching may be combined. The stretching ratio can be appropriately set within the range where the alignment regulating force is generated on the surface of the base material. When a resin whose base material has a positive intrinsic birefringence is used as a material, molecules are oriented in the stretching direction and an orientation axis is developed in the stretching direction. Stretching can be performed using a known stretching machine such as a tenter stretching machine.
基材の面内方向の位相差Ｒｅは、好ましくは１０ｎｍ以上、より好ましくは５０ｎｍ以上であり、一方好ましくは５００ｎｍ以下であり、より好ましくは３００ｎｍ以下である。基材の複屈折Δｎの下限は、好ましくは０．００００５０以上、より好ましくは０．００００７０以上であり、一方、基材の複屈折Δｎの上限は好ましくは０．００７５００以下、より好ましくは０．００７０００以下である。特に、基材の材料として、上に述べた脂環式構造含有重合体を含む樹脂又はトリアセチルセルロースを含む樹脂を用い、当該範囲内の光学特性を付与することにより、基材の厚み方向全体に亘って分子ダイレクターが略均一に配向し、良好な配向規制力を基材表面に与えることができる。 The retardation Re in the in-plane direction of the substrate is preferably 10 nm or more, more preferably 50 nm or more, while preferably 500 nm or less, more preferably 300 nm or less. The lower limit of the birefringence Δn of the substrate is preferably 0.000050 or more, more preferably 0.000070 or more, while the upper limit of the birefringence Δn of the substrate is preferably 0.007500 or less, more preferably 0. It is 007000 or less. In particular, by using a resin containing the alicyclic structure-containing polymer described above or a resin containing triacetyl cellulose as the material of the base material, and by imparting optical properties within the range, the entire thickness direction of the base material can be improved. The molecular director can be oriented substantially uniformly over the entire length, and a good orientation control force can be applied to the surface of the substrate.
〔３．工程（Ｉ）〕
本発明の光学積層体の製造方法の工程（Ｉ）では、基材上に、直接、第１の液晶組成物を塗布し、第１の液晶組成物の層を得る。
[3. Process (I)]
In step (I) of the method for producing an optical layered body of the present invention, the first liquid crystal composition is directly applied onto the substrate to obtain a layer of the first liquid crystal composition.
基材上への、液晶組成物の「直接」の塗布とは、基材の表面に、他の層を介さずに液晶組成物を塗布することである。配向規制力を有する基材を採用し、その表面に液晶組成物を直接塗布すると、所望の方向に遅相軸を有する光学異方性層を得ることができる。
液晶組成物を基材上に塗布する場合、基材を適度の張力（通常、１００〜５００Ｎ／ｍ）でテンションを掛けて、基材の搬送ばたつきを少なくし平面性を維持したまま塗布することが好ましい。平面性とは、基材の幅手方向および搬送方向に垂直な上下方向の振れ量であり、理想的には０ｍｍであるが、通常、１ｍｍ以下である。
また、液晶組成物を塗布する側の基材面の表面粗さ（Ｒａ）は、好ましくは０．０５μｍ以下、より好ましくは０．００５μｍ以下である。この上限以下であれば、塗布ムラが少なく、平面性に優れた光学異方性層を得ることができる。表面粗さ（Ｒａ）は、ＪＩＳ Ｂ０６０１に準じて測定することができる。
“Direct” application of the liquid crystal composition onto the substrate means application of the liquid crystal composition onto the surface of the substrate without interposing other layers. When a substrate having an alignment controlling force is adopted and the surface of the substrate is directly coated with the liquid crystal composition, an optically anisotropic layer having a slow axis in a desired direction can be obtained.
When the liquid crystal composition is applied onto a substrate, the substrate should be applied with an appropriate tension (usually 100 to 500 N/m) to reduce the conveyance flutter of the substrate and maintain the flatness. Is preferred. The flatness is a shake amount in the vertical direction perpendicular to the width direction and the conveyance direction of the base material, and is ideally 0 mm, but is usually 1 mm or less.
The surface roughness (Ra) of the surface of the substrate on which the liquid crystal composition is applied is preferably 0.05 μm or less, more preferably 0.005 μm or less. When it is at most the upper limit, it is possible to obtain an optically anisotropic layer having less uneven coating and excellent flatness. The surface roughness (Ra) can be measured according to JIS B0601.
工程（Ｉ）への基材の供給は、上に述べた特定の長尺状の基材のロールを用意し、これから基材を繰り出すことにより行いうる。 The supply of the base material to the step (I) can be performed by preparing the roll of the specific long base material described above and feeding the base material from the roll.
第１の液晶組成物の塗布の具体的な操作の例としては、カーテンコーティング法、押し出しコーティング法、ロールコーティング法、スピンコーティング法、ディップコーティング法、バーコーティング法、スプレーコーティング法、スライドコーティング法、印刷コーティング法、グラビアコーティング法、ダイコーティング法、キャップコーティング法、及びディッピング法が挙げられる。 Examples of specific operations for applying the first liquid crystal composition include curtain coating method, extrusion coating method, roll coating method, spin coating method, dip coating method, bar coating method, spray coating method, slide coating method, The printing coating method, the gravure coating method, the die coating method, the cap coating method, and the dipping method are mentioned.
第１の液晶組成物の層の厚みは、特に限定されず、第１光学異方性層の厚みが所望の値となるよう適宜調整しうる。塗布の際の温度等の条件は、塗布及びその後の工程を円滑に行うことができる温度に適宜設定しうる。 The thickness of the layer of the first liquid crystal composition is not particularly limited, and can be appropriately adjusted so that the thickness of the first optically anisotropic layer has a desired value. Conditions such as the temperature at the time of coating can be appropriately set to a temperature at which the coating and the subsequent steps can be smoothly performed.
〔３．１．第１の液晶組成物〕
第１の液晶組成物は、第１の液晶化合物を含有する組成物である。
[3.1. First liquid crystal composition]
The first liquid crystal composition is a composition containing the first liquid crystal compound.
本願において、第１の液晶組成物の成分としての第１の液晶化合物とは、第１の液晶組成物に配合し配向させた際に、液晶相を呈しうる化合物である。重合性液晶化合物とは、かかる液晶相を呈した状態で第１の液晶組成物中で重合し、液晶相における分子の配向を維持したまま重合体となりうる液晶化合物である。
また、本願において、第１の液晶組成物の成分であって、重合性を有する化合物（重合性液晶化合物及びその他の重合性を有する化合物等）を総称して単に「重合性化合物」ということがある。
In the present application, the first liquid crystal compound as a component of the first liquid crystal composition is a compound that can exhibit a liquid crystal phase when blended with the first liquid crystal composition and aligned. The polymerizable liquid crystal compound is a liquid crystal compound which is polymerized in the first liquid crystal composition in a state of exhibiting such a liquid crystal phase and can be a polymer while maintaining the alignment of molecules in the liquid crystal phase.
In addition, in the present application, the polymerizable compounds (polymerizable liquid crystal compounds and other polymerizable compounds, etc.) that are components of the first liquid crystal composition are collectively referred to simply as “polymerizable compounds”. is there.
〔３．１．１．重合性液晶化合物〕
重合性液晶化合物の例としては、重合性基を有する液晶化合物、側鎖型液晶ポリマーを形成しうる化合物、円盤状液晶性化合物などが挙げられる。重合性基を有する液晶化合物の例としては、特開平１１−５１３３６０号公報、特開２００２−０３００４２号公報、特開２００４−２０４１９０号公報、特開２００５−２６３７８９号公報、特開２００７−１１９４１５号公報、特開２００７−１８６４３０号公報などに記載された重合性基を有する棒状液晶化合物、並びに国際公開第ＷＯ２０１２／１４７９０４号に記載される逆波長分散液晶化合物などが挙げられる。また、側鎖型液晶ポリマー化合物としては、例えば、特開２００３−１７７２４２号公報などに記載の側鎖型液晶ポリマー化合物などが挙げられる。また、好ましい液晶化合物の例を製品名で挙げると、ＢＡＳＦ社製「ＬＣ２４２」等が挙げられる。円盤状液晶性化合物の具体例としては、特開平８−５０２０６号公報、文献（C. Destrade et al., Mol. Crysr. Liq. Cryst., vol. 71, page 111 (1981) ；日本化学会編、季刊化学総説、Ｎｏ．２２、液晶の化学、第５章、第１０章第２節(1994)；B. Kohne et al., Angew. Chem. Soc. Chem. Comm., page 1794 (1985)；J. Zhang et al., J. Am. Chem. Soc., vol. 116, page 2655 (1994)）に記載されている。重合性液晶化合物としては、これらの液晶化合物及び以下に述べる他の液晶化合物のうちの、１種類を単独で用いてもよく、２種類以上を任意の比率で組み合わせて用いてもよい。
[3.1.1. Polymerizable liquid crystal compound]
Examples of the polymerizable liquid crystal compound include a liquid crystal compound having a polymerizable group, a compound capable of forming a side chain type liquid crystal polymer, and a discotic liquid crystal compound. Examples of the liquid crystal compound having a polymerizable group include JP-A Nos. 11-513360, 2002-030042, 2004-204190, 2005-263789, and 2007-119415. Examples thereof include rod-like liquid crystal compounds having a polymerizable group described in JP-A-2007-186430, and reverse wavelength dispersion liquid crystal compounds described in International Publication No. WO2012/147904. Examples of the side chain type liquid crystal polymer compound include the side chain type liquid crystal polymer compound described in JP 2003-177242 A and the like. In addition, examples of preferable liquid crystal compounds by product name include “LC242” manufactured by BASF. Specific examples of the discotic liquid crystal compound include JP-A-8-50206, C. Destrade et al., Mol. Crysr. Liq. Cryst., vol. 71, page 111 (1981); Chemical Society of Japan. Ed., Quarterly Chemistry Review, No. 22, Chemistry of Liquid Crystals, Chapter 5, Chapter 10, Section 2 (1994); B. Kohne et al., Angew. Chem. Soc. Chem. Comm., page 1794 (1985). ); J. Zhang et al., J. Am. Chem. Soc., vol. 116, page 2655 (1994)). As the polymerizable liquid crystal compound, one of these liquid crystal compounds and other liquid crystal compounds described below may be used alone, or two or more thereof may be used in combination at an arbitrary ratio.
重合性液晶化合物のさらなる例として、下記の一般式（１）で表される棒状液晶性化合物が挙げられる。
Ｒ１−Ｃ１−Ｄ１−Ｃ３−Ｍ−Ｃ４−Ｄ２−Ｃ２−Ｒ２ （１）
Further examples of the polymerizable liquid crystal compound include rod-like liquid crystal compounds represented by the following general formula (1).
R 1 -C 1 -D 1 -C 3 -M-C 4 -D 2 -C 2 -R 2 (1)
一般式（１）において、Ｒ１及びＲ２は、それぞれ独立して、重合性官能基を表す。重合性官能基としては、例えば、カルボキシル基、（メタ）アクリル基、エポキシ基、チオエポキシ基、メルカプト基、イソシアネート基、イソチオシアネート基、オキセタン基、チエタニル基、アジリジニル基、ピロール基、ビニル基、アリル基、フマレート基、シンナモイル基、オキサゾリン基、ヒドロキシル基、アルコキシシリル基、及びアミノ基などが挙げられる。（メタ）アクリルとは、アクリル及びメタクリルのことを指す。 In the general formula (1), R 1 and R 2 each independently represent a polymerizable functional group. Examples of the polymerizable functional group include a carboxyl group, a (meth)acrylic group, an epoxy group, a thioepoxy group, a mercapto group, an isocyanate group, an isothiocyanate group, an oxetane group, a thietanyl group, an aziridinyl group, a pyrrole group, a vinyl group, and an allyl group. Group, fumarate group, cinnamoyl group, oxazoline group, hydroxyl group, alkoxysilyl group, amino group and the like. (Meth)acrylic refers to acrylic and methacrylic.
一般式（１）において、Ｄ１及びＤ２は、それぞれ独立して、単結合、炭素原子数１〜２０個の直鎖状又は分岐鎖状のメチレン基及びアルキレン基等の二価の飽和炭化水素基、並びに、炭素原子数１〜２０個の直鎖状又は分岐鎖状のアルキレンオキサイド基からなる群より選択される基を表す。 In the general formula (1), D 1 and D 2 are each independently a single bond, a linear or branched methylene group having 1 to 20 carbon atoms, and a divalent saturated carbon atom such as an alkylene group. It represents a hydrogen group and a group selected from the group consisting of a linear or branched alkylene oxide group having 1 to 20 carbon atoms.
一般式（１）において、Ｃ１〜Ｃ４は、それぞれ独立して、単結合、−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＣＯ−、−ＣＳ−、−ＯＣＯ−、−ＣＨ２−、−ＯＣＨ２−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−ＮＨＣＯ−、−ＯＣＯＯ−、−ＣＨ２ＣＯＯ−、及び−ＣＨ２ＯＣＯ−からなる群より選択される基を表す。
In the general formula (1), C 1 to C 4 are each independently a single bond, —O—, —S—, —S—S—, —CO—, —CS—, —OCO—, —CH. 2 -, - OCH 2 -, - CH = N-N = CH -, - NHCO -, - OCOO -, -
一般式（１）において、Ｍはメソゲン基を表す。Ｍの具体例を挙げると、非置換又は置換基を有していてもよい、アゾメチン類、アゾキシ類、フェニル類、ビフェニル類、ターフェニル類、ナフタレン類、アントラセン類、安息香酸エステル類、シクロヘキサンカルボン酸フェニルエステル類、シアノフェニルシクロヘキサン類、シアノ置換フェニルピリミジン類、アルコキシ置換フェニルピリミジン類、フェニルジオキサン類、トラン類、アルケニルシクロヘキシルベンゾニトリル類の群から選択された２〜４個の骨格を、−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＣＯ−、−ＣＳ−、−ＯＣＯ−、−ＣＨ２−、−ＯＣＨ２−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−、−ＮＨＣＯ−、−ＯＣＯＯ−、−ＣＨ２ＣＯＯ−、及び−ＣＨ２ＯＣＯ−等の結合基によって結合されて形成される基を表す。
In the general formula (1), M represents a mesogen group. Specific examples of M include azomethines, azoxys, phenyls, biphenyls, terphenyls, naphthalenes, anthracenes, benzoates, and cyclohexanecarboxylic which may be unsubstituted or have a substituent. 2 to 4 skeletons selected from the group consisting of acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolans, alkenylcyclohexylbenzonitriles, -O -, - S -, - S -S -, - CO -, - CS -, - OCO -, - CH 2 -, - OCH 2 -, - CH = N-N = CH -, - NHCO -, - OCOO -, -
前記のメソゲン基Ｍが有しうる置換基としては、例えば、ハロゲン原子、置換基を有してもよい炭素原子数１〜１０のアルキル基、シアノ基、ニトロ基、−Ｏ−Ｒ３、−Ｏ−Ｃ（＝Ｏ）−Ｒ３、−Ｃ（＝Ｏ）−Ｏ−Ｒ３、−Ｏ−Ｃ（＝Ｏ）−Ｏ−Ｒ３、−ＮＲ３−Ｃ（＝Ｏ）−Ｒ３、−Ｃ（＝Ｏ）−ＮＲ３Ｒ４、または−Ｏ−Ｃ（＝Ｏ）−ＮＲ３Ｒ４を表す。
ここで、Ｒ３及びＲ４は、水素原子又は炭素原子数１〜１０のアルキル基を表す。Ｒ３及びＲ４がアルキル基である場合、当該アルキル基には、−Ｏ−、−Ｓ−、−Ｏ−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−ＮＲ５−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−ＮＲ５−、−ＮＲ５−、または−Ｃ（＝Ｏ）−が介在していてもよい（ただし、−Ｏ−および−Ｓ−がそれぞれ２以上隣接して介在する場合を除く。）。ここで、Ｒ５は、水素原子または炭素原子数１〜６のアルキル基を表す。前記「置換基を有してもよい炭素原子数１〜１０個のアルキル基」における置換基としては、ハロゲン原子、ヒドロキシル基、カルボキシル基、シアノ基、アミノ基、炭素原子数１〜６個のアルコキシ基、炭素原子数２〜８個のアルコキシアルコキシ基、炭素原子数３〜１５個のアルコキシアルコキシアルコキシ基、炭素原子数２〜７個のアルコキシカルボニル基、炭素原子数２〜７個のアルキルカルボニルオキシ基、炭素原子数２〜７個のアルコキシカルボニルオキシ基等が挙げられる。
Examples of the substituent that the mesogen group M may have include a halogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, a cyano group, a nitro group, —O—R 3 , — O-C (= O) -R 3, -C (= O) -O-R 3, -O-C (= O) -O-R 3, -NR 3 -C (= O) -R 3, -C (= O) represents the -NR 3 R 4 or -O-C (= O) -NR 3 R 4,.
