JP2017102479A - Polarization element, circularly polarizing plate, and method of manufacturing those - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new polarization element provided with a polarization layer and a photo-alignment layer, and a circular polarizer including the polarization element, and to provide a method of manufacturing those.SOLUTION: A polarizer is obtained by providing a photo-alignment layer and a polarization layer on transparent base material in this order, and the photo-alignment layer is formed of a polymer having a photoreactive group. A polarization element is provided in which the polarization layer is formed of a composition containing a polymerizable smectic liquid crystal compound and a dichroic dye. A circularly polarizing plate obtained by further providing a retardation layer on the polarization layer of the polarization element or a circularly polarizing plate obtained by replacing the transparent base material of the polarization element with a retardation film is provided.SELECTED DRAWING: None

Description

  The present invention relates to a polarizing element, a circularly polarizing plate, a manufacturing method thereof, and the like.

  Generally, a polarizing element used in a liquid crystal display device uses a film made of polyvinyl alcohol (PVA) dyed with iodine as an alignment layer (Non-patent Document 1).

Published by Hachiji Suzuki, “Until the creation of a liquid crystal display”, Nikkan Kogyo Shimbun, November 28, 2005

  The present invention provides a novel polarizing element provided with a specific polarizing layer and a photo-alignment layer, a circular polarizer including the polarizing element, and methods for producing them.

［式（Ａ’）中、
ｎは、０又は１を表す。
Ｘ^１は、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−Ｎ＝Ｎ−、−ＣＨ＝ＣＨ−又は−ＣＨ_２−を表す。
Ｙ^１は、単結合又は−Ｏ−を表す。
Ｒ^１及びＲ^２はそれぞれ独立に、水素原子、炭素数１〜４のアルキル基又は炭素数１〜４のアルコキシ基を表す。
＊は、ポリマー主鎖に対する結合手を表す。］
〔５〕前記〔１〕〜〔４〕のいずれか記載の偏光素子の製造方法であり、
前記透明基材上に、
前記光反応性基を有するポリマーと溶剤とを含有する組成物を塗布して、該透明基材上に第１塗布膜を形成する工程と、
該第１塗布膜から該溶剤を乾燥除去することにより、該透明基材上に第１乾燥被膜を形成して、第１積層体を得る工程と、
該第１乾燥被膜に偏光ＵＶを照射することにより、該第１乾燥被膜から光配向層を形成して第２積層体を得る工程と、
該第２積層体にある該光配向層上に、重合性スメクチック液晶化合物、二色性色素、重合開始剤及び溶剤を含有する組成物を塗布して、該光配向層上に第２塗布膜を形成する工程と、
該第２塗布膜を、該第２塗布膜中に含まれる該重合性スメクチック液晶化合物が重合しない条件で乾燥することにより、該光配向層上に第２乾燥被膜を形成して第３積層体を得る工程と、
該第２乾燥被膜中の該重合性スメクチック液晶化合物をスメクチック液晶状態とした後、該スメクチック液晶状態を保持したまま、該重合性スメクチック液晶化合物を重合させることにより、該第２乾燥被膜から偏光層を形成する工程と
を有する製造方法。
〔６〕形状が、フィルム状且つ長尺状である、前記〔１〕〜〔４〕のいずれか記載の偏光素子。
〔７〕前記〔６〕記載の偏光素子の製造方法であり、
透明基材が第１の巻芯に巻き取られている第１ロールを準備する工程と、
該第１ロールから、該透明基材を連続的に送り出す工程と、
前記光反応性基を有するポリマーと溶剤とを含有する組成物を塗布して、該透明基材上に第１塗布膜を連続的に形成する工程と、
該第１塗布膜から該溶剤を乾燥除去することにより、該透明基材上に第１乾燥被膜を形成して、第１積層体を連続的に得る工程と、
該第１乾燥被膜に偏光ＵＶを照射することにより、該第１積層体の搬送方向に対して、略４５°の角度に配向方向を有する光配向層を形成して、第２積層体を連続的に得る工程と、
該光配向層上に、重合性スメクチック液晶化合物、二色性色素、重合開始剤及び溶剤を含有する組成物を塗布して、該光配向層上に第２塗布膜を連続的に形成する工程と
該第２塗布膜を、該第２塗布膜中に含まれる該重合性スメクチック液晶化合物が重合しない条件で乾燥することにより、該光配向層上に第２乾燥被膜を形成して第３積層体を連続的に得る工程と、
該第２乾燥被膜中に含まれる該重合性スメクチック液晶化合物をスメクチック液晶状態とした後、該スメクチック液晶状態を保持したまま、該重合性スメクチック液晶化合物を重合させることにより、該第３積層体の搬送方向に対して、４５°の角度に吸収軸を有する偏光層を形成して、偏光素子を連続的に得る工程と、
連続的に得られた偏光素子を第２の巻芯に巻き取り、第２ロールを得る工程と
を有する製造方法。
〔８〕前記〔１〕〜〔４〕のいずれか記載の偏光素子を備えた液晶表示装置。
〔９〕前記〔１〕〜〔４〕のいずれか記載の偏光素子を、液晶セル内部に配置することにより備えた液晶表示装置。
〔１０〕前記〔１〕〜〔４〕のいずれか記載の偏光素子と、位相差フィルムとを、前記偏光層の吸収軸と前記位相差フィルムの遅相軸のなす角度が、略４５°となるように積層した円偏光板であり、
波長５５０ｎｍの光で測定した楕円率の値が８０％以上であり、
前記位相差フィルムが、波長５５０ｎｍの光で測定した正面リタデーションの値が１００〜１５０ｎｍの範囲のフィルムである円偏光板。
〔１１〕前記位相差フィルムが、可視光に対する正面リタデーションの値が、波長が短くなるに従って小さくなる特性を有する、前記〔１０〕記載の円偏光板。
〔１２〕形状が、フィルム状且つ長尺状である、前記〔１０〕又は〔１１〕記載の円偏光板。
〔１３〕前記〔１２〕記載の円偏光板の製造方法であり、
位相差フィルムが第３の巻芯に巻き取られている第３ロールを準備する工程と、
前記偏光素子が第２の巻芯に巻き取られている第２ロールを準備する工程と、
該第２ロールから該偏光素子を連続的に巻き出すとともに、該第３ロールから該位相差フィルムを連続的に巻き出す工程と、
連続的に巻き出された偏光素子の偏光層と、連続的に巻き出された位相差フィルムとを張り合わせる工程と
を有する製造方法。
〔１４〕前記〔１〕〜〔４〕のいずれか記載の偏光素子に含まれる透明基材を、位相差性を有する位相差フィルムに置き換え、前記位相差フィルムの遅相軸と、前記偏光層の吸収軸のなす角度が、略４５°に積層してなる円偏光板であり、
波長５５０ｎｍの光で測定した楕円率の値が８０％以上であり、
前記位相差フィルムが、波長５５０ｎｍの光で測定した正面リタデーションの値が１００〜１５０ｎｍの範囲のフィルムである円偏光板。
〔１５〕形状が、フィルム状且つ長尺状である、前記〔１４〕記載の円偏光板。
〔１６〕前記〔１５〕記載の円偏光板の製造方法であり、
位相差フィルムが第１の巻芯に巻き取られている第１ロールを準備する工程と、
該第１ロールから、該位相差フィルムを連続的に送り出す工程と、
前記光反応性基を有するポリマーと溶剤とを含有する組成物を塗布して、該位相差フィルム上に第１塗布膜を連続的に形成する工程と、
該第１塗布膜から該溶剤を乾燥除去して、該透明基材上に第１乾燥被膜を形成して、第１積層体を連続的に得る工程と、
該第１乾燥被膜に偏光ＵＶを照射することにより、該第１積層体の搬送方向に対して、略４５°の角度に配向方向を有する光配向層を形成して、第２積層体を連続的に得る工程と、
該光配向層上に、重合性スメクチック液晶化合物、二色性色素、重合開始剤及び溶剤を含有する組成物を塗布して、該光配向層上に第２塗布膜を連続的に形成する工程と
該第２塗布膜を、該第２塗布膜中に含まれる該重合性スメクチック液晶化合物が重合しない条件で乾燥することにより、該光配向層上に第２乾燥被膜を形成して第３積層体を連続的に得る工程と、
該第２乾燥被膜中に含まれる該重合性スメクチック液晶化合物をスメクチック液晶状態とした後、該スメクチック液晶状態を保持したまま、該重合性スメクチック液晶化合物を重合させることにより、該第３積層体の搬送方向に対して、４５°の角度に吸収軸を有する偏光層を形成して、円偏光板を連続的に得る工程と、
連続的に得られた円偏光板を第２の巻芯に巻き取り、第２ロールを得る工程と
を有する製造方法。
〔１７〕前記〔１０〕、〔１１〕及び〔１４〕のいずれか記載の円偏光板と、有機ＥＬ素子とを備えた有機ＥＬ表示装置。 The present invention includes the following inventions [1] to [17].
[1] A polarizer in which a photo-alignment layer and a polarizing layer are provided in this order on a transparent substrate,
The photo-alignment layer is formed from a polymer having a photoreactive group,
The polarizing layer is
A polarizing element which is formed from a composition containing a polymerizable smectic liquid crystal compound and a dichroic dye.
[2] The polarizing element according to [1], wherein the polarizing layer is a polarizing layer from which a Bragg peak is obtained in X-ray diffraction measurement.
[3] The polarizing element according to [1] or [2], wherein the composition contains two or more polymerizable smectic liquid crystal compounds.
[4] The polarizing element according to any one of [1] to [3], wherein the polymer having a photoreactive group is a polymer containing a group represented by the formula (A ′).

[In the formula (A ′),
n represents 0 or 1.
X ¹ represents a single bond, —O—, —COO—, —OCO—, —N═N—, —CH═CH— or —CH ₂ —.
Y ¹ represents a single bond or —O—.
R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
* Represents a bond to the polymer main chain. ]
[5] A method for producing a polarizing element according to any one of [1] to [4],
On the transparent substrate,
Applying a composition containing a polymer having a photoreactive group and a solvent to form a first coating film on the transparent substrate;
Forming the first dry film on the transparent substrate by drying and removing the solvent from the first coating film to obtain a first laminate;
Irradiating the first dry film with polarized UV to form a photo-alignment layer from the first dry film to obtain a second laminate;
A composition containing a polymerizable smectic liquid crystal compound, a dichroic dye, a polymerization initiator and a solvent is applied onto the photo-alignment layer in the second laminate, and a second coating film is applied onto the photo-alignment layer. Forming a step;
The second coating film is dried under a condition in which the polymerizable smectic liquid crystal compound contained in the second coating film is not polymerized, thereby forming a second dry film on the photo-alignment layer to form a third laminate. Obtaining
The polymerizable smectic liquid crystal compound in the second dry film is changed to a smectic liquid crystal state, and then the polymerizable smectic liquid crystal compound is polymerized while the smectic liquid crystal state is maintained, whereby a polarizing layer is formed from the second dry film. The manufacturing method which has a process of forming.
[6] The polarizing element according to any one of [1] to [4], wherein the shape is a film and a long shape.
[7] The method for producing a polarizing element according to [6],
Preparing a first roll in which a transparent substrate is wound around a first core;
Continuously feeding the transparent substrate from the first roll;
Applying a composition containing a polymer having a photoreactive group and a solvent, and continuously forming a first coating film on the transparent substrate;
Forming the first dry film on the transparent substrate by drying and removing the solvent from the first coating film, and continuously obtaining the first laminate;
By irradiating the first dry film with polarized UV, a photo-alignment layer having an orientation direction at an angle of about 45 ° with respect to the transport direction of the first laminate is formed, and the second laminate is continuously formed. And the process of obtaining
A step of coating a composition containing a polymerizable smectic liquid crystal compound, a dichroic dye, a polymerization initiator and a solvent on the photo-alignment layer, and continuously forming a second coating film on the photo-alignment layer. And the second coating film is dried under a condition in which the polymerizable smectic liquid crystal compound contained in the second coating film is not polymerized, thereby forming a second dry film on the photo-alignment layer to form a third laminate. Obtaining a body continuously;
The polymerizable smectic liquid crystal compound contained in the second dry film is changed to a smectic liquid crystal state, and then the polymerizable smectic liquid crystal compound is polymerized while maintaining the smectic liquid crystal state. Forming a polarizing layer having an absorption axis at an angle of 45 ° with respect to the transport direction to obtain a polarizing element continuously;
The manufacturing method which has the process of winding up the polarizing element obtained continuously on the 2nd core, and obtaining the 2nd roll.
[8] A liquid crystal display device comprising the polarizing element according to any one of [1] to [4].
[9] A liquid crystal display device comprising the polarizing element according to any one of [1] to [4] disposed in a liquid crystal cell.
[10] The polarizing element according to any one of [1] to [4], and a retardation film, wherein an angle formed by an absorption axis of the polarizing layer and a slow axis of the retardation film is approximately 45 °. Is a circularly polarizing plate laminated so that
The ellipticity value measured with light having a wavelength of 550 nm is 80% or more,
A circularly polarizing plate in which the retardation film is a film having a front retardation value of 100 to 150 nm measured with light having a wavelength of 550 nm.
[11] The circularly polarizing plate according to [10], wherein the retardation film has a property that a value of front retardation with respect to visible light decreases as the wavelength decreases.
[12] The circularly polarizing plate according to [10] or [11], wherein the shape is a film and a long shape.
[13] The method for producing a circularly polarizing plate according to [12],
Preparing a third roll in which a retardation film is wound around a third core;
Preparing a second roll in which the polarizing element is wound around a second core;
A step of continuously unwinding the polarizing element from the second roll and unwinding the retardation film from the third roll;
The manufacturing method which has the process of bonding the polarizing layer of the polarizing element unwound continuously, and the retardation film unwound continuously.
[14] The transparent substrate contained in the polarizing element according to any one of [1] to [4] is replaced with a retardation film having retardation, and the slow axis of the retardation film, and the polarizing layer The angle formed by the absorption axis is a circularly polarizing plate formed by laminating at approximately 45 °,
The ellipticity value measured with light having a wavelength of 550 nm is 80% or more,
A circularly polarizing plate in which the retardation film is a film having a front retardation value of 100 to 150 nm measured with light having a wavelength of 550 nm.
[15] The circularly polarizing plate according to [14], wherein the shape is a film and a long shape.
[16] The method for producing a circularly polarizing plate according to [15],
Preparing a first roll in which a phase difference film is wound around a first core;
A step of continuously feeding out the retardation film from the first roll;
Applying a composition containing a polymer having a photoreactive group and a solvent, and continuously forming a first coating film on the retardation film;
A step of drying and removing the solvent from the first coating film to form a first dry film on the transparent substrate to obtain a first laminate continuously;
By irradiating the first dry film with polarized UV, a photo-alignment layer having an orientation direction at an angle of about 45 ° with respect to the transport direction of the first laminate is formed, and the second laminate is continuously formed. And the process of obtaining
A step of coating a composition containing a polymerizable smectic liquid crystal compound, a dichroic dye, a polymerization initiator and a solvent on the photo-alignment layer, and continuously forming a second coating film on the photo-alignment layer. And the second coating film is dried under a condition in which the polymerizable smectic liquid crystal compound contained in the second coating film is not polymerized, thereby forming a second dry film on the photo-alignment layer to form a third laminate. Obtaining a body continuously;
The polymerizable smectic liquid crystal compound contained in the second dry film is changed to a smectic liquid crystal state, and then the polymerizable smectic liquid crystal compound is polymerized while maintaining the smectic liquid crystal state. Forming a polarizing layer having an absorption axis at an angle of 45 ° with respect to the transport direction to obtain a circularly polarizing plate continuously;
The manufacturing method which has the process of winding up the circularly-polarizing plate obtained continuously on the 2nd core, and obtaining the 2nd roll.
[17] An organic EL display device comprising the circularly polarizing plate according to any one of [10], [11] and [14], and an organic EL element.

