JP5973911B2 - Optical element, and retardation film, optical film and image display apparatus having the optical element - Google Patents
Optical element, and retardation film, optical film and image display apparatus having the optical element Download PDFInfo
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- JP5973911B2 JP5973911B2 JP2012513771A JP2012513771A JP5973911B2 JP 5973911 B2 JP5973911 B2 JP 5973911B2 JP 2012513771 A JP2012513771 A JP 2012513771A JP 2012513771 A JP2012513771 A JP 2012513771A JP 5973911 B2 JP5973911 B2 JP 5973911B2
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
- G02F1/133634—Birefringent elements, e.g. for optical compensation the refractive index Nz perpendicular to the element surface being different from in-plane refractive indices Nx and Ny, e.g. biaxial or with normal optical axis
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2413/00—Indexing scheme related to G02F1/13363, i.e. to birefringent elements, e.g. for optical compensation, characterised by the number, position, orientation or value of the compensation plates
- G02F2413/12—Biaxial compensators
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Description
本発明は、液晶表示装置等の画像表示装置に有用な光学素子ならびにこれを用いた偏光フィルムの視野角改良方法に関する。 The present invention relates to an optical element useful for an image display device such as a liquid crystal display device and a method for improving the viewing angle of a polarizing film using the same.
液晶表示装置において必須の部材である偏光フィルムは、例えば、下記のようにして得ることが出来る。
まず、水溶性の二色性染料や多ヨウ素イオン等の二色性色素を含浸させたポリビニルアルコールフィルムをホウ酸温水溶液中で一軸延伸するか、または、ポリビニルアルコールフィルムを一軸延伸し、次いで脱水反応により、ポリエン構造を形成させることにより偏光素子を得る。次いで、表層がアルカリ処理されたトリアセチルセルロースフィルム、または、シクロオレフィンポリマーなどの保護フィルムで、該偏光素子を、接着剤を用いて挟持することにより、目的とする偏光版を得ることが出来る。The polarizing film which is an essential member in the liquid crystal display device can be obtained, for example, as follows.
First, a polyvinyl alcohol film impregnated with a water-soluble dichroic dye or a dichroic dye such as polyiodine ion is uniaxially stretched in a boric acid warm aqueous solution, or the polyvinyl alcohol film is uniaxially stretched and then dehydrated. A polarizing element is obtained by forming a polyene structure by reaction. Next, the target polarizing plate can be obtained by sandwiching the polarizing element with an adhesive using a protective film such as a triacetyl cellulose film whose surface layer has been subjected to alkali treatment or a cycloolefin polymer.
しかしながら、このような偏光素子または偏光フィルムを２枚用い、各々の吸収軸を直交するように配置した場合、正面方向からの各々の吸収軸方向とは異なる方向に観察位置を傾斜させると、入射側の偏光素子または偏光フィルムを通過した偏光が出射側偏光板に十分に吸収されず光が漏れてしまうという、いわゆる偏光素子または偏光フィルムの視野角依存性の問題があった。この現象は、垂直配向（ＶＡ）型、インプレーンスイッチング（ＩＰＳ）型、ベンドネマチック（ＯＣＢ）型等の種々の液晶セルを用いた液晶表示装置の視野角特性に特に大きな影響を与えていた。 However, when two such polarizing elements or polarizing films are used and the absorption axes are arranged so as to be orthogonal to each other, if the observation position is tilted in a direction different from the respective absorption axis directions from the front direction, the incident light is incident. There is a problem of the viewing angle dependency of the so-called polarizing element or polarizing film that the polarized light that has passed through the polarizing element or polarizing film on the side is not sufficiently absorbed by the output side polarizing plate and light leaks. This phenomenon has a particularly large influence on the viewing angle characteristics of a liquid crystal display device using various liquid crystal cells such as a vertical alignment (VA) type, an in-plane switching (IPS) type, and a bend nematic (OCB) type.
そのような課題に対して、特許文献１では、位相差フィルムの光学定数を規定することにより、斜め視野における液晶層や光学補償部材の影響を低減し、斜め方向の黒輝度の改善および色付きの低減をする方法が提案されている。また、非特許文献１では２枚の位相差板を用いて偏光フィルムの視野角依存性を低減する方法が開示されている。 For such a problem, in Patent Document 1, by defining the optical constant of the retardation film, the influence of the liquid crystal layer and the optical compensation member in the oblique visual field is reduced, the black luminance in the oblique direction is improved, and the colored film is colored. A reduction method has been proposed. Non-Patent Document 1 discloses a method of reducing the viewing angle dependency of a polarizing film using two retardation plates.
しかしながら、特許文献１の方法では、十分に視野角依存性を改善することができ無い。また、非特許文献１の方法では、用いる位相差フィルムの波長依存性により、特定の波長の視野角依存性は改善できても他の波長については不十分なため、着色した光が漏れてしまう。
こうした、偏光フィルムの視野角改良効果の波長依存性については、特許文献２あるいは非特許文献２にあるような方法により、効果的に改善できるものの、複数のフィルムを積層しなければならないという煩雑さがある。However, the method of Patent Document 1 cannot sufficiently improve the viewing angle dependency. In addition, in the method of Non-Patent Document 1, colored light leaks because the wavelength dependency of the retardation film to be used can improve the viewing angle dependency of a specific wavelength but other wavelengths are insufficient. .
Although the wavelength dependency of the viewing angle improvement effect of the polarizing film can be effectively improved by the method as described in
以上のように、偏光素子または偏光フィルムの視野角依存性を改良する方法は種々あるものの、視野角改良効果の波長依存性と複数のフィルムを用いる煩雑さとを同時に解決することはできなかった。そこで本発明は、複数のフィルムを用いること無しに、偏光素子または偏光フィルムの視野角依存性を改善すると共に、波長依存性をも低減する光学素子を提供することを目的とする。 As described above, although there are various methods for improving the viewing angle dependency of the polarizing element or the polarizing film, the wavelength dependency of the viewing angle improving effect and the complexity of using a plurality of films cannot be solved at the same time. Accordingly, an object of the present invention is to provide an optical element that improves the viewing angle dependency of the polarizing element or the polarizing film and also reduces the wavelength dependency without using a plurality of films.
本発明者らは、少なくとも２種類以上の二色性色素を含有させた３次元屈折率がｎｘ＞ｎｚ＞ｎｙであって、かつ、Ｎｚ係数が０．２〜０．７である光学異方層からなる光学素子（位相差素子）または該光学素子を透明基板上に有する位相差フィルムが上記の課題解決のために非常に有用であることを見出した。なお、本明細書においてＮｚ係数とは、（nx―nz）／(nx―ny)の値を意味する。
例えば、該光学素子を偏光フィルム上に形成する等により、この光学素子を設けた偏光フィルムを作成し、この光学素子付き偏光フィルムと通常の偏光フィルムとを、該光学素子が偏光素子間に配置されるように、両偏光素子の吸収軸を直交させて配置した場合上記問題を解決出来ること、即ち、正面方向からの各々の吸収軸方向とは異なる方向に観察位置を傾斜させても、光の抜けが低減され、かつ、漏れたわずかな光も着色することなく、偏光フィルムの視野角依存性および視野角改善効果の波長依存性も大幅に低減できることを新規に見出し、本発明に至った。即ち本発明は、下記の発明に関する。The inventors of the present invention have a three-dimensional refractive index containing at least two or more types of dichroic dyes, nx>nz> ny and an Nz coefficient of 0.2 to 0.7. It has been found that an optical element comprising a layer (retardation element) or a retardation film having the optical element on a transparent substrate is very useful for solving the above problems. In this specification, the Nz coefficient means a value of (nx−nz) / (nx−ny).
For example, by forming the optical element on a polarizing film, a polarizing film provided with the optical element is created, and the polarizing film with the optical element and a normal polarizing film are disposed between the polarizing elements. As described above, when the absorption axes of the two polarizing elements are arranged orthogonally, the above problem can be solved, that is, even if the observation position is inclined in a direction different from the respective absorption axis directions from the front direction, The present inventors have newly found that the viewing angle dependency of the polarizing film and the wavelength dependency of the viewing angle improvement effect can be greatly reduced without coloring the slight leaked light, and the present invention has been achieved. . That is, the present invention relates to the following inventions.
(１） 少なくとも２種の有機色素を含み、面内の最大屈折率をnx、ｎxと面内で直交する屈折率をny、面に対して鉛直方向の屈折率をnzとした時、３次元屈折率がｎx＞ｎｚ＞ｎyで、（nx―nz）／(nx―ny)が０．２〜０．７である着色及び配向された光学異方層からなる光学素子。
(２) 前記有機色素の少なくとも一つの有機色素の極大吸収波長が３８０ｎｍ以上５５０ｎｍ未満であり、他方の少なくとも一つの有機色素の極大吸収波長が５５０ｎｍ以上７８０ｎｍ以下であることを特徴とする上記（１）に記載の光学素子。
(３) 前記有機色素がアゾ系化合物、アントラキノン系化合物、ペリレン化合物、キノフタロン系化合物、ナフトキノン系化合物またはメロシアニン系化合物である上記（１）または（２）に記載の光学素子。
(４) 測定波長５５０nmでの、光学異方層の面内位相差値が１３０nm〜３００nmであることを特徴とする上記（１）〜（３）の何れか一項に記載の光学素子。
(５) 上記（１）〜（４）の何れか一項に記載の光学素子を有する位相差フィルム。
(６) 上記（１）〜（４）の何れか一項に記載の光学素子または上記（５）に記載の位相差フィルムと、他の位相差フィルムとを積層した複合位相差フィルム。
(７) 他の位相差フィルムが、ネガティブCプレートまたはポジティブCプレートであることを特徴とする上記（６）に記載の複合位相差フィルム
(８) 上記（１）〜（４）の何れか一項に記載の光学素子と偏光フィルムを積層してなる光学フィルム。
(９) 上記（５）に記載の位相差フィルムと偏光フィルムを積層してなる光学フィルム。(1) It contains at least two kinds of organic dyes, the maximum refractive index in the plane is nx, the refractive index orthogonal to nx in the plane is ny, and the refractive index in the direction perpendicular to the plane is nz. An optical element comprising a colored and oriented optically anisotropic layer having a refractive index of nx>nz> ny and (nx−nz) / (nx−ny) of 0.2 to 0.7.