Here, R 3 and R 4 represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. When R 3 and R 4 are alkyl groups, the alkyl groups include —O—, —S—, —O—C(═O)—, —C(═O)—O—, —O—C. (= O) -O -, - NR 5 -C (= O) -, - C (= O) -NR 5 -, - NR 5 -, or -C (= O) - may be interposed (However, the case where two or more -O- and -S- are adjacently interposed is excluded.). Here, R 5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the substituent in the above-mentioned "alkyl group having 1 to 10 carbon atoms which may have a substituent" include a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, an amino group, and a carbon atom having 1 to 6 carbon atoms. Alkoxy group, alkoxyalkoxy group having 2 to 8 carbon atoms, alkoxyalkoxyalkoxy group having 3 to 15 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, alkylcarbonyl having 2 to 7 carbon atoms Examples thereof include an oxy group and an alkoxycarbonyloxy group having 2 to 7 carbon atoms.
〔３．１．２．第１の液晶組成物のその他の成分〕
第１の液晶組成物は、重合性液晶化合物に加えて、必要に応じて、以下に例示するもの等の任意の成分を含みうる。
[3.1.2. Other Components of First Liquid Crystal Composition]
The first liquid crystal composition may contain, in addition to the polymerizable liquid crystal compound, any component such as those exemplified below, if necessary.
第１の液晶組成物は、重合開始剤を含みうる。重合開始剤としては、第１の液晶組成物中の、重合性液晶化合物、及びその他の重合性化合物が有する重合性基の種類に応じて適宜選択しうる。例えば、重合性基がラジカル重合性であればラジカル重合開始剤を、アニオン重合性の基であればアニオン重合開始剤を、カチオン重合性の基であればカチオン重合開始剤を、それぞれ使用しうる。 The first liquid crystal composition may include a polymerization initiator. The polymerization initiator may be appropriately selected depending on the type of the polymerizable liquid crystal compound in the first liquid crystal composition and the polymerizable group contained in the other polymerizable compound. For example, if the polymerizable group is radically polymerizable, a radical polymerization initiator may be used, if it is an anionic polymerizable group, an anionic polymerization initiator may be used, and if it is a cationically polymerizable group, a cationic polymerization initiator may be used. ..
ラジカル重合開始剤としては、加熱することにより、重合性化合物の重合を開始しえる活性種が発生する化合物である熱ラジカル発生剤；及び可視光線、紫外線（ｉ線など）、遠紫外線、電子線、Ｘ線等の露光光の露光により、重合性化合物の重合を開始しえる活性種が発生する化合物である光ラジカル発生剤；のいずれも使用可能であるが、光ラジカル発生剤を使用するのが好適である。 As the radical polymerization initiator, a heat radical generator that is a compound that generates an active species capable of initiating the polymerization of a polymerizable compound when heated; and visible light, ultraviolet light (i-ray, etc.), far ultraviolet light, electron beam , A photoradical generator that is a compound that generates an active species capable of initiating the polymerization of a polymerizable compound when exposed to exposure light such as X-rays; however, a photoradical generator is used. Is preferred.
光ラジカル発生剤としては、例えば、国際公開第ＷＯ２０１２／１４７９０４号に記載される、アセトフェノン系化合物、ビイミダゾール系化合物、トリアジン系化合物、Ｏ−アシルオキシム系化合物、オニウム塩系化合物、ベンゾイン系化合物、ベンゾフェノン系化合物、α−ジケトン系化合物、多核キノン系化合物、キサントン系化合物、ジアゾ系化合物、イミドスルホナート系化合物等を挙げることができる。 Examples of the photoradical generator include acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds described in International Publication No. WO2012/147904. Examples thereof include a benzophenone compound, an α-diketone compound, a polynuclear quinone compound, a xanthone compound, a diazo compound, and an imidosulfonate compound.
前記アニオン重合開始剤としては、例えば、アルキルリチウム化合物；ビフェニル、ナフタレン、ピレン等の、モノリチウム塩又はモノナトリウム塩；ジリチウム塩やトリリチウム塩等の多官能性開始剤；等が挙げられる。 Examples of the anionic polymerization initiator include alkyllithium compounds; monolithium salts or monosodium salts such as biphenyl, naphthalene, and pyrene; polyfunctional initiators such as dilithium salts and trilithium salts; and the like.
また、前記カチオン重合開始剤としては、例えば、硫酸、リン酸、過塩素酸、トリフルオロメタンスルホン酸等のプロトン酸；三フッ化ホウ素、塩化アルミニウム、四塩化チタン、四塩化スズのようなルイス酸；芳香族オニウム塩又は芳香族オニウム塩と、還元剤との併用系；が挙げられる。 Examples of the cationic polymerization initiator include protonic acids such as sulfuric acid, phosphoric acid, perchloric acid and trifluoromethanesulfonic acid; Lewis acids such as boron trifluoride, aluminum chloride, titanium tetrachloride and tin tetrachloride. An aromatic onium salt or a combination system of an aromatic onium salt and a reducing agent;
重合開始剤としては、市販品を用いうる。例えば、ＢＡＳＦ社製の、商品名：Ｉｒｇａｃｕｒｅ９０７、商品名：Ｉｒｇａｃｕｒｅ１８４、商品名：Ｉｒｇａｃｕｒｅ３６９、品名：Ｉｒｇａｃｕｒｅ６５１、品名：Ｉｒｇａｃｕｒｅ８１９、品名：Ｉｒｇａｃｕｒｅ９０７、品名：Ｉｒｇａｃｕｒｅ３７９、及び商品名：Ｉｒｇａｃｕｒｅ ＯＸＥ０２、ＡＤＥＫＡ社製の、商品名：アデカオプトマーＮ１９１９を用いうる。
これらの重合開始剤は一種単独で、又は二種以上を組合わせて用いることができる。
第１の液晶組成物において、重合開始剤の配合割合は、重合性化合物１００重量部に対し、通常、０．１〜３０重量部、好ましくは０．５〜１０重量部である。
A commercially available product may be used as the polymerization initiator. For example, trade names: Irgacure 907, trade names: Irgacure 184, trade names: Irgacure 369, product names: Irgacure 651, product names: Irgacure 819, product names: Irgacure 907, product names: Irgacure 379E, Ac, Og, and Iacure UR, Iacure O, and Irgacure Og. Trade name: ADEKA OPTOMER N1919 can be used.
These polymerization initiators may be used alone or in combination of two or more.
In the first liquid crystal composition, the mixing ratio of the polymerization initiator is usually 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymerizable compound.
第１の液晶組成物は、表面張力を調整するための、界面活性剤を含みうる。当該界面活性剤としては、特に限定はないが、通常、ノニオン系界面活性剤が好ましい。当該ノニオン系界面活性剤としては、例えば、分子量が数千程度のオリゴマーであるノニオン系界面活性剤等が挙げられる。
界面活性剤としては、市販品を用いうる。例えば、これらの界面活性剤の具体例としては、ＯＭＮＯＶＡ社ＰｏｌｙＦｏｘの「ＰＦ−１５１Ｎ」、「ＰＦ−６３６」、「ＰＦ−６３２０」、「ＰＦ−６５６」、「ＰＦ−６５２０」、「ＰＦ−３３２０」、「ＰＦ−６５１」、「ＰＦ−６５２」；ネオス社フタージェントの「ＦＴＸ−２０９Ｆ」、「ＦＴＸ−２０８Ｇ」、「ＦＴＸ−２０４Ｄ」；セイミケミカル社サーフロンの「ＫＨ−４０」、「Ｓ−４２０」等を用いることができる。また、界面活性剤は、１種類を単独で用いてもよく、２種類以上を任意の比率で組み合わせて用いてもよい。
第１の液晶組成物において、界面活性剤の配合割合は、重合性化合物１００重量部に対し、通常、０．０１〜１０重量部、好ましくは０．１〜２重量部である。
The first liquid crystal composition may include a surfactant for adjusting the surface tension. The surfactant is not particularly limited, but usually a nonionic surfactant is preferable. Examples of the nonionic surfactant include nonionic surfactants which are oligomers having a molecular weight of about several thousand.
A commercially available product may be used as the surfactant. For example, as specific examples of these surfactants, "PF-151N", "PF-636", "PF-6320", "PF-656", "PF-6520", "PF-" of PolyFox of OMNOVA. 3320", "PF-651", "PF-652";"FTX-209F","FTX-208G","FTX-204D" of Neos Co., Ltd. Futgent; S-420" or the like can be used. Further, one kind of the surfactant may be used alone, or two or more kinds thereof may be used in combination at an arbitrary ratio.
In the first liquid crystal composition, the mixing ratio of the surfactant is usually 0.01 to 10 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the polymerizable compound.
第１の液晶組成物は、有機溶媒等の溶媒を含みうる。かかる有機溶媒の例としては、シクロペンタノン、シクロヘキサノン、メチルエチルケトン、アセトン、メチルイソブチルケトン等のケトン類；酢酸ブチル、酢酸アミル等の酢酸エステル類；クロロホルム、ジクロロメタン、ジクロロエタン等のハロゲン化炭化水素類；１，４−ジオキサン、シクロペンチルメチルエーテル、テトラヒドロフラン、テトラヒドロピラン、１，３−ジオキソラン、１，２−ジメトキシエタン等のエーテル類；及びトルエン、キシレン、メシチレン等の芳香族炭化水素が挙げられる。溶媒の沸点は、取り扱い性に優れる観点から、６０〜２５０℃であることが好ましく、６０〜１５０℃であることがより好ましい。溶媒の使用量は、重合性化合物１００重量部に対し、通常、１００〜１０００重量部である。 The first liquid crystal composition may include a solvent such as an organic solvent. Examples of such organic solvents include ketones such as cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone and methyl isobutyl ketone; acetic acid esters such as butyl acetate and amyl acetate; halogenated hydrocarbons such as chloroform, dichloromethane and dichloroethane; Ethers such as 1,4-dioxane, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, 1,3-dioxolane and 1,2-dimethoxyethane; and aromatic hydrocarbons such as toluene, xylene and mesitylene. The boiling point of the solvent is preferably 60 to 250°C, and more preferably 60 to 150°C from the viewpoint of excellent handleability. The amount of the solvent used is usually 100 to 1000 parts by weight with respect to 100 parts by weight of the polymerizable compound.
第１の液晶組成物は、さらに、金属、金属錯体、染料、顔料、蛍光材料、燐光材料、レベリング剤、チキソ剤、ゲル化剤、多糖類、紫外線吸収剤、赤外線吸収剤、抗酸化剤、イオン交換樹脂、酸化チタン等の金属酸化物等の任意の添加剤を含みうる。本発明の重合性組成物において、かかる任意の添加剤の配合割合は、重合性化合物１００重量部に対し、通常、各々０．１〜２０重量部である。 The first liquid crystal composition further comprises a metal, a metal complex, a dye, a pigment, a fluorescent material, a phosphorescent material, a leveling agent, a thixotropic agent, a gelling agent, a polysaccharide, an ultraviolet absorber, an infrared absorber, an antioxidant, It may contain optional additives such as ion exchange resins and metal oxides such as titanium oxide. In the polymerizable composition of the present invention, the compounding ratio of such optional additives is usually 0.1 to 20 parts by weight per 100 parts by weight of the polymerizable compound.
第１の液晶組成物は、通常、上に述べた成分を混合することにより、調製することができる。 The first liquid crystal composition can usually be prepared by mixing the components described above.
〔４．工程（ＩＩ）〕
本発明の光学積層体の製造方法の工程（ＩＩ）では、第１の液晶組成物の層中の第１の液晶化合物を配向させ、第１の液晶組成物の層に不活性ガス雰囲気下で活性エネルギー線を照射し第１の液晶組成物を硬化させ、第１光学異方性層を形成する。
[4. Step (II)]
In the step (II) of the method for producing an optical layered body of the present invention, the first liquid crystal compound in the layer of the first liquid crystal composition is aligned, and the layer of the first liquid crystal composition is subjected to an inert gas atmosphere. The first liquid crystal composition is cured by irradiation with active energy rays to form a first optically anisotropic layer.
第１の液晶化合物の配向は、塗布により直ちに達成される場合もあるが、必要に応じて、塗布の後に、加温などの配向処理を施すことにより達成される場合もある。配向処理の条件は、使用する液晶組成物の性質に応じて適宜設定しうるが、例えば、５０〜１６０℃の温度条件において３０秒間〜５分間処理する条件としうる。用いる液晶組成物の組成及び処理条件を適宜設定することにより、基材の配向軸の方向と同一方向に沿った配向を達成しうる。 The alignment of the first liquid crystal compound may be achieved immediately by coating, or may be achieved by performing an alignment treatment such as heating after coating, if necessary. The conditions for the alignment treatment may be appropriately set depending on the properties of the liquid crystal composition used, and for example, the conditions may be such that the treatment is performed at a temperature of 50 to 160° C. for 30 seconds to 5 minutes. By appropriately setting the composition of the liquid crystal composition to be used and the treatment conditions, it is possible to achieve the alignment along the same direction as the alignment axis of the substrate.
配向の後直ちに活性エネルギー線照射を行ってもよいが、配向の後直ちに活性エネルギー線照射の前に、必要に応じて液晶組成物の層を乾燥させる工程を行なってもよい。かかる乾燥は、自然乾燥、加熱乾燥、減圧乾燥、減圧加熱乾燥等の乾燥方法で達成しうる。かかる乾燥により、液晶組成物の層から、溶媒を除去することができる。 Irradiation with active energy rays may be carried out immediately after orientation, but a step of drying the layer of the liquid crystal composition may be carried out immediately after irradiation with active energy rays immediately after orientation. Such drying can be achieved by a drying method such as natural drying, heat drying, reduced pressure drying, and reduced pressure heat drying. By such drying, the solvent can be removed from the layer of the liquid crystal composition.
活性エネルギー線照射は、不活性ガス雰囲気下で行う。不活性ガスの例としては、窒素及びアルゴンが挙げられ、低コストであることから窒素が好ましい。不活性ガス雰囲気の酸素濃度は、好ましくは３％以下、より好ましくは１％以下、特に好ましくは５００ｐｐｍ以下である。 Irradiation with active energy rays is performed in an inert gas atmosphere. Examples of the inert gas include nitrogen and argon, and nitrogen is preferable because of its low cost. The oxygen concentration in the inert gas atmosphere is preferably 3% or less, more preferably 1% or less, and particularly preferably 500 ppm or less.