  According to the present invention, a novel polarizing element provided with a specific polarizing layer and a photo-alignment layer, and a novel circularly polarizing plate including the polarizing element can be provided.

It is a cross-sectional schematic diagram which shows the simplest structure of the polarizing element of this invention. It is a cross-sectional schematic diagram which shows the principal part of the manufacturing method of the polarizing element of this invention. It is a schematic diagram which shows the method of irradiating polarized light UV to a 1st dry film in photo-alignment operation. It is a schematic cross section which shows the principal part of the continuous manufacturing method (Roll to Roll format) of the polarizing element of this invention. It is a figure which represents typically the relationship between the orientation direction D2 of a photo-alignment layer, and the conveyance direction D1 of a film. It is a schematic cross section which shows the cross-sectional structure of the liquid crystal display device using the polarizing element of this invention. It is an expansion schematic cross section which shows the layer order of the polarizing element of this invention provided in the liquid crystal display device. It is an expansion schematic cross section which shows the layer order of the polarizing element of this invention provided in the liquid crystal display device. It is a schematic cross section which shows the cross-sectional structure of the liquid crystal display device (in-cell format) using the polarizing element of this invention. It is a cross-sectional schematic diagram which shows the simplest structure of the circularly-polarizing plate of this invention. It is a schematic cross section which shows the principal part of the continuous manufacturing method of the circularly-polarizing plate of this invention. It is a schematic cross section which shows the cross-sectional structure of EL display apparatus using the polarizing element of this invention. It is an expansion schematic cross section which shows the layer order of the polarizing element of this invention provided in EL display apparatus. It is a schematic cross section which shows the cross-sectional structure of EL display apparatus using the polarizing element of this invention. It is a schematic cross section which shows the cross-sectional structure of the projection type liquid crystal display device using the polarizing element of this invention.

The polarizing element of the present invention (hereinafter sometimes referred to as “the present polarizing element”) is a transparent base material in which a photo-alignment layer and a polarizing layer are provided in this order.
The photo-alignment layer is formed from a polymer having a photoreactive group, and the polarizing layer is formed from a composition containing a polymerizable smectic liquid crystal compound and a dichroic dye. It is preferable that the composition further contains a solvent. This polarizing element is not only suitably used for a liquid crystal display device, but also by using this polarizing element as will be described later, a circularly polarizing plate suitably used for an organic EL display device (hereinafter referred to as “this circularly polarized light” in some cases). Board ") can also be manufactured. Hereinafter, this polarizing element and its manufacturing method, and this circularly-polarizing plate and its manufacturing method are demonstrated, referring drawings as needed. Note that the dimensions of the drawings attached to the present specification are arbitrary for easy viewing.

FIG. 1 is a schematic cross-sectional view showing the simplest configuration of the present polarizing element. On the transparent base material 1, the photo-alignment layer 2 and the polarizing layer 3 are laminated in this order, and the polarizing element 100 is formed. For example, the polarizing element 100 can be manufactured by a manufacturing method including the following steps (hereinafter, referred to as “the manufacturing method A” in some cases).

(Step A1) A step of applying a composition containing a polymer having a photoreactive group and a solvent on a transparent substrate to form a first coating film on the transparent substrate;
(Step A2) A step of forming a first dry film on the transparent substrate by drying and removing the solvent from the first coating film to obtain a first laminate;
(Step A3) A step of obtaining a second laminate by forming a photo-alignment layer from the first dry coating by irradiating polarized UV to the first dry coating of the first laminate;
(Step A4) A composition containing a polymerizable smectic liquid crystal compound, a dichroic dye and a solvent is applied onto the photo-alignment layer of the second laminate, and a second coating film is formed on the photo-alignment layer. Forming a step;
(Step A5) The second coating film is dried under a condition in which the polymerizable smectic liquid crystal compound contained in the second coating film is not polymerized, thereby forming a second dry film on the photo-alignment layer. Obtaining a third laminate;
(Step A6) After making the polymerizable smectic liquid crystal compound in the second dry film of the third laminate into a smectic liquid crystal state, the polymerizable smectic liquid crystal compound is polymerized while maintaining the smectic liquid crystal state. Forming a polarizing layer from the second dry film

FIG. 2 is a schematic cross-sectional view showing the main part of the method for manufacturing the polarizing element 100 (the manufacturing method A) comprising (step A1) to (step A6). Hereinafter, this manufacturing method is demonstrated for every process.

<Process A1>
Step A1 is a step of forming the first coating film on the transparent substrate.

<Transparent substrate>
In step A1, first, a transparent substrate 1 is prepared. A transparent base material here is a base material which has the transparency which can permeate | transmit light, especially visible light. The transparency refers to a characteristic that the transmittance with respect to a light beam having a wavelength of 380 to 780 nm is 80% or more. Specific examples of such transparent substrates include glass substrates, plastic translucent sheets, and translucent films. Examples of the plastic constituting the translucent sheet or translucent film include polyolefins such as polyethylene, polypropylene and norbornene polymers; cyclic olefin resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylates; Acid esters; cellulose esters such as triacetylcellulose, diacetylcellulose and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; composed of any plastic such as polyphenylene sulfide and polyphenylene oxide Base materials. Among the specific examples of the transparent substrate described above, a plastic light-transmitting film, that is, a polymer film is preferable in view of a preferable plastic light-transmitting sheet and light-transmitting film. Among the polymer films, a polymer film made of cellulose ester, cyclic olefin resin, polyethylene terephthalate or polymethacrylic acid ester is particularly preferable because it can be easily obtained from the market or has excellent transparency. Is preferred. In producing the polarizing element using such a transparent substrate, the transparent substrate can be easily handled without causing damage such as tearing when the transparent substrate is transported or stored. A support base material or the like may be pasted. Moreover, although mentioned later, when manufacturing a circularly-polarizing plate from this polarizing element, retardation may be provided to this transparent base material. In this case, a polymer film is prepared as a transparent substrate, and the polymer film is subjected to stretching treatment to impart retardation to the polymer film to obtain a retardation film. A conductive film may be used as the transparent substrate 1. The method for imparting retardation to the transparent substrate (polymer film) will be described later.

Among the polymer films, when phase difference is imparted, films made of cellulose ester or cyclic olefin resin (cellulose ester film, cyclic olefin resin film) are easy to control the retardation value. preferable. Hereinafter, these two types of polymer films will be described in detail.
The cellulose ester constituting the cellulose ester film is one in which at least a part of hydroxyl groups contained in cellulose is converted to acetate ester. A cellulose ester film comprising such a cellulose ester can be easily obtained from the market. Examples of commercially available triacetyl cellulose films include “Fujitac Film” (Fuji Photo Film Co., Ltd.); “KC8UX2M”, “KC8UY” and “KC4UY” (Konica Minolta Opto Co., Ltd.). Such a commercially available cellulose ester film (triacetyl cellulose film) can be used as a transparent substrate as it is or after imparting phase difference as needed. Further, the surface of the prepared transparent substrate can be used as the transparent substrate 1 after performing surface treatment such as antiglare treatment, hard coat treatment, antistatic treatment and antireflection treatment.

  In order to impart retardation to the polymer film, as described above, the polymer film is stretched. Any polymer film made of plastic, that is, a thermoplastic resin can be stretched, but a cyclic olefin-based resin film is preferable in that the retardation can be easily controlled. The cyclic olefin resin constituting the cyclic olefin resin film is composed of, for example, a polymer or copolymer (cyclic olefin resin) of a cyclic olefin such as norbornene or a polycyclic norbornene monomer. The olefin resin may partially contain a ring opening. Moreover, what hydrogenated the cyclic olefin resin containing a ring opening part may be used. Further, the cyclic olefin resin is, for example, a copolymer of a cyclic olefin and a chain olefin or a vinylated aromatic compound (such as styrene) in that the transparency is not significantly impaired or the hygroscopicity is not significantly increased. It may be. The cyclic olefin resin may have a polar group introduced in its molecule.

  When the cyclic olefin resin is a copolymer of a cyclic olefin and an aromatic compound having a chain olefin or a vinyl group, the chain olefin is ethylene, propylene, or the like, and a vinylated aromatic Examples of the compound include styrene, α-methylstyrene, and alkyl-substituted styrene. In such a copolymer, the content ratio of the structural unit derived from the cyclic olefin is in the range of 50 mol% or less, for example, about 15 to 50 mol% with respect to all the structural units of the cyclic olefin resin. When the cyclic olefin-based resin is a terpolymer obtained from a cyclic olefin, a chain olefin, and a vinylated aromatic compound, for example, the content ratio of the structural unit derived from the chain olefin is the cyclic olefin. It is about 5-80 mol% with respect to all the structural units of a resin, and the content rate of the structural unit derived from a vinylated aromatic compound is about 5-80 mol%. Such a terpolymer cyclic olefin resin has the advantage that the amount of expensive cyclic olefin used can be relatively reduced when the cyclic olefin resin is produced.

  Cyclic olefin resins that can produce a cyclic olefin resin film are readily available from the market. Commercially available cyclic olefin-based resins include “Topas” [Ticona (Germany)]; “Arton” [JSR Corporation]; “ZEONOR” and “ZEONEX” [Nippon Zeon Corporation] “Apel” [Mitsui Chemicals, Inc.] and the like. Such a cyclic olefin-based resin can be formed into a film (cyclic olefin-based resin film) by, for example, known film forming means such as a solvent casting method or a melt extrusion method. Moreover, the cyclic olefin resin film already marketed with the form of a film can also be used. Examples of such commercially available cyclic olefin resin films include “Essina” and “SCA40” [Sekisui Chemical Co., Ltd.]; “Zeonor Film” [Optes Co., Ltd.]; “Arton Film” [JSR Co., Ltd.] ] Etc. are mentioned. In addition, what is described in “” here is a product name, and so on.

  Next, a method for imparting retardation to the polymer film will be briefly described. The polymer film can be provided with retardation by a known stretching method. For example, a roll (winding body) in which a polymer film is wound on a roll is prepared, the film is continuously unwound from the winding body, and the unwound film is conveyed to a heating furnace. The set temperature of the heating furnace is in the range of near the glass transition temperature (° C.) to [glass transition temperature +100] (° C.) of the polymer film, preferably near the glass transition temperature (° C.) to [glass transition temperature +50] (° C. ). In the heating furnace, when the film is stretched in the direction of travel or in the direction perpendicular to the direction of travel, the transport direction and tension are adjusted, and the film is uniaxially or biaxially stretched at an arbitrary angle. . The draw ratio is usually in the range of about 1.1 to 6 times, preferably in the range of about 1.1 to 3.5 times. In addition, the method of stretching in an oblique direction is not particularly limited as long as the orientation axis can be continuously inclined to a desired angle, and a known stretching method can be employed. Examples of such a stretching method include the methods described in JP-A-50-83482 and JP-A-2-113920.

  When used as the transparent substrate 1, the thickness of the polymer film is preferably thin in terms of weight that allows practical handling and sufficient transparency, but if it is too thin There is a tendency that the strength is lowered and the processability is inferior. Therefore, an appropriate thickness of these films is, for example, about 5 to 300 μm, preferably 20 to 200 μm. When using this polarizing element as a circularly-polarizing plate mentioned later, since it is assumed that the display apparatus using the said circularly-polarizing plate is a mobile use, about 20-100 micrometers of film thickness is especially preferable. In addition, when giving retardation to a film by extending | stretching, the thickness after extending | stretching is determined by the thickness of the film before extending | stretching, and a draw ratio.

  In step A1, by providing the photo-alignment layer 2 on the transparent substrate 1, the first laminate 101 having the transparent substrate 1 and the photo-alignment layer 2, preferably the transparent substrate 1 and the photo-alignment layer 2 is used. The first stacked body 101 is stacked. In addition, when surface treatments, such as a hard-coat process, are given to the said transparent base material 1, what is necessary is just to form a photo-alignment layer in the surface on the opposite side with respect to the said surface-treated surface.

<Photo alignment layer>
In forming the photo-alignment layer, first, a composition containing a polymer having a photoreactive group and a solvent (hereinafter sometimes referred to as “photo-alignment layer forming composition”) is prepared. The photoreactive group refers to a group that generates liquid crystal alignment ability when irradiated with light (light irradiation). The photoreactive group in the present invention is specifically a liquid crystal alignment such as an alignment induction or isomerization reaction, dimerization reaction, photocrosslinking reaction, or photodecomposition reaction of a polymer molecule caused by light irradiation. It causes a photoreaction that is the origin of Noh. Among the photoreactive groups, those utilizing a dimerization reaction or a photocrosslinking reaction are preferable because they are excellent in orientation and a polymerizable smectic liquid crystal compound maintains a smectic liquid crystal state when a polarizing layer described later is formed. As the photoreactive group capable of causing the above reaction, those having an unsaturated bond, particularly a double bond are preferable, and a carbon-carbon double bond (C═C bond), a carbon-nitrogen double bond (C = N bond), a group having at least one selected from the group consisting of a nitrogen-nitrogen double bond (N = N bond) and a carbon-oxygen double bond (C = O bond) is particularly preferable.