(2) The maximum absorption wavelength of at least one organic dye of the organic dye is 380 nm or more and less than 550 nm, and the maximum absorption wavelength of the other at least one organic dye is 550 nm or more and 780 nm or less (1) ) Optical element.
(3) The optical element according to (1) or (2), wherein the organic dye is an azo compound, an anthraquinone compound, a perylene compound, a quinophthalone compound, a naphthoquinone compound, or a merocyanine compound.
(4) The optical element according to any one of (1) to (3) above, wherein an in-plane retardation value of the optical anisotropic layer at a measurement wavelength of 550 nm is 130 nm to 300 nm.
(5) A retardation film having the optical element according to any one of (1) to (4) above.
(6) A composite retardation film obtained by laminating the optical element according to any one of (1) to (4) above or the retardation film according to (5) above and another retardation film.
(7) The composite retardation film as described in (6) above, wherein the other retardation film is a negative C plate or a positive C plate.
(8) An optical film formed by laminating the optical element according to any one of (1) to (4) above and a polarizing film.
(9) An optical film obtained by laminating the retardation film according to (5) and a polarizing film.
(１０） 上記（６）または（７）に記載の複合位相差フィルムと偏光フィルムを積層してなる光学フィルム。
(１１) 光学素子の遅相軸と偏光フィルムの吸収軸が直交になるよう積層した上記（８）に記載の光学フィルム。
(１２) 位相差フィルムの遅相軸と偏光フィルムの吸収軸が直交になるよう積層した上記（９）に記載の光学フィルム。
(１３) 上記（１）〜（４）の何れか一項に記載の光学素子、上記（５）に記載の位相差フィルム、上記（６）または（７）に記載の複合位相差フィルム及び上記（８）〜（１２）の何れか一項に記載の光学フィルムからなる群から選ばれる少なくとも一つを備えてなる画像表示装置。
(１４) 画像表示装置が液晶表示装置である、上記（１３）に記載の画像表示装置。
(１５) 光学異方層が、極大吸収波長が３８０ｎｍ以上５５０ｎｍ未満である有機色素と極大吸収波長が５５０ｎｍ以上７８０ｎｍ以下である有機色素のそれぞれを少なくとも一つずつ、オリゴフェニル化合物及び、下記一般式（Ａ）で示される化合物とを含む組成物から形成された層である上記（１）に記載の光学素子、
式中、Ｘは−Ｏ−ＣＨ２−ｐｈ−ＣＨ２−Ｏ−、−Ｏ−ＣＯ−ｐｈ−ＣＯ−Ｏ−または−ＮＨ−ＣＯ−ｐｈ−ＣＯ−ＮＨ−を表し、ｐｈはスルホ置換を有してもよいパラフェニレン基を表し、ｎは繰り返し数を示す。(10) An optical film obtained by laminating the composite retardation film according to (6) or (7) above and a polarizing film.
(11) The optical film according to (8), wherein the optical film is laminated so that the slow axis of the optical element and the absorption axis of the polarizing film are orthogonal to each other.
(12) The optical film according to (9), wherein the retardation film is laminated so that the slow axis of the retardation film and the absorption axis of the polarizing film are orthogonal to each other.
(13) The optical element according to any one of (1) to (4), the retardation film according to (5), the composite retardation film according to (6) or (7), and the above An image display device comprising at least one selected from the group consisting of the optical films according to any one of (8) to (12).
(14) The image display device according to (13), wherein the image display device is a liquid crystal display device.
(15) The optically anisotropic layer includes at least one of an organic dye having a maximum absorption wavelength of 380 nm to less than 550 nm and an organic dye having a maximum absorption wavelength of 550 nm to 780 nm, an oligophenyl compound, and the following general formula: The optical element according to the above (1), which is a layer formed from a composition comprising the compound represented by (A),
In the formula, X represents -O-CH2-ph-CH2-O-, -O-CO-ph-CO-O- or -NH-CO-ph-CO-NH-, and ph has sulfo substitution. Represents an optional paraphenylene group, and n represents the number of repetitions.
(１６) 極大吸収波長が３８０ｎｍ以上５５０ｎｍ未満である有機色素として、
下記一般式（Ｂ）
（式中Ｘはスルホ基またはカルボキシ基、Ｒ１、Ｒ２は各々独立に水素原子、Ｃ１〜Ｃ４アルキル基、Ｃ１〜Ｃ４アルコキシル基を示し、ｎは１または２を示す。）
で表されるアゾ化合物またはその塩を、
また、極大吸収波長が５５０ｎｍ以上７８０ｎｍ以下である有機色素として下記一般式（Ｃ）
（式中、Ｑ21は、スルホン酸基を１個または２個有し、さらに水酸基またはＣ１〜Ｃ４アルコキシ基を有していてもよいナフチル基を、Ｑ22、Ｑ23はそれぞれ独立にフェニレン基またはナフチレン基（これらの基は置換基としてＣ１〜Ｃ４アルキル基、Ｃ１〜Ｃ４アルコキシ基、水酸基およびスルホン酸基からなる群から選ばれた１種または２種の置換基を１個または２個有する）を、Ｒ21は水素原子、Ｃ１〜Ｃ４アルキル基、アセチル基、ベンゾイル基または置換もしくは無置換のフェニル基を、Ｒ23、Ｒ24はそれぞれ独立に水素原子、水酸基、スルホン酸基、Ｃ１〜Ｃ４アルキル基またはＣ１〜Ｃ４アルコキシ基を、ｑは０または１を、ｒは１または２を表す。）
で表される化合物またはその塩、
を含む上記（１５）に記載の光学素子。(16) As an organic dye having a maximum absorption wavelength of 380 nm or more and less than 550 nm,
The following general formula (B)
(Wherein X represents a sulfo group or a carboxy group, R 1 and R 2 each independently represents a hydrogen atom, a C1 to C4 alkyl group, or a C1 to C4 alkoxyl group, and n represents 1 or 2)
An azo compound represented by
Further, as an organic dye having a maximum absorption wavelength of 550 nm or more and 780 nm or less, the following general formula (C)
(Wherein Q 21 is a naphthyl group having one or two sulfonic acid groups and further having a hydroxyl group or a C1-C4 alkoxy group, and Q 22 and Q 23 are each independently a phenylene group. Or a naphthylene group (these groups have one or two substituents selected from the group consisting of a C1-C4 alkyl group, a C1-C4 alkoxy group, a hydroxyl group and a sulfonic acid group as a substituent. R 21 is a hydrogen atom, a C1-C4 alkyl group, an acetyl group, a benzoyl group or a substituted or unsubstituted phenyl group, R 23 and R 24 are each independently a hydrogen atom, a hydroxyl group, a sulfonic acid group, A C4 alkyl group or a C1-C4 alkoxy group, q represents 0 or 1, and r represents 1 or 2.)
Or a salt thereof,
The optical element according to (15), comprising:
本発明の光学素子は、位相差を生じさせる機能を有し、位相差素子としてして有用であり、該光学素子を透明基板フィルム上に設けることにより位相差フィルムとして使用することが出来る。特に、偏光フィルム上に該光学素子、又は該光学素子を有する位相差フィルムを有する光学フィルム（以下においては光学素子付き偏光フィルムとも言う）は、液晶表示装置における観察位置の傾斜による光の抜けを低減し、かつ、漏れたわずかな光も着色することなく、偏光フィルムの視野角依存性および視野角改善効果の波長依存性を大幅に低減できるという効果を有する。即ち、上記光学素子付き偏光フィルムと通常の偏光フィルムとを、光学素子が偏光素子間に配置されるように、各々の吸収軸を直交させて配置した場合、正面方向からの各々の吸収軸方向とは異なる方向に観察位置を傾斜させても、光の抜けが低減され、かつ、漏れたわずかな光も着色することなく、偏光フィルムの視野角依存性および視野角改善効果の波長依存性も大幅に低減できる。また、この光学素子を設けた偏光フィルムを液晶ディスプレイに用いることで、液晶ディスプレイの視野角特性も向上させることができる。 The optical element of the present invention has a function of causing a phase difference and is useful as a phase difference element. By providing the optical element on a transparent substrate film, the optical element can be used as a phase difference film. In particular, the optical film having the optical element or the retardation film having the optical element on the polarizing film (hereinafter, also referred to as a polarizing film with an optical element) prevents light from leaking due to the inclination of the observation position in the liquid crystal display device. There is an effect that the viewing angle dependence of the polarizing film and the wavelength dependence of the viewing angle improvement effect can be greatly reduced without reducing and coloring even slight leaked light. That is, when the polarizing film with an optical element and a normal polarizing film are arranged with their absorption axes orthogonal to each other so that the optical elements are arranged between the polarizing elements, the respective absorption axis directions from the front direction Even if the observation position is tilted in a different direction, the omission of light is reduced, and even the slight leaked light is not colored, and the viewing angle dependence of the polarizing film and the wavelength dependence of the viewing angle improvement effect are also improved. It can be greatly reduced. Moreover, the viewing angle characteristic of a liquid crystal display can also be improved by using the polarizing film provided with this optical element for a liquid crystal display.
１．偏光フィルム
１ａ．偏光フィルム
２．光学異方層
３．吸収軸
４．進相軸
５．粘着剤
６．基材
７. 離型性基材
８．ガラス板
９．測定サンプル
１０．方位角θ
１１．極角φ
１２．正面方向（θ,φ)＝(０,０)
１３．φが０−１８０°軸1. Polarizing film 1a. 1.