活性エネルギー線照射のその他の条件は、液晶組成物の成分の性質に適合した条件を適宜選択しうる。照射される活性エネルギー線には、可視光線、紫外線、及び赤外線等の光、並びに電子線等の任意のエネルギー線が含まれうる。なかでも、操作が簡便なことから、紫外線等の光を照射する方法が好ましい。紫外線照射時の温度の上限は、基材のガラス転移温度（Ｔｇ）以下とすることが好ましい。通常、１５０℃以下、好ましくは１００℃以下、特に好ましくは８０℃以下の範囲である。紫外線照射時の温度の下限は、１５℃以上としうる。紫外線照射強度は、通常、０．１ｍＷ／ｃｍ２〜１０００ｍＷ／ｃｍ２の範囲、好ましくは０．５ｍＷ／ｃｍ２〜６００ｍＷ／ｃｍ２の範囲である。紫外線照射時間は、１秒〜３００秒の範囲、好ましくは５秒〜１００秒の範囲である。紫外線積算光量（ｍＪ／ｃｍ２）＝紫外線照射強度（ｍＷ／ｃｍ２）×照射時間（秒）で求められる。積算光量は、好ましくは１０〜５０００ｍＪ／ｃｍ２の範囲である。紫外線照射光源としては、高圧水銀灯、メタルハライドランプ、低圧水銀灯を用いることができる。 As the other conditions for irradiation with active energy rays, conditions suitable for the properties of the components of the liquid crystal composition can be appropriately selected. The active energy rays to be irradiated may include light such as visible rays, ultraviolet rays, and infrared rays, and arbitrary energy rays such as electron rays. Among them, the method of irradiating light such as ultraviolet rays is preferable because the operation is simple. It is preferable that the upper limit of the temperature at the time of ultraviolet irradiation is set to the glass transition temperature (Tg) of the substrate or lower. It is usually 150° C. or lower, preferably 100° C. or lower, and particularly preferably 80° C. or lower. The lower limit of the temperature during UV irradiation may be 15°C or higher. Ultraviolet irradiation intensity is usually, 0.1mW / cm 2 ~1000mW / cm 2 range, preferably in the range of 0.5mW / cm 2 ~600mW / cm 2 . The ultraviolet irradiation time is in the range of 1 second to 300 seconds, preferably 5 seconds to 100 seconds. It is determined by the integrated amount of ultraviolet rays (mJ/cm 2 )=UV irradiation intensity (mW/cm 2 )×irradiation time (seconds). The integrated light amount is preferably in the range of 10 to 5000 mJ/cm 2 . As the ultraviolet irradiation light source, a high pressure mercury lamp, a metal halide lamp, or a low pressure mercury lamp can be used.
活性エネルギー線の照射は、塗布面側（基材／第１の液晶組成物の層の積層物の、第１の液晶組成物の層が形成されている側）に行うこともできるが、基材の透明度が十分に高ければ、裏面側（液晶組成物の層が形成されている側とは反対側）から行うこともできる。 Irradiation with active energy rays can be performed on the coated surface side (the side of the laminate of the substrate/first liquid crystal composition layer on which the first liquid crystal composition layer is formed), If the transparency of the material is sufficiently high, it can be performed from the back surface side (the side opposite to the side on which the liquid crystal composition layer is formed).
工程（ＩＩ）の結果得られる第１光学異方性層の表面の鉛筆硬度は、好ましくはＢ以上、好ましくは４Ｈ以下である。前記鉛筆硬度がＢ未満の場合、耐擦傷性が不足し、搬送工程でキズが発生しやすくなる場合がある。また、前記鉛筆硬度が４Ｈを越える場合、光学異方性層が脆くなりすぎてクラック発生率が高くなる場合がある。このような高い表面硬度を有する第１光学異方性層は、上に述べた不活性ガス雰囲気下等の条件を満たす活性エネルギー線照射を行うことにより、容易に得ることができる。鉛筆硬度は、ＪＩＳ Ｋ５６００−５−４に基づき測定しうる。 The pencil hardness of the surface of the first optically anisotropic layer obtained as a result of the step (II) is preferably B or more, and preferably 4H or less. If the pencil hardness is less than B, the scratch resistance may be insufficient, and scratches may easily occur in the carrying step. If the pencil hardness exceeds 4H, the optically anisotropic layer may become too brittle and the crack generation rate may increase. The first optically anisotropic layer having such a high surface hardness can be easily obtained by performing active energy ray irradiation under the above-described conditions such as the inert gas atmosphere. The pencil hardness can be measured based on JIS K5600-5-4.
〔５．工程（ＩＩＩ）〕
本発明の光学積層体の製造方法の工程（ＩＩＩ）では、第１光学異方性層上に、直接、光配向材料を含む液（以下において「光配向材料液」ということがある。）を塗布して光配向材料液の層を得て、不活性ガス雰囲気下、基材の幅手方向と異なる方向の照射偏光方向を有する偏光紫外線を光配向材料の層に照射し、光配向層を形成する。
光配向材料を基材上に形成された第１光学異方性層上に塗布する場合、基材を適度の張力（通常、１００〜５００Ｎ／ｍ）でテンションを掛けて、基材の搬送ばたつきを少なくし平面性を維持したまま塗布することが好ましい。平面性とは、基材の幅手方向および搬送方向に垂直な上下方向の振れ量であり、理想的には０ｍｍであるが、通常、１ｍｍ以下である。
[5. Step (III)]
In step (III) of the method for producing an optical layered body of the present invention, a liquid containing a photo-alignment material (hereinafter, may be referred to as “photo-alignment material liquid”) directly on the first optically anisotropic layer. After coating to obtain a layer of the photo-alignment material liquid, the layer of the photo-alignment material is irradiated with polarized ultraviolet light having an irradiation polarization direction different from the width direction of the base material in an inert gas atmosphere to form the photo-alignment layer. Form.
When the photo-alignment material is applied on the first optically anisotropic layer formed on the base material, the base material is tensioned with an appropriate tension (usually 100 to 500 N/m), and the base material is fluttered. It is preferable that the amount is reduced to maintain the flatness. The flatness is a shake amount in the vertical direction perpendicular to the width direction and the conveyance direction of the base material, and is ideally 0 mm, but is usually 1 mm or less.
このように第１光学異方性層上に直接光配向層を形成することにより、薄い光学積層体を簡便に形成することができる。また、本発明の製造方法では、上に述べた特定の方法により第１光学異方性層を形成することにより、表面硬度が高い第１光学異方性層が得られるので、その上にさらに直接光配向層を形成しても、表面にスジ状の傷を形成する傾向が少ない。 By thus forming the photo-alignment layer directly on the first optically anisotropic layer, a thin optical laminate can be easily formed. Further, in the production method of the present invention, the first optically anisotropic layer having a high surface hardness can be obtained by forming the first optically anisotropic layer by the above-described specific method. Even if the photo-alignment layer is directly formed, there is little tendency to form streaky scratches on the surface.
光配向材料とは、光配向材料とは、偏光を照射されることにより不可逆的に配向する材料である。このような光配向材料の例としては、偏光を照射することにより分子そのものを変化させる光反応タイプである特許第４２６７０８０号公報に記載のＰＰＮ層に使用されるＰＰＮ材料、特許第４６４７７８２号公報に記載のＬＰＰ／ＬＣＰ混合物、特許第２５４３６６６号公報に記載のＰＰＮ材料、また、偏光を照射することによりシス−トランス光異性化によって分子形状を変化させる光異性化タイプである特許第４８１６００３号公報、特許第４９３５９８２号公報、特許第５０５７１５７号公報、特許第５０７６８１０号公報に記載のアゾベンゼン系材料などが挙げられる。これらは１種類を単独で用いてもよく、２種類以上を任意の比率で組み合わせて用いてもよい。このような材料を用いて層を形成することにより、光配向層、即ち配向規制力を有し、偏光の照射により配向規制方向を制御しうる層を得ることができる。 The photo-alignment material is a material that is irreversibly aligned by being irradiated with polarized light. As an example of such a photo-alignment material, a PPN material used for a PPN layer described in Japanese Patent No. 4267080, which is a photo-reactive type in which molecules themselves are changed by irradiating polarized light, and Japanese Patent No. 4647782 are described. The LPP/LCP mixture described, the PPN material described in Japanese Patent No. 2543666, and the photo-isomerization type that changes the molecular shape by cis-trans photo-isomerization by irradiating polarized light, Japanese Patent No. 4816003, Examples include azobenzene-based materials described in Japanese Patent No. 4935982, Japanese Patent No. 5057157, and Japanese Patent No. 5076810. These may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios. By forming a layer using such a material, a photo-alignment layer, that is, a layer having an alignment regulating force and capable of controlling the alignment regulating direction by irradiation of polarized light can be obtained.
光配向材料液中の光配向材料の割合は、０．５〜３０重量％としうる。光配向材料の割合が上記範囲よりも多いと、第１光学異方性層上に光配向層を塗工する塗布方式によっては、平面粗さに優れた配向層を形成することが困難となる場合があり、また、上記範囲よりも薄いと、溶媒の乾燥負荷が増加するため、塗布速度を所望の範囲にできない可能性がある。光配向材料液のその他の成分は、特に限定されず、溶媒等の任意の成分を含みうる。溶媒の種類は光配向材料等を所望の濃度に溶解できるもの、および第１光学異方性層を溶解させないものであれば特に限定されず、光配向材料に適合するものを適宜選択して用いうる。具体的には、メタノール、エタノール等のアルコール系溶剤、エチレングリコール、プロピレングリコール、１，３−ブタンジオール等のジオール系溶剤、テトラヒドロフラン、２−メトキシエターノール、２−ブトキシエタノール、２−（２−エトキシエトキシ）エタノール、２−（２−ブトキシエトキシ）エタノール等のエーテル系溶剤、２−ピロリドン、Ｎ−メチルピロリドン、ジメチルホルムアミド、ジメチルアセトアミド等のアミド系溶剤、γ−ブチロラクトン、クロロベンゼン、ジメチルスルホキシド等の有機溶媒を用いうる。これらは、単独で使用することもできるし、２種類以上混合して使用することもできる。 The proportion of the photo-alignment material in the photo-alignment material liquid may be 0.5 to 30% by weight. If the proportion of the photo-alignment material is higher than the above range, it may be difficult to form an alignment layer having excellent planar roughness depending on the coating method of coating the photo-alignment layer on the first optically anisotropic layer. In some cases, if it is less than the above range, the drying load of the solvent increases, so that the coating speed may not be within the desired range. Other components of the photo-alignment material liquid are not particularly limited and may include any component such as a solvent. The type of solvent is not particularly limited as long as it can dissolve the photo-alignment material and the like to a desired concentration and does not dissolve the first optically anisotropic layer, and a solvent that is compatible with the photo-alignment material is appropriately selected and used. sell. Specifically, alcohol solvents such as methanol and ethanol, diol solvents such as ethylene glycol, propylene glycol, and 1,3-butanediol, tetrahydrofuran, 2-methoxyethanol, 2-butoxyethanol, 2-(2- Ether-based solvents such as ethoxyethoxy)ethanol and 2-(2-butoxyethoxy)ethanol, amide-based solvents such as 2-pyrrolidone, N-methylpyrrolidone, dimethylformamide and dimethylacetamide, γ-butyrolactone, chlorobenzene and dimethylsulfoxide. Organic solvents can be used. These may be used alone or in combination of two or more.
光配向材料液の塗布の具体的な操作は、特に限定されず、その例としては、第１の液晶組成物の塗布のための例として挙げたものと同様のものが挙げられる。 The specific operation of applying the photo-alignment material liquid is not particularly limited, and examples thereof include the same operations as those given as examples for applying the first liquid crystal composition.
光配向材料液の層の厚みは、特に限定されず、光配向層の厚みが所望の値となるよう適宜調整しうる。塗布の際の温度等の条件は、塗布及びその後の工程を円滑に行うことができる温度に適宜設定しうる。 The thickness of the layer of the photo-alignment material liquid is not particularly limited, and can be appropriately adjusted so that the thickness of the photo-alignment layer has a desired value. Conditions such as the temperature at the time of coating can be appropriately set to a temperature at which the coating and the subsequent steps can be smoothly performed.
偏光紫外線は、通常、直線偏光紫外線である。偏光紫外線の照射は、不活性ガス雰囲気下で行う。不活性ガスの例としては、窒素及びアルゴンが挙げられ、低コストであることから窒素が好ましい。不活性ガス雰囲気の酸素濃度は、好ましくは３％以下、より好ましくは１％以下、特に好ましくは５００ｐｐｍ以下である。 The polarized UV is usually linearly polarized UV. Irradiation of polarized ultraviolet rays is performed in an inert gas atmosphere. Examples of the inert gas include nitrogen and argon, and nitrogen is preferable because of its low cost. The oxygen concentration in the inert gas atmosphere is preferably 3% or less, more preferably 1% or less, and particularly preferably 500 ppm or less.
偏光紫外線の照射は、光配向材料液の層の塗布面側（光配向材料液の層の、第１光学異方性層側と反対側）から照射することもでき、その反対側から照射することもできるが、塗布面側から照射することが、製造効率や高品質な層を得る観点から好ましい。 Irradiation of polarized ultraviolet light can also be performed from the coating surface side of the layer of the photo-alignment material liquid (the side of the photo-alignment material liquid layer opposite to the first optically anisotropic layer side), or from the opposite side. However, irradiation from the coated surface side is preferable from the viewpoint of production efficiency and obtaining a high quality layer.
偏光紫外線の「照射偏光方向」とは、偏光紫外線により光配向材料の配向を規制する方向である。偏光紫外線の具体的な照射の態様としては、正面照射（即ち照射面に対して垂直な方向からの照射）、及び斜め照射（即ち照射面に対して垂直でない方向からの照射）が挙げられ、使用する光配向材料に適合する態様を適宜採用しうる。正面照射がより垂直に近いほど、光配向材料の反応が効率的に進行する。正面照射を行った場合、使用する光配向材料により、偏光紫外線の偏光方向（電場の振動面の方向）と平行または垂直な方向に光配向材料が配向する。偏光紫外線の偏光方向と平行な方向に配向する光配向材料を選定すれば、その方向が「照射偏光方向」となり、偏光方向と平行な方向に配向規制力を付与することができる。 The “irradiation polarization direction” of polarized ultraviolet light is a direction in which the orientation of the photo-alignment material is regulated by the polarized ultraviolet light. Specific modes of irradiation of polarized ultraviolet light include front irradiation (that is, irradiation from a direction perpendicular to the irradiation surface) and oblique irradiation (that is, irradiation from a direction that is not perpendicular to the irradiation surface). A mode suitable for the photo-alignment material used can be appropriately adopted. The closer the front irradiation is to the vertical, the more efficiently the reaction of the photo-alignment material proceeds. When the front irradiation is performed, the photo-alignment material is oriented in a direction parallel or perpendicular to the polarization direction of the polarized ultraviolet light (direction of vibration plane of electric field) depending on the photo-alignment material used. If a photo-alignment material that is aligned in a direction parallel to the polarization direction of polarized ultraviolet light is selected, that direction becomes the "irradiation polarization direction", and the alignment regulating force can be imparted in the direction parallel to the polarization direction.
照射偏光方向は、基材の幅手方向と異なる方向に設定される。照射偏光方向と基材の幅手方向とがなす角度は、具体的には０°超９０°未満としうる。照射偏光方向をこのような範囲の角度に設定することにより、本発明の光学積層体を、円偏光板等の効率的な製造を可能にする材料とすることができる。より具体的には、照射偏光方向と基材の幅手方向とがなす角度を、略１５°又は略７５°といった特定の範囲とすることにより、広帯域反射防止フィルムの材料として有用に用いうる光学積層体を、効率的に製造することができる。 The irradiation polarization direction is set to a direction different from the width direction of the base material. The angle formed by the irradiation polarization direction and the width direction of the substrate may be specifically more than 0° and less than 90°. By setting the irradiation polarization direction to an angle within such a range, the optical layered body of the present invention can be used as a material that enables efficient production of a circularly polarizing plate or the like. More specifically, when the angle formed by the irradiation polarization direction and the width direction of the base material is set to a specific range such as approximately 15° or approximately 75°, it can be effectively used as a material for a broadband antireflection film. The laminated body can be efficiently manufactured.