Examples of the photoreactive group having a C═C bond include a vinyl group, a polyene group, a stilbene group, a stilbazole group, a stilbazolium group, a chalcone group, and a cinnamoyl group. Examples of the photoreactive group having a C═N bond include groups having a structure such as an aromatic Schiff base and an aromatic hydrazone. Examples of the photoreactive group having an N = N bond include an azobenzene group, an azonaphthalene group, an aromatic heterocyclic azo group, a bisazo group and a formazan group, and those having a basic structure of azoxybenzene. Examples of the photoreactive group having a C═O bond include a benzophenone group, a coumarin group, an anthraquinone group, and a maleimide group. These groups may have a substituent such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, and a halogenated alkyl group.
Among them, a photoreactive group capable of causing a photodimerization reaction is preferable, and a cinnamoyl group and a chalcone group have a relatively small amount of polarized light irradiation necessary for photoalignment, and a photoalignment layer having excellent thermal stability and temporal stability. It is preferable because it is easily obtained. Further, as the polymer having a photoreactive group, a polymer having a cinnamoyl group in which the terminal portion of the polymer side chain has a cinnamic acid structure is particularly preferable.

［式（Ａ’）中、
ｎは、０又は１を表す。
Ｘ^１は、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−Ｎ＝Ｎ−、−ＣＨ＝ＣＨ−又は−ＣＨ_２−を表す。
Ｙ^１は、単結合又は−Ｏ−を表す。
Ｒ^１及びＲ^２はそれぞれ独立に、水素原子、炭素数１〜４のアルキル基又は炭素数１〜４のアルコキシ基を表す。
＊は、ポリマー主鎖に対する結合手を表す。］ A polymer having a particularly preferable photoreactive group is, for example, the formula (A ′) because the composition for forming a photo-alignment layer is easy to handle and an alignment layer realizing a highly durable alignment is easily obtained. In the side chain (hereinafter sometimes referred to as “polymer (A ′)”).

[In the formula (A ′),
n represents 0 or 1.
X ¹ represents a single bond, —O—, —COO—, —OCO—, —N═N—, —CH═CH— or —CH ₂ —.
Y ¹ represents a single bond or —O—.
R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
* Represents a bond to the polymer main chain. ]

In formula (A ′), when X ¹ is any ^one of a single bond, —O—, —COO—, —OCO—, —N═N—, —C═C—, and —CH ₂ —, a polymer (A ′) It is particularly preferable because it can be easily produced.

In the formula (A ′), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a halogenated alkyl group, a halogenated alkoxy group, a cyano group, a nitro group, an alkyl group, an alkoxy group, an aryl group, or an allyloxy group. Represents an alkoxycarbonyl group, a carboxyl group, a sulfonic acid group, an amino group or a hydroxy group, and the carboxyl group and the sulfonic acid group may form a salt with an alkali metal ion. Among these, R ¹ and R ² are more preferably each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, and a butyl group, and examples of the alkoxy group include a methoxy group, an ethoxy group, and a butoxy group.

The main chain of the polymer (A ′) is not particularly limited, but a (meth) acrylic acid ester unit represented by the formula (M-1) or the formula (M-2); the formula (M-3) or the formula (M− (Meth) acrylamide unit represented by 4); vinyl ether unit represented by formula (M-5) or formula (M-6); represented by formula (M-7) or formula (M-8) ( When the polymer (A) has a main chain composed of one selected from the group consisting of (methyl) styrene units and vinyl ester units represented by formula (M-9) or formula (M-10). Among them, it is more preferable that the polymer (A ′) has a main chain composed of units selected from the group consisting of (meth) acrylic acid ester units and (meth) acrylamide units. The “main chain of the polymer (A ′)” herein refers to the longest molecular chain among the molecular chains of the polymer (A ′).

  The unit represented by any one of the formulas (M-1) to (M-10) and the group represented by the formula (A ′) may be bonded via an appropriate linking group even if they are directly bonded. You may do it. This linking group has a carbonyloxy group (ester bond), an oxygen atom (ether bond), an imide group, a carbonylimino group (amide bond), an iminocarbonylimino group (urethane bond), and a substituent. And a divalent aliphatic hydrocarbon group which may have a substituent, a divalent aromatic hydrocarbon group which may have a substituent, and a divalent group formed by combining these. Specific examples of the divalent aromatic hydrocarbon group which may have a substituent include a phenylene group, a 2-methoxy-1,4-phenylene group, a 3-methoxy-1,4-phenylene group, and 2-ethoxy. Examples include -1,4-phenylene group, 3-ethoxy-1,4-phenylene group, 2,3,5-trimethoxy-1,4-phenylene group, and the like. Among these, the linking group is preferably an aliphatic hydrocarbon group, and more preferably an alkanediyl group having 1 to 11 carbon atoms which may have a substituent. Examples of such alkanediyl groups include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group and undecamethylene group. These may be linear or branched. Moreover, this alkanediyl group may have a substituent. This substituent is, for example, an alkoxy group having 1 to 4 carbon atoms.

［式（Ａ）中、
Ｘ^１、Ｙ^１、Ｒ^１、Ｒ^２及びｎは式（Ａ’）と同義であり、
Ｓ^１は、炭素数１〜１１のアルカンジイル基であり、

で表される構造は、式（Ｍ−１）〜式（Ｍ−１０）のいずれかで表される構造である。］ In other words, as the structural unit having a group represented by the formula (A ′), a structural unit represented by the formula (A) (hereinafter referred to as “structural unit (A)” in some cases, the structural unit (A) Is preferably referred to as “polymer (A)”.

[In the formula (A),
X ¹ , Y ¹ , R ¹ , R ² and n are as defined in formula (A ′),
S ¹ is an alkanediyl group having 1 to 11 carbon atoms,

Is a structure represented by any one of formulas (M-1) to (M-10). ]

The molecular weight of the polymer (A ′) or the polymer (A) is represented by, for example, a weight average molecular weight in terms of polystyrene determined by a gel permeation method (GPC method), and a range of 1 × 10 ³ to 1 × 10 ⁷ is preferable. . However, if the molecular weight is too high, the solubility in a solvent is lowered, making it difficult to prepare the composition for forming an alignment film, and the sensitivity to light irradiation tends to decrease, so 1 × 10 ⁴ to 1 × range of 10 ⁶ is preferred.

［式（Ｂ）中、
ｍは、０又は１を表す。
Ｓ^２は、炭素数１〜１１のアルカンジイル基を表す。

で表される構造は、式（Ｍ−１）〜式（Ｍ−１０）のいずれかで表される構造である。］ Ｘ^２は、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−Ｎ＝Ｎ−、−ＣＨ＝ＣＨ−又は−ＣＨ_２−を表す。
Ｙ^１は、単結合又は−Ｏ−を表す。
Ｒ^３及びＲ^４はそれぞれ独立に、水素原子、炭素数１〜４のアルキル基又は炭素数１〜４のアルコキシ基を表す。］ In addition to the structural unit (A), the polymer (A) may have a structural unit represented by the formula (B) (hereinafter sometimes referred to as “structural unit (B)”).

[In the formula (B)
m represents 0 or 1.
S ² represents an alkanediyl group having 1 to 11 carbon atoms.

Is a structure represented by any one of formulas (M-1) to (M-10). X ² represents a single bond, —O—, —COO—, —OCO—, —N═N—, —CH═CH— or —CH ₂ —.
Y ¹ represents a single bond or —O—.
R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. ]

In Formula (B), specific examples of S ² are the same as the specific examples of S ^{1 in} Formula (A), and specific examples of the alkyl group and alkoxy group of R ³ and R ⁴ are the same as those in Formula (A). The same as the specific examples of R ¹ and R ² of

  When the molar fractions of the structural unit (A) and the structural unit (B) with respect to all the structural units of the polymer (A) are p and q (p + q is 1), 0.25 <p ≦ 1 and It is preferable to satisfy the relationship of 0 ≦ q <0.75 [where the polymer (A) has the structural unit (A) and p is 1 when the polymer (A) is the structural unit (A ). The polymer composed of the structural unit (A) may be one type or two or more types of the structural unit (A). ]. However, the polymer (A) has structural units other than the structural unit (A) and the structural unit (B) (hereinafter sometimes referred to as “other structural units”) as long as the alignment ability by light irradiation is not significantly impaired. It may be.

  The polymer (A) can be produced by (co) polymerizing a monomer that derives the structural unit (A) and, if necessary, a monomer that induces the structural unit (B) or another structural unit. The (co) polymerization usually employs an addition polymerization method, and examples of the addition polymerization include radical polymerization, chain polymerization such as anionic polymerization and cationic polymerization, and coordination polymerization. The polymerization conditions are set so that the molecular weight of the preferred polymer (A) described above is satisfied according to the type and amount of the monomer used.

  The polymer (A) has been described in detail as a preferred polymer having a photoreactive group. The composition for forming an alignment layer is a polymer having a photoreactive group (preferably, the polymer (A) ) In a suitable solvent. Such a solvent can be appropriately selected as long as the polymer having the photoreactive group can be dissolved and an alignment layer-forming composition having an appropriate viscosity can be obtained. For example, methanol, ethanol, ethylene glycol, isopropyl alcohol , Alcohol solvents such as propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone or propylene glycol methyl ether acetate and ethyl lactate Ketone ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone; pentane, hexa And aliphatic hydrocarbon solvents such as heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; N-methylpyrrolidone; Examples thereof include amide solvents such as N, N-dimethylformamide, γ-butyrolactone and dimethylacetamide. These solvents may be used alone or in combination of two or more.

  The concentration of the polymer having a photoreactive group with respect to the composition for forming a photo-alignment layer can be adjusted as appropriate depending on the type of the polymer and the thickness of the photo-alignment layer 2 of the polarizing element 100 to be produced. The content is preferably at least 0.2% by mass, and particularly preferably in the range of 0.3 to 10% by mass. Further, the composition for forming an alignment layer contains a polymer material such as polyvinyl alcohol or polyimide and a photosensitizer as long as the characteristics of the photo-alignment layer 2 of the polarizing element 100 are not significantly impaired. May be.

  As a method of applying the composition for forming a photo-alignment film on the transparent substrate 1, a coating method such as a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method and an applicator method, A known method such as a printing method such as a flexo method is employed. In addition, when implementing this polarizing element manufacture by the continuous manufacturing method of the Roll to Roll format mentioned later, the printing methods, such as the gravure coating method, the die coating method, or a flexo method, are normally employ | adopted.

<Process A2>
Again, with reference to FIG. 2, process A2 of this manufacturing method A is demonstrated.
In the step A2, the first coating film formed on the transparent substrate 1 in the step A1 is dried, so that the solvent contained in the first coating film (the solvent used for the photo-alignment layer forming composition) ) Is removed by drying to form the first dry film 2A on the transparent substrate 1 to obtain the first laminate 101. For drying and removing the solvent, the first laminate is heated at an appropriate temperature to remove the solvent (heating method), and the first laminate 101 is sealed in a suitable pressure vessel. Thereafter, the method can be carried out by drying and removing the solvent by reducing the pressure in the container (pressure reduction method), ventilation drying (aeration method), natural drying, or a combination of these methods. In addition, when manufacturing this polarizing element in the continuous form of the Roll to Roll form mentioned later, a heating method is normally employ | adopted. By removing the solvent by drying, the first coating film is converted into the first dry film 2A, whereby the first laminate 101 is obtained.

The thickness of the first dry film 2A of the first laminated body 101 thus obtained is determined so that the alignment layer 2 obtained by the step A3 described later has a desired thickness. The thickness of the alignment layer 2 is, for example, 10 nm to 10000 nm, preferably 10 nm to 1000 nm.
The thickness of the predetermined alignment layer 2 can be controlled by adjusting the solid content concentration of the composition for forming a photo-alignment layer and the coating conditions for the transparent substrate 1 of the composition for forming a photo-alignment layer in the step A1.

<Process A3>
Subsequently, the first dry film 2A of the first laminate 101 is irradiated with polarized UV (polarized ultraviolet light), thereby aligning the polymer having a photoreactive group contained in the first dry film 2A, and liquid crystal. The second laminate 102 is formed by imparting alignment ability (hereinafter, referred to as “photo-alignment operation” in some cases). In the photo-alignment operation, in order to irradiate the first dry film 2A with the polarized UV, the form of irradiating the polarized UV directly from the first dry film 2A side of the first laminate (shown in FIG. 3A). Even in the format (A)), the polarized UV is applied to the first dry coating 2A by irradiating polarized UV on the transparent substrate 1 side of the first laminate and transmitting the polarized UV into the transparent substrate 1. The irradiation form (form (B) shown in FIG. 3B) may be used. In any of these types, the polarized UV to be irradiated may be either linearly polarized UV or elliptically polarized UV. However, in order to perform the optical alignment operation efficiently, elliptically polarized UV close to linearly polarized light or extinction ratio. It is preferred to use high linearly polarized UV. The polarized UV is particularly preferably substantially parallel light. However, when the photo-alignment operation is performed according to the format (B), the transparent substrate 1 in the first laminate 101 to be used is preferably as high as possible.

  The polarized UV to be irradiated preferably has a wavelength region in which the photoreactive group of the polymer having a photoreactive group contained in the first dry film can absorb light energy. For example, when the photoreactive group is a cinnamoyl group as in the polymer (A ′), UV (ultraviolet light) having a wavelength in the range of 250 to 400 nm is particularly preferable. Examples of the light source used for the photo-alignment operation include xenon lamps; high-pressure mercury lamps; ultrahigh-pressure mercury lamps; metal halide lamps; ultraviolet lasers such as KrF and ArF. When the polymer (A ′) having a cinnamoyl group as a photoreactive group is used, the light source used for the photo-alignment operation is preferably a high-pressure mercury lamp or an ultrahigh-pressure mercury lamp metal halide lamp. The reason is that these lamps have high emission intensity of ultraviolet rays having a wavelength of 313 nm. If the light from the light source passes through a suitable polarizer 200 and is irradiated to the first stacked body, the first stacked body is irradiated with polarized UV light. As such a polarizer 200, a polarizing prism such as a polarizing filter, Glan Thompson, or Grantera, or a wire grid type polarizer can be used.