11 Polar angle φ
12 Front direction (θ, φ) = (0,0)
13. φ is 0-180 ° axis
以下、本発明を詳細に説明する。
本発明の光学素子は、少なくとも２種類の有機色素を含んだ下記に定義される二軸性の層からなる。本発明で言う二軸性とは、３次元屈折率がｎｘ＞ｎｚ＞ｎｙの関係を満足し、且つＮｚ係数が０．２〜０．７、好ましくは、０．３〜０．５であることを意味する。ここで、ｎｘとは、面内の最大屈折率であり、ｎｙとは、ｎｘと面内で直交する屈折率であり、ｎｚとは、面に対して鉛直方向の屈折率を表す。また、Ｎｚ係数とは、(ｎｘ−ｎｚ)／(ｎｘ−ｎｙ)からなる値を表す。この範囲外では液晶表示装置に適用したときの視野角改良などの効果が乏しくなる、もしくは斜め方向からの色付きが生じる恐れがある。
この二軸性を示すためには、フィルムを延伸させる方法と、液晶性組成物を配向するように塗布し、乾燥し、塗膜または塗膜層を形成させる方法（以下配向塗膜形成法とも言う）等が挙げられる。
フィルムを延伸する方法としては、例えば、特開２００６−２９１１９２号公報、ＷＯ２００６／１１７９８１号公報等に記載の方法がが挙げられる。 液晶性組成物を塗布して配向させる方法としては、例えば、特表２００９−５４０３４５号公報、Ｗ０２０１０／０２０９２８号公報、特開２００６−４８０７８号公報、特開２００６−３１６１３８号公報等に記載の方法が挙げられる。Hereinafter, the present invention will be described in detail.
The optical element of the present invention comprises a biaxial layer defined below containing at least two kinds of organic dyes. The biaxiality referred to in the present invention means that the three-dimensional refractive index satisfies the relationship of nx>nz> ny, and the Nz coefficient is 0.2 to 0.7, preferably 0.3 to 0.5. Means that. Here, nx is the maximum refractive index in the plane, ny is the refractive index orthogonal to nx in the plane, and nz represents the refractive index in the vertical direction with respect to the plane. Further, the Nz coefficient represents a value consisting of (nx−nz) / (nx−ny). Outside this range, the effect of improving the viewing angle when applied to a liquid crystal display device may be poor, or coloring from an oblique direction may occur.
In order to show this biaxiality, a method of stretching a film and a method of applying a liquid crystal composition so as to be oriented and drying to form a coating film or a coating film layer (hereinafter referred to as an orientation coating film forming method) Say).
Examples of the method for stretching the film include methods described in JP-A-2006-291192, WO2006 / 117981, and the like. Examples of the method for applying and aligning the liquid crystalline composition include the methods described in JP-T-2009-540345, W02010 / 020928, JP-A-2006-48078, JP-A-2006-316138, and the like. Is mentioned.
本発明においては、上記後者の配向塗膜形成法が好ましい。
この液晶性組成物を塗布して配向させる方法の中で、共役π系と、超分子間で非共有結合を形成することが出来る官能基とを有する少なくとも１つの多環式有機化合物を含む超分子(supuramolecule)からなるリオトロピック液晶性を示す液晶性組成物を用いることが好ましい。そのようなリオトロピック液晶性を有する多環式有機化合物としては例えば、オリゴフェニル化合物、ビベンズイミダゾール化合物、アセトナフトキノサリン化合物、トリアジン化合物等が挙げられる。オリゴフェニル化合物の例を表１に、ビベンズイミダゾール化合物の例を表２にそれぞれ示す。アセトナフトキノサリン化合物の例を表３に示す。また、トリアジン化合物の例を表４に示す。
本発明においては上記リオトロピック液晶性を有する化合物のうちオリゴフェニル化合物が好ましい。オリゴフェニル化合物の中で好ましい化合物は酸素原子、窒素原子及び硫黄原子からなる群から選択される少なくとも１つの異項原子を含む５または６員複素環を介して、ベンゼン環、ビフェニル環及びナフタレン環からなる群から選択される少なくとも２個の環が結合した化合物であり、該ベンゼン環、ビフェニル環またはナフタレン環は１つのスルホ基を有するのが好ましい。In the present invention, the latter method for forming an oriented coating film is preferred.
In the method of applying and aligning the liquid crystalline composition, a super-compound comprising at least one polycyclic organic compound having a conjugated π system and a functional group capable of forming a non-covalent bond between supramolecules. It is preferable to use a liquid crystalline composition exhibiting lyotropic liquid crystallinity composed of supuramolecule. Examples of such polycyclic organic compounds having lyotropic liquid crystallinity include oligophenyl compounds, bibenzimidazole compounds, acetonaphthoquinosaline compounds, and triazine compounds. Examples of oligophenyl compounds are shown in Table 1, and examples of bibenzimidazole compounds are shown in Table 2, respectively. Examples of acetonaphthoquinosaline compounds are shown in Table 3. Examples of triazine compounds are shown in Table 4.
In the present invention, among the compounds having the above lyotropic liquid crystallinity, an oligophenyl compound is preferable. Among the oligophenyl compounds, preferred compounds are a benzene ring, a biphenyl ring and a naphthalene ring via a 5- or 6-membered heterocyclic ring containing at least one hetero atom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom. It is preferable that at least two rings selected from the group consisting of are bonded to each other, and the benzene ring, biphenyl ring or naphthalene ring preferably has one sulfo group.
例えば、好ましい化合物の１つとして下記一般式（Ｄ）で表される化合物を挙げることが出来る。
式中Ｙ１は−Ｏ−、−ＮＨ−または−ＳＯ２−、Ｙ２は単結合、−Ｏ−または−ＮＨ−、Ａ１及びＡ２は独立に、ベンゼン環、ナフタレン環またはビフェニル環を表し、スルホ基（ＨＳＯ３）はそれらの環上に置換しているものとする。
これらの化合物の中でも４，４’−（５，５’−ジオキシドジベンゾ[b,d]チエン−３，７−ジイル）ジベンゼンスルホニックアシッド（4,4'-(5,5'-dioxidodibenzo[b,d]thiene-3,7-diyl)dibenzenesulfonic acid)が好ましい。
このような化合物を含む液晶性組成物は、例えば、せん断による配向処理を行った際に、ｎｘ＞ｎｚ＞ｎｙの関係を満足するように配向することを特徴とする。For example, a compound represented by the following general formula (D) can be given as one preferred compound.
In the formula, Y 1 represents —O—, —NH— or —SO 2 —, Y 2 represents a single bond, —O— or —NH—, A 1 and A 2 independently represent a benzene ring, a naphthalene ring or a biphenyl ring, The sulfo group (HSO 3 ) is substituted on those rings.
Among these compounds, 4,4 '-(5,5'-dioxidedibenzo [b, d] thien-3,7-diyl) dibenzene sulfonic acid (4,4'-(5,5'-dioxidodibenzo [b, d] thiene-3,7-diyl) dibenzenesulfonic acid) is preferred.
The liquid crystalline composition containing such a compound is characterized by being aligned so as to satisfy the relationship of nx>nz> ny, for example, when an alignment treatment by shearing is performed.
本発明においては、上記の液晶性化合物と後記有機染料を含む液晶組成物を配向塗膜形成法によって、フィルム等の基板上に、配向された液晶組成物の乾燥塗膜層を形成させることにより、光学異方層からなる光学素子を有する基板とすることができる。
また、上記のリオトロピック液晶性を示す単数または複数の化合物の他に液晶性を示すポリマーを、リオトロピック液晶性を示す組成物に添加することも可能である。
例えば、ＷＯ２０１０／０２０９２８号公報（１６−１７頁）に代表される棒状分子の液晶ポリマーがあり、その具体例を表５に示す。このような液晶性を示すポリマーを添加することにより、得られる光学素子のｎｘ、ｎｙ、ｎｚの関係を調整したり、耐久性を向上させたりすることができるため好ましい。In the present invention, a liquid crystal composition containing the above-mentioned liquid crystalline compound and an organic dye described later is formed on a substrate such as a film by forming a dry coating layer of the aligned liquid crystal composition on a substrate such as a film. And a substrate having an optical element composed of an optically anisotropic layer.
In addition to the compound or compounds exhibiting lyotropic liquid crystal properties, a polymer exhibiting liquid crystal properties may be added to the composition exhibiting lyotropic liquid crystal properties.
For example, there are rod-shaped liquid crystal polymers represented by WO2010 / 020928 (pages 16-17), and specific examples thereof are shown in Table 5. It is preferable to add such a polymer exhibiting liquid crystallinity because the relationship between nx, ny, and nz of the obtained optical element can be adjusted and the durability can be improved.
上記棒状分子の液晶性ポリマーの中で、下記一般式（Ａ）で示される化合物が好ましい。
式中、Ｘは−Ｏ−ＣＨ２−ｐｈ−ＣＨ２−Ｏ−、−Ｏ−ＣＯ−ｐｈ−ＣＯ−Ｏ−または−ＮＨ−ＣＯ−ｐｈ−ＣＯ−ＮＨ−を、ｐｈはスルホ置換を有してもよいパラフェニレン基を、ｎは繰り返し数を表す。
該液晶性ポリマーの重量平均分子数は１，０００〜２００，０００程度であり、好ましくは、２，０００〜１００，０００程度である。また、場合により、該重量平均分子数は３，０００〜７０，０００程度、または４，０００〜７０，０００程度であってもよい。Among the rod-like liquid crystalline polymers, compounds represented by the following general formula (A) are preferable.
Wherein X is —O—
The weight average molecular number of the liquid crystalline polymer is about 1,000 to 200,000, preferably about 2,000 to 100,000. In some cases, the weight average molecular number may be about 3,000 to 70,000, or about 4,000 to 70,000.