偏光紫外線照射のその他の条件は、液晶組成物の成分の性質に適合した条件を適宜選択しうる。偏光紫外線照射時の温度の上限は、基材のガラス転移温度（Ｔｇ）以下とすることが好ましい。通常、１５０℃以下、好ましくは１００℃以下、特に好ましくは８０℃以下の範囲である。紫外線照射時の温度の下限は、１５℃以上としうる。紫外線照射強度は、通常、０．０１ｍＷ／ｃｍ２〜２００ｍＷ／ｃｍ２の範囲、好ましくは０．１ｍＷ／ｃｍ２〜１５０ｍＷ／ｃｍ２の範囲である。紫外線照射時間は０．１秒〜６０秒の範囲、好ましくは１秒〜３０秒の範囲である。積算光量は、好ましくは５０〜１００００ｍＪ／ｃｍ２、より好ましくは１００〜５０００ｍＪ／ｃｍ２の範囲である。
偏光紫外線の最大出力波長は、３００ｎｍ〜５００ｎｍの範囲内であることが好ましい。また、出射される光量のうち、波長３００ｎｍ〜５００ｎｍの光に由来する光量が５０％以上であることが好ましい。この範囲の波長の偏光紫外線を用いることで、光配向性材料の反応が効率的に進行する。
As other conditions of the polarized ultraviolet irradiation, conditions suitable for the properties of the components of the liquid crystal composition can be appropriately selected. The upper limit of the temperature at the time of irradiation with polarized ultraviolet rays is preferably set to the glass transition temperature (Tg) of the substrate or lower. It is usually 150° C. or lower, preferably 100° C. or lower, and particularly preferably 80° C. or lower. The lower limit of the temperature during UV irradiation may be 15°C or higher. Ultraviolet irradiation intensity is usually, 0.01mW / cm 2 ~200mW / cm 2 range, preferably in the range of 0.1mW / cm 2 ~150mW / cm 2 . The ultraviolet irradiation time is in the range of 0.1 second to 60 seconds, preferably 1 second to 30 seconds. The integrated light amount is preferably in the range of 50 to 10000 mJ/cm 2 , more preferably 100 to 5000 mJ/cm 2 .
The maximum output wavelength of polarized ultraviolet light is preferably in the range of 300 nm to 500 nm. Further, it is preferable that, of the emitted light amount, the light amount derived from the light having a wavelength of 300 nm to 500 nm is 50% or more. By using polarized ultraviolet light having a wavelength in this range, the reaction of the photo-alignment material proceeds efficiently.
本発明の製造方法では、工程（ＩＩ）において照射される活性エネルギー線の照射量及び工程（ＩＩＩ）において照射される偏光紫外線照射量の合計の積算光量が、好ましくは１０００ｍＪ／ｃｍ２以上、より好ましくは２０００ｍＪ／ｃｍ２以上である。当該合計の積算光量の上限は、特に限定されないが、例えば１００００ｍＪ／ｃｍ２以下としうる。このような高い積算光量での照射を行うことにより、その上に直接第２光学異方性層を形成する際に、その表面のスジ状の傷の形成をさらに低減することができる。 In the production method of the present invention, the total integrated light amount of the irradiation amount of the active energy ray irradiated in the step (II) and the polarized ultraviolet light irradiation amount irradiated in the step (III) is preferably 1000 mJ/cm 2 or more, It is preferably 2000 mJ/cm 2 or more. The upper limit of the total integrated light amount is not particularly limited, but may be 10,000 mJ/cm 2 or less, for example. By performing irradiation with such a high integrated light amount, it is possible to further reduce the formation of streak-like scratches on the surface of the second optically anisotropic layer when it is directly formed thereon.
工程（ＩＩＩ）の結果得られる光配向層の厚みは、第２光学異方性層の配向を規制する配向規制力が得られる厚みに適宜調整しうる。具体的には、好ましくは０．００１μｍ以上、より好ましくは０．０１μｍ以上であり、好ましくは５μｍ以下、より好ましくは２μｍ以下である。 The thickness of the photo-alignment layer obtained as a result of the step (III) can be appropriately adjusted to a thickness at which the alignment regulating force for regulating the alignment of the second optically anisotropic layer can be obtained. Specifically, it is preferably 0.001 μm or more, more preferably 0.01 μm or more, preferably 5 μm or less, more preferably 2 μm or less.
工程（ＩＩＩ）の結果得られる光配向層の表面の鉛筆硬度は、好ましくはＢ以上、好ましくは４Ｈ以下である。前記鉛筆硬度がＢ未満の場合、耐擦傷性が不足し搬送工程でキズが発生しやすくなる場合がある。また、前記鉛筆硬度が４Ｈを越える場合、光配向層が脆くなりすぎてクラック発生率が高くなる場合がある。このような高い表面硬度を有する光配向層は、上に述べた不活性ガス雰囲気下等の条件を満たす偏光紫外線照射を行うことにより、容易に得ることができる。第１光学異方性層の表面の鉛筆硬度、及光配向層の表面の鉛筆硬度がいずれもＢ以上であることにより、その上に直接第２光学異方性層を形成する際に、その表面のスジ状の傷の形成をさらに低減することができる。 The pencil hardness of the surface of the photo-alignment layer obtained as a result of the step (III) is preferably B or higher, and preferably 4H or lower. When the pencil hardness is less than B, the scratch resistance may be insufficient and scratches may easily occur in the carrying step. If the pencil hardness exceeds 4H, the photo-alignment layer may become too brittle and the crack generation rate may increase. The photo-alignment layer having such a high surface hardness can be easily obtained by irradiating polarized ultraviolet rays satisfying the conditions such as the above-mentioned inert gas atmosphere. When the pencil hardness of the surface of the first optically anisotropic layer and the pencil hardness of the surface of the photo-alignment layer are both B or more, when the second optically anisotropic layer is directly formed thereon, The formation of streak-like scratches on the surface can be further reduced.
〔６．工程（ＩＶ）〕
本発明の光学積層体の製造方法の工程（ＩＶ）では、光配向層上に、直接、第２の液晶化合物を含有する第２の液晶組成物を塗布して第２の液晶組成物の層を得て、第２の液晶組成物の層中の第２の液晶化合物を配向させ、第２の液晶組成物の層に活性エネルギー線を照射し第２の液晶組成物を硬化させ、第２光学異方性層を形成する。第２の液晶組成物は、第１の液晶組成物と同一の組成物であってもよく、異なる組成物であってもよい。その例としては、第１の液晶組成物の例として上に述べたものと同様のものが挙げられる。
[6. Step (IV)]
In step (IV) of the method for producing an optical layered body of the present invention, the second liquid crystal composition containing the second liquid crystal compound is directly applied onto the photo-alignment layer to form a layer of the second liquid crystal composition. Then, the second liquid crystal compound in the layer of the second liquid crystal composition is aligned, and the layer of the second liquid crystal composition is irradiated with an active energy ray to cure the second liquid crystal composition, An optically anisotropic layer is formed. The second liquid crystal composition may be the same composition as the first liquid crystal composition or a different composition. Examples thereof include the same as those described above as the example of the first liquid crystal composition.
第２の液晶化合物の塗布、配向、活性エネルギー線の照射の態様の具体例も、第１の液晶組成物に関するものの例として上に述べたものと同様のものが挙げられる。工程（ＩＶ）における活性エネルギー線の照射は、既に形成された強固な第１光学異方性層及び光配向層の上に第２光学異方性層を形成する工程であるので、必ずしも不活性ガス雰囲気下で行う必要は無いが、工程（ＩＩ）と同様の不活性ガス雰囲気下で行うことにより、より高品質な光学異方性層を形成することができる。 Specific examples of aspects of application of the second liquid crystal compound, alignment, and irradiation with active energy rays include the same as those described above as examples of those relating to the first liquid crystal composition. Irradiation with the active energy ray in the step (IV) is a step of forming the second optically anisotropic layer on the already formed strong first optically anisotropic layer and photo-alignment layer, and therefore is not necessarily inactive. It is not necessary to perform it in a gas atmosphere, but a higher quality optically anisotropic layer can be formed by performing it in the same inert gas atmosphere as in step (II).
本発明の製造方法により得られた光学積層体においては、上に述べた特定の方法により第１光学異方性層及び光配向層を形成することにより、表面硬度が高く、表面の性状が良好な光配向膜が得られるので、その上にさらに第２光学異方性層を形成しても、表面にスジ状の傷を形成する傾向が少なく、塗布ムラ（第２の液晶組成物の塗布のムラに起因する、光学異方性層の表面のムラ）が少ない第２光学異方性層を得ることができる。 In the optical layered body obtained by the production method of the present invention, the surface hardness is high and the surface properties are good by forming the first optically anisotropic layer and the photo-alignment layer by the specific method described above. Since an excellent photo-alignment film can be obtained, even if a second optically anisotropic layer is further formed on it, there is little tendency to form streak-like scratches on the surface, and uneven coating (application of the second liquid crystal composition It is possible to obtain a second optically anisotropic layer having less unevenness of the surface of the optically anisotropic layer due to the unevenness of.
〔７．光学異方性層の光学的特性等〕
好ましい態様において、第１光学異方性層及び前記第２光学異方性層の一方はλ／４波長板であり、他方がλ／２波長板である。具体的には、測定波長５９０ｎｍで測定した面内レターデーションＲｅが、１０８ｎｍ〜１６８ｎｍの範囲である場合、λ／４波長板として使用しうる。また測定波長５９０ｎｍで測定した面内レターデーションＲｅが２４５ｎｍ〜３０５ｎｍの範囲である場合、λ／２波長板として使用しうる。より具体的には、λ／４波長板の場合、測定波長５９０ｎｍで測定した面内レターデーションＲｅは、好ましくは１２８ｎｍ〜１４８ｎｍ、より好ましくは１３３ｎｍ〜１４３ｎｍの範囲である。またλ／２波長板の場合、測定波長５９０ｎｍで測定した面内レターデーションＲｅは、好ましくは２６５ｎｍ〜２８５ｎｍ、より好ましくは２７０ｎｍ〜２８０ｎｍの範囲である。ここで、面内レターデーションＲｅは、下記式に従って算出する。
Ｒｅ＝（ｎｘ−ｎｙ）×ｄ（式中、ｎｘは、光学異方性層の面内の遅相軸方向の屈折率（面内の最大屈折率）であり、ｎｙは、光学異方性層の面内の遅相軸に垂直な方向の屈折率であり、ｄは、光学異方性層の厚み（ｎｍ）である。）第１光学異方性層及び第２光学異方性層が、このようなλ／４波長板及びλ／２波長板の組み合わせである場合、それを利用して、λ／４波長板又はλ／２波長板を有する円偏光板等の光学素子を容易に製造しうる。
[7. Optical characteristics of optically anisotropic layer]
In a preferred embodiment, one of the first optically anisotropic layer and the second optically anisotropic layer is a λ/4 wavelength plate, and the other is a λ/2 wavelength plate. Specifically, when the in-plane retardation Re measured at a measurement wavelength of 590 nm is in the range of 108 nm to 168 nm, it can be used as a λ/4 wavelength plate. When the in-plane retardation Re measured at a measurement wavelength of 590 nm is in the range of 245 nm to 305 nm, it can be used as a λ/2 wave plate. More specifically, in the case of a λ/4 wavelength plate, the in-plane retardation Re measured at a measurement wavelength of 590 nm is preferably 128 nm to 148 nm, more preferably 133 nm to 143 nm. In the case of a λ/2 wavelength plate, the in-plane retardation Re measured at a measurement wavelength of 590 nm is preferably 265 nm to 285 nm, more preferably 270 nm to 280 nm. Here, the in-plane retardation Re is calculated according to the following formula.
Re=(nx−ny)×d (where nx is the in-plane slow axis direction refractive index of the optically anisotropic layer (maximum in-plane refractive index), and ny is the optical anisotropy. The refractive index of the layer in the direction perpendicular to the slow axis, and d is the thickness (nm) of the optically anisotropic layer.) First optically anisotropic layer and second optically anisotropic layer Is a combination of such a λ/4 wavelength plate and a λ/2 wavelength plate, it can be used to facilitate an optical element such as a λ/4 wavelength plate or a circularly polarizing plate having a λ/2 wavelength plate. Can be manufactured.
第１光学異方性層の遅相軸方向は、基材の配向軸と平行となりうる。また、第２光学異方性層の遅相軸方向は、偏光紫外線の照射偏光方向と平行となりうる。
より具体的には、第１光学異方性層の遅相軸と基材の幅手方向とがなす角度を、略７５°又は略１５°といった特定の範囲としうる。また、第２光学異方性層の遅相軸と基材の幅手方向とがなす角度を、略１５°又は略７５°といった特定の範囲としうる。また、第１光学異方性層の遅相軸と第２光学異方性層の遅相軸とがなす角は、好ましくは５５°〜６５°、より好ましくは５６°〜６４°、さらにより好ましくは５７°〜６３°としうる。遅相軸をこのような特定の範囲とすることにより、広帯域反射防止フィルムの材料として有用に用いうる光学積層体を、効率的に製造することができる。
The slow axis direction of the first optically anisotropic layer may be parallel to the alignment axis of the base material. Also, the slow axis direction of the second optically anisotropic layer may be parallel to the irradiation polarization direction of the polarized ultraviolet light.
More specifically, the angle formed by the slow axis of the first optically anisotropic layer and the width direction of the substrate can be set to a specific range such as approximately 75° or approximately 15°. Further, the angle formed by the slow axis of the second optically anisotropic layer and the width direction of the base material may be in a specific range such as approximately 15° or approximately 75°. The angle formed by the slow axis of the first optically anisotropic layer and the slow axis of the second optically anisotropic layer is preferably 55° to 65°, more preferably 56° to 64°, and even more preferably It may preferably be 57° to 63°. By setting the slow axis in such a specific range, an optical laminate that can be effectively used as a material for a broadband antireflection film can be efficiently produced.
光学異方性層において、液晶化合物は、液晶相を呈した状態のまま固体となり、硬化液晶分子を形成しうる。
第１光学異方性層の硬化液晶分子は、好ましくは、基材の配向軸の方向と略同一方向に沿ったホモジニアス配向規則性を有しうる。また、第２光学異方性層の硬化液晶分子は、好ましくは、偏光紫外線の照射偏光方向と略同一方向に沿ったホモジニアス配向規則性を有しうる。ここで、「ホモジニアス配向規則性を有する」とは、硬化液晶分子のメソゲンの長軸方向をフィルム面に投影して得られる線の平均方向が、フィルム面に水平なある一の方向（例えば基材フィルムの表面ダイレクターの方向）に整列することをいう。さらに、ある所定の方向に「沿った」ホモジニアス配向規則性とは、当該整列方向が、前記所定の方向に略一致することをいう。例えば、前記所定の方向とは、基材等の配向規制方向である。硬化液晶分子がホモジニアス配向規則性を有しているか否か、及びその整列方向は、ＡｘｏＳｃａｎ（Ａｘｏｍｅｔｒｉｃｓ社製）に代表されるような位相差計を用いた遅相軸方向の測定と、遅相軸方向における入射角毎のレターデーション分布の測定とにより確認しうる。硬化液晶分子が、棒状の分子構造を有する重合性液晶化合物を重合させてなるものである場合は、通常は、当該重合性液晶化合物のメソゲンの長軸方向が、硬化液晶分子のメソゲンの長軸方向となる。
In the optically anisotropic layer, the liquid crystal compound becomes a solid while exhibiting a liquid crystal phase and can form a cured liquid crystal molecule.