  As described above, the optical alignment operation has been described with reference to FIG. 3. In order to irradiate the first laminated body 101 with polarized UV light, as shown in FIG. 3, in the plane direction of the first laminated body 101. On the other hand, it is not always necessary that the irradiation direction of the polarized UV is substantially vertical, and the irradiation direction of the polarized UV may be inclined with respect to the surface direction of the first stacked body 101. The irradiation direction of polarized UV with respect to the surface direction of the first laminate 101 is determined so that the obtained photo-alignment layer 2 has a desired absorption axis according to the type of light source and polarizer used for the photo-alignment operation. It is done.

<Process A4>
In Step A4 to Step A6 of the manufacturing method A, the polarizing layer 3 is provided on the photo-alignment layer 2 of the second laminate 102 obtained through the step A3.
The polarizing layer of the polarizing element is formed by the method as described above. Again, this method will be described. First, a composition containing a polymerizable smectic liquid crystal compound, a dichroic dye and a solvent (hereinafter, sometimes referred to as “polarizing layer forming composition”) is prepared. In step A4, the polarizing layer forming composition is applied onto the alignment layer 2 to form a second coating film.

First, the components of the polarizing layer forming composition will be described.
The polymerizable smectic liquid crystal compound contained in the composition for forming a polarizing layer is a compound having a polymerizable group and exhibiting a smectic phase liquid crystal state. The polymerizable group means a group involved in the polymerization reaction of the polymerizable smectic liquid crystal compound.

  The liquid crystal state exhibited by the polymerizable smectic liquid crystal compound is preferably a higher order smectic phase. The high-order smectic phase here means a smectic B phase, a smectic D phase, a smectic E phase, a smectic F phase, a smectic G phase, a smectic H phase, a smectic I phase, a smectic J phase, a smectic K phase, and a smectic L phase. Among them, a smectic B phase, a smectic F phase, a smectic I phase, a tilted smectic F phase and a tilted smectic I phase are preferable, and a smectic B phase is more preferable. Depending on the liquid crystal state exhibited by the polymerizable smectic liquid crystal compound, the present polarizing element having a polarizing layer having a high degree of alignment order is produced.

Preferable polymerizable smectic liquid crystal compositions include, for example, a compound represented by the formula (1) (hereinafter sometimes referred to as “compound (1)”).

^{U 1 -V 1 -W 1 -X 10} -Y 10 -X 20 -Y 20 -X 30 -W 2 -V 2 -U 2 (1) [ in the formula (1),
X ¹⁰ , X ²⁰ and X ³⁰ each independently represent a p-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent. However, at least one of X ¹ , X ² and X ³ is a p-phenylene group which may have a substituent.
Y ¹⁰ and ^{Y 20,} independently of one _{another, -CH 2 CH 2 -, -} CH 2 O -, - COO -, - OCOO-, a single ^{bond, -N = N -, - CR} a = CR b -, - C≡C— or —CR ^a ═N— is represented. R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
U ¹ represents a hydrogen atom or a polymerizable group.
U ² represents a polymerizable group.
W ¹ and W ² each independently represent a single bond, —O—, —S—, —COO— or —OCOO—.
V ¹ and V ² each independently represent an optionally substituted alkanediyl group having 1 to 20 carbon atoms, and —CH ₂ — constituting the alkanediyl group is —O—, — S- or -NH- may be substituted. ]

In the compound (1), as described above, at least one of X ¹⁰ , X ²⁰ and X ³⁰ is a 1,4-phenylene group which may have a substituent. Are preferably a p-phenylene group which may have a substituent.
The p-phenylene group is preferably unsubstituted. The cyclohexane-1,4-diyl group is preferably a trans-cyclohexane-1,4-diyl group, and the trans-cyclohexane-1,4-diyl group is also unsubstituted. Is more preferable.

Examples of the substituent that the p-phenylene group or the cyclohexane-1,4-diyl group optionally has include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a butyl group; a cyano group; a halogen atom Etc. In addition, —CH ₂ — constituting the cyclohexane-1,4-diyl group may be replaced by —O—, —S— or —NR—. R is a C1-C6 alkyl group or a phenyl group.

Y ¹⁰ of the compound (1) is preferably —CH ₂ CH ₂ —, —COO— or a single bond, and Y ²⁰ is preferably —CH ₂ CH ₂ — or —CH ₂ O—.

U ² is a polymerizable group. U ¹ is a hydrogen atom or a polymerizable group, and preferably a polymerizable group. That is, both U ¹ and U ² are preferably a polymerizable group, and both are preferably a photopolymerizable group. Here, the photopolymerizable group refers to a group that can participate in a polymerization reaction by an active radical or an acid generated from a photopolymerization initiator described later. The use of a polymerizable smectic liquid crystal compound having a photopolymerizable group is also advantageous in that the polymerizable smectic liquid crystal compound can be polymerized under a lower temperature condition.

In the compound (1), the photopolymerizable groups of U ¹ and U ² may be different from each other, but are preferably the same type. Examples of the photopolymerizable group include a vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, and oxetanyl group. Among them, acryloyloxy group, methacryloyloxy group, vinyloxy group, oxiranyl group and oxetanyl group are preferable, and acryloyloxy group is more preferable.

Examples of the alkanediyl group of V ¹ and V ² include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5. -Diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane-1,14-diyl group and icosane And a -1,20-diyl group. V ¹ and V ² are preferably alkanediyl groups having 2 to 12 carbon atoms, and more preferably alkanediyl groups having 6 to 12 carbon atoms.
Examples of the substituent that the alkanediyl group optionally has include a cyano group and a halogen atom. The alkanediyl group is preferably unsubstituted, and is an unsubstituted and linear alkanediyl group. It is more preferable that

W ¹ and W ² are independently of each other, preferably a single bond or —O—.

  Examples of compound (1) include compounds represented by any one of formulas (1-1) to (1-23). When a specific example of the compound (1) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably a trans isomer.

The exemplified compound (1) can be used alone or in admixture of two or more for the composition for forming a polarizing layer. Further, two or more polymerizable smectic compounds may be used, and at least one of the two or more polymerizable smectic compounds may be the compound (1). In the following description, the case where a single type of polymerizable smectic liquid crystal compound is used and the case where two or more types of polymerizable smectic liquid crystal compounds are used may be collectively referred to as “polymerizable smectic liquid crystal compound”.
When the compound (1) is used in the composition for forming a polarizing layer, the phase transition temperature of the compound (1) is obtained in advance, and the polarization is performed so that the compound (1) can be polymerized under a temperature condition lower than the phase transition temperature. Components other than the compound (1) [polymerizable smectic liquid crystal compound] of the layer forming composition are adjusted.
Examples of the component capable of controlling the polymerization temperature include a photopolymerization initiator, a photosensitizer, and a polymerization inhibitor described later. The polymerization temperature of compound (1) can be controlled by adjusting these types and amounts as appropriate. In addition, also when using the mixture of 2 or more types of compounds (1) [polymerizable smectic liquid crystal composition] for the polarizing layer formation composition, the phase transition temperature of the mixture of the 2 or more types of compounds (1) Then, the polymerization temperature is controlled in the same manner as in the case of the polymerizable smectic liquid crystal compound.

  Among the exemplified compounds (1), formula (1-2), formula (1-3), formula (1-4), formula (1-6), formula (1-7), formula (1- 8) At least one selected from the group consisting of those represented by formula (1-13), formula (1-14) and formula (1-15) is preferred. These compounds (1) can easily change the liquid crystal state of a higher-order smectic phase under temperature conditions lower than the phase transition temperature by mixing or by interaction with the photopolymerization initiator used together. Since a supercooled state can be obtained with sufficient retention, the compound (1) can be polymerized. More specifically, due to the interaction with the photopolymerization initiator, these compounds (1) sufficiently exhibit a liquid crystal state of a high-order smectic phase under a temperature condition of 70 ° C. or less, preferably 60 ° C. or less. It can be polymerized while being held.

  As described above, the compound (1) contained in the polarizing layer forming composition may be a single species or a plurality of species, but is preferably a plurality of species.

  70-99.9 mass% is preferable with respect to solid content of the said composition for polarizing layer formation, and, as for the content rate of the compound (1) in the said composition for polarizing layer formation, 90-99.9 mass% is more. preferable. If the content rate of a compound (1) exists in the said range, there exists a tendency for the orientation of a compound (1) to become high. Here, solid content means the total amount of the component remove | excluding volatile components, such as a solvent, from this polarizing layer formation composition. In addition, when multiple types of compound (1) is contained in this composition for polarizing layer formation, the total content rate should just be said range.

  The composition for forming a polarizing layer preferably contains a leveling agent. The leveling agent has a function of adjusting the fluidity of the polymerizable smectic liquid crystal compound and flattening the first coating film obtained by coating the composition for forming a polarizing layer. And so on. The leveling agent is more preferably at least one selected from the group consisting of a leveling agent having a polyacrylate compound as a main component and a leveling agent having a fluorine atom-containing compound as a main component.

  Leveling agents mainly composed of polyacrylate compounds include “BYK-350”, “BYK-352”, “BYK-353”, “BYK-354”, “BYK-355”, “BYK-358N”, “ BYK-361N ”,“ BYK-380 ”,“ BYK-381 ”,“ BYK-392 ”[BYK Chemie], and the like.

  Leveling agents mainly composed of fluorine atom-containing compounds include "Megafac R-08", "R-30", "R-90", "F-410", "F-411", "F-443", "F-445", "F-470", "F-471", "F-477", "F-479", "F-482" and the same "F-483" [DIC Corporation]; "Surflon S-381", "S-382", "S-383", "S-393", "SC-101", "SC" -105 "," KH-40 "and" SA-100 "[AGC Seimi Chemical Co., Ltd.];" E1830 "," E5844 "[Daikin Fine Chemical Laboratory Co., Ltd.];" F-top EF301 "," EF303 " ", EF351" and "EF352" [Mitsubishi Materials Child Kasei Co., Ltd.] and the like.

  When the leveling agent is contained in the polarizing layer forming composition, the content is preferably 0.3 parts by mass or more and 5 parts by mass or less, and 0.5 parts by mass or more with respect to 100 parts by mass of the polymerizable liquid crystal compound. 3 parts by mass or less is more preferable. When the content of the leveling agent is within the above range, it is easy to horizontally align the polymerizable smectic liquid crystal compound, and the obtained polarizing layer tends to be smoother. If the content of the leveling agent with respect to the polymerizable smectic liquid crystal compound exceeds the above range, unevenness tends to occur in the obtained polarizing layer. In addition, this polarizing layer formation composition may contain 2 or more types of leveling agents.

  The polarizing layer forming composition contains a dichroic dye. The dichroic dye as used herein refers to a dye having a property that the absorbance in the major axis direction of the molecule is different from the absorbance in the minor axis direction. The dichroic dye is not particularly limited as long as it has such properties, and may be a dye or a pigment. A plurality of these dyes may be used, a plurality of pigments may be used, or a dye and a pigment may be combined.

  The dichroic dye preferably has a maximum absorption wavelength (λMAX) in the range of 300 to 700 nm. Examples of such dichroic dyes include acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes and anthraquinone dyes, and among them, azo dyes are preferable. Examples of the azo dyes include monoazo dyes, bisazo dyes, trisazo dyes, tetrakisazo dyes, and stilbene azo dyes, with bisazo dyes and trisazo dyes being preferred.

Examples of the azo dye include a compound represented by the formula (2) (hereinafter sometimes referred to as “compound (2)”).
_{^{A 1 (-N = N-A}} 2) p -N = N-A 3 (2)
[In Formula (2),
A ¹ and A ³ are each independently a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a monovalent heterocyclic group which may have a substituent. Represents. A ² represents a p-phenylene group which may have a substituent, a naphthalene-1,4-diyl group which may have a substituent, or a divalent heterocyclic ring which may have a substituent. Represents a group. p represents an integer of 1 to 4. When p is an integer greater than or equal to ² , several A2 may mutually be same or different. ]

  Examples of the monovalent heterocyclic group include groups in which one hydrogen atom has been removed from a heterocyclic compound such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, oxazole and benzoxazole. A group obtained by removing two hydrogen atoms from a heterocyclic compound corresponds to a divalent heterocyclic group, and specific examples of the heterocyclic compound are as described above.

As a substituent which the phenyl group, naphthyl group and monovalent heterocyclic group in A ¹ and A ³ and the p-phenylene group, naphthalene-1,4-diyl group and divalent heterocyclic group in A ² optionally have Is an alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group and a butoxy group; a fluorinated alkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group; a cyano group; Nitro group; halogen atom; substituted or unsubstituted amino group such as amino group, diethylamino group and pyrrolidino group (substituted amino group is an amino group having one or two alkyl groups having 1 to 6 carbon atoms, or two This means an amino group in which substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 8 carbon atoms, and the unsubstituted amino group is —NH ₂ . In addition, the specific example of a C1-C6 alkyl group is the same as what was illustrated with the substituent which the phenylene group etc. of a compound (1) have arbitrarily.

  Among the compounds (2), compounds represented by any one of the following formulas (2-1) to (2-6) are preferable.

［式（２−１）〜（２−６）中、
Ｂ^１〜Ｂ^２０は、互いに独立に、水素原子、炭素数１〜６のアルキル基、炭素数１〜４のアルコキシ基、シアノ基、ニトロ基、置換又は無置換のアミノ基（置換アミノ基及び無置換アミノ基の定義は前記のとおり）、塩素原子又はトリフルオロメチル基を表す。
ｎ１、ｎ２、ｎ３及びｎ４は、互いに独立に０〜３の整数を表す。
ｎ１が２以上である場合、複数のＢ^２は互いに同一でも異なっていてもよく、
ｎ２が２以上である場合、複数のＢ^６は互いに同一でも異なっていてもよく、
ｎ３が２以上である場合、複数のＢ^９は互いに同一でも異なっていてもよく、
ｎ４が２以上である場合、複数のＢ¹⁴は互いに同一でも異なっていてもよい。］

[In the formulas (2-1) to (2-6),
B ^{1 to} B ²⁰ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, a nitro group, a substituted or unsubstituted amino group (a substituted amino group and As defined above, the unsubstituted amino group represents a chlorine atom or a trifluoromethyl group.
n1, n2, n3 and n4 each independently represents an integer of 0 to 3.
when n1 is 2 or more, the plurality of B ² may be the same as or different from each other;
when n2 is 2 or more, the plurality of B ⁶ may be the same as or different from each other;
when n3 is 2 or more, the plurality of B ⁹ may be the same as or different from each other;
When n4 is 2 or more, the plurality of B ¹⁴ may be the same as or different from each other. ]

［式（２−７）中、
Ｒ^１〜Ｒ^８は、互いに独立に、水素原子、−Ｒ^ｘ、−ＮＨ_２、−ＮＨＲ^ｘ、−ＮＲ^ｘ _２、−ＳＲ^ｘ又はハロゲン原子を表す。
Ｒ^ｘは、炭素数１〜４のアルキル基又は炭素数６〜１２のアリール基を表す。］ As said anthraquinone pigment | dye, the compound represented by Formula (2-7) is preferable.