上記の、２種類以上の有機色素、リオトロピック液晶性を有する多環式有機化合物、及び、好ましくは、更に、上記液晶性ポリマーを含む液晶性組成物は、塗布液とするために通常溶媒を含む。用いられる溶媒は、溶解性に優れ、かつ、組成物に溶媒が溶解した状態でリオトロピック性を示すものであれば特に制限は無いが、例えば、水、アルコール類、エーテル類、セロソルブ類、カルボン酸類、ジメチルスルホキシドなどが挙げられる。本発明においては取り扱いの点等から水が好ましい。これらは単独あるいは、複数の混合物として用いることができる。また、ジメチルホルムアミド、グリセリン、エチレングリコール、などの水溶性の溶剤が添加されていても良い。これらの添加物は易溶性や水溶液の乾燥速度を調整するために用いることが出来る。
溶媒の量は、該液晶性組成物を塗布することができる濃度であれば特に限定されない。例えば、溶媒を含む液晶性組成物において、該組成物の総量に対して、固形分濃度は通常５〜５０重量％、好ましくは８〜３０重量％である。
また、該液晶性組成物の粘度が、Ｅ型粘度計２５℃で測定した時の粘度で２００〜１０００ｍＰａ・ｓの時、リオトロピック液晶の生成に好適であり、この範囲の粘度の時、ＭＤ方向にせん断力をかけて塗布または塗工することにより、液晶の配向が、ＭＤ方向と垂直な方向に配向されるので好ましい。The above-mentioned two or more organic dyes, a polycyclic organic compound having lyotropic liquid crystallinity, and preferably, the liquid crystalline composition containing the above liquid crystalline polymer usually contains a solvent for forming a coating solution. . The solvent used is not particularly limited as long as it has excellent solubility and exhibits lyotropic properties in a state where the solvent is dissolved in the composition. For example, water, alcohols, ethers, cellosolves, carboxylic acids And dimethyl sulfoxide. In the present invention, water is preferable from the viewpoint of handling. These can be used alone or as a mixture. A water-soluble solvent such as dimethylformamide, glycerin, or ethylene glycol may be added. These additives can be used to adjust the solubility or the drying rate of the aqueous solution.
The amount of the solvent is not particularly limited as long as it is a concentration at which the liquid crystalline composition can be applied. For example, in a liquid crystal composition containing a solvent, the solid content concentration is usually 5 to 50% by weight, preferably 8 to 30% by weight, based on the total amount of the composition.
Moreover, when the viscosity of the liquid crystalline composition is 200 to 1000 mPa · s when measured with an E-type viscometer at 25 ° C., it is suitable for producing a lyotropic liquid crystal. It is preferable to apply or apply a shearing force to the liquid crystal because the liquid crystal is aligned in a direction perpendicular to the MD direction.
本発明の光学素子に用いる少なくとも２種の有機色素としては、アゾ系化合物、アントラキノン系化合物、ペリレン化合物、キノフタロン系化合物、ナフトキノン系化合物またはメロシアニン系化合物などが挙げられ、同種の染料であっても、異種の染料であっても支障は無い。通常は同種の化合物が好ましい。より好ましくは、２色性を示すアゾ系化合物である。例えば、『機能性色素の応用』（入江正浩監修、シーエムシー出版）９８−１００頁に記載のアゾ系化合物、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｙｅｌｌｏｗ２８、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｙｅｌｌｏｗ４４、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｏｒａｎｇｅ２６、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｏｒａｎｇｅ１０７、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｏｒａｎｇｅ７１、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｒｅｄ２、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｒｅｄ３１、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｒｅｄ７９、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｒｅｄ２４７、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｇｒｅｅｎ８０、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｂｌｕｅ２０２、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｂｌａｃｋ１７、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｂｌｕｅ８３、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｏｒａｎｇｅ３９、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｒｅｄ７９、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｒｅｄ８１、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｙｅｌｌｏｗ１２、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｂｌｕｅ６７、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｒｅｄ３９、Ｃ．Ｉ．Ａｃｉｄ．Ｒｅｄ３７、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｇｒｅｅｎ５９、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｏｒａｎｇｅ７２、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｒｅｄ８９、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｒｅｄ８３、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｖｉｏｌｅｔ４８、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｂｌｕｅ９０並びに、特開２００１−３３６２７号公報、特開２００２−２９６４１７号公報、特開２００３−２１５３３８号公報、ＷＯ２００４／０９２２８２号公報、特開２００１−０５６４１１２号公報、特開２００１−０２７７０８号公報、特開平１１−２１８６１１号公報、特開平１１−２１８６１０号公報、特開昭６０−１５６７５９号公報、特開２００１−３３６２７号公報、特許２６２２７４８号公報及び特許第３９６３９７９号公報に記載された有機染料等が挙げられる。 Examples of at least two kinds of organic dyes used in the optical element of the present invention include azo compounds, anthraquinone compounds, perylene compounds, quinophthalone compounds, naphthoquinone compounds, merocyanine compounds, and the like. Even different types of dyes will not cause any problems. Usually, the same kind of compound is preferred. More preferably, it is an azo compound showing dichroism. For example, an azo compound described in “Application of Functional Dye” (supervised by Masahiro Irie, CMC Publishing) pages 98-100, C.I. I. Direct. Yellow 28, C.I. I. Direct. Yellow 44, C.I. I. Direct. Orange 26, C.I. I. Direct. Orange 107, C.I. I. Direct. Orange 71, C.I. I. Direct. Red2, C.I. I. Direct. Red31, C.I. I. Direct. Red 79, C.I. I. Direct. Red247, C.I. I. Direct. Green 80, C.I. I. Direct. Blue 202, C.I. I. Direct. Black 17, C.I. I. Direct. Blue 83, C.I. I. Direct. Orange 39, C.I. I. Direct. Red 79, C.I. I. Direct. Red 81, C.I. I. Direct. Yellow 12, C.I. I. Direct. Blue67, C.I. I. Direct. Red 39, C.I. I. Acid. Red 37, C.I. I. Direct. Green 59, C.I. I. Direct. Orange 72, C.I. I. Direct. Red 89, C.I. I. Direct. Red 83, C.I. I. Direct. Violet 48, C.I. I. Direct. Blue90, JP 2001-33627 A, JP 2002-296417 A, JP 2003-215338 A, WO 2004/092822, JP 2001-0564112 A, JP 2001-027708 A, Special Organic dyes and the like described in Kaihei 11-218611, JP-A-11-218610, JP-A-60-156759, JP-A-2001-33627, Japanese Patent No. 2622748, and Japanese Patent No. 396379 Can be mentioned.
本発明の光学素子または位相差フィルムの形成に用いられる少なくとも２種の有機色素は、好ましくは、少なくとも一つの有機色素の極大吸収波長は３８０ｎｍ以上５５０ｎｍ未満であり、他方の少なくとも一つの有機色素の極大吸収波長が５５０ｎｍ以上７８０ｎｍ以下である。より好ましくは、有機色素の少なくとも一つの有機色素（第一の色素）の極大吸収波長が４３０ｎｍ以上４７０ｎｍ以下であり、他方の少なくとも一つの有機色素（第二の色素）の極大吸収波長が５７０ｎｍ以上６３０ｎｍ以下である。第一の色素として、例えば、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｏｒａｎｇｅ３９、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｏｒａｎｇｅ７１、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｏｒａｎｇｅ２６、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｏｒａｎｇｅ１０７並びにＷＯ２００７／１３８９８０号公報に記載された有機染料が挙げられる。
中でも下記一般式（Ｂ）で表されるアゾ化合物またはその塩が好ましい。
式中Ｘはスルホ基またはカルボキシ基、Ｒ１、Ｒ２は各々独立に水素原子、Ｃ１〜Ｃ４アルキル基、Ｃ１〜Ｃ４アルコキシル基を示し、ｎは１または２を示す。The at least two organic dyes used for forming the optical element or the retardation film of the present invention preferably have at least one organic dye having a maximum absorption wavelength of 380 nm or more and less than 550 nm, and the other at least one organic dye. The maximum absorption wavelength is 550 nm or more and 780 nm or less. More preferably, the maximum absorption wavelength of at least one organic dye (first dye) of the organic dye is 430 nm or more and 470 nm or less, and the maximum absorption wavelength of the other at least one organic dye (second dye) is 570 nm or more. It is 630 nm or less. Examples of the first dye include C.I. I. Direct. Orange 39, C.I. I. Direct. Orange 71, C.I. I. Direct. Orange 26, C.I. I. Direct. Examples thereof include organic dyes described in Orange 107 and WO 2007/138980.
Among these, an azo compound represented by the following general formula (B) or a salt thereof is preferable.
In the formula, X represents a sulfo group or a carboxy group, R 1 and R 2 each independently represent a hydrogen atom, a C1 to C4 alkyl group, or a C1 to C4 alkoxyl group, and n represents 1 or 2.
第二の色素としては、例えば、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｂｌｕｅ２０２、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｂｌａｃｋ１７、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｂｌｕｅ８３、Ｄｉｒｅｃｔ．Ｇｒｅｅｎ５１、特開２００１−３３６２７号公報並びに特許第３９６３９７９号公報（００２２〜００２７）に記載された有機染料が挙げられる。
好ましい色素として、下記一般式（Ｃ）で表される化合物またはその塩を挙げることができる。
Preferred examples of the dye include a compound represented by the following general formula (C) or a salt thereof.
このように、極大吸収波長が異なる２種以上の色素を含有させることにより、本発明の光学素子は顕著に優れた効果を発揮する。例えば、本発明の光学素子を設けた偏光フィルムと通常の偏光フィルムとを、光学素子が偏光素子間に配置されるように、各々の吸収軸を直交させて配置した場合、正面方向からの各々の吸収軸方向とは異なる方向に観察位置を傾斜させても、光の抜けが低減され、かつ、漏れたわずかな光も着色することなく、偏光フィルムの視野角依存性および視野角改善効果の波長依存性も大幅に低減できる。 Thus, the optical element of this invention exhibits the outstanding effect by containing 2 or more types of pigment | dyes from which maximum absorption wavelength differs. For example, when a polarizing film provided with the optical element of the present invention and a normal polarizing film are arranged with their absorption axes orthogonal to each other so that the optical element is arranged between the polarizing elements, each from the front direction Even if the observation position is tilted in a direction different from the absorption axis direction, the light omission is reduced and the viewing angle dependency of the polarizing film and the effect of improving the viewing angle are reduced without coloring the slight leaked light. Wavelength dependence can also be greatly reduced.