The cured liquid crystal molecules of the first optically anisotropic layer may preferably have a homogeneous alignment regularity along a direction substantially the same as the alignment axis direction of the substrate. In addition, the cured liquid crystal molecules of the second optically anisotropic layer may preferably have a homogeneous alignment regularity along a direction substantially the same as the irradiation polarization direction of polarized ultraviolet light. Here, “having a homogeneous alignment regularity” means that the average direction of the lines obtained by projecting the long axis direction of the mesogens of the cured liquid crystal molecules on the film surface is a certain direction (for example, the base The direction of the surface director of the material film). Further, the homogeneous alignment regularity “along the certain direction” means that the alignment direction substantially coincides with the certain direction. For example, the predetermined direction is an orientation control direction of the base material or the like. Whether or not the cured liquid crystal molecules have a homogeneous alignment regularity and the alignment direction thereof are measured in a slow axis direction using a retarder represented by AxoScan (manufactured by Axometrics) and a slow phase direction. This can be confirmed by measuring the retardation distribution for each incident angle in the axial direction. When the cured liquid crystal molecule is formed by polymerizing a polymerizable liquid crystal compound having a rod-shaped molecular structure, usually, the major axis direction of the mesogen of the polymerizable liquid crystal compound is the major axis of the mesogen of the cured liquid crystal molecule. Direction.
基材として上に説明した所定の配向軸を有するものを用い、さらに光学異方性層の材料を適宜選択することにより、光学異方性層に、遅相軸の方向と略同一方向に沿ったホモジニアス配向規則性等の配向規則性を付与することができ、その結果、このような配向規則性を有する光学異方性層を得ることができる。 By using a substrate having the above-described predetermined orientation axis as the base material, and further selecting the material of the optically anisotropic layer as appropriate, the optically anisotropic layer can be formed along the same direction as the slow axis direction. Further, orientation regularity such as homogeneous orientation regularity can be imparted, and as a result, an optically anisotropic layer having such orientation regularity can be obtained.
光学異方性層の厚みは、特に限定されず、レターデーションなどの特性を所望の範囲とできるよう適宜調整することができる。具体的には、厚みの下限は０．５μｍ以上であることが好ましく、１．０μｍ以上であることがより好ましく、一方厚みの上限は１０μｍ以下であることが好ましく、７μｍ以下であることがより好ましく、５μｍ以下であることがさらにより好ましい。第１の液晶組成物及び第２の液晶組成物として、同じ組成物を用いる場合、光学異方性層の厚みを異なる厚みに調整することにより、一方をλ／４波長板、他方をλ／２波長板とすることができる。
光学異方性層の長さ及び幅は、基材と同様の長尺状のフィルム状の形状とすることができ、これを、必要に応じて所望の用途に適合した矩形などの形状に裁断することができる。
The thickness of the optically anisotropic layer is not particularly limited and can be appropriately adjusted so that characteristics such as retardation can be set in a desired range. Specifically, the lower limit of the thickness is preferably 0.5 μm or more, more preferably 1.0 μm or more, while the upper limit of the thickness is preferably 10 μm or less, more preferably 7 μm or less. The thickness is preferably 5 μm or less, and more preferably 5 μm or less. When the same composition is used as the first liquid crystal composition and the second liquid crystal composition, one of the λ/4 wavelength plates and the other of λ/ It can be a two-wave plate.
The length and width of the optically anisotropic layer can be a long film-like shape similar to that of the base material, and this is cut into a shape such as a rectangle suitable for a desired application, if necessary. can do.
〔８．光学異方性積層体〕
本発明の光学異方性積層体は、第１光学異方性層、光配向膜、及び第２光学異方性層をこの順に備える光学異方性積層体であって、前記本発明の光学積層体より基材を剥離してなる。本願においては、光学積層体より得られたこのような構成を有する積層体を、光学積層体と文言上区別するため「光学異方性積層体」と称する。
[8. Optically anisotropic laminate]
The optically anisotropic laminate of the present invention is an optically anisotropic laminate comprising a first optically anisotropic layer, a photo-alignment film and a second optically anisotropic layer in this order, The base material is peeled off from the laminate. In the present application, the laminated body having such a structure obtained from the optical laminated body is referred to as an “optical anisotropic laminated body” in order to distinguish it from the optical laminated body.
本発明の光学異方性積層体は、必要に応じてさらに、光学異方性層を保護するため光学異方性層に貼合された、マスキングフィルム等の保護フィルムを含みうる。マスキングフィルムとしては、既知のもの（例えば、トレテガー社製のＦＦ１０２５、「ＦＦ１０３５」；サンエー化研社製の「ＳＡＴ１１６Ｔ」、「ＳＡＴ２０３８Ｔ−ＪＳＬ」及び「ＳＡＴ４５３８Ｔ−ＪＳＬ」；藤森工業社製の「ＮＢＯ−０４２４」、「ＴＦＢ−Ｋ００１」、「ＴＦＢ−Ｋ０４２１」及び「ＴＦＢ−Ｋ２０２」；日立化成社製の「ＤＴ−２２００−２５」及び「Ｋ−６０４０」；寺岡製作所社製の「６０１０＃７５」、「６０１０＃１００」、「６０１１＃７５」及び「６０９３＃７５」）を用いうる。このようなマスキングフィルムを有する光学異方性積層体からは、光学異方性層を他の部材に容易に転写することができる。したがって、光学異方性層を有する光学素子を容易に製造することができる。 The optically anisotropic laminate of the present invention may further include a protective film such as a masking film attached to the optically anisotropic layer to protect the optically anisotropic layer, if necessary. Known masking films (for example, FF1025 and FF1035 manufactured by Treteger Co.; “SAT116T”, “SAT2038T-JSL” and “SAT4538T-JSL” manufactured by San-A Kaken Co., Ltd.; “NBO” manufactured by Fujimori Kogyo Co., Ltd. “-0424”, “TFB-K001”, “TFB-K0421” and “TFB-K202”; “DT-2200-25” and “K-6040” manufactured by Hitachi Chemical Co., Ltd.; “6010#75” manufactured by Teraoka Seisakusho. , “6010#100”, “6011#75” and “6093#75”) can be used. From the optically anisotropic laminate having such a masking film, the optically anisotropic layer can be easily transferred to another member. Therefore, an optical element having an optically anisotropic layer can be easily manufactured.
〔９．円偏光板〕
本発明の円偏光板は、前記本発明の光学異方性積層体と、長尺状の直線偏光子とをロールツーロールで貼合してなる。ロールツーロールでの貼合とは、長尺状のフィルムのロールからフィルムを繰り出し、これを搬送し、搬送ライン上で他のフィルムとの貼合の工程を行い、さらに得られた貼合物を巻き取りロールとする態様の貼合をいう。例えば、直線偏光子と光学異方性積層体とを貼合する場合、長尺状の光学異方性積層体のロールから光学異方性積層体を繰り出し、これを搬送し、搬送ライン上で直線偏光子との貼合の工程を行い、得られた貼合物を巻き取りロールとすることにより、ロールツーロールでの貼合を行いうる。この場合において、直線偏光子も、ロールから繰り出して貼合の工程に供給しうる。光学異方性積層体と貼合する直線偏光子としては、予め偏光子保護フィルムと貼合された複層構造の状態のものを用い、これを貼合してもよい。
[9. Circular polarizing plate]
The circularly polarizing plate of the present invention is obtained by laminating the optically anisotropic laminate of the present invention and a long linear polarizer by roll-to-roll. Roll-to-roll bonding is the process of feeding a film from a long film roll, transporting it, and performing the process of bonding with other films on the transportation line, and further obtaining the bonded product. Is used as a take-up roll. For example, when laminating a linear polarizer and an optically anisotropic laminate, the optically anisotropic laminate is unrolled from a long roll of the optically anisotropic laminate, and this is conveyed, on a conveying line. Roll-to-roll bonding can be performed by performing a step of bonding with a linear polarizer and using the obtained bonded product as a winding roll. In this case, the linear polarizer can also be fed from the roll and supplied to the bonding step. As the linear polarizer to be bonded to the optically anisotropic laminate, one having a multi-layer structure that is previously bonded to the polarizer protective film may be used, and this may be bonded.
本発明に用いる偏光子に自然光を入射させると一方の偏光だけが透過する。本発明に用いる偏光子の偏光度は特に限定されないが、好ましくは９８％以上、より好ましくは９９％以上である。偏光子の平均厚みは好ましくは５〜８０μｍである。 When natural light is incident on the polarizer used in the present invention, only one polarized light is transmitted. The degree of polarization of the polarizer used in the present invention is not particularly limited, but is preferably 98% or more, more preferably 99% or more. The average thickness of the polarizer is preferably 5 to 80 μm.
直線偏光子としては、液晶表示装置、及びその他の光学装置等の装置に用いられている既知の偏光子を用いうる。直線偏光子の例としては、ポリビニルアルコールフィルムにヨウ素又は二色性染料を吸着させた後、ホウ酸浴中で一軸延伸することによって得られるもの、及びポリビニルアルコールフィルムにヨウ素又は二色性染料を吸着させ延伸しさらに分子鎖中のポリビニルアルコール単位の一部をポリビニレン単位に変性することによって得られるものが挙げられる。直線偏光子の他の例としては、グリッド偏光子、多層偏光子、コレステリック液晶偏光子などの偏光を反射光と透過光に分離する機能を有する偏光子が挙げられる。これらのうちポリビニルアルコールを含有する偏光子が好ましい。また、直線偏光子としては、市販の製品（例えばサンリッツ社製、商品名「ＨＬＣ２−５６１８Ｓ」、「ＬＬＣ２−９２１８Ｓ」、「ＨＬＣ２−２５１８）、日東電工社製、商品名「ＴＥＧ１４６５ＤＵ」、「ＳＥＧ１４２３ＤＵ」、「ＳＥＧ５４２５ＤＵ」等）を用いうる。 As the linear polarizer, a known polarizer used in devices such as liquid crystal display devices and other optical devices can be used. Examples of the linear polarizer, after adsorbing iodine or dichroic dye on the polyvinyl alcohol film, those obtained by uniaxially stretching in a boric acid bath, and iodine or dichroic dye on the polyvinyl alcohol film Examples thereof include those obtained by adsorbing and stretching, and further modifying a part of polyvinyl alcohol units in the molecular chain into polyvinylene units. Other examples of linear polarizers include grid polarizers, multilayer polarizers, cholesteric liquid crystal polarizers, and other polarizers having the function of separating polarized light into reflected light and transmitted light. Of these, a polarizer containing polyvinyl alcohol is preferable. Further, as the linear polarizer, commercially available products (for example, manufactured by Sanritz Co., Ltd., trade names “HLC2-5618S”, “LLC2-9218S”, “HLC2-2518”), manufactured by Nitto Denko Corporation, trade names “TEG1465DU”, “SEG1423DU”. ,"SEG5425DU", etc.) can be used.
光学異方性積層体と、直線偏光子との貼合は、光学異方性積層体の、直線偏光子と貼合する側の光学異方性層が、λ／２波長板となり、且つ、直線偏光子の透過軸と、直線偏光子と貼合する側の光学異方性層の遅相軸とがなす角が１０〜２０°又は７０〜８０°となるよう行う。 For the bonding of the optically anisotropic laminate and the linear polarizer, the optically anisotropic layer on the side of the optically anisotropic laminate to be bonded to the linear polarizer is a λ/2 wavelength plate, and The angle formed by the transmission axis of the linear polarizer and the slow axis of the optically anisotropic layer on the side where the linear polarizer is attached is 10 to 20° or 70 to 80°.
本発明にかかるある製品（光学積層体、光学異方性積層体、円偏光板、表示装置等）において、面内の光学軸（遅相軸、透過軸、透過軸等）の方向及び幾何学的方向（フィルムの長手方向及び幅手方向等）の角度関係は、ある方向のシフトを正、他の方向のシフトを負として規定され、当該正及び負の方向は、当該製品内の構成要素において共通に規定される。例えば、ある円偏光板において、「直線偏光子の透過軸の方向に対するλ／２波長板の遅相軸の方向が１５°であり直線偏光子の透過軸の方向に対する１／４λ波長板の遅相軸の方向が７５°である」とは、下記の２通りの場合を表す：
・当該円偏光板を、そのある一方の面から観察すると、λ／２波長板の遅相軸の方向が、直線偏光子の透過軸の方向から時計周りに１５°シフトし、且つ１／４λ波長板の遅相軸の方向が、直線偏光子の透過軸の方向から時計周りに７５°シフトしている。
・当該円偏光板を、そのある一方の面から観察すると、λ／２波長板の遅相軸の方向が、直線偏光子の透過軸の方向から反時計周りに１５°シフトし、且つ１／４λ波長板の遅相軸の方向が、直線偏光子の透過軸の方向から反時計周りに７５°シフトしている。
In a certain product (optical laminate, optically anisotropic laminate, circularly polarizing plate, display device, etc.) according to the present invention, the direction and geometry of the in-plane optical axis (slow axis, transmission axis, transmission axis, etc.) The angular relationship between the target directions (longitudinal direction and width direction of the film, etc.) is defined as a shift in one direction being positive and a shift in the other direction being negative. The positive and negative directions are the constituent elements in the product. Commonly prescribed in. For example, in a certain circularly polarizing plate, “the direction of the slow axis of the λ/2 wavelength plate with respect to the direction of the transmission axis of the linear polarizer is 15°, and the retardation of the quarter wavelength plate with respect to the direction of the transmission axis of the linear polarizer is 1/4. "The direction of the phase axis is 75°" means the following two cases:
When observing the circularly polarizing plate from one side thereof, the direction of the slow axis of the λ/2 wave plate is shifted by 15° clockwise from the direction of the transmission axis of the linear polarizer, and 1/4λ The direction of the slow axis of the wave plate is shifted by 75° clockwise from the direction of the transmission axis of the linear polarizer.
When observing the circularly polarizing plate from one surface thereof, the direction of the slow axis of the λ/2 wave plate is shifted by 15° counterclockwise from the direction of the transmission axis of the linear polarizer, and 1/ The direction of the slow axis of the 4λ wavelength plate is shifted by 75° counterclockwise from the direction of the transmission axis of the linear polarizer.
本発明の円偏光板の好ましい例としては、以下の例（ａ）及び例（ｂ）が挙げられる。
例（ａ）：直線偏光子、λ／２波長板、及びλ／４波長板をこの順に有し、直線偏光子の透過軸の方向に対するλ／２波長板の遅相軸の方向が略１５°であり直線偏光子の透過軸の方向に対する１／４λ波長板の遅相軸の方向が略７５°である。
例（ｂ）：直線偏光子、λ／２波長板、及びλ／４波長板をこの順に有し、直線偏光子の透過軸の方向に対するλ／２波長板の遅相軸の方向が略７５°であり直線偏光子の透過軸の方向に対する１／４λ波長板の遅相軸の方向が略１５°である。
Preferable examples of the circularly polarizing plate of the present invention include the following examples (a) and (b).
Example (a): A linear polarizer, a λ/2 wave plate, and a λ/4 wave plate are provided in this order, and the direction of the slow axis of the λ/2 wave plate is approximately 15 with respect to the direction of the transmission axis of the linear polarizer. And the direction of the slow axis of the quarter-wave plate is approximately 75° with respect to the direction of the transmission axis of the linear polarizer.
Example (b): A linear polarizer, a λ/2 wave plate, and a λ/4 wave plate are provided in this order, and the direction of the slow axis of the λ/2 wave plate is approximately 75 with respect to the direction of the transmission axis of the linear polarizer. And the direction of the slow axis of the quarter-wave plate is about 15° with respect to the direction of the transmission axis of the linear polarizer.