[In the formula (2-7),
R ^{1 to} R ⁸ each independently represent a hydrogen atom, —R ^x , —NH ₂ , —NHR ^x , —NR ^x ₂ , —SR ^x, or a halogen atom.
R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]

［式（２−８）中、
Ｒ^９〜Ｒ^１５は、互いに独立に、水素原子、−Ｒ^ｘ、−ＮＨ_２、−ＮＨＲ^ｘ、−ＮＲ^ｘ _２、−ＳＲ^ｘ又はハロゲン原子を表す。
Ｒ^ｘは、炭素数１〜４のアルキル基又は炭素数６〜１２のアリール基を表す。］ As the acridine dye, a compound represented by the formula (2-8) is preferable.

[In the formula (2-8),
R ^{9 to} R ¹⁵ each independently represent a hydrogen atom, —R ^x , —NH ₂ , —NHR ^x , —NR ^x ₂ , —SR ^x, or a halogen atom.
R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]

［式（２−９）中、
Ｒ^１６〜Ｒ^２３は、互いに独立に、水素原子、−Ｒ^ｘ、−ＮＨ_２、−ＮＨＲ^ｘ、−ＮＲ^ｘ _２、−ＳＲ^ｘ又はハロゲン原子を表す。
Ｒ^ｘは、炭素数１〜４のアルキル基又は炭素数６〜１２のアリール基を表す。］ As the oxazone dye, a compound represented by the formula (2-9) is preferable.

[In Formula (2-9),
R ¹⁶ to R ²³ independently represent a hydrogen _{^{atom, -R x, -NH 2, -NHR}} x, -NR x 2, -SR x , or halogen atom.
R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]

In the above formula (2-7), formula (2-8) and formula (2-9), the alkyl group having 1 to 6 carbon atoms of R ^x is a methyl group, an ethyl group, a propyl group, a butyl group, Examples thereof include a pentyl group and a hexyl group, and examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a toluyl group, a xylyl group, and a naphthyl group.

［式（２−１０）中、
Ｄ^１及びＤ^２は、互いに独立に、式（２−１０ａ）〜式（２−１０ｄ）のいずれかで表される基を表す。

ｎ５は１〜３の整数を表す。］ As the cyanine dye, a compound represented by the formula (2-10) and a compound represented by the formula (2-11) are preferable.

[In the formula (2-10),
D ¹ and D ² each independently represent a group represented by any one of formulas (2-10a) to (2-10d).

n5 represents an integer of 1 to 3. ]

［式（２−１１）中、
Ｄ^３及びＤ^４は、互いに独立に、式（２−１１ａ）〜式（２−１１ｈ）のいずれかで表される基を表す。

ｎ６は１〜３の整数を表す。］

[In the formula (2-11),
D ³ and D ⁴ each independently represent a group represented by any one of formulas (2-11a) to (2-11h).

n6 represents an integer of 1 to 3. ]

  The content of the dichroic dye in the polarizing layer forming composition can be adjusted as appropriate according to the type of the dichroic dye, and is, for example, 0 with respect to a total of 100 parts by mass of the polymerizable smectic liquid crystal compound. .1 to 50 parts by mass is preferable, 0.1 to 20 parts by mass is more preferable, and 0.1 to 10 parts by mass is further preferable. If the content of the dichroic dye is within this range, the polymerizable smectic liquid crystal compound can be polymerized without disturbing the orientation of the polymerizable smectic liquid crystal compound. When there is too much content of a dichroic dye, there exists a possibility of inhibiting the orientation of a polymerizable smectic liquid crystal compound. Therefore, the content of the dichroic dye can be determined within a range in which the polymerizable smectic liquid crystal compound can maintain a liquid crystal state of a higher order smectic phase.

  The polarizing layer forming composition contains a solvent. As the solvent, a preferable one can be appropriately selected in consideration of the solubility of the polymerizable smectic liquid crystal compound to be used. However, an inert solvent that does not significantly disturb the progress of the polymerization reaction of the polymerizable smectic liquid crystal compound is preferable. Examples of such a solvent are the same as those exemplified as the solvent for preparing the polarizing layer forming composition. The solvent for preparing the composition for forming a polarizing layer may be used alone or in combination of two or more.

As for content of a solvent, 50-98 mass% is preferable with respect to the total amount of the said composition for polarizing layer formation. In other words, the solid content in the composition for forming a polarizing layer is preferably 2 to 50% by mass. When the solid content is 2% by mass or more, dichroism necessary for the polarizing layer of the polarizing element is obtained.
On the other hand, when the solid content is 50% by mass or less, since the viscosity of the composition for forming a polarizing layer is lowered, the thickness of the polarizing layer tends to be substantially uniform, so that unevenness in the polarizing layer is less likely to occur. There is. Moreover, this solid content can be determined so that the thickness of the polarizing layer mentioned later can be formed.

  The composition for forming a polarizing layer preferably contains a polymerization initiator. The polymerization initiator is a compound capable of initiating a polymerization reaction of a polymerizable smectic liquid crystal compound, and a photopolymerization initiator is preferable in that the polymerization reaction can be initiated under a lower temperature condition. Specifically, a compound capable of generating an active radical or an acid by the action of light under this temperature condition is used as a photopolymerization initiator. Among the photopolymerization initiators, those that generate radicals by the action of light are more preferable.

  Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts, and sulfonium salts.

Hereinafter, specific examples of this photopolymerization initiator will be given.
Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl). ) Benzophenone and 2,4,6-trimethylbenzophenone.

  Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl). ) Butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1 -[4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1- ON oligomers.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Naphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 [2- (5-Methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1 , 3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4-bis (trichloro Methyl)- - such as [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  A photopolymerization initiator that can be easily obtained from the market can also be used. Commercially available photopolymerization initiators include “Irgacure 907”, “Irgacure 184”, “Irgacure 651”, “Irgacure 819”, “Irgacure 250”, “Irgacure 369” (Ciba Japan Co., Ltd.); “Sake All BZ”, “Sake All Z”, “Sake All BEE” (Seiko Chemical Co., Ltd.); “Kayacure BP100” (Nippon Kayaku Co., Ltd.); “Kaya Cure UVI-6992” (manufactured by Dow); “Adekaoptomer SP-152”, “Adekaoptomer SP-170” (ADEKA); “TAZ-A”, “TAZ-PP” (Nihon Shibel Hegner); and “TAZ-104” (Sanwa) Chemical Corporation).

  When the polarizing layer forming composition contains a polymerization initiator, the content can be appropriately adjusted according to the type and amount of the polymerizable smectic liquid crystal compound contained in the polarizing layer forming composition, For example, the content of the polymerization initiator with respect to 100 parts by mass in total of the polymerizable smectic liquid crystal compound is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, and 0.5 to 8 parts by mass. Further preferred. If the content of the polymerizable initiator is within this range, the polymerizable smectic liquid crystal compound can be polymerized without disturbing the orientation of the polymerizable smectic liquid crystal compound, so that the polymerizable smectic liquid crystal compound exhibits a liquid crystal state of a higher order smectic phase. Polymerization can be carried out while being held.

  When the composition for forming a polarizing layer contains a photopolymerization initiator, the composition for forming a polarizing layer may contain a photosensitizer. Examples of the photosensitizer include xanthone compounds such as xanthone and thioxanthone (for example, 2,4-diethylthioxanthone and 2-isopropylthioxanthone); anthracene and alkoxy group-containing anthracene (for example, dibutoxyanthracene) and the like. Anthracene compounds; phenothiazine, rubrene, and the like.

  When the composition for forming a polarizing layer contains a photopolymerization initiator and a photosensitizer, the polymerization reaction of the polymerizable smectic liquid crystal compound contained in the composition for forming a polarizing layer can be further accelerated. . The amount of the photosensitizer used can be appropriately adjusted according to the type and amount of the photopolymerization initiator and polymerizable smectic liquid crystal compound used together. For example, the total amount of the polymerizable smectic liquid crystal compound is 100 parts by mass. 0.1-30 mass parts is preferable, 0.5-10 mass parts is more preferable, 0.5-8 mass parts is further more preferable.

  It has been explained that a polymerization reaction of a polymerizable smectic liquid crystal compound can be promoted by including a photosensitizer in the composition for forming a polarizing layer, but in order to make the polymerization reaction proceed stably, the polarizing film is formed. The composition may contain a polymerization inhibitor appropriately. By containing the polymerization inhibitor, the degree of progress of the polymerization reaction of the polymerizable smectic liquid crystal compound can be controlled.

  Examples of the polymerization inhibitor include radicals such as hydroquinone, alkoxy group-containing hydroquinone, alkoxy group-containing catechol (eg, butyl catechol), pyrogallol, 2,2,6,6-tetramethyl-1-piperidinyloxy radical, and the like. Supplementary agents; thiophenols; β-naphthylamines and β-naphthols.

  In the case where a polymerization inhibitor is contained in the polarizing layer forming composition, the content can be appropriately adjusted according to the type and amount of the polymerizable smectic liquid crystal compound used, the amount of photosensitizer used, and the like. For example, the content of the polymerization inhibitor is preferably from 0.1 to 30 parts by weight, more preferably from 0.5 to 10 parts by weight, and from 0.5 to 8 parts by weight based on 100 parts by weight of the total of the polymerizable smectic liquid crystal compounds. Further preferred. If the content of the polymerization inhibitor is within this range, the polymerizable smectic liquid crystal compound can be polymerized without disturbing the orientation of the polymerizable smectic liquid crystal compound contained in the polarizing layer forming composition. However, it is possible to carry out polymerization while maintaining the liquid crystal state of a higher-order smectic phase in a good condition.

  The composition for forming a polarizing layer described above is applied onto the photo-alignment layer 2 of the second laminated plate to obtain a second coating film, and the polymerizable smectic liquid crystal compound contained in the second coating film is The 2nd dry film 3A is formed by drying on the conditions which are not superposed | polymerized. As a result, the third stacked body 103 is obtained.

  As a method (coating method) for applying the composition for forming a polarizing film on the photo-alignment layer 2 of the first laminate, for example, in the step A1, the composition for forming a photo-alignment layer is applied on the transparent substrate. The same method as that exemplified as the method of applying to 1.

<Process A5>
Subsequently, in step A5, by drying the second coating film of the second laminated plate, the solvent is removed from the second coating film to form a second dry film 3A. The method for removing the solvent is usually the same as the method described when forming the first dry film from the first coating film in the step A2, but the polymerizable smectic liquid crystal compound contained in the second coating film can be used. Drying conditions are set so that does not polymerize.

<Process A6>
In step A6, the polymerizable smectic liquid crystal compound is polymerized while maintaining the liquid crystal state of the polymerizable smectic liquid crystal compound contained in the second dry coating 3A in the smectic liquid crystal (laminate 104), thereby polarizing layer 3 Form. In the laminate 104, a layer in which the polymerizable smectic liquid crystal compound in the second dry coating 3A is changed to a smectic liquid crystal state is referred to as “layer 3B”.

  The liquid crystal state of the polymerizable smectic liquid crystal compound contained in the second dry film 3A is changed to the smectic liquid crystal state (hereinafter, sometimes referred to as “smectic phase” or “smectic phase liquid crystal state”) to form the layer 3B. The second dry film may be held at an appropriate temperature. In other words, if the third laminated plate 103 provided with the second dry film is held at an appropriate temperature obtained from the phase transition temperature. Good. In forming the layer 3B in the smectic phase liquid crystal state, after once changing the liquid crystal state of the polymerizable smectic liquid crystal composition contained in the second dry coating 3A to a nematic phase (nematic liquid crystal state), It is preferable to transfer the nematic phase to a smectic phase. In order to form a smectic phase via a nematic phase in this way, for example, the polymerizable smectic liquid crystal compound contained in the second dry film is heated to a temperature higher than the temperature at which the nematic phase transitions to the liquid crystal state, and then the polymerization is performed. A method is adopted in which the conductive smectic liquid crystal compound is cooled to a temperature at which the liquid crystal state of the smectic phase is exhibited.

  When the polymerizable smectic liquid crystal compound in the second dry film is changed to a smectic liquid crystal state, or the polymerizable smectic liquid crystal compound is changed to a smectic liquid crystal state via a nematic liquid crystal state, the phase of the polymerizable smectic liquid crystal compound to be used By measuring the transition temperature, the conditions for controlling the liquid crystal state (heating conditions) can be easily obtained. The measurement conditions for measuring the phase transition temperature will be described in the examples of the present application.

  When polymerizing the polymerizable smectic liquid crystal compound, a composition for forming a polarizing layer comprising at least two polymerizable liquid crystal smectic compounds as the polymerizable smectic liquid crystal compound in order to maintain a liquid crystal state in a smectic phase satisfactorily. Is preferably used. When the composition for forming a polarizing layer in which the content ratio of each polymerizable smectic liquid crystal compound in the polymerizable smectic liquid crystal composition is adjusted is used, after the liquid crystal state of the smectic phase is formed via the nematic phase, It is possible to form a supercooled state, and there is an advantage that a high-order smectic phase liquid crystal state can be easily maintained.