上記の有機色素の合計濃度は透過率が大幅に低下しない程度に添加する。好ましくは、コーティング液の固形分の総量に対して、０．０１〜１０重量％、好ましくは、０．１〜５重量％、より好ましくは０．１〜３重量％である。また、第一の色素と第二の色素の割合は、適宜選択することが出来、第一の色素１重量部に対して、第二の色素を０．１〜１０重量部、好ましくは０．２〜５重量部、より好ましくは０．５〜２重量部、最も好ましくは０．７〜１．５重量部の割合である。 The total concentration of the above organic dyes is added to such an extent that the transmittance is not significantly reduced. Preferably, it is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.1 to 3% by weight, based on the total amount of the solid content of the coating liquid. The ratio of the first dye and the second dye can be appropriately selected. The amount of the second dye is 0.1 to 10 parts by weight, preferably 0. The ratio is 2 to 5 parts by weight, more preferably 0.5 to 2 parts by weight, and most preferably 0.7 to 1.5 parts by weight.
本発明の光学素子を位相差フィルムとして利用する場合は、前記リオトロピック液晶性を有する多環式有機化合物と有機色素を含む液晶性組成物、好ましくは、更に、前記液晶性ポリマーを含む液晶性組成物を透明基材へ塗布し配向させ、該基材上に光学異方層を形成させることにより、位相差フィルムとすることができる。また、直接偏光フィルムへ液晶性組成物を塗布して、偏光フィルム上に配向した光学異方層を直接形成し、本発明の光学素子を備えた偏光フィルムとしても良い。また、場合により、最初に転写用基材（離型性基材）上に、上記配向した光学異方層を形成し、該光学異方層を偏光フィルム上に転写してもよい。
好ましくは、偏光板のＭＤ方向(Machine Direction）に対して垂直方向に配向させ光学異方層を形成させる。塗布方法としては、均一に塗布し配向させられるものであれば、特に制限はない。スライドコータ、スロットダイコータ、バーコータ、ロッドコータ、ロールコータ、カーテンコータ、スプレイコータ、リップダイコータ、バキュームダイコータ、グラビアコータ、リバースグラビアコータ、マイクログラビアコータなどの適切なコータを用いて機材に塗布する方法や金属ドラムの上に展開する方法が挙げられる。好ましくは、ダイコータ類またはグラビアコータ類の使用であり、グラビアコータ類の場合にはスムージングロールの併用も有効である。乾燥手段に特に制限はなく、自然乾燥、減圧乾燥、加熱乾燥、減圧加熱乾燥などが用いられる。加熱乾燥手段としては空気循環式乾燥オーブンや熱ロールなどの任意の乾燥装置を用いた乾燥方法が用いられる。好ましい乾燥方法としては、０℃〜４０℃の低温で、かつ相対湿度６０％以下で乾燥する方法である。When the optical element of the present invention is used as a retardation film, a liquid crystalline composition comprising the polycyclic organic compound having lyotropic liquid crystallinity and an organic dye, preferably a liquid crystalline composition further comprising the liquid crystalline polymer. A phase difference film can be obtained by applying an object to a transparent substrate and orienting it to form an optically anisotropic layer on the substrate. Alternatively, a liquid crystal composition may be directly applied to a polarizing film to directly form an optically anisotropic layer oriented on the polarizing film, and a polarizing film including the optical element of the present invention may be used. In some cases, the oriented optical anisotropic layer may be first formed on a transfer substrate (releasing substrate), and the optical anisotropic layer may be transferred onto a polarizing film.
Preferably, the optically anisotropic layer is formed by being oriented in a direction perpendicular to the MD direction (Machine Direction) of the polarizing plate. The application method is not particularly limited as long as it can be uniformly applied and oriented. Applying to equipment using an appropriate coater such as slide coater, slot die coater, bar coater, rod coater, roll coater, curtain coater, spray coater, lip die coater, vacuum die coater, gravure coater, reverse gravure coater, micro gravure coater, etc. There is a method of spreading on a metal drum. Preferably, die coaters or gravure coaters are used, and in the case of gravure coaters, the use of a smoothing roll is also effective. There is no particular limitation on the drying means, and natural drying, vacuum drying, heat drying, vacuum heat drying and the like are used. As the heating and drying means, a drying method using an arbitrary drying apparatus such as an air circulation type drying oven or a hot roll is used. A preferred drying method is a method of drying at a low temperature of 0 ° C. to 40 ° C. and a relative humidity of 60% or less.
本発明の位相差フィルムに用いられる基材としては、通常、透明なプラスチック基材あるいはガラスが用いられ、プラスチック基材が好ましい。本発明に用いられるプラスチック基板としては、アクリル樹脂、ポリカーボネート樹脂、エポキシ樹脂、セルロース樹脂などが挙げられ、例えば、トリアセチルセルロース（ＴＡＣ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、シンジオタクチックポリスチレン（ＳＰＳ）、ポリフェニレンスルフィド（ＰＰＳ）、ポリカーボネート（ＰＣ）、ポリアクリレート（ＰＡｒ）、ポリスルホン（ＰＳＦ）、ポリエステルスルホン（ＰＥＳ）、ポリエーテルイミド（ＰＥＩ）、環状ポリオレフィン、ポリイミド（ＰＩ）などが挙げられる。好ましくはＴＡＣである。基材厚みは用途によるほかは特に限定されないが、一般的には、１μｍ〜１０００μｍの範囲である。また、各フィルムの表面は、本発明で用いる組成物のぬれ性を調整するために、コロナ処理やプラズマ処理、アルカリ処理、プライマー処理といった表面処理を施すことが好ましい。 As the substrate used for the retardation film of the present invention, a transparent plastic substrate or glass is usually used, and a plastic substrate is preferable. Examples of the plastic substrate used in the present invention include acrylic resin, polycarbonate resin, epoxy resin, and cellulose resin. For example, triacetyl cellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and syndiotactic. Tic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), polyacrylate (PAr), polysulfone (PSF), polyester sulfone (PES), polyetherimide (PEI), cyclic polyolefin, polyimide (PI), etc. Can be mentioned. TAC is preferred. The thickness of the substrate is not particularly limited except for the application, but is generally in the range of 1 μm to 1000 μm. The surface of each film is preferably subjected to surface treatment such as corona treatment, plasma treatment, alkali treatment, and primer treatment in order to adjust the wettability of the composition used in the present invention.
本発明の光学異方層または位相差フィルムは、測定波長５５０ｎｍでの面内位相差値が１３０〜３００ｎｍである。好ましくは、１５０〜２７０ｎｍ、さらに好ましくは１８０〜２５０ｎｍである。 光学異方層の厚みは、液晶セルの方式や面内位相差値などの種々の光学パラメーターに依存することから一概には言えないが、通常０．１〜１０μｍである。さらに、好ましくは、０．１〜２μｍである。 The optical anisotropic layer or retardation film of the present invention has an in-plane retardation value of 130 to 300 nm at a measurement wavelength of 550 nm. Preferably, it is 150-270 nm, More preferably, it is 180-250 nm. Although the thickness of the optically anisotropic layer depends on various optical parameters such as a liquid crystal cell system and an in-plane retardation value, it cannot be generally specified, but is usually 0.1 to 10 μm. Furthermore, it is preferably 0.1 to 2 μm.
上記の光学異方層は、成膜後は耐水性を高めるための処理を行なうことができる。例えば、レーキ剤を用いて水に不溶性または難溶性の基に置換する方法が挙げられる。レーキ剤としては、Ｎｉ２＋、Ｃａ２＋、Ｆｅ３＋、Ｃｕ２＋、Ｚｎ２＋、Ａｌ３＋、Ｐｄ２＋、Ｃｄ２＋、Ｐｂ２＋、Ｓｎ２＋、Ｃｏ２＋、Ｍｎ２＋、Ｂａ２＋、Ｃｅ３＋などの金属イオンの塩もしくは、有機アミンの塩が挙げられる。これらのレーキ剤は単独で用いても良く、２種類以上が任意の比率及び組み合わせで併用してもよい。The optically anisotropic layer can be subjected to a treatment for improving water resistance after film formation. For example, a method of substituting with a group insoluble or hardly soluble in water using a lake agent. As a rake agent, metal ions such as Ni 2+ , Ca 2+ , Fe 3+ , Cu 2+ , Zn 2+ , Al 3+ , Pd 2+ , Cd 2+ , Pb 2+ , Sn 2+ , Co 2+ , Mn 2+ , Ba 2+ , and Ce 3+ Or a salt of an organic amine. These rake agents may be used alone or in combination of two or more in any ratio and combination.
また別の方法として光学異方層上に保護層を設ける方法が挙げられる。保護層に用いられる材料は特に限定されるものではなく、例えば、ウレタン樹脂、エポキシ樹脂、アクリル樹脂などが挙げられ、これらは単独で用いても良く、２種類以上併用しても良い。好ましくは疎水性の材料であり、更に好ましくはポリウレタン樹脂の使用である。柔軟性に優れたポリウレタン樹脂は光学異方層の配向状態を乱すことなく、光学異方層上への積層が可能である。 Another method is to provide a protective layer on the optically anisotropic layer. The material used for the protective layer is not particularly limited, and examples thereof include a urethane resin, an epoxy resin, and an acrylic resin, and these may be used alone or in combination of two or more. A hydrophobic material is preferred, and a polyurethane resin is more preferred. A polyurethane resin excellent in flexibility can be laminated on the optical anisotropic layer without disturbing the orientation state of the optical anisotropic layer.
上記キレート剤を用いる方法、および保護層を設ける方法は、併用して行なうことも可能である。
本発明の位相差フィルムは目的の特性値を得るために、基材上に光学異方層を積層することも可能である。この場合のキレート剤を用いた耐水化処理、および/または保護層を設ける耐水化処理は、各層ごとに行なっても良く、全ての光学異方層積層後に行なっても良い。The method of using the chelating agent and the method of providing a protective layer can be performed in combination.
In the retardation film of the present invention, an optical anisotropic layer can be laminated on a substrate in order to obtain a desired characteristic value. In this case, the water resistance treatment using a chelating agent and / or the water resistance treatment for providing a protective layer may be performed for each layer or after all the optical anisotropic layers are laminated.