本発明の製造方法で得られた光学積層体から、光学異方性積層体及び円偏光板を順次製造する工程を、図面を参照して説明する。図１は、本発明の製造方法で得られた光学積層体の一例を模式的に示す断面図であり、図２は、図１に示す光学積層体から得た光学異方性積層体の一例を模式的に示す断面図であり、図３は、図２に示す光学異方性積層体から得た円偏光板の一例を模式的に示す断面図である。 A process of sequentially manufacturing an optically anisotropic laminate and a circularly polarizing plate from the optical laminate obtained by the production method of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view schematically showing an example of the optical laminate obtained by the manufacturing method of the present invention, and FIG. 2 is an example of the optically anisotropic laminate obtained from the optical laminate shown in FIG. 3 is a cross-sectional view schematically showing, and FIG. 3 is a cross-sectional view schematically showing an example of a circularly polarizing plate obtained from the optically anisotropic laminate shown in FIG.
図１において、光学積層体１００は、基材１１１と、その面上に形成された第１光学異方性層１２１（λ／４）、その面上に形成された光配向層１３１、及びその面上に形成された第２光学異方性層１２２（λ／２）を備える。この例では、第１光学積層体１２１（λ／４）はλ／４波長板であり、一方第２光学異方性層１２２（λ／２）はλ／２波長板である。図２に示す光学異方性積層体２００は、光学積層体１００から基材１１１を剥離してなるものである。図３に示す円偏光板３００は、図２に示す光学異方性積層体２００の第２光学異方性層１２２（λ／２）側の面に、直線偏光子１４１を貼合してなるものである。
In FIG. 1, an optical
一般に、容易に入手しうる長尺の直線偏光子の多くは、その幅手方向に透過軸を有する。このような円偏光板３００において、第１光学異方性層１２１（λ／４）の遅相軸、第２光学異方性層１２２（λ／２）の遅相軸、及び直線偏光子の透過軸の関係の好ましい例は、下記例（３００−ａ）及び（３００−ｂ）の通りである。
Generally, most of the long linear polarizers that are easily available have a transmission axis in the width direction. In such a circularly
例（３００−ａ）：
直線偏光子の透過軸方向：幅手方向
第１光学異方性層１２１（λ／４）の遅相軸方向：幅手方向となす角略７５°
第２光学異方性層１２２（λ／２）の遅相軸方向：幅手方向となす角略１５°
Example (300-a):
Transmission axis direction of linear polarizer: width direction Slow axis direction of first optically anisotropic layer 121 (λ/4): angle formed with width direction about 75°
Slow axis direction of the second optically anisotropic layer 122 (λ/2): an angle formed with the width direction of about 15°
例（３００−ｂ）：
直線偏光子の透過軸方向：幅手方向
第１光学異方性層１２１（λ／４）の遅相軸方向：幅手方向となす角略１５°
第２光学異方性層１２２（λ／２）の遅相軸方向：幅手方向となす角略７５°
Example (300-b):
Transmission axis direction of linear polarizer: width direction Slow axis direction of first optically anisotropic layer 121 (λ/4): angle formed with width direction of about 15°
Slow axis direction of the second optically anisotropic layer 122 (λ/2): an angle formed with the width direction of about 75°
図４は、本発明の製造方法で得られた光学積層体の別の一例を模式的に示す断面図であり、図５は、図４に示す光学積層体から得た光学異方性積層体の一例を模式的に示す断面図であり、図６は、図５に示す光学異方性積層体から得た円偏光板の一例を模式的に示す断面図である。 FIG. 4 is a sectional view schematically showing another example of the optical layered body obtained by the manufacturing method of the present invention, and FIG. 5 is an optically anisotropic layered body obtained from the optical layered body shown in FIG. 6 is a sectional view schematically showing an example, and FIG. 6 is a sectional view schematically showing an example of a circularly polarizing plate obtained from the optically anisotropic laminate shown in FIG.
図４において、光学積層体４００は、基材１１１と、その面上に形成された第１光学異方性層４２２（λ／２）、その面上に形成された光配向層１３１、及びその面上に形成された第２光学異方性層４２１（λ／４）を備える。この例では、第１光学積層体４２２（λ／２）はλ／２波長板であり、一方第２光学異方性層４２１（λ／４）はλ／４波長板である。図５に示す光学異方性積層体５００は、光学積層体５００から基材１１１を剥離してなるものである。図６に示す円偏光板６００は、図５に示す光学異方性積層体５００の第１光学異方性層４２２（λ／２）側の面に、直線偏光子１４１を貼合してなるものである。
In FIG. 4, the optical
このような円偏光板６００において、第１光学異方性層４２２（λ／２）の遅相軸、第２光学異方性層４２１（λ／４）の遅相軸、及び直線偏光子の透過軸の関係の好ましい例は、下記例（６００−ａ）及び（６００−ｂ）の通りである。
In such a circularly
例（６００−ａ）：
直線偏光子の透過軸方向：幅手方向
第１光学異方性層４２２（λ／２）の遅相軸方向：幅手方向となす角略１５°
第２光学異方性層４２１（λ／４）の遅相軸方向：幅手方向となす角略７５°
Example (600-a):
Transmission axis direction of linear polarizer: width direction Slow axis direction of first optically anisotropic layer 422 (λ/2): angle formed with width direction of about 15°
Slow axis direction of the second optically anisotropic layer 421 (λ/4): an angle of approximately 75° with the width direction
例（６００−ｂ）：
直線偏光子の透過軸方向：幅手方向
第１光学異方性層４２２（λ／２）の遅相軸方向：幅手方向となす角略７５°
第２光学異方性層４２１（λ／４）の遅相軸方向：幅手方向となす角略１５°
Example (600-b):
Transmission axis direction of linear polarizer: width direction Slow axis direction of first optically anisotropic layer 422 (λ/2): angle formed with width direction about 75°
The slow axis direction of the second optically anisotropic layer 421 (λ/4): an angle formed with the width direction of about 15°
このような円偏光板は、ロールツーロールで製造することができ、且つ、長尺の形状の長手方向に平行な方向及び幅手方向に平行な方向に切断することにより、表示装置の反射防止フィルムとして適用可能な矩形の形状に切り出すことができるため、高品質の円偏光板として効率的に製造することが可能となる。 Such a circularly polarizing plate can be manufactured by roll-to-roll, and by cutting the long shape in a direction parallel to the longitudinal direction and a direction parallel to the width direction, antireflection of the display device is prevented. Since it can be cut into a rectangular shape applicable as a film, it becomes possible to efficiently manufacture a high-quality circularly polarizing plate.
本発明の円偏光板は、必要に応じてその他の任意の層を有していてもよい。任意の層の例としては、他の部材と接着するための接着層、フィルムの滑り性を良くするマット層、耐衝撃性ポリメタクリレート樹脂層などのハードコート層、反射防止層、防汚層等が挙げられる。 The circularly polarizing plate of the present invention may have any other layer as required. Examples of the optional layer include an adhesive layer for adhering to other members, a mat layer for improving the slipperiness of the film, a hard coat layer such as an impact-resistant polymethacrylate resin layer, an antireflection layer, an antifouling layer, etc. Are listed.
〔１０．有機エレクトロルミネッセンス表示装置〕
本発明の有機エレクトロルミネッセンス表示装置は、前記本発明の円偏光板を備える。本発明の有機エレクトロルミネッセンス表示装置において、円偏光板は、反射防止フィルムとして機能しうる。即ち、表示装置の表面に、上に述べた構成を有する円偏光板を、直線偏光子側の面が視認側に向くように設けることにより、装置外部から入射した光が装置内で反射して装置外部へ出射することを抑制することができ、その結果、表示装置の表示面のぎらつきなどの不所望な減少を抑制しうる。具体的には、装置外部から入射した光は、その一部の直線偏光のみが直線偏光子を通過し、次にそれが光学異方性層を通過することにより円偏光となる。ここでいう円偏光としては、実質的に反射防止機能を発現する範囲であれば楕円偏光も包含される。円偏光は、装置内の光を反射する構成要素（有機ＥＬ素子中の反射電極等）により反射され、再び光学異方性層を通過することにより、入射した直線偏光の偏光軸と直交する方向に偏光軸を有する直線偏光となり、直線偏光子を通過しなくなる。これにより、反射防止の機能が達成される。
[10. Organic electroluminescence display device)
An organic electroluminescence display device of the present invention includes the circularly polarizing plate of the present invention. In the organic electroluminescent display device of the present invention, the circularly polarizing plate can function as an antireflection film. That is, by providing the circularly polarizing plate having the above-described configuration on the surface of the display device so that the surface on the linear polarizer side faces the viewing side, light incident from the outside of the device is reflected inside the device. It is possible to suppress emission to the outside of the device, and as a result, it is possible to suppress undesired reduction of glare on the display surface of the display device. Specifically, in the light incident from the outside of the device, only a part of the linearly polarized light passes through the linear polarizer, and then it passes through the optically anisotropic layer to become circularly polarized light. The circularly polarized light referred to here includes elliptically polarized light as long as it is a range in which the antireflection function is substantially exhibited. Circularly polarized light is reflected by a component that reflects light inside the device (a reflective electrode in an organic EL element, etc.), and passes through the optically anisotropic layer again, so that it is a direction orthogonal to the polarization axis of the incident linearly polarized light. It becomes a linearly polarized light having a polarization axis at and does not pass through the linear polarizer. Thereby, the antireflection function is achieved.
以下、実施例を示して本発明について具体的に説明するが、本発明は以下に説明する実施例に限定されるものではなく、本発明の特許請求の範囲及びその均等の範囲を逸脱しない範囲において任意に変更して実施してもよい。
以下の説明において、量を表す「％」及び「部」は、別に断らない限り重量基準である。また、以下に説明する操作は、別に断らない限り、常温及び常圧の条件において行った。
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the examples described below, and does not depart from the scope of claims of the present invention and the scope of equivalents thereof. In any case, it may be changed and implemented.
In the following description, "%" and "parts" representing amounts are by weight unless otherwise specified. Further, the operations described below were performed under the conditions of normal temperature and normal pressure unless otherwise specified.
〔位相差値および遅相軸方向の測定方法〕
測定対象物を偏光解析装置（アクソメトリクス社製「ＡｘｏＳｃａｎ」）のステージに設置し、４方位角方位（０°、４５°、９０°、１３５°）に対し、極角−５０°〜５０°の範囲でデータを取得し、これにより位相差値及び遅相軸方向を測定した。
測定対象物が、延伸基材と他の層との複層物である場合は、取得したデータを多層解析ソフト（アクソメトリクス社製「Ｍｕｌｔｉ−Ｌａｙｅｒ Ａｎａｌｙｓｉｓ」）に入力し、延伸基材の物性を既知とし、光学異方性層の三次元屈折率および配向角をフィッティングパラメータとして算出し、それにより位相差値、遅相軸方向、及び（測定対象物が光学積層体である場合は）第１光学異方性層の遅相軸と第２光学異方性層の遅相軸との交差角度を求めた。
[Measurement method of phase difference value and slow axis direction]
The measurement target is installed on a stage of a polarization analyzer (“AxoScan” manufactured by Axometrics Co., Ltd.), and polar angles are −50° to 50° with respect to 4 azimuth angles (0°, 45°, 90°, 135°). The data was acquired in the range of, and thereby the phase difference value and the slow axis direction were measured.
When the measurement target is a multi-layered product of a stretched base material and another layer, the acquired data is input to a multilayer analysis software ("Multi-Layer Analysis" manufactured by Axometrics Co., Ltd.) to obtain the physical properties of the stretched base material. Is known, and the three-dimensional refractive index and orientation angle of the optically anisotropic layer are calculated as fitting parameters, whereby the retardation value, the slow axis direction, and (when the measurement target is an optical laminate) the The crossing angle between the slow axis of the first optically anisotropic layer and the slow axis of the second optically anisotropic layer was determined.
〔基材の配向軸方向と第１光学異方性層の遅相軸方向とのズレの測定方法〕
基材に第１の液晶組成物を塗布する前に、基材の第１の液晶組成物塗布面と反対の面に基準線を描いた。工程（Ｉ）、（ＩＩ）を経て、第１光学異方性層を形成した後、第１光学異方性層の面に、基材の基準面と重なる位置に、基準線を描いた。その後、第１光学異方性層を粘着剤を介してガラス板に転写し、基材から剥離した。その後、基材の配向軸方向及び第１光学異方性層の遅相軸のそれぞれを、ＡｘｏＳｃａｎ（アクソメトリクス社製）を用いて測定し、基材と配向軸方向と基材上の基準線とがなす角度、及び第１光学異方性層の遅相軸と第１光学異方性層上の基準線とがなす角度を求めた。これらの角度から、基材の配向軸方向と第１光学異方性層の遅相軸方向とのズレを求めた。
[Measurement Method of Deviation between Orientation Axis of Substrate and Slow Axis of First Optically Anisotropic Layer]
Before applying the first liquid crystal composition to the substrate, a reference line was drawn on the surface of the substrate opposite to the surface on which the first liquid crystal composition was applied. After forming the first optically anisotropic layer through steps (I) and (II), a reference line was drawn on the surface of the first optically anisotropic layer at a position overlapping with the reference surface of the substrate. Then, the first optically anisotropic layer was transferred to a glass plate via a pressure sensitive adhesive and peeled from the substrate. Then, each of the orientation axis direction of the substrate and the slow axis of the first optically anisotropic layer was measured using AxoScan (manufactured by Axometrics Co., Ltd.), and the substrate, orientation axis direction and reference line on the substrate were measured. The angle formed by and the angle formed by the slow axis of the first optically anisotropic layer and the reference line on the first optically anisotropic layer were determined. From these angles, the deviation between the orientation axis direction of the substrate and the slow axis direction of the first optically anisotropic layer was determined.
〔表面硬度〕
光学異方性層及び光配向層の表面硬度は、ＪＩＳＫ５６００−５−４に基づき、鉛筆硬度を測定して評価した。
〔surface hardness〕
The surface hardness of the optically anisotropic layer and the photo-alignment layer was evaluated by measuring the pencil hardness based on JISK5600-5-4.
〔表面傷の評価〕
光配向層及び第２光学異方性層の表面傷は、以下の評価基準に基づいて評価した。
良：偏光顕微鏡で観察した時に、スジ状の傷が無い。
可：偏光顕微鏡で観察した時に、スジ状の傷が少しある。
不良：偏光顕微鏡で観察した時に、スジ状の傷が多数ある。
[Evaluation of surface scratches]
The surface scratches of the photo-alignment layer and the second optically anisotropic layer were evaluated based on the following evaluation criteria.
Good: There is no streak-like scratch when observed with a polarizing microscope.
Fair: There are some streak-like scratches when observed with a polarizing microscope.
Poor: There are many streak-like scratches when observed with a polarizing microscope.
〔塗布ムラの評価〕
第２光学異方性層の塗布ムラは、以下の評価基準に基づいて評価した。
良：偏光顕微鏡で観察した時に、ムラが無い。
不良：偏光顕微鏡で観察した時に、ムラがある。
[Evaluation of coating unevenness]
The coating unevenness of the second optically anisotropic layer was evaluated based on the following evaluation criteria.
Good: There is no unevenness when observed with a polarizing microscope.
Poor: There is unevenness when observed with a polarizing microscope.
〔製造例１：延伸前基材Ａ〕
熱可塑性ノルボルネン樹脂のペレット（日本ゼオン株式会社製、商品名「ＺＥＯＮＯＲ１４２０Ｒ」、Ｔｇ１３７℃）を１００℃で５時間乾燥させた。乾燥させたペレットを押し出し機に供給し、押し出し機内で溶融させ、ポリマーパイプおよびポリマーフィルターを通し、Ｔダイからキャスティングドラム上にシート状に押し出し、冷却し、マスキングフィルム（トレテガー社製、ＦＦ１０２５）で保護しながら巻取り、厚み８０μｍ、幅１４９０ｍｍの延伸前基材のロール（Ａ）を得た。
[Production Example 1: Base material A before stretching]
Pellets of thermoplastic norbornene resin (manufactured by Nippon Zeon Co., Ltd., trade name “ZEONOR 1420R”, Tg 137° C.) were dried at 100° C. for 5 hours. The dried pellets are fed to an extruder, melted in the extruder, passed through a polymer pipe and a polymer filter, extruded in a sheet form from a T die onto a casting drum, cooled, and then masked with a masking film (FF1025 manufactured by Treteger). It was wound up while being protected to obtain a roll (A) of a base material before stretching having a thickness of 80 μm and a width of 1490 mm.