  Here, after the photopolymerization initiator is contained in the composition for forming a polarizing layer and the liquid crystal state of the polymerizable smectic liquid crystal compound in the second dry film is changed to a smectic phase, the liquid crystal state of the smectic phase is maintained. The method for photopolymerizing the polymerizable smectic liquid crystal compound will be described in detail. In the photopolymerization, the light applied to the second dry film includes the type of photopolymerization initiator contained in the second dry film, or the type of polymerizable smectic liquid crystal compound (in particular, the light possessed by the polymerizable smectic liquid crystal compound). Depending on the kind of the polymerization group) and the amount thereof, it can be carried out with light selected from the group consisting of visible light, ultraviolet light and laser light, or an active electron beam. Among these, ultraviolet light is preferable in that it is easy to control the progress of the polymerization reaction and that apparatuses widely used in the field as photopolymerization apparatuses can be used. Therefore, it is preferable to select the type of the polymerizable smectic liquid crystal compound or photopolymerization initiator contained in the polarizing layer forming composition so that it can be photopolymerized by ultraviolet light. Moreover, when superposing | polymerizing, superposition | polymerization temperature can also be controlled by cooling a 2nd dry film with a suitable cooling means with ultraviolet light irradiation. If the polymerization of the polymerizable smectic liquid crystal compound can be carried out at a lower temperature by employing such a cooling means, even if the transparent substrate 1 and the photo-alignment layer 2 described above have relatively low heat resistance, it is appropriate. There is also an advantage that the polarizing layer 3 can be formed. In the photopolymerization, the patterned polarizing layer 3 can also be obtained by performing masking or development.

  By performing photopolymerization as described above, the polymerizable smectic liquid crystal compound is polymerized while maintaining the liquid crystal state of the smectic phase, preferably the higher-order smectic phase as exemplified above, and the polarizing layer 3 is formed. Thus, the polarizing element 100 is obtained. A polarizing layer 3 obtained by polymerizing a polymerizable smectic liquid crystal compound while maintaining a liquid crystal state of a smectic phase is obtained by polymerizing a polymerizable liquid crystal compound or the like while maintaining a liquid crystal state of a conventional polarizing layer, that is, a nematic phase. There is an advantage that the polarization performance is much higher than that of the polarizing layer obtained.

  The thickness of the polarizing layer 3 thus formed is preferably in the range of 0.5 to 10 μm, and more preferably in the range of 0.5 to 3 μm. Therefore, the thickness of the second coating film is determined in consideration of the thickness of the obtained polarizing layer 3. The thickness of the polarizing layer 3 is determined by measurement with an interference film thickness meter, a laser microscope or a stylus thickness meter.

  In addition, the polarizing layer 3 thus formed is particularly preferable when a Bragg peak is obtained in the X-ray diffraction measurement. Examples of the polarizing layer 3 from which such a Bragg peak can be obtained include a polarizing layer 3 that exhibits a diffraction peak derived from a hexatic phase or a crystal phase. Examples of the measurement conditions for such X-ray diffraction measurement include the conditions described in the examples of the present application.

<Continuous manufacturing method of this polarizing element>
As mentioned above, although the outline | summary of the manufacturing method (this manufacturing method A) of this polarizing element was demonstrated, when manufacturing this polarizing element commercially, the method which can manufacture this polarizing element continuously is calculated | required. Such a continuous manufacturing method is based on the Roll to Roll format, and is sometimes referred to as “the present manufacturing method B”.

The production method B is, for example,
Preparing a first roll in which a transparent substrate is wound around a first core;
Continuously feeding the transparent substrate from the first roll;
Applying a composition containing a polymer having a photoreactive group and a solvent, and continuously forming a first coating film on the transparent substrate;
Forming the first dry film on the transparent substrate by drying and removing the solvent from the first coating film, and continuously obtaining the first laminate;
By irradiating the first dry film with polarized UV, a photo-alignment layer having an orientation direction at an angle of about 45 ° with respect to the transport direction of the first laminate is formed, and the second laminate is continuously formed. And the process of obtaining
Applying a composition containing a polymerizable smectic liquid crystal compound, a dichroic dye and a solvent on the photo-alignment layer, and continuously forming a second coating film on the photo-alignment layer; The coating film is dried under the condition that the polymerizable smectic liquid crystal compound contained in the second coating film is not polymerized to form a second dry film on the photo-alignment layer, thereby continuously forming the third laminate. A process of obtaining
The polymerizable smectic liquid crystal compound contained in the second dry film is changed to a smectic liquid crystal state, and then the polymerizable smectic liquid crystal compound is polymerized while maintaining the smectic liquid crystal state. Forming a polarizing layer having an absorption axis at an angle of 45 ° with respect to the transport direction to obtain a polarizing element continuously;
A step of winding the continuously obtained polarizing element around a second core to obtain a second roll. Here, with reference to FIG. 4, the principal part of this manufacturing method B is demonstrated.

  The first roll 210 in which the transparent base material is wound around the first core 210A can be easily obtained from the market, for example. As a transparent base material which can be obtained from the market in the form of such a roll, the film etc. which consist of a cellulose ester, cyclic olefin resin, a polyethylene terephthalate, or a polymethacrylic acid ester are mentioned among the transparent base materials already illustrated. Moreover, when using this polarizing element as a circularly-polarizing plate, the transparent base material to which phase difference was previously given can also be easily obtained from a market, for example, the retardation film which consists of a cellulose ester or cyclic olefin resin etc. are mentioned. It is done.

  Subsequently, the transparent substrate is unwound from the first roll 210. The method for unwinding the transparent substrate is performed by installing an appropriate rotating means on the core 210A of the first roll 210 and rotating the first roll 210 by the rotating means. Alternatively, a suitable auxiliary roll 300 may be installed in the direction of transporting the transparent base material from the first roll 210 and the transparent base material may be unwound by the rotating means of the auxiliary roll 300. Further, the first winding core 210A and the auxiliary roll 300 may be provided with a rotating means so that the transparent substrate is unwound while applying an appropriate tension to the transparent substrate.

  When the transparent base material unwound from the first roll 210 passes through the coating device 211A, the alignment film forming composition is applied onto the surface of the transparent base material by the coating device 211A. As described above, in order to continuously apply the alignment film forming composition as described above, the coating apparatus 211A is a printing method such as a gravure coating method, a die coating method, or a flexo method.

  The film that has passed through the coating apparatus 211A corresponds to a laminate of the above-described transparent substrate and the first coating film. Thus, the transparent base material on which the first coating film is formed (laminated) is conveyed to the drying furnace 212A and heated by the drying furnace 212A to the first laminated body including the transparent base material and the first dry film. And convert. For example, a hot air drying furnace or the like is used as the drying furnace 212A. The set temperature of the drying furnace 212A is determined according to the type of the solvent contained in the alignment film forming composition applied by the coating apparatus 211A. The drying furnace 212A may be divided into appropriate zones, and the set temperature may be different for each of the divided zones. A plurality of drying furnaces are arranged in series, and each drying is performed at different set temperatures. The film may be transported sequentially through the plurality of drying furnaces while operating the furnace.

  The first laminate continuously formed by passing through the heating furnace 212A is subsequently polarized on the surface of the laminate on the first dry film side or the transparent substrate side by the polarized UV irradiation device 213A. When UV is irradiated, the first dry film is converted into a light polarizing layer. At that time, the angle formed by the film transport direction D1 and the alignment direction D2 of the formed photo-alignment layer is set to approximately 45 °. FIG. 5 is a diagram schematically showing the relationship between the orientation direction D2 of the photo-alignment layer formed after irradiation with polarized UV light and the film transport direction D1. That is, FIG. 5 shows that when the surface of the first laminate after passing through the polarized UV irradiation apparatus 213A is viewed in the film transport direction D1 and the alignment direction D2 of the photo-alignment layer, the angle between them is approximately 45 °. Indicates that

  Thus, after the 1st laminated body formed continuously passes the coating device 211B and the composition for polarizing layer formation is apply | coated on the photo-alignment layer of this 1st laminated body, drying furnace 212B The polymerizable smectic liquid crystal compound contained in the second laminate or the second dry film of the second laminate becomes a laminate in which a smectic liquid crystal state is formed. The drying furnace 212B has a role of drying and removing the solvent from the polarizing layer forming composition applied on the photo-alignment layer, and the polymerizable smectic liquid crystal compound contained in the second dry film is in a smectic phase liquid crystal state. As such, it plays a role of giving thermal energy to the second dry film. In addition, as described above, in order to make the polymerizable smectic liquid crystal compound into a smectic phase liquid crystal state, in order to make the polymerizable smectic liquid crystal compound into a nematic phase liquid crystal state, It is necessary to perform multi-stage heat treatment on the first laminated body under different heating conditions. Therefore, as described in the drying furnace 212A, the drying furnace 212B is composed of a plurality of zones having different set temperatures or a plurality of drying furnaces having different set temperatures, and the plurality of drying furnaces are connected in series. It is preferable to be in the form of installation.

  The film that has passed through the drying oven 212B is sufficiently irradiated with light while the solvent contained in the polarizing layer forming composition is sufficiently removed and the polymerizable smectic liquid crystal compound in the second dry film maintains the liquid crystal state of the smectic phase. It is conveyed to the device 213B. By the light irradiation by the light irradiation device 213B, the polymerizable smectic liquid crystal compound is photopolymerized while maintaining the liquid crystal state to form a polarizing layer, and the polarizing element is continuously formed.

  The present polarizing element thus continuously formed is wound around the second core 220A, and the form of the second roll 220 is obtained. When the formed polarizing element is wound up to obtain the second roll, winding using an appropriate spacer may be performed.

  In this way, the transparent substrate passes through the first roll from the first roll in the order of the coating device 211A, the drying furnace 212A, the polarized UV irradiation device 213A, the coating device 211B, the drying furnace 212A, and the light irradiation device 213A. On the material, a photo-alignment layer and a polarizing film are formed in the same manner as in steps A2 to A6 of manufacturing method A, and the polarizing element is continuously manufactured.

  Moreover, in this manufacturing method B shown in FIG. 4, although the method of manufacturing continuously from a transparent base material to this polarizing element was shown, for example, a transparent base material is a coating device 211A, a drying furnace from a 1st roll. By passing 212A and polarized UV irradiation device 213A in this order, the first laminated body formed continuously is wound around the core, and the first laminated body is manufactured in the form of a roll. The polarizing element may be manufactured by unwinding one laminated body and passing the unwound first laminated body in the order of the coating device 211B, the drying furnace 212A, and the light irradiation device 213A.

  The polarizing element obtained by the present manufacturing method B has a film shape and a long shape. When this polarizing element is used for a liquid crystal display device to be described later, the polarizing element is used after being cut to a desired size in accordance with the scale of the liquid crystal display device.

  As described above, the configuration and the manufacturing method of the polarizing element have been described mainly with respect to the case of the laminate of the transparent base material / the photo-alignment layer / the polarizing layer, but the polarizing element has layers or films other than these. It may be laminated. As already described, the polarizing element may further include a retardation film, or may further include an antireflection layer or a brightness enhancement film. Further, as will be described later, a circularly polarizing plate can be formed by combining with a retardation film (preferably a quarter-wave plate). The quarter-wave plate used when manufacturing the circularly polarizing plate preferably has a characteristic that the in-plane retardation value with respect to visible light becomes smaller as the wavelength becomes shorter.

<Advantageous effect of this polarizing element>
This polarizing element can be manufactured more advantageously than conventional polarizing elements in that the manufacturing method can easily form a polarizing layer having a desired polarization direction by a photo-alignment operation when forming the photo-alignment layer. In addition, even if the long polarizing element is manufactured by the manufacturing method B, it is possible to form a polarizing layer having an absorption axis that is not horizontal with respect to the longitudinal direction of the polarizing element. For example, by setting the absorption axis of the polarizing layer of the polarizing element to 45 °, the polarizing element and the quarter wavelength plate are bonded to each other by roll-to-roll bonding as will be described later. The polarizing plate is easy to manufacture, and the productivity of the circular polarizing plate is greatly improved.

<Application of this polarizing element>
This polarizing element can be used for various display devices. A display device is a device having a display element and includes a light-emitting element or a light-emitting device as a light-emitting source. Examples of the display device include a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, an electron emission display device (for example, a field emission display device (FED), a surface field emission display device (SED). )), Electronic paper (display device using electronic ink or electrophoretic element, plasma display device, projection display device (eg, display device having a grating light valve (GLV) display device, digital micromirror device (DMD)), and Examples of the liquid crystal display device include a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct view liquid crystal display device, and a projection liquid crystal display device. These display devices may be display devices that display a two-dimensional image. And it may be a stereoscopic display apparatus for displaying a three-dimensional image.
On the other hand, the present circle changing plate can be effectively used particularly for a display device of an organic electroluminescence (EL) display device or an inorganic electroluminescence (EL) display device.

6 and 9 are schematic views schematically showing a cross-sectional configuration of a liquid crystal display device (hereinafter, sometimes referred to as “the present liquid crystal display device”) 10 using the polarizing element. The liquid crystal layer 17 is sandwiched between two bases 14a and a substrate 14b.
FIG. 12 is a schematic view schematically showing a cross-sectional configuration of an EL display device using the present polarizing element (hereinafter sometimes referred to as “the present EL display device”).
FIG. 13 is a schematic view schematically showing a configuration of a projection type liquid crystal display device using the present polarizing element.

First, the liquid crystal display device 10 shown in FIG. 6 will be described.
A color filter 15 is disposed on the liquid crystal layer 17 side of the substrate 14a. The color filter 15 is disposed at a position facing the pixel electrode 22 across the liquid crystal layer 17, and the black matrix 20 is disposed at a position facing the boundary between the pixel electrodes. The transparent electrode 16 is disposed on the liquid crystal layer 17 side so as to cover the color filter 15 and the black matrix 20.
An overcoat layer (not shown) may be provided between the color filter 15 and the transparent electrode 16.

  Thin film transistors 21 and pixel electrodes 22 are regularly arranged on the liquid crystal layer 17 side of the substrate 14b. The pixel electrode 22 is disposed at a position facing the color filter 15 with the liquid crystal layer 17 interposed therebetween. An interlayer insulating film 18 having a connection hole (not shown) is disposed between the thin film transistor 21 and the pixel electrode 22.

A glass substrate and a plastic substrate are used as the substrate 14a and the substrate 14b.
As the glass substrate or plastic substrate, the same material as that exemplified as the transparent base material of the polarizing element can be adopted. Moreover, the transparent base material 1 of this polarizing element may serve as the board | substrate 14a and the board | substrate 14b. When manufacturing the color filter 15 and the thin film transistor 21 formed on the substrate, a glass substrate or a quartz substrate is preferable when a process of heating to a high temperature is required.