本発明の光学素子、または位相差フィルムは偏光フィルムもしくは他の位相差フィルムと組み合わせて用いられる。好ましくは、図１に示されるように、光学素子または位相差フィルム２の遅相軸４と偏光フィルム１の吸収軸３が直交になるよう積層する。積層するには図１のように直接偏光フィルム１に塗布し光学異方層２を形成させる。
図２のように光学異方層２を基材上に形成した位相差フィルムの光学異方層側をアクリル系粘着剤５を介して偏光フィルム１もしくは他の位相差フィルムと積層する。
もしくは、図３のように基材７上に形成した光学異方層２をアクリル系粘着剤を介して偏光フィルム１もしくは他の位相差フィルムと貼合し基材７を剥離して、光学異方層２を偏光フィルム１もしくは他の位相差フィルムへ転写してもよい。
本発明の位相差フィルムは他の位相差フィルムと積層して用いることも可能であり、例えば、ネガティブＣプレートまたはポジティブＣプレートと組み合わせて使用することが出来る。The optical element or retardation film of the present invention is used in combination with a polarizing film or other retardation film. Preferably, as shown in FIG. 1, the optical element or the
As shown in FIG. 2, the optical anisotropic layer side of the retardation film having the optical
Alternatively, the optically
The retardation film of the present invention can be used by being laminated with other retardation films, and for example, it can be used in combination with a negative C plate or a positive C plate.
本発明の光学素子付き偏光フィルムの作成に使用される偏光フィルムは、通常使用される偏光フィルムであれば何れも使用することが出来る。該偏光フィルムに用いられる偏光素子（偏光子）は、光源からの光を偏光にする機能を有する素子であれば特に制限は無く、特定の方向の光を吸収して偏光にする吸収型偏光素子及び特定の方向の光を反射して偏光にする反射型偏光素子のいずれも用いることができる。吸収型偏光素子としては、例えば、染料や多価のヨウ素イオン等の二色性色素を含有するポリビニルアルコール系フィルム等の親水性高分子フィルムを一軸延伸して得られる偏光素子、ポリビニルアルコール系フィルムの一軸延伸の前後に酸により脱水してポリエン構造を形成して得られる偏光素子、及び、一定方向に配向するよう処理された配向膜上にリオトロピック液晶状態を発現する二色性色素の溶液を塗布し、その後に溶剤を除去して得られる偏光素子等が挙げられる。一方、反射型偏光素子としては、例えば、複屈折の異なる多数の積層体からなる偏光素子、選択反射域を有するコレステリック液晶と１／４波長板とを組み合わせてなる偏光素子、及び、基板上に微細なワイヤーグリッドを設けた偏光素子等が挙げられる。本発明の効果をより効果的に得るためには、偏光素子として偏光特性に優れている、染料または多価のヨウ素イオン等の二色性色素を含有するポリビニルアルコール系フィルム等の親水性高分子フィルムを一軸延伸して得られる偏光素子、または、ポリビニルアルコール系フィルムの一軸延伸の前後に酸により脱水してポリエン構造を形成して得られる偏光素子を用いることが好ましい。 As the polarizing film used for producing the polarizing film with an optical element of the present invention, any polarizing film that is usually used can be used. The polarizing element (polarizer) used in the polarizing film is not particularly limited as long as it is an element having a function of polarizing light from a light source and absorbs light in a specific direction to be polarized. Any reflective polarizing element that reflects light in a specific direction to be polarized can be used. As an absorptive polarizing element, for example, a polarizing element obtained by uniaxially stretching a hydrophilic polymer film such as a polyvinyl alcohol film containing a dichroic dye such as a dye or polyvalent iodine ion, a polyvinyl alcohol film A polarizing element obtained by dehydrating with an acid before and after uniaxial stretching to form a polyene structure, and a solution of a dichroic dye that develops a lyotropic liquid crystal state on an alignment film that has been processed to align in a certain direction Examples thereof include a polarizing element obtained by applying and then removing the solvent. On the other hand, as a reflective polarizing element, for example, a polarizing element composed of a large number of laminated bodies having different birefringence, a polarizing element formed by combining a cholesteric liquid crystal having a selective reflection region and a quarter wavelength plate, and a substrate Examples thereof include a polarizing element provided with a fine wire grid. In order to obtain the effect of the present invention more effectively, a hydrophilic polymer such as a polyvinyl alcohol film containing a dichroic dye such as a dye or polyvalent iodine ion, which is excellent in polarization characteristics as a polarizing element. It is preferable to use a polarizing element obtained by uniaxially stretching a film, or a polarizing element obtained by forming a polyene structure by dehydration with an acid before and after uniaxial stretching of a polyvinyl alcohol film.
上記偏光素子は、従来の方法により製造することができる。例えば染料及び多価のヨウ素イオン等の二色性色素を含有するポリビニルアルコール系フィルムからなる偏光素子の場合、まず、ポリビニルアルコール系フィルムを温水等で膨潤させた後、二色性色素を溶解した染色槽に浸漬し、該フィルムを染色し、ついで、硼酸や硼砂といった架橋剤を含む槽で一軸方向に延伸し、乾燥させることにより、該偏光素子を得ることができる。染色に使用する色素としては、ヨウ素−ヨウ化カリウム水溶液、『機能性色素の応用』（入江正浩監修、シーエムシー出版）９８−１００頁に記載のアゾ系化合物、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｙｅｌｌｏｗ１２、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｙｅｌｌｏｗ２８、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｙｅｌｌｏｗ４４、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｏｒａｎｇｅ２６、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｏｒａｎｇｅ３９、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｏｒａｎｇｅ１０７、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｒｅｄ２、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｒｅｄ３１、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｒｅｄ７９、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｒｅｄ８１、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｒｅｄ２４７、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｇｒｅｅｎ８０、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｇｒｅｅｎ５９、並びに、特開２００１−３３６２７、特開２００２−２９６４１７、特開２００３−２１５３３８、ＷＯ２００４／０９２２８２、特開２００１−０５６４１１２、特開２００１−０２７７０８、特開平１１−２１８６１１、特開平１１−２１８６１０、特開昭６０−１５６７５９号、特開２００１−３３６２７及び特許２６２２７４８号公報に記載された有機染料等が挙げられる。これらの二色性色素は遊離酸の他、アルカリ金属塩（例えばＮａ塩、Ｋ塩及びＬｉ塩等）、アンモニウム塩、アミン類の塩、または錯塩（例えばＣｕ錯体、Ｎｉ錯体及びＣｏ錯体等）等が挙げられる。偏光素子の性能は二色性色素の持つ二色性や延伸時の延伸倍率等で調整することができる。 The polarizing element can be manufactured by a conventional method. For example, in the case of a polarizing element comprising a polyvinyl alcohol film containing a dichroic dye such as a dye and polyvalent iodine ions, the polyvinyl alcohol film was first swollen with warm water and then the dichroic dye was dissolved. The polarizing element can be obtained by immersing in a dyeing tank, dyeing the film, then stretching in a uniaxial direction in a tank containing a crosslinking agent such as boric acid or borax and drying. Examples of the dye used for dyeing include iodine-potassium iodide aqueous solution, azo compound described in “Application of Functional Dye” (supervised by Masahiro Irie, CMMC Publishing) pages 98-100, C.I. I. Direct. Yellow 12, C.I. I. Direct. Yellow 28, C.I. I. Direct. Yellow 44, C.I. I. Direct. Orange 26, C.I. I. Direct. Orange 39, C.I. I. Direct. Orange 107, C.I. I. Direct. Red2, C.I. I. Direct. Red31, C.I. I. Direct. Red 79, C.I. I. Direct. Red 81, C.I. I. Direct. Red247, C.I. I. Direct. Green 80, C.I. I. Direct. Green 59, and JP 2001-33627, JP 2002-296417, JP 2003-215338, WO 2004/092282, JP 2001-0564112, JP 2001-027708, JP 11-218611, JP 11-218610, Examples thereof include organic dyes described in JP-A-60-156759, JP-A-2001-33627, and JP-A-2622748. These dichroic dyes are free acids, alkali metal salts (for example, Na salts, K salts and Li salts), ammonium salts, salts of amines, or complex salts (for example, Cu complexes, Ni complexes and Co complexes). Etc. The performance of the polarizing element can be adjusted by the dichroism of the dichroic dye, the stretch ratio during stretching, and the like.
本発明の光学異方層（光学素子）若しくは本発明の位相差フィルム、または、該光学異方層（光学素子）または該位相差フィルムと他の位相差フィルムとを積層した複合位相差フィルムを、画像表示装置の光通路内、例えば液晶表示装置の少なくとも液晶セルの片側等に偏光板と組み合わせて配置することで、本発明の画像表示装置、例えば液晶表示装置を得ることができる。液晶表示装置は用いる液晶セルの種類によって種々のモードがあるが、何れの場合にも本発明の光学異方層（光学素子）を設けた偏光フィルムを使用できる。例えばＶＡ（ヴァーティカリーアラインメント）型、ＩＰＳ（インプレーンスイッチング）型、ＯＣＢ（オプティカリーコンペンセイテッドベンド）型、ＴＮ（ツイステッドネマティック）型、ＳＴＮ（スーパーツイステッドネマティック）型など種々のモードの液晶表示装置に、本発明の位相差フィルムを使用することができる。それぞれの視野角特性に応じて光学異方層（光学素子）または各位相差フィルムのＮＺ係数及び位相差値を調整すればよい。An optically anisotropic layer (optical element) of the present invention or a retardation film of the present invention, or a composite retardation film obtained by laminating the optically anisotropic layer (optical element) or the retardation film and another retardation film. The image display device of the present invention, for example, a liquid crystal display device can be obtained by disposing it in combination with a polarizing plate in the light path of the image display device, for example, at least one side of the liquid crystal cell of the liquid crystal display device. The liquid crystal display device has various modes depending on the type of the liquid crystal cell to be used. In any case, a polarizing film provided with the optical anisotropic layer (optical element) of the present invention can be used. For example, VA (vertical alignment), IPS (in-plane switching), OCB (optically compensated bend), TN (twisted nematic), STN (super twisted nematic), etc. The retardation film of the present invention can be used in the apparatus. What is necessary is just to adjust the NZ coefficient and retardation value of an optically anisotropic layer (optical element) or each retardation film according to each viewing angle characteristic.
以下、実施例により本発明をさらに詳細に説明するが、本発明はこれらによって限定されるものではない。
なお、配合例及び実施例において部は重量部を、％は重量％をそれぞれ意味する。EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these.