〔製造例２：延伸前基材Ｂ〕
熱可塑性ノルボルネン樹脂のペレットを、Ｔｇ１２６℃のもの（日本ゼオン株式会社製）に変更し、Ｔダイを変更した他は、製造例１と同様にして、厚み１００μｍ、幅１４９０ｍｍの延伸前基材のロール（Ｂ）を得た。
[Production Example 2: Base material B before stretching]
The thermoplastic norbornene resin pellets were changed to those having a Tg of 126° C. (manufactured by Nippon Zeon Co., Ltd.) and the T-die was changed, in the same manner as in Production Example 1 to prepare a base material before stretching having a thickness of 100 μm and a width of 1490 mm. A roll (B) was obtained.
〔製造例３：延伸前基材Ｃ〕
熱可塑性ノルボルネン樹脂のペレットを、Ｔｇ１２６℃のもの（日本ゼオン株式会社製）に変更し、Ｔダイを変更した他は、製造例１と同様にして、厚み６０μｍ、幅１３５０ｍｍの延伸前基材のロール（Ｃ）を得た。
[Production Example 3: Base material C before stretching]
A thermoplastic norbornene resin pellet having a Tg of 126° C. (manufactured by Nippon Zeon Co., Ltd.) was used, and the T die was changed, in the same manner as in Production Example 1 to prepare a pre-stretch base material having a thickness of 60 μm and a width of 1350 mm. A roll (C) was obtained.
〔製造例４：液晶組成物Ａ〕
重合性液晶化合物（商品名「ＬＣ２４２」ＢＡＳＦ社製、式（Ａ１）で示される化合物）２４．１５部、界面活性剤（商品名「フタージェントＦＴＸ−２０９Ｆ」、ネオス社製）０．１２部、重合開始剤（商品名「ＩＲＧＡＣＵＲＥ３７９」、ＢＡＳＦ社製）０．７３部、及び溶媒（メチルエチルケトン）７５．００部を混合し、液晶組成物を調製した。
[Production Example 4: Liquid crystal composition A]
Polymerizable liquid crystal compound (trade name "LC242" manufactured by BASF, compound represented by formula (A1)) 24.15 parts, surfactant (trade name "Futgent FTX-209F" manufactured by Neos) 0.12 parts A polymerization initiator (trade name “IRGACURE379”, manufactured by BASF) 0.73 part and a solvent (methyl ethyl ketone) 75.00 parts were mixed to prepare a liquid crystal composition.
〔実施例１〕
（１−１．延伸基材）
製造例１で得た長尺の延伸前基材Ａを、ロール（Ａ）から引き出し、連続的にマスキングフィルムを剥離してテンター延伸機に供給し、基材の配向角が幅手方向に対して１５°となるように斜め延伸を行った。新たなマスキングフィルム（トレテガー社製、ＦＦ１０２５）で保護しながら延伸された基材を巻き取り、延伸基材のロールを得た。得られた延伸基材の遅相軸は幅手方向に対して１５°、Ｒｅは２６５ｎｍ、膜厚は４０μｍであった。また、液晶組成物を塗布する面の表面粗さ（Ｒａ）は、０．００５μｍであった。
[Example 1]
(1-1. Stretched substrate)
The long pre-stretching base material A obtained in Production Example 1 was pulled out from the roll (A), the masking film was continuously peeled off, and the tenter stretching machine was supplied with the orientation angle of the base material in the width direction. Was obliquely stretched so as to be 15°. The stretched base material was wound up while being protected by a new masking film (FF1025, manufactured by Treteger Co., Ltd.) to obtain a stretched base material roll. The slow axis of the obtained stretched base material was 15° with respect to the width direction, Re was 265 nm, and the film thickness was 40 μm. The surface roughness (Ra) of the surface on which the liquid crystal composition was applied was 0.005 μm.
（１−２．工程（Ｉ））
（１−１）で得た延伸基材のロールから、延伸基材を繰り出し、連続的にマスキングフィルムを剥離して搬送した。搬送される延伸基材の、マスキングフィルムが貼合されていた側の面上に直接、製造例４で得た液晶組成物Ａを、ダイコーターを使用して室温２５℃にて塗布し、液晶組成物の層を形成した。
(1-2. Process (I))
The stretched base material was fed out from the roll of the stretched base material obtained in (1-1), and the masking film was continuously peeled off and conveyed. The liquid crystal composition A obtained in Production Example 4 was applied directly to the surface of the conveyed stretched base material on the side where the masking film had been bonded at a room temperature of 25° C. using a die coater. A layer of composition was formed.
（１−３．工程（ＩＩ））
（１−２）で延伸基材上に形成した液晶組成物の層を、１１０℃で２．５分間配向処理した。その後、窒素雰囲気下（酸素濃度０．１％以下）、積算光量１０００ｍＪ／ｃｍ２の紫外線を基材裏面側（液晶組成物の層が形成されている側とは反対側）に照射して、液晶組成物の層を硬化させた。これにより、延伸基材上に、Ｒｅ２４０ｎｍ、乾燥膜厚２．２μｍの、ホモジニアス配向した第１光学異方性層を形成し、（第１光学異方性層）／（延伸基材）の層構成を有する複層物を得た。第１光学異方性層の遅相軸方向と、基材の配向軸方向とのズレは１°であり、第１光学異方性層の表面硬度はＦであった。
(1-3. Step (II))
The layer of the liquid crystal composition formed on the stretched substrate in (1-2) was oriented at 110° C. for 2.5 minutes. Then, in a nitrogen atmosphere (oxygen concentration of 0.1% or less), the back surface of the substrate (the side opposite to the side on which the layer of the liquid crystal composition is formed) is irradiated with ultraviolet rays having an integrated light amount of 1000 mJ/cm 2 , The layer of liquid crystal composition was cured. As a result, a homogeneously oriented first optically anisotropic layer having a Re 240 nm and a dry film thickness of 2.2 μm is formed on the stretched substrate, and the (first optically anisotropic layer)/(stretched substrate) layer is formed. A multi-layered product having the constitution was obtained. The deviation between the slow axis direction of the first optically anisotropic layer and the orientation axis direction of the substrate was 1°, and the surface hardness of the first optically anisotropic layer was F.
（１−４．工程（ＩＩＩ））
（１−３）で得た複層物の第１光学異方性層側の面上に、光配向材料液（ＤＩＣ社製：ＬＩＡ−０２、固形分１重量％、溶媒２−ブトキシエタノール９９重量％）を＃２バーにより塗布し、８０℃にて２分間乾燥させて、光配向材料液の層を形成した。その後、光配向材料液の層の塗布面側（光配向材料液の層の、光学異方性層側と反対側）に、３１３ｎｍ付近の波長の直線偏光紫外線を照射し、光配向材料液の層を硬化させた。照射の方向の極角は０°（照射面に対して垂直）とし、直線偏光紫外線の偏光方向の方位角は、基材の幅手方向に対して７５°とした。照射の環境は、窒素雰囲気下（酸素濃度０．１％以下）、室温２５℃とした。照射の積算光量は５００ｍＪ／ｃｍ２とした。これにより、厚み０．０５μｍの光配向層を形成し、（光配向層）／（第１光学異方性層）／（延伸基材）の層構成を有する複層物を得た。光配向層の表面硬度はＢであった。光配向層の表面を偏光顕微鏡で観察し、表面傷の状態を評価したところ、「良」（スジ状の傷が無し）と判定された。
(1-4. Step (III))
On the surface of the multi-layered product obtained in (1-3) on the side of the first optical anisotropic layer, a photo-alignment material liquid (manufactured by DIC: LIA-02, solid content 1% by weight, solvent 2-butoxyethanol 99). % By weight) and dried at 80° C. for 2 minutes to form a layer of photo-alignment material liquid. After that, the coated surface side of the layer of the photo-alignment material liquid (the side opposite to the optically anisotropic layer side of the layer of the photo-alignment material liquid) is irradiated with linearly polarized ultraviolet light having a wavelength of about 313 nm, and The layer was cured. The polar angle of the irradiation direction was 0° (perpendicular to the irradiation surface), and the azimuth angle of the polarization direction of the linearly polarized ultraviolet light was 75° with respect to the width direction of the base material. The irradiation environment was a room temperature of 25° C. under a nitrogen atmosphere (oxygen concentration of 0.1% or less). The integrated light amount of irradiation was 500 mJ/cm 2 . As a result, a photo-alignment layer having a thickness of 0.05 μm was formed, and a multilayer product having a layer structure of (photo-alignment layer)/(first optical anisotropic layer)/(stretched substrate) was obtained. The surface hardness of the photo-alignment layer was B. When the surface of the photo-alignment layer was observed with a polarizing microscope and the state of surface scratches was evaluated, it was determined to be “good” (no streak-like scratches).
（１−５．工程（ＩＶ））
（１−４）で得た複層物の光配向層側の面上に、製造例４で得た液晶組成物Ａを、ダイコーターを使用して室温２５℃で塗布し、液晶組成物の層を形成した。この液晶組成物の層を１１０℃で２．５分間配向処理した。その後、窒素雰囲気下（酸素濃度０．１％以下）、２０００ｍＪ／ｃｍ２以上の紫外線を塗布面側（液晶組成物の層の、光配向層と反対側）に照射して、液晶組成物の層を硬化させた。これにより、光配向層上に、Ｒｅ１４５ｎｍ、乾燥膜厚１．１μｍの、ホモジニアス配向した第２光学異方性層を形成し、（第２光学異方性層）／（光配向層）／（第１光学異方性層）／（延伸基材）の層構成を有する光学積層体を得た。第２光学異方性層の遅相軸方向と、光配向層方向とのズレは１°であり、第２光学異方性層の表面硬度はＨＢであった。第２光学異方性層の表面を偏光顕微鏡で観察し、塗布ムラ及び表面傷の状態を評価したところ、塗布ムラは「良」（ムラなし）、表面傷は「可」（スジ状の傷が少しある）と判定された。
(1-5. Step (IV))
The liquid crystal composition A obtained in Production Example 4 was applied onto the surface of the multi-layered product obtained in (1-4) on the photo-alignment layer side at a room temperature of 25° C. using a die coater to give a liquid crystal composition. Layers were formed. The layer of the liquid crystal composition was aligned at 110° C. for 2.5 minutes. Then, in a nitrogen atmosphere (oxygen concentration of 0.1% or less), the coating surface side (the side of the liquid crystal composition layer opposite to the photo-alignment layer) is irradiated with ultraviolet rays of 2000 mJ/cm 2 or more to give a liquid crystal composition. The layer was cured. As a result, a homogeneously oriented second optically anisotropic layer having a Re of 145 nm and a dry film thickness of 1.1 μm is formed on the optical orientation layer, and the second optical anisotropic layer/(optical orientation layer)/( An optical laminate having a layer structure of (first optically anisotropic layer)/(stretched substrate) was obtained. The deviation between the slow axis direction of the second optically anisotropic layer and the direction of the photo-alignment layer was 1°, and the surface hardness of the second optically anisotropic layer was HB. When the surface of the second optically anisotropic layer was observed with a polarizing microscope and the state of coating unevenness and surface scratches was evaluated, the coating unevenness was “good” (no unevenness) and the surface scratches were “good” (streak-like scratches). There is a little)).
〔実施例２〕
（２−１．延伸基材）
製造例２で得た長尺の延伸前基材Ｂを、ロール（Ｂ）から引き出し、連続的にマスキングフィルムを剥離してテンター延伸機に供給し、斜め延伸、及びそれに続く縦延伸を連続的に行った。その結果、基材の配向角は幅手方向に対して７５°となった。新たなマスキングフィルム（トレテガー社製、ＦＦ１０２５）で保護しながら延伸された基材を巻き取り、延伸基材のロールを得た。得られた延伸基材の遅相軸は幅手方向に対して７５°、Ｒｅは１４０ｎｍ、膜厚は５７μｍであった。
[Example 2]
(2-1. Stretched substrate)
The long pre-stretched base material B obtained in Production Example 2 is pulled out from the roll (B), the masking film is continuously peeled off, and the tenter stretcher is supplied with the slanted stretch and the subsequent longitudinal stretch. Went to. As a result, the orientation angle of the substrate was 75° with respect to the width direction. The stretched base material was wound up while being protected by a new masking film (FF1025, manufactured by Treteger Co., Ltd.) to obtain a stretched base material roll. The slow axis of the obtained stretched base material was 75° with respect to the width direction, Re was 140 nm, and the film thickness was 57 μm.
（２−２．工程（Ｉ）〜（ＩＶ））
下記の事項を変更した他は実施例１の（１−２）〜（１−５）と同一の操作で光学積層体を製造し評価した。評価結果を表１〜表４に示す。
・（１−２）において、延伸基材として、実施例１の（１−１）で得たものに代えて、（２−１）で得たものを用いた。
・（１−３）において、紫外線の照射の積算光量を２０００ｍＪ／ｃｍ２に変更した。
・（１−２）における液晶組成物の塗布厚みを調整した。その結果、（１−３）において得られた第１光学異方性層のＲｅは１４５ｎｍ、乾燥膜厚は１．１μｍであった。
・（１−４）において、直線偏光紫外線の偏光方向の方位角は、基材の幅手方向に対して１５°とした。
・（１−５）において、液晶組成物の塗布厚みを調整した。得られた第２光学異方性層のＲｅは２６０ｎｍ、乾燥膜厚は２．２μｍであった。
(2-2. Steps (I) to (IV))
An optical layered body was manufactured and evaluated by the same operations as in (1-2) to (1-5) of Example 1 except that the following matters were changed. The evaluation results are shown in Tables 1 to 4.
In (1-2), as the stretched base material, the one obtained in (2-1) was used in place of the one obtained in (1-1) of Example 1.
-In (1-3), the integrated light amount of ultraviolet irradiation was changed to 2000 mJ/cm 2 .
The coating thickness of the liquid crystal composition in (1-2) was adjusted. As a result, Re of the first optically anisotropic layer obtained in (1-3) was 145 nm, and the dry film thickness was 1.1 μm.
In (1-4), the azimuth angle of the polarization direction of the linearly polarized ultraviolet light was 15° with respect to the width direction of the base material.
-In (1-5), the coating thickness of the liquid crystal composition was adjusted. The Re of the obtained second optically anisotropic layer was 260 nm, and the dry film thickness was 2.2 μm.
〔実施例３〕
（３−１．延伸基材）
製造例１で得た長尺の延伸前基材Ａを、ロール（Ａ）から引き出し、連続的にマスキングフィルムを剥離してテンター延伸機に供給し、斜め延伸、及びそれに続く縦延伸を連続的に行った。その結果、基材の配向角は幅手方向に対して７５°となった。新たなマスキングフィルム（トレテガー社製、ＦＦ１０２５）で保護しながら延伸された基材を巻き取り、延伸基材のロールを得た。得られた延伸基材の遅相軸は幅手方向に対して７５°、Ｒｅは１４４ｎｍ、膜厚は５４μｍであった。
[Example 3]
(3-1. Stretched substrate)
The long pre-stretching base material A obtained in Production Example 1 is pulled out from the roll (A), the masking film is continuously peeled off, and the tenter stretching machine is supplied with the diagonal stretching and the subsequent longitudinal stretching continuously. Went to. As a result, the orientation angle of the substrate was 75° with respect to the width direction. The stretched base material was wound up while being protected by a new masking film (FF1025, manufactured by Treteger Co., Ltd.) to obtain a stretched base material roll. The slow axis of the obtained stretched base material was 75° with respect to the width direction, Re was 144 nm, and the film thickness was 54 μm.