  As the thin film transistor, an optimum one can be adopted according to the material of the substrate 14b. Examples of the thin film transistor 21 include a high-temperature polysilicon transistor formed on a quartz substrate, a low-temperature polysilicon transistor formed on a glass substrate, and an amorphous silicon transistor formed on a glass substrate or a plastic substrate. In order to reduce the size of the present liquid crystal display device, a driver IC may be formed on the substrate 14b.

  A liquid crystal layer 17 is disposed between the transparent electrode 16 and the pixel electrode 22. In the liquid crystal layer 17, spacers 23 are arranged in order to keep the distance between the substrate 14a and the substrate 14b constant. In FIG. 2, columnar spacers are illustrated, but the spacers are not limited to columnar shapes, and the shape is arbitrary as long as the distance between the substrate 14 a and the substrate 14 b can be kept constant.

  Of the layers formed on the substrate 14a and the substrate 14b, an alignment layer for aligning the liquid crystal in a desired direction may be disposed on the surface in contact with the liquid crystal layer 17. In addition, this polarizing element can be arrange | positioned inside a liquid crystal cell, ie, this polarizing element can also be arrange | positioned in the surface side which touches the liquid-crystal layer 17. FIG. Hereinafter, such a format is referred to as an “in-cell format”. Details of the in-cell format will be described later.

  Each member is laminated in the order of the substrate 14a, the color filter 15 and the black matrix 20, the transparent electrode 16, the liquid crystal layer 17, the pixel electrode 22, the interlayer insulating film 18 and the thin film transistor 21, and the substrate 14b.

Among the substrates 14a and 14b sandwiching the liquid crystal layer 17, polarizers 12a and 12b are provided outside the substrate 14b, and at least one of these is the present polarizing element.
Furthermore, it is preferable that retardation layers (for example, quarter-wave plates and optical compensation films) 13a and 13b are laminated. Of the polarizers 12 a and 12 b, the function of converting incident light into linearly polarized light can be imparted to the liquid crystal display device 10 by disposing the polarizing element on the polarizer 12 b. The retardation films 13a and 13b may not be arranged depending on the structure of the liquid crystal display device and the type of the liquid crystal compound contained in the liquid crystal layer 17, and the polarizing element in which the transparent substrate is a retardation film. When the (circular polarizing plate) is used, the retardation film can be a retardation layer, and therefore the retardation layer 13a and / or 13b in FIG. 6 can be omitted. A polarizing film may be further provided on the light emitting side (outside) of the polarizing element.
Further, an antireflection film for preventing reflection of external light may be arranged outside the present polarizing element (outside when a polarizing film is further provided on the present polarizing element).

  As described above, the polarizing element can be used for the polarizer 12a or 12b of the liquid crystal display device 10 of FIG. By providing the polarizing element in the polarizer 12a and / or 12b, there is an effect that the liquid crystal display device 10 can be thinned.

When this polarizing element is used for the polarizer 12a or 12b, the stacking order is not particularly limited.
This will be described with reference to an enlarged view of portions A and B surrounded by a dotted line in FIG.

  FIG. 7 is an enlarged schematic cross-sectional view of a portion A in FIG. (A1) in FIG. 7 shows that when the polarizing element 100 is used as the polarizer 12a, the polarizing layer 3, the photo-alignment layer 2, and the transparent substrate 1 are arranged in this order from the retardation layer 13a side. It shows that the polarizing element 1 is provided. 7A2 shows that the polarizing element 1 is provided so that the transparent substrate 1, the photo-alignment layer 2, and the polarizing layer 3 are arranged in this order from the phase difference layer 13a side. Show.

  FIG. 8 is an enlarged schematic view of a portion B in FIG. (B1) in FIG. 8 shows that when the polarizing element 100 is used as the polarizer 12b, the transparent substrate 1, the photo-alignment layer 2, and the polarizing layer 3 are arranged in this order from the retardation film 13b side. A polarizing element 100 is provided. (B2) in FIG. 8 shows that when the polarizing element 100 is used as the polarizer 12b, the polarizing layer 3, the photo-alignment layer 2, and the transparent substrate 1 are arranged in this order from the retardation film 13b side. A polarizing element 100 is provided.

A backlight unit, which is a light source, is disposed outside the polarizer 12b. The backlight unit includes a light source, a light guide, a reflector, a diffusion sheet, and a viewing angle adjustment sheet.
Examples of the light source include electroluminescence, a cold cathode tube, a hot cathode tube, a light emitting diode (LED), a laser light source, and a mercury lamp. In addition, the type of the polarizing element can be selected in accordance with the characteristics of such a light source.

  When the present liquid crystal display device 10 is a transmissive liquid crystal display device, white light emitted from a light source in the backlight unit is incident on the light guide, and the path is changed by the reflecting plate and diffused by the diffusion sheet. The diffused light is adjusted to have a desired directivity by the viewing angle adjusting sheet, and then enters the polarizer 12b from the backlight unit.

  Of the incident light that is non-polarized light, only one linearly polarized light passes through the polarizer 12b of the liquid crystal panel. This linearly polarized light is converted into circularly polarized light or elliptically polarized light by the retardation layer 13b, and sequentially passes through the substrate 14b, the pixel electrode 22 and the like to reach the liquid crystal layer 17.

  Here, depending on the presence or absence of a potential difference between the pixel electrode 22 and the transparent electrode 16 facing the pixel electrode 22, the alignment state of the liquid crystal molecules contained in the liquid crystal layer 17 changes, and the luminance of the light emitted from the liquid crystal display device 10 is controlled. Is done. When the liquid crystal layer 17 is in an alignment state in which the polarized light is transmitted as it is, the polarized light is transmitted through the liquid crystal layer 17 and the transparent electrode 16, and light in a specific wavelength range is transmitted through the color filter 15 and reaches the polarizer 12a. Therefore, the liquid crystal display device displays the color determined by the color filter brightest.

  On the contrary, when the liquid crystal layer 17 is in an alignment state in which the polarized light is converted and transmitted, the light transmitted through the liquid crystal layer 17, the transparent electrode 16, and the color filter 15 is absorbed by the polarizer 12a. As a result, this pixel displays black. In the intermediate alignment state between these two states, the luminance of light emitted from the liquid crystal display device 10 is also intermediate between the two, so that this pixel displays an intermediate color.

  In the case where the present liquid crystal display device 10 is a transflective liquid crystal display device, it is preferable to use a laminate in which a quarter wavelength plate is further laminated on the polarizing layer side of the polarizing element (circular polarizing plate). At this time, the pixel electrode 22 has a transmissive portion formed of a transparent material and a reflective portion formed of a material that reflects light. In the transmissive portion, an image is displayed in the same manner as in the transmissive liquid crystal display device described above. Is displayed. On the other hand, in the reflection portion, external light is incident on the liquid crystal display device, and circularly polarized light that has passed through the polarizing element passes through the liquid crystal layer 17 due to the action of the quarter wavelength plate further provided in the polarizing element, and the pixel electrode. 22 is reflected and used for display.

Next, a preferred in-cell type liquid crystal display device (the present liquid crystal display device 24) using this polarizing element will be described with reference to FIG.
In the present liquid crystal display device 24, the substrate 14a, the polarizer 12a, the retardation film 13a, the color filter 15 and the black matrix 20, the transparent electrode 16, the liquid crystal layer 17, the pixel electrode 22, the interlayer insulating film 18 and the thin film transistor 21, and the retardation film. 13b, polarizer b, substrate 14b, and backlight unit 19 are laminated in this order, and in this configuration, the polarizing element is preferably used as the polarizer 12a. In this configuration, in the polarizing element, the transparent base material, the photo-alignment layer 2 and the polarizing layer 3 may be arranged in this order so that the transparent base material in the polarizing element also serves as the substrate 14a. In the present liquid crystal display device 24 provided with the present polarizing element in such a configuration, a function of making incident light linearly polarized light is given. Similar to the liquid crystal display device 10, the retardation layers 13 a and 13 b may not be arranged depending on the type of liquid crystal compound included in the liquid crystal layer 17.

  Next, the EL display device 30 using the polarizing element will be described with reference to FIG. When using this polarizing element for this EL display device, it is preferable to use it after making this polarizing element into this circularly-polarizing plate. There are two embodiments of this circularly polarizing plate. Therefore, before describing the configuration of the EL display device 30 and the like, two embodiments of the present circularly polarizing plate will be described with reference to FIG.

  FIG. 10A is a cross-sectional view schematically showing the first embodiment of the circularly polarizing plate 110. The first embodiment is a circular polarizing plate 110 in which a retardation layer (retardation film) 4 is further provided on the polarizing layer 3 of the polarizing element 100. FIG. 10B is a cross-sectional view schematically showing the second embodiment of the circularly polarizing plate 110. In this second embodiment, a transparent substrate 1 (retardation film 4) to which a phase difference is imparted in advance is used as the transparent substrate 1 used when the polarizing element 100 is manufactured. This is the circularly polarizing plate 110 in which the material 1 itself has a function as the retardation layer 4.

  Here, a manufacturing method of the present circularly polarizing plate 110 will be described. In the present manufacturing method A or the present manufacturing method B for manufacturing the polarizing element 100, the second embodiment of the circularly polarizing plate 110 has been previously provided with a retardation as the transparent substrate 1 as described above. 1, ie, by using a retardation film. 1st Embodiment of this circularly-polarizing plate 110 adheres retardation layer 4 by bonding retardation film on the polarizing layer 3 of this polarizing element 1 manufactured by this manufacturing method A or this manufacturing method B. As shown in FIG. What is necessary is just to form. When the polarizing element 100 is manufactured in the form of the second roll 220 by the manufacturing method B, the polarizing element 100 is unwound from the second roll 220, cut into a predetermined size, and then cut. Although the form which bonds a retardation film to this made polarizing element 100 may be sufficient, a shape is a film form and a elongate shape by preparing the 3rd roll by which the retardation film is wound up by the winding core. The circularly polarizing plate 110 can also be manufactured continuously.

A method for continuously manufacturing the first embodiment of the circularly polarizing plate 110 will be described with reference to FIG. Such a manufacturing method is:
A step of continuously unwinding the polarizing element 100 from the second roll 220 and unwinding the retardation film continuously from a third roll 230 on which the retardation film is wound;
The circularly polarizing plate 110 is obtained by continuously laminating the polarizing layer provided on the polarizing element 100 unwound from the second roll 220 and the retardation film unwound from the third roll. Forming, and
The circularly polarizing plate 110 thus formed is wound around a fourth core 240A to obtain a fourth roll 240. This method is so-called Roll to Roll bonding.

  As mentioned above, although the manufacturing method of 1st Embodiment of this circularly-polarizing plate 110 was demonstrated, when bonding the polarizing layer 3 of this polarizing element 100, and retardation film, using an appropriate adhesive, The polarizing layer 3 and the retardation film may be bonded via an adhesive layer formed from an adhesive.

Next, the EL display device including the circular polarizing plate 110 will be described with reference to FIG.
In the EL display device 30, an organic functional layer 36 that is a light source and a cathode electrode 37 are laminated on a substrate 33 on which a pixel electrode 35 is formed. A circularly polarizing plate 31 is disposed on the opposite side of the organic functional layer 36 across the substrate 33, and the circularly polarizing plate 110 is used as the circularly polarizing plate 31. By applying a positive voltage to the pixel electrode 35 and a negative voltage to the cathode electrode 37 and applying a direct current between the pixel electrode 35 and the cathode electrode 37, the organic functional layer 36 emits light. The organic functional layer 36 that is a light emitting source includes an electron transport layer, a light emitting layer, a hole transport layer, and the like. The light emitted from the organic functional layer 36 passes through the pixel electrode 35, the interlayer insulating film 34, the substrate 33, and the circularly polarizing plate 31 (this circularly polarizing plate 110). Although the organic EL display device having the organic functional layer 36 will be described, the present invention may be applied to an inorganic EL display device having an inorganic functional layer.

  In order to manufacture the EL display device 30, first, the thin film transistor 40 is formed in a desired shape on the substrate 33. Then, an interlayer insulating film 34 is formed, and then a pixel electrode 35 is formed by sputtering and patterned. Thereafter, the organic functional layer 36 is laminated.

  Next, the circularly polarizing plate 31 (the present circularly polarizing plate 110) is provided on the surface of the substrate 33 opposite to the surface on which the thin film transistor 40 is provided.

  When this circularly polarizing plate 110 is used as the circularly polarizing plate 31, the stacking order will be described with reference to an enlarged view of a portion C surrounded by a dotted line in FIG. When the circular polarizing plate 110 is used as the circular polarizing plate 31, the retardation layer 4 in the circular polarizing plate 110 is disposed on the substrate 33 side. (C1) in FIG. 12 is an enlarged view using the first embodiment of the circularly polarizing plate 110 as the circularly polarizing plate 31, and (C2) in FIG. 12 shows the second embodiment of the circularly polarizing plate 110. 3 is an enlarged view used as a circularly polarizing plate 31. FIG.

  Next, members other than the polarizing element 31 (circularly polarizing plate 110) of the EL display device 30 will be briefly described.

Examples of the substrate 33 include a sapphire glass substrate, a quartz glass substrate, a soda glass substrate and a ceramic substrate such as alumina; a metal substrate such as copper; a plastic substrate.
Although not shown, a heat conductive film may be formed on the substrate 33. Examples of the thermally conductive film include a diamond thin film (DLC or the like). When the pixel electrode 35 is a reflection type, light is emitted in the opposite direction to the substrate 33. Therefore, not only a transparent material but also a non-permeable material such as stainless steel can be used. A single substrate may be formed, or a plurality of substrates may be bonded together with an adhesive to form a laminated substrate. Further, these substrates are not limited to plate-like ones, and may be films.

  For example, a polycrystalline silicon transistor may be used as the thin film transistor 40. The thin film transistor 40 is provided at the end of the pixel electrode 35 and has a size of about 10 to 30 μm. The size of the pixel electrode 35 is about 20 μm × 20 μm to 300 μm × 300 μm.

  On the substrate 33, wiring electrodes of the thin film transistor 40 are provided. The wiring electrode has a low resistance and has a function of suppressing resistance by being electrically connected to the pixel electrode 35. In general, the wiring electrode includes Al, Al and transition metals (except for Ti), Ti or Those containing any one or more of titanium nitride (TiN) are used.