In the blending examples and examples, “part” means “part by weight” and “%” means “% by weight”.
配合例１
特表２００９−５４０３４５号公報に記載の下記化合物１３．６部、
ＷＯ２０１０／０２０９２８号公報に記載の下記化合物２．４部、
水８４部、及びＷＯ２００７／１３８９８０号公報に記載の有機染料 （Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｏｒａｎｇｅ３９）０．０８部及び特許第３９６３９７９号公報に記載の下記有機染料０．０８部、
を均一に混合溶解し固形分が約１６％の溶液を調製した。該溶液の粘度はＥ型粘度計２５℃の測定で、３３０ｍＰａ・ｓであった。Formulation Example 1
13.6 parts of the following compound described in JP-T-2009-540345,
2.4 parts of the following compound described in WO2010 / 020928,
84 parts of water, and 0.08 part of organic dye (CI Direct. Orange 39) described in WO2007 / 138980 and 0.08 part of organic dye described in Japanese Patent No. 3963979,
Were mixed and dissolved to prepare a solution having a solid content of about 16%. The viscosity of the solution was 330 mPa · s as measured by an E-type viscometer at 25 ° C.
配合例２
上記配合例１において、特許３９６３９７９号公報に記載の上記有機染料０．０８部の代わりに、Ｃ．Ｉ．Ｄｉｒｅｃｔ．Ｂｌｕｅ６７を０．０８部使用する以外は、配合例１と同様にして固形分が約１６％の溶液を調製した。該溶液の粘度はＥ型粘度計２５℃の測定で、３３０ｍＰａ・ｓであった。Formulation Example 2
In the above Formulation Example 1, in place of 0.08 part of the organic dye described in Japanese Patent No. 3963799, C.I. I. Direct. A solution having a solid content of about 16% was prepared in the same manner as in Formulation Example 1 except that 0.08 part of Blue67 was used. The viscosity of the solution was 330 mPa · s as measured by an E-type viscometer at 25 ° C.
配合例３
上記配合例１において、有機染料のＣ．Ｉ．Ｄｉｒｅｃｔ．Ｏｒａｎｇｅ３９及び特許３９６３９７９号公報に記載の上記有機染料の両者の配合を止める以外は、配合例１と同様にして固形分が約１６％の溶液を調製した。該溶液の粘度はＥ型粘度計２５℃の測定で、３３０ｍＰａ・ｓであった。Formulation Example 3
In the above Formulation Example 1, the organic dye C.I. I. Direct. A solution having a solid content of about 16% was prepared in the same manner as in Formulation Example 1 except that the blending of both of the organic dyes described in Orange 39 and Japanese Patent No. 3963379 was stopped. The viscosity of the solution was 330 mPa · s as measured by an E-type viscometer at 25 ° C.
配合例４
上記配合例１において、有機染料としてＣ．Ｉ．Ｄｉｒｅｃｔ．Ｏｒａｎｇｅ３９の配合を止める以外は、配合例１と同様にして固形分が約１６％の溶液を調製した。該溶液の粘度はＥ型粘度計２５℃の測定で、３３０ｍＰａ・ｓであった。Formulation Example 4
In the above Formulation Example 1, C.I. I. Direct. A solution having a solid content of about 16% was prepared in the same manner as in Formulation Example 1 except that the blending of Orange 39 was stopped. The viscosity of the solution was 330 mPa · s as measured by an E-type viscometer at 25 ° C.
実施例１
配合例１で得られた溶液を沃素系偏光板１ａ（商品名：ＳＫＮ、株式会社ポラテクノ製）上に乾燥後の厚みが１．０μｍになるように塗布しワイヤーバー（♯１０）を用いてＭＤ方向にせん断応力をかけ、コンプレッサーエアーを噴きつけ乾燥させた。さらに、塗布面に１０％硝酸バリウム水溶液を霧吹きにて吹きつけ、再度コンプレッサーエアーを噴きつけ乾燥させて光学異方層を形成し、本発明の光学素子付き偏光フィルム（光学フィルム）を作製した。Example 1
The solution obtained in Formulation Example 1 was applied onto iodine-based
実施例２
配合例１で調製した溶液の代わりに配合例２で調製した溶液を使用し、実施例１と同様にして、本発明の光学素子付き偏光フィルム（光学フィルム）を作製した。Example 2
Using the solution prepared in Formulation Example 2 instead of the solution prepared in Formulation Example 1, a polarizing film with an optical element (optical film) of the present invention was produced in the same manner as in Example 1.
実施例３
配合例１で調製した溶液を表面をアルカリ処理をしたトリアセチルセルロース（ＴＡＣ）フィルム上に乾燥後の厚みが１．０μｍになるように塗布し、ワイヤーバー（♯１０）を用いてＭＤ方向にせん断応力をかけ、コンプレッサーエアーを噴きつけ乾燥させた。さらに、塗布面に１０％硝酸バリウム水溶液を霧吹きにて吹きつけ、再度コンプレッサーエアーを噴きつけ乾燥させ、フィルム上に光学異方層を有する位相差フィルムを作製した。この位相差フィルムのＴＡＣフィルム面と沃素系偏光板１ａ（商品名：ＳＫＮ、株式会社ポラテクノ製）を、位相差フィルムの遅相軸と偏光板の吸収軸が直交するようアクリル粘着剤５（商品名：ＰＴＲ−２５００、日本化薬株式会社製）にて貼り合せたフィルムを作製した。Example 3
The solution prepared in Formulation Example 1 was applied onto a triacetylcellulose (TAC) film whose surface was alkali-treated so that the thickness after drying was 1.0 μm, and the wire bar (# 10) was used in the MD direction. Shear stress was applied, and compressor air was sprayed to dry. Further, a 10% barium nitrate aqueous solution was sprayed onto the coated surface by spraying, and compressed air was sprayed again to dry, thereby producing a retardation film having an optically anisotropic layer on the film. The TAC film surface of the retardation film and the iodine-based
比較例１
実施例１で使用した光学異方層をもたない沃素系偏光板１ａ（商品名：ＳＫＮ、株式会社ポラテクノ製）をそのまま使用した。Comparative Example 1
The iodine
比較例２
配合例１で調製した溶液の代わりに配合例３で調製した溶液を使用し、実施例１と同様の操作を行い、比較用の光学異方層を有する偏光フィルムを得た。Comparative Example 2
Using the solution prepared in Formulation Example 3 instead of the solution prepared in Formulation Example 1, the same operation as in Example 1 was performed to obtain a polarizing film having a comparative optically anisotropic layer.
比較例３
配合例１で調製した溶液の代わりに配合例４で調製した溶液を使用し、実施例１と同様の操作を行い、比較用の光学異方層を有する偏光フィルムを得た。Comparative Example 3
Using the solution prepared in Formulation Example 4 instead of the solution prepared in Formulation Example 1, the same operation as in Example 1 was performed to obtain a polarizing film having a comparative optically anisotropic layer.
上記で得られた各光学異方層の、ｎｘ、ｎｚ、ｎｙ及び、Ｎｚ係数は下記の通りであった。
nx ny nz NZ係数
実施例１ 1.81 1.60 1.73 0.38
実施例２ 1.80 1.60 1.73 0.35
実施例３ 1.81 1.60 1.73 0.38
比較例１（光学異方層無し）
比較例２ 1.80 1.59 1.73 0.33
比較例３ 1.80 1.60 1.73 0.35The nx, nz, ny and Nz coefficients of each optical anisotropic layer obtained above were as follows.
nx ny nz NZ factor Example 1 1.81 1.60 1.73 0.38
Example 2 1.80 1.60 1.73 0.35
Example 3 1.81 1.60 1.73 0.38
Comparative Example 1 (no optical anisotropic layer)
Comparative Example 2 1.80 1.59 1.73 0.33
Comparative Example 3 1.80 1.60 1.73 0.35
また、上記光学異方層における測定波長５５０ｎｍでの面内位相差値は下記の通りであった。
実施例１ 205nm
実施例２ 205nm
実施例３ 215nm
比較例１ （光学異方層無し）
比較例２ 195nm
比較例３ 200nmThe in-plane retardation value at the measurement wavelength of 550 nm in the optically anisotropic layer was as follows.
Example 1 205nm
Example 2 205 nm
Example 3 215 nm
Comparative Example 1 (no optical anisotropic layer)
Comparative Example 2 195 nm
Comparative Example 3 200nm
＜光学特性：斜め方向の黒輝度＞
図４に示すように実施例１〜２および実施例３で得られた光学異方層を形成した光学フィルム（本発明の光学素子付き偏光フィルム）の光学異方層側２をアクリル系粘着剤５（商品名 ＰＴＲ−２５００、日本化薬株式会社製）を介してガラス板８の片面に貼り合わせた。ガラス板８の反対側面にも沃素系偏光板１ａ（商品名 ＳＫＮ、株式会社ポラテクノ社製）をアクリル粘着剤５（商品名 ＰＴＲ−２５００、日本化薬株式会社製）を介して、沃素系偏光板１ａ（商品名 ＳＫＮ、株式会社ポラテクノ社製）のお互いの吸収軸が直交になるように配し、光学特性試験用の積層サンプル（光学系）を作成した。また、比較例１〜３についても同様にして、光学特性試験用の積層サンプル（光学系）を作成した。<Optical characteristics: Black luminance in oblique direction>
As shown in FIG. 4, the optical
上記構成の積層サンプルを図６に示すように極角０°、方位角０°と極角５０°、方位角４５°から測定し視感度補正直交透過率Ｙｃ（０，０）、Ｙｃ（５０，４５）を求めた。透過率測定は、分光光度計（日立分光株式会社製 Ｕ−４１００）を用いた。斜め方向の黒輝度はＹｃ値が小さいほど良好である。実施例１および比較例１〜２について図７で直交透過率波形を示す。また、実施例１〜３および比較例１〜３についての結果を表６に示す。
本発明の光学素子を備えた液晶パネルを用いたものでは、図７から明らかな様に、波長４５０〜７００ｎｍ程度において波長によらず、直交透過率が一様に低く、かつ表６から判る様に、斜め方向の黒輝度Ｙｃ値が低く、また、斜め方向の色つきも、無いかまたは非常に少ないことが判る。As shown in FIG. 6, the laminated sample having the above configuration is measured from a polar angle of 0 °, an azimuth angle of 0 °, a polar angle of 50 °, and an azimuth angle of 45 °, and the visibility corrected orthogonal transmittances Yc (0,0) and Yc (50 45). The transmittance measurement was performed using a spectrophotometer (U-4100 manufactured by Hitachi Spectroscopic Co., Ltd.). The black luminance in the oblique direction is better as the Yc value is smaller. The orthogonal transmittance waveform is shown in FIG. 7 for Example 1 and Comparative Examples 1-2. Table 6 shows the results for Examples 1 to 3 and Comparative Examples 1 to 3.