（３−２．工程（Ｉ）〜（ＩＶ））
下記の事項を変更した他は実施例１の（１−２）〜（１−５）と同一の操作で光学積層体を製造し評価した。評価結果を表１〜表４に示す。
・（１−２）において、延伸基材として、実施例１の（１−１）で得たものに代えて、（３−１）で得たものを用いた。
・（１−３）において、紫外線の照射の積算光量を１５００ｍＪ／ｃｍ２に変更した。また、得られた第１光学異方性層の厚み等が若干変動し、Ｒｅは２４５ｎｍ、乾燥膜厚は２．１μｍであった。
・（１−４）において、直線偏光紫外線の偏光方向の方位角は、基材の幅手方向に対して１５°とした。
・（１−５）において、得られた第２光学異方性層の厚み等が若干変動し、Ｒｅは１４８ｎｍ、乾燥膜厚は１．２μｍであった。
(3-2. Steps (I) to (IV))
An optical layered body was manufactured and evaluated by the same operations as in (1-2) to (1-5) of Example 1 except that the following matters were changed. The evaluation results are shown in Tables 1 to 4.
In (1-2), as the stretched base material, instead of the stretched base material obtained in (1-1) of Example 1, the one obtained in (3-1) was used.
-In (1-3), the integrated light amount of ultraviolet irradiation was changed to 1500 mJ/cm 2 . Further, the thickness and the like of the obtained first optically anisotropic layer were slightly changed, Re was 245 nm, and the dry film thickness was 2.1 μm.
In (1-4), the azimuth angle of the polarization direction of the linearly polarized ultraviolet light was 15° with respect to the width direction of the base material.
In (1-5), the thickness and the like of the obtained second optically anisotropic layer were slightly changed, Re was 148 nm, and the dry film thickness was 1.2 μm.
〔実施例４〕
下記の事項を変更した他は実施例１と同一の操作で光学積層体を製造し評価した。評価結果を表１〜表４に示す。
・（１−１）において、製造例１で得た延伸前基材Ａに代えて、製造例３で得た延伸前基材Ｃを用いた。得られた延伸基材の遅相軸は幅手方向に対して１５°、Ｒｅは１４１ｎｍ、膜厚は２５μｍであった。
・（１−２）において、延伸基材として、実施例１の（１−１）で得たものに代えて、（４−１）で得たものを用いた。
・（１−３）において、紫外線の照射を、基材裏面側ではなく塗布面側（液晶組成物の層が形成されている側）への照射とした。また、積算光量は５００ｍＪ／ｃｍ２に変更した。
・（１−２）における液晶組成物の塗布厚みを調整した。その結果、（１−３）において得られた第１光学異方性層のＲｅは１４８ｎｍ、乾燥膜厚は１．２μｍであった。
・（１−５）において、液晶組成物の塗布厚みを調整した。得られた第２光学異方性層のＲｅは２５５ｎｍ、乾燥膜厚は２．１μｍであった。
[Example 4]
An optical layered body was manufactured and evaluated by the same operation as in Example 1 except that the following matters were changed. The evaluation results are shown in Tables 1 to 4.
In (1-1), the pre-stretch base material C obtained in Production Example 3 was used in place of the pre-stretch base material A obtained in Production Example 1. The slow axis of the obtained stretched substrate was 15° with respect to the width direction, Re was 141 nm, and the film thickness was 25 μm.
In (1-2), as the stretched base material, the one obtained in (4-1) was used instead of the one obtained in (1-1) of Example 1.
In (1-3), the irradiation of ultraviolet rays was performed not on the back surface side of the substrate but on the coating surface side (the side where the liquid crystal composition layer is formed). Further, the integrated light amount was changed to 500 mJ/cm 2 .
The coating thickness of the liquid crystal composition in (1-2) was adjusted. As a result, Re of the first optically anisotropic layer obtained in (1-3) was 148 nm, and the dry film thickness was 1.2 μm.
-In (1-5), the coating thickness of the liquid crystal composition was adjusted. The Re of the obtained second optically anisotropic layer was 255 nm, and the dry film thickness was 2.1 μm.
〔実施例５〕
下記の事項を変更した他は実施例１と同一の操作で光学積層体を製造し評価した。評価結果を表１〜表４に示す。
・（１−３）において、紫外線の照射の積算光量を１５００ｍＪ／ｃｍ２に変更した。また、得られた第１光学異方性層の厚み等が若干変動し、Ｒｅは２３５ｎｍ、乾燥膜厚は２．１μｍであった。
・（１−４）において、直線偏光紫外線の積算光量を１０００ｍＪ／ｃｍ２に変更した。
・（１−５）において、得られた第２光学異方性層の厚み等が若干変動し、Ｒｅは１４４ｎｍ、乾燥膜厚は１．１μｍであった。
[Example 5]
An optical layered body was manufactured and evaluated by the same operation as in Example 1 except that the following matters were changed. The evaluation results are shown in Tables 1 to 4.
-In (1-3), the integrated light amount of ultraviolet irradiation was changed to 1500 mJ/cm 2 . Further, the thickness and the like of the obtained first optically anisotropic layer were slightly changed, Re was 235 nm, and the dry film thickness was 2.1 μm.
-In (1-4), the integrated light amount of linearly polarized ultraviolet light was changed to 1000 mJ/cm 2 .
In (1-5), the thickness and the like of the obtained second optically anisotropic layer were slightly changed, Re was 144 nm, and the dry film thickness was 1.1 μm.
〔比較例１〕
下記の事項を変更した他は実施例１の（１−１）〜（１−４）と同一の操作を行い、複層物を得て評価した。但し、光配向層の状態が不良であったため、実施例１の工程（１−５）に相当する工程は行わなかった。評価結果を表１〜表４に示す。
・（１−３）において、紫外線の照射の積算光量を２００ｍＪ／ｃｍ２に変更し、照射の環境を、窒素雰囲気下ではなく、空気下に変更した。また、得られた第１光学異方性層の厚み等が若干変動し、Ｒｅは２３３ｎｍ、乾燥膜厚は２．１μｍであった。
・（１−４）において、直線偏光紫外線の積算光量を２００ｍＪ／ｃｍ２に変更し、照射の環境を、窒素雰囲気下ではなく、空気下に変更した。
[Comparative Example 1]
The same operations as (1-1) to (1-4) of Example 1 were performed except that the following matters were changed, and a multilayer product was obtained and evaluated. However, since the state of the photo-alignment layer was poor, the step corresponding to the step (1-5) of Example 1 was not performed. The evaluation results are shown in Tables 1 to 4.
-In (1-3), the integrated light amount of ultraviolet irradiation was changed to 200 mJ/cm 2 , and the irradiation environment was changed to air instead of nitrogen atmosphere. Further, the thickness and the like of the obtained first optically anisotropic layer were slightly changed, Re was 233 nm, and the dry film thickness was 2.1 μm.
In (1-4), the integrated light amount of linearly polarized ultraviolet light was changed to 200 mJ/cm 2 , and the irradiation environment was changed to air instead of nitrogen atmosphere.
〔比較例２〕
下記の事項を変更した他は実施例１と同一の操作を行い、複層物を得て評価した。評価結果を表１〜表４に示す。
・（１−３）において、紫外線の照射の積算光量を５００ｍＪ／ｃｍ２に変更した。
・（１−４）において、直線偏光紫外線の積算光量を２００ｍＪ／ｃｍ２に変更し、照射の環境を、窒素雰囲気下ではなく、空気下に変更した。
[Comparative Example 2]
The same operation as in Example 1 was performed except that the following items were changed, and a multilayer product was obtained and evaluated. The evaluation results are shown in Tables 1 to 4.
-In (1-3), the integrated light amount of ultraviolet irradiation was changed to 500 mJ/cm 2 .
In (1-4), the integrated light amount of linearly polarized ultraviolet light was changed to 200 mJ/cm 2 , and the irradiation environment was changed to air instead of nitrogen atmosphere.
実施例及び比較例の結果から、本発明によれば、基材上に第１光学異方性層、光配向層、及び第２光学異方性層を順次形成する製造方法で、各層の表面傷及び塗布ムラの少ない光学積層体を容易に製造することができ、従って、そのような光学異方性層を備えた円偏光板等の製造を効率的に行いうることが分かる。 From the results of the examples and the comparative examples, according to the present invention, the surface of each layer is a production method in which the first optically anisotropic layer, the photo-alignment layer, and the second optically anisotropic layer are sequentially formed on the substrate. It can be seen that an optical laminate having few scratches and coating unevenness can be easily produced, and thus a circularly polarizing plate or the like provided with such an optically anisotropic layer can be efficiently produced.
１００：光学積層体
１１１：基材
１２１（λ／４）：第１光学異方性層
１３１：光配向層
１２２（λ／２）：第２光学異方性層
２００：光学異方性積層体
３００：円偏光板
１４１：直線偏光子
４００：光学積層体
４２２（λ／２）：第１光学異方性層
４２１（λ／４）：第２光学異方性層
５００：光学異方性積層体
６００：円偏光板
100: Optical laminate 111: Substrate 121 (λ/4): First optical anisotropic layer 131: Photo-alignment layer 122 (λ/2): Second optical anisotropic layer 200: Optical anisotropic laminate 300: Circularly polarizing plate 141: Linear polarizer 400: Optical laminated body 422 (λ/2): First optical anisotropic layer 421 (λ/4): Second optical anisotropic layer 500: Optical anisotropic laminated layer Body 600: circularly polarizing plate
Claims (8)
長尺状の基材上に、直接、第１の液晶化合物を含有する第１の液晶組成物を塗布し、第１の液晶組成物の層を得る工程（Ｉ）、
前記第１の液晶組成物の層中の前記第１の液晶化合物を配向させ、前記第１の液晶組成物の層に不活性ガス雰囲気下で活性エネルギー線を照射し前記第１の液晶組成物を硬化させ、表面の鉛筆硬度がＨＢ以上４Ｈ以下である第１光学異方性層を形成する工程（ＩＩ）、
前記第１光学異方性層上に、直接、光配向材料を含む液を塗布して光配向材料を含む液の層を得て、不活性ガス雰囲気下、前記基材の幅手方向と異なる方向の照射偏光方向を有する偏光紫外線を前記光配向材料を含む液の層に照射し、前記光配向材料を含む液を硬化させ表面の鉛筆硬度がＢ以上４Ｈ以下である光配向層を形成する工程（ＩＩＩ）、及び
前記光配向層上に、直接、第２の液晶化合物を含有する第２の液晶組成物を塗布して第２の液晶組成物の層を得て、前記第２の液晶組成物の層中の前記第２の液晶化合物を配向させ、前記第２の液晶組成物の層に活性エネルギー線を照射し前記第２の液晶組成物を硬化させ、第２光学異方性層を形成する工程（ＩＶ）
を含み、
前記工程（ＩＩ）における照射の積算光量が１０００ｍＪ／ｃｍ２以上であり、前記工程（ＩＩＩ）における照射の積算光量が５００ｍＪ／ｃｍ ２ 以上である、製造方法。 A method of manufacturing an optical layered body,
A step (I) of directly applying a first liquid crystal composition containing a first liquid crystal compound onto a long substrate to obtain a layer of the first liquid crystal composition,
The first liquid crystal composition is prepared by aligning the first liquid crystal compound in the layer of the first liquid crystal composition, and irradiating the layer of the first liquid crystal composition with an active energy ray under an inert gas atmosphere. (II), in which the first optical anisotropic layer having a pencil hardness of HB or more and 4H or less is cured.
A liquid containing a photo-alignment material is directly applied onto the first optically anisotropic layer to obtain a layer of a liquid containing the photo-alignment material, which is different from the width direction of the substrate in an inert gas atmosphere. Irradiation to the layer of the liquid containing the photo-alignment material by irradiating the layer of the liquid containing the photo-alignment material with polarized ultraviolet light having a polarization direction to form a photo-alignment layer having a pencil hardness of B or more and 4H or less. Step (III), and directly coating the second liquid crystal composition containing the second liquid crystal compound on the photo-alignment layer to obtain a layer of the second liquid crystal composition, and the second liquid crystal. A second optically anisotropic layer, in which the second liquid crystal compound in the composition layer is aligned, and the second liquid crystal composition layer is irradiated with an active energy ray to cure the second liquid crystal composition; Forming step (IV)
Including
The integrated quantity of light irradiation in the step (II) is Ri Der 1000 mJ / cm 2 or more, the accumulated amount of irradiation in the step (III) is 500 mJ / cm 2 or more, the production method.
前記工程（ＩＩＩ）における前記照射偏光方向が、前記幅手方向となす角度が１０〜２０°又は７０〜８０°である、製造方法。 It is a manufacturing method of the optical laminated body of Claim 1, Comprising:
The manufacturing method, wherein the irradiation polarization direction in the step (III) forms an angle with the width direction of 10 to 20° or 70 to 80°.
前記工程（ＩＩ）および前記工程（ＩＩＩ）における照射の積算光量の合計が１５００ｍＪ／ｃｍ２以上である、製造方法。 It is a manufacturing method of the optical laminated body of Claim 1 or 2, Comprising:
The manufacturing method, wherein the total of the integrated light amounts of irradiation in the step (II) and the step (III) is 1500 mJ/cm 2 or more.
前記工程（ＩＩＩ）における照射の積算光量が１０００ｍＪ／ｃｍ２以上である、製造方法。 It is a manufacturing method of the optical laminated body of any one of Claims 1-3, Comprising:
The manufacturing method, wherein the integrated light amount of irradiation in the step (III) is 1000 mJ/cm 2 or more.
前記基材として延伸前基材を延伸して得られた延伸基材を用いる、製造方法。 It is a manufacturing method of the optical laminated body of any one of Claims 1-4, Comprising:
A manufacturing method using a stretched substrate obtained by stretching a substrate before stretching as the substrate.
前記工程（ＩＩＩ）における基材の張力が１００〜５００Ｎ／ｍである、製造方法。 The manufacturing method, wherein the tension of the base material in the step (III) is 100 to 500 N/m.
前記光学積層体より前記基材を剥離して、光学異方性積層体を得る工程と、
前記光学異方性積層体と、長尺状の直線偏光子とをロールツーロールで貼合する貼合工程と、を含み、
前記光学異方性積層体は、第１光学異方性層、光配向膜、及び第２光学異方性層をこの順に備え、
前記光学異方性積層体の、前記直線偏光子と貼合する側の前記光学異方性層が、λ／２波長板であり、
前記貼合工程において、前記直線偏光子の透過軸と、前記直線偏光子と貼合する側の前記光学異方性層の遅相軸とがなす角が１０〜２０°又は７０〜８０°となるように前記光学異方性積層体と、前記直線偏光子とを貼合する、円偏光板の製造方法。 A method of manufacturing a circularly polarizing plate using the optical laminate manufactured by the method according to any one of claims 1 to 6
Peeling the substrate from the optical laminate to obtain an optically anisotropic laminate,
A laminating step of laminating the optically anisotropic laminate and a long linear polarizer with roll-to-roll,
The optically anisotropic laminate has a first optically anisotropic layer, a photo-alignment film, and a second optically anisotropic layer in this order,
The optically anisotropic layer on the side of the optically anisotropic laminate that is bonded to the linear polarizer is a λ/2 wavelength plate,
In the bonding step, the angle formed by the transmission axis of the linear polarizer and the slow axis of the optically anisotropic layer on the side bonded to the linear polarizer is 10 to 20° or 70 to 80°. A method for producing a circularly polarizing plate, comprising laminating the optically anisotropic laminate and the linear polarizer so that
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