In the case of using the liquid crystal panel provided with the optical element of the present invention, as apparent from FIG. 7, the orthogonal transmittance is uniformly low regardless of the wavelength at a wavelength of about 450 to 700 nm, and as can be seen from Table 6. Further, it can be seen that the black luminance Yc value in the oblique direction is low, and there is no or very little coloration in the oblique direction.
＜光学特性：斜め方向の色付き＞
ＩＰＳモードの液晶セルを含む液晶表示装置［日立製作所株式会社製液晶テレビ 商品名「Ｗｏｏｏ」］から、液晶パネルを取り出し、液晶セルのバックライト側に配置されていた光学フィルムを一部取り除いて、上記液晶セルのガラス面（表裏）を洗浄した。この液晶セルのバックライト側に、実施例１〜３で得られた光学異方層を形成してなるフィルムの光学異方層側２をアクリル系粘着剤５（商品名：ＰＴＲ−２５００、日本化薬株式会社製）を介して貼り合わせた。貼り合わせは、光学異方層および位相差フィルムの遅相軸とパネルの長辺方向を平行にした。これにより、バックライト側に貼り合せた実施例１および実施例２で得られた光学異方層を形成してなるフィルムの偏光板（商品名：ＳＫＮ、株式会社ポラテクノ製）の吸収軸と、当該セルの表面側偏光板の吸収軸は直交となる。得られた液晶パネルを試験に用いた。また、比較例１〜３についても同様にして、試験用の液晶パネルを作成した。<Optical characteristics: Colored diagonally>
Remove the liquid crystal panel from the liquid crystal display device [LCD manufactured by Hitachi, Ltd., trade name “Wooo]” including the liquid crystal cell in IPS mode, and remove part of the optical film placed on the backlight side of the liquid crystal cell. The glass surface (front and back) of the liquid crystal cell was washed. The optical
得られた試験用液晶パネルをバックライトの上に設置し、液晶表示装置とした。液晶表示装置に黒画面を表示させ、暗室でバックライトを点灯させてから、３０分経過した後、目視で斜め方向（方位角４５°、極角５０°）から着色の程度を観察した。実施例１〜３および比較例１〜３についての観察結果を表６に示す。 The obtained test liquid crystal panel was placed on a backlight to obtain a liquid crystal display device. After the black screen was displayed on the liquid crystal display device and the backlight was turned on in the dark room, after 30 minutes had elapsed, the degree of coloring was observed visually from an oblique direction (azimuth angle 45 °, polar angle 50 °). Table 6 shows the observation results for Examples 1 to 3 and Comparative Examples 1 to 3.
◎：着色なし
○：少し着色あり
△：着色あり
×：大きく着色あり
上記の評価結果を下記表１に示す。◎: Not colored ○: Slightly colored △: Colored ×: Largely colored
The evaluation results are shown in Table 1 below.
（表６）
Ｙｃ（０,０) Ｙｃ（５０,４５） 斜め方向の色付き評価
実施例１ ０．０１％ ０．２０％ ◎
実施例２ ０．０１％ ０．２７％ ○
実施例３ ０．０１％ ０．２１％ ◎
比較例１ ０．０１％ ０．４７％ ×
比較例２ ０．０１％ ０．３０％ △
比較例３ ０．０１％ ０．２８％ △(Table 6)
Yc (0,0) Yc (50,45) Colored evaluation example 1 in an oblique direction 0.01% 0.20% A
Example 2 0.01% 0.27% ○
Example 3 0.01% 0.21%
Comparative Example 1 0.01% 0.47% ×
Comparative Example 2 0.01% 0.30%
Comparative Example 3 0.01% 0.28%
本発明の光学素子を備えた光学フィルムを用いることにより、多数の位相差フィルムを用いることなく、４５０〜７００ｎｍ程度の範囲の波長においては波長に関係なく、直交透過率を一様に低く抑えることが出来る。また、斜め方向の黒輝度も低く抑えることができると共に、斜め方向の色つきを無くすかまたは顕著に低く抑えることができるので、光学素子として極めて有用である。 By using the optical film provided with the optical element of the present invention, the orthogonal transmittance is uniformly suppressed at a wavelength in the range of about 450 to 700 nm without using a large number of retardation films regardless of the wavelength. I can do it. Further, the black luminance in the oblique direction can be suppressed to a low level, and coloring in the oblique direction can be eliminated or significantly reduced, so that it is extremely useful as an optical element.
Claims (14)
前記有機色素の少なくとも一つの有機色素の極大吸収波長が３８０ｎｍ以上５５０ｎｍ未満であり、他方の少なくとも一つの有機色素の極大吸収波長が５５０ｎｍ以上７８０ｎｍ以下であることを特徴とする光学素子。
（式中、Ｘは−Ｏ−ＣＨ２−ｐｈ−ＣＨ２−Ｏ−、−Ｏ−ＣＯ−ｐｈ−ＣＯ−Ｏ−または−ＮＨ−ＣＯ−ｐｈ−ＣＯ−ＮＨ−を表し、ｐｈはスルホ置換を有してもよいパラフェニレン基を表し、ｎは繰り返し数を示す。） It includes at least two organic dyes, an oligophenyl compound, and a compound represented by the following general formula (A). The maximum refractive index in the plane is nx, the refractive index orthogonal to nx in the plane is ny, Colored and oriented optics in which the three-dimensional refractive index is nx>nz> ny and (nx−nz) / (nx−ny) is 0.2 to 0.7 when the vertical refractive index is nz. Ri Do from anisotropic layer,
An optical element, wherein a maximum absorption wavelength of at least one organic dye of the organic dye is from 380 nm to less than 550 nm, and a maximum absorption wavelength of the other at least one organic dye is from 550 nm to 780 nm .
(In the formula, X represents -O-CH2-ph-CH2-O-, -O-CO-ph-CO-O- or -NH-CO-ph-CO-NH-, and ph has sulfo-substitution. to represent which may paraphenylene group, n represents shows the number of repetitions.)
下記一般式（Ｂ）
（式中、Ｘはスルホ基またはカルボキシ基、Ｒ１、Ｒ２は各々独立に水素原子、Ｃ１〜Ｃ４アルキル基、Ｃ１〜Ｃ４アルコキシル基を示し、ｎは１または２を示す。）
で表されるアゾ化合物またはその塩を、
また、極大吸収波長が５５０ｎｍ以上７８０ｎｍ以下である有機色素として下記一般式（Ｃ）
（式中、Ｑ21は、スルホン酸基を１個または２個有し、さらに水酸基またはＣ１〜Ｃ４アルコキシ基を有していてもよいナフチル基を、Ｑ22、Ｑ23はそれぞれ独立にフェニレン基またはナフチレン基（これらの基は置換基としてＣ１〜Ｃ４アルキル基、Ｃ１〜Ｃ４アルコキシ基、水酸基およびスルホン酸基からなる群から選ばれた１種または２種の置換基を１個または２個有する）を、Ｒ21は水素原子、Ｃ１〜Ｃ４アルキル基、アセチル基、ベンゾイル基または置換もしくは無置換のフェニル基を、Ｒ23、Ｒ24はそれぞれ独立に水素原子、水酸基、スルホン酸基、Ｃ１〜Ｃ４アルキル基またはＣ１〜Ｃ４アルコキシ基を、ｑは０または１を、ｒは１または２を表す。）
で表される化合物またはその塩、
を含む請求項１に記載の光学素子。 As an organic dye having a maximum absorption wavelength of 380 nm or more and less than 550 nm,
The following general formula (B)
(In the formula , X represents a sulfo group or a carboxy group, R 1 and R 2 each independently represents a hydrogen atom, a C1 to C4 alkyl group, or a C1 to C4 alkoxyl group, and n represents 1 or 2.)
An azo compound represented by
Further, as an organic dye having a maximum absorption wavelength of 550 nm or more and 780 nm or less, the following general formula (C)
(Wherein Q 21 is a naphthyl group having one or two sulfonic acid groups and further having a hydroxyl group or a C1-C4 alkoxy group, and Q 22 and Q 23 are each independently a phenylene group. Or a naphthylene group (these groups have one or two substituents selected from the group consisting of a C1-C4 alkyl group, a C1-C4 alkoxy group, a hydroxyl group and a sulfonic acid group as a substituent. R 21 is a hydrogen atom, a C1-C4 alkyl group, an acetyl group, a benzoyl group or a substituted or unsubstituted phenyl group, R 23 and R 24 are each independently a hydrogen atom, a hydroxyl group, a sulfonic acid group, A C4 alkyl group or a C1-C4 alkoxy group, q represents 0 or 1, and r represents 1 or 2.)
Or a salt thereof,
The optical element according to claim 1 , comprising:
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| PCT/JP2011/002541 WO2011138869A1 (en) | 2010-05-07 | 2011-05-02 | Optical element and method for improving viewing angle of polarizing film using same |
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| JP6769921B2 (en) | 2017-04-28 | 2020-10-14 | 日東電工株式会社 | Manufacturing method of liquid crystal alignment film |
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| CN102884456A (en) | 2013-01-16 |
| JPWO2011138869A1 (en) | 2013-07-22 |
| KR20130080789A (en) | 2013-07-15 |
| WO2011138869A1 (en) | 2011-11-10 |
| CN102884456B (en) | 2014-12-31 |
| TWI541529B (en) | 2016-07-11 |
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