An interlayer insulating film 34 is provided between the thin film transistor 40 and the pixel electrode 35. The interlayer insulating film 34 is formed by sputtering or vacuum deposition of an inorganic material such as silicon oxide such as SiO ₂ or silicon nitride, a silicon oxide layer formed by SOG (spin-on-glass), a photoresist, a polyimide. In addition, any film may be used as long as it has insulating properties, such as a coating film of a resin material such as an acrylic resin.

  A rib 41 is formed on the interlayer insulating film 34. The rib 41 is disposed in the peripheral portion (between adjacent pixels) of the pixel electrode 35. Examples of the material of the rib 41 include acrylic resin and polyimide resin. The thickness of the rib 41 is preferably 1.0 μm or more and 3.5 μm, more preferably 1.5 μm or more and 2.5 μm or less.

  Next, an EL element including a pixel electrode 35 that is a transparent electrode, an organic functional layer 36 that is a light emission source, and a cathode electrode 37 will be described. Each of the organic functional layers 36 includes at least one hole transport layer and a light emitting layer, and sequentially includes, for example, an electron injection transport layer, a light emitting layer, a hole transport layer, and a hole injection layer.

Examples of the pixel electrode 35 include ITO (tin-doped indium oxide), IZO (zinc-doped indium oxide), IGZO, ZnO, SnO _2, and In ₂ O _3. ITO and IZO are particularly preferable. The pixel electrode 35 only needs to have a certain thickness or more that can sufficiently inject holes, and is preferably about 10 to 500 nm.
The pixel electrode 35 can be formed by an evaporation method (preferably a sputtering method). The sputtering gas is not particularly limited, and an inert gas such as Ar, He, Ne, Kr and Xe, or a mixed gas thereof may be used.

As a constituent material of the cathode electrode 37, for example, metal elements such as K, Li, Na, Mg, La, Ce, Ca, Sr, Ba, Al, Ag, In, Sn, Zn, and Zr may be used. In order to improve the operational stability of the electrode, it is preferable to use a two-component or three-component alloy system selected from the exemplified metal elements. Examples of the alloy system include Ag · Mg (Ag: 1 to 20 at%), Al·Li (Li: 0.3 to 14 at%), In · Mg (Mg: 50 to 80 at%), and Al · Ca (Ca: 5 to 20 at%) is preferable.
The cathode electrode 37 is formed by vapor deposition or sputtering. The thickness of the cathode electrode 37 is 0.1 nm or more, preferably 1 to 500 nm or more.

The hole injection layer has a function of facilitating the injection of holes from the pixel electrode 35, and the hole transport layer has a function of transporting holes and a function of blocking electrons. Also called transport layer.
The thickness of the light-emitting layer, the combined thickness of the hole injection layer and the hole transport layer, and the thickness of the electron injection / transport layer are not particularly limited and may vary depending on the formation method, but should be about 5 to 100 nm. Is preferred. Various organic compounds can be used for the hole injection layer and the hole transport layer. For the formation of the hole injecting and transporting layer, the light emitting layer and the electron injecting and transporting layer, a vacuum deposition method can be used in that a homogeneous thin film can be formed.

  Examples of the organic functional layer 36 that is a light emission source include those that use light emission (fluorescence) from singlet excitons, those that use light emission (phosphorescence) from triplet excitons, and those from singlet excitons. Including those using luminescence (fluorescence) and those using triplet excitons (phosphorescence), those formed with organic matter, those formed with organic matter and those formed with inorganic matter , A high molecular material, a low molecular material, a high molecular material and a low molecular material, and the like can be used. However, the present invention is not limited thereto, and an organic functional layer 36 using various known materials for EL elements can be used for the EL display device 30.

  A desiccant 38 is disposed in the space between the cathode electrode 37 and the sealing lid 39. This is because the organic functional layer 36 is vulnerable to humidity. Moisture is absorbed by the desiccant 38 to prevent the organic functional layer 36 from deteriorating.

FIG. 14 is a schematic diagram illustrating a cross-sectional configuration of another aspect of the EL display device 30. This EL display device 30 has a sealing structure using a thin film sealing film 41, and can obtain emitted light from the opposite surface of the array substrate.
As the thin film sealing film 41, it is preferable to use a DLC film obtained by evaporating DLC (diamond-like carbon) on an electrolytic capacitor film. The DLC film has a characteristic that moisture permeability is extremely poor, and has high moisture-proof performance. Further, a DLC film or the like may be directly deposited on the surface of the cathode electrode 37. Further, the thin film sealing film 41 may be formed by laminating a resin thin film and a metal thin film in multiple layers.

  As described above, the novel polarizing element (the present polarizing element) according to the present invention and the novel display device (the present liquid crystal display device and the present EL display device) including the present polarizing element are provided.

Finally, a projection type liquid crystal display device using the polarizing element 100 will be described.
FIG. 15 is a schematic view showing a projection type liquid crystal display device using the polarizing element 100.
The polarizing element 100 is used as the polarizer 142 and / or the polarizer 143 of the projection type liquid crystal display device.

  A light bundle emitted from a light source (for example, a high-pressure mercury lamp) 111 that is a light emission source first passes through a first lens array 112, a second lens array 113, a polarization conversion element 114, and a superimposing lens 115. The luminance is uniformed and polarized in the cross section of the anti-beam bundle.

  Specifically, the light bundle emitted from the light source 111 is divided into a number of minute light bundles by the first lens array 112 in which minute lenses 112a are formed in a matrix. The second lens array 113 and the superimposing lens 115 are provided so that each of the divided light bundles irradiates the entire three liquid crystal panels 140R, 140G, and 140B that are illumination targets. The liquid crystal panel incident side surface has almost uniform illuminance as a whole.

  The polarization conversion element 114 is configured by a polarization beam splitter array, and is disposed between the second lens array 113 and the superimposing lens 115. As a result, random polarized light from the light source is converted into polarized light having a specific polarization direction in advance, thereby reducing the amount of light loss in the incident side polarizer described later, thereby improving the screen brightness.

  The light whose luminance is uniformed and polarized as described above is sequentially converted into the red channel, the green channel, and the blue channel by the dichroic mirrors 121, 123, and 132 for separation into the three primary colors of RGB via the reflection mirror 122. These are separated and enter the liquid crystal panels 140R, 140G, and 140B, respectively.

  In the liquid crystal panels 140R, 140G, and 140B, a polarizer 142 is disposed on the incident side, and a polarizer 143 is disposed on the exit side. The polarizing element 100 can be used for the polarizer 142 and the polarizer 143.

  The polarizer 142 and the polarizer 143 arranged in the RGB optical paths are arranged so that the absorption axes thereof are orthogonal to each other. Each of the liquid crystal panels 140R, 140G, and 140B arranged in each optical path has a function of converting a polarization state controlled for each pixel by an image signal into a light amount.

  The polarizing element 100 is useful as a polarizing film having excellent durability in any optical path of a blue channel, a green channel, and a red channel by selecting a type of dichroic dye suitable for the corresponding channel.

  An optical image created by transmitting incident light with different transmittance for each pixel according to the image data of the liquid crystal panels 140R, 140G, and 140B is synthesized by the cross dichroic prism 150, and is projected by the projection lens 170 to the screen 180. Is enlarged and projected.

  Electronic paper is displayed by molecules such as optical anisotropy and dye molecule orientation, displayed by particles such as electrophoresis, particle movement, particle rotation, and phase change, and one end of the film moves And the like, those displayed by molecular color development / phase change, those displayed by light absorption of molecules, and those displayed by self-emission by combining electrons and holes. More specifically, microcapsule type electrophoresis, horizontal movement type electrophoresis, vertical movement type electrophoresis, spherical twist ball, magnetic twist ball, cylindrical twist ball method, charged toner, electronic powder fluid, magnetophoretic type, magnetic thermosensitive Formula, electrowetting, light scattering (transparency / transparency change), cholesteric liquid crystal / photoconductive layer, cholesteric liquid crystal, bistable nematic liquid crystal, ferroelectric liquid crystal, dichroic dye / liquid crystal dispersion type, movable film, leuco dye And color erasing, photochromic, electrochromic, electrodeposition, flexible organic EL, and the like. The electronic paper may be used not only for personal use of text and images but also for advertisement display (signage) or the like. According to this polarizing element, the thickness of the electronic paper can be reduced.

  As a stereoscopic display device, for example, a method of arranging different retardation films alternately like a micropole method has been proposed (Japanese Patent Laid-Open No. 2002-185983), but when the optical film of the present invention is used as a polarizing film, Since patterning is easy by printing, inkjet, photolithography, etc., the manufacturing process of the display device can be shortened, and a retardation film is not required.

  Hereinafter, the present invention will be described in more detail with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

Synthesis example 1 of polymer having photoreactive group
Polymer 1 and polymer 2 were synthesized as polymers having photoreactive groups.

Synthesis Example 1: Synthesis of Polymer 1 Polymer 1 is composed of the following structural units.
[Polymer 1]

[Synthesis scheme of polymer 1]

[Synthesis of Compound (a1-1-1)]
50 g (258 mmol) of ferulic acid was dissolved in 360 g of methanol. To the obtained solution, 10 g of sulfuric acid was added at room temperature, and the temperature was raised until the solvent was refluxed, followed by reaction for 2 hours under reflux. After cooling the resulting reaction solution, 150 g of ice and 150 g of water were added. The supernatant was removed by decantation, and further 150 g of water at 5 ° C. was added for crystallization. The obtained white crystals were filtered, and the filtered white crystals were further washed with 1M aqueous sodium hydrogen carbonate solution and water, and then dried under vacuum to obtain 22.2 g of compound (a1-1-1). The yield was 83% based on ferulic acid.

[Synthesis of Compound (b1-1-1)]
25 g (120 mmol) of the compound (a1-1-1) was dissolved in 250 g of dimethylacetamide. To the obtained solution, 33.19 g (240 mmol) of potassium carbonate and 1.99 g (12 mmol) of potassium iodide were added. To the obtained dispersion, 6-chlorohexanol was added dropwise, stirred at room temperature for 1 hour, and then stirred at 70 ° C. for 8 hours. The obtained reaction solution was filtered to remove insoluble matters. To the filtrate, 200 g of methyl isobutyl ketone and 300 g of water were added, stirred and allowed to stand, and separated to recover the organic layer. 200 g of water was added to the collected organic layer, and the water washing operations of stirring, standing and liquid separation were repeated twice. The solvent was removed from the recovered organic layer by distillation under reduced pressure using an evaporator to obtain a crude product of compound (b1-1-1).

[Synthesis of Compound (c1-1-1)]
The total amount of the crude product of the compound (b1-1-1) was dissolved in 185 g of ethanol.
To the obtained solution, 92 g of water and 14.41 g (360 mmol) of sodium hydroxide were added and stirred at 80 ° C. for 1 hour. After the reaction solution was cooled to about 3 ° C., a 2M hydrochloric acid aqueous solution was added while maintaining the temperature at 5 ° C. or lower to adjust the pH to 2. The acid precipitated white precipitate was collected by filtration, further washed twice with a mixed solution of 100 g of water and 80 g of methanol, and dried under vacuum to obtain 30.4 g of compound (c1-1-1). The yield was 86% based on the compound (a1-1-1).

[Synthesis of Compound (M1-1-1)]
27.46 g (93 mmol) of the compound (c1-1-1) was dissolved in 280 g of chloroform. To the obtained solution, 2.06 g of BHT (di-t-butyl-hydroxytoluene) and 37.73 g (373 mmol) of triethylamine were added as a polymerization inhibitor and stirred under ice cooling. To the reaction solution, 29.26 g (260 mmol) of methacrylic acid chloride was added dropwise, and the mixture was stirred at 5 ° C. or lower for 5 hours. To the obtained reaction solution, 5.7 g of dimethylaminopyridine and 190 g of water were added and stirred at room temperature for 12 hours. After allowing to stand, the organic layer was recovered, 100 g of 2N hydrochloric acid aqueous solution was added to the organic layer, and washing operations of stirring, standing, and liquid separation were repeated twice. The organic layer was recovered, 300 g of n-heptane was added, and the precipitated crystals were collected by filtration. The mixture was washed twice with a mixed solvent consisting of 100 g of water and 80 g of methanol, and then vacuum-dried to obtain 22.0 g of compound (M1-1-1). The yield was 65% based on the compound (c1-1-1).

[Synthesis of Polymer 1]
In a Schlenk tube, 1.00 g (2.76 mmol) of the compound (M1-1-1) and 10 g of tetrahydrofuran were added, and after deoxygenation, 2.27 mg of azobisisobutyronitrile (AIBN) was introduced while flowing nitrogen. And stirred at 60 ° C. for 72 hours. The obtained reaction solution was added to 200 g of toluene. The precipitate was collected by filtration, washed with heptane, and then vacuum-dried to obtain 0.75 g of polymer 1. The yield was 75% based on the compound (M1-1-1). From the GPC measurement, the obtained polymer 1 had a number average molecular weight of 28,200, Mw / Mn of 1.82, and a monomer content of 0.5%.

（なお、括弧に付した数値は、ポリマー２の全構造単位に対する各構造単位のモル分率を表す。） Synthesis Example 2: Synthesis of Polymer 2 Macromolecules, Vol. 39, no. 26 (2006), a polymer 2 having the following structure was synthesized.

(The numerical value in parentheses represents the mole fraction of each structural unit with respect to all the structural units of polymer 2.)

Synthesis of Polymerizable Smectic Liquid Crystal Compound As a polymerizable smectic liquid crystal compound (in the following description, the polymerizable smectic liquid crystal compound is abbreviated as “polymerizable liquid crystal compound”), compound (1-6), compound (1- 7), Compound (1-8), Compound (1-13) and Compound (1-14) were synthesized.

Synthesis Example 3: Compound (1-6) (compound represented by the following formula (1-6))
Compound (1-6) was prepared according to Lub et al. Trav. Chim. It was synthesized by the method described in Pays-Bas, 115, 321-328 (1996).

Synthesis Examples 4 to 7: Synthesis of Compound (1-7), Compound (1-8), Compound (1-13), and Compound (1-14) Compound (1-7) (in the following formula (1-7) A compound represented by the following formula (1-8), a compound (1-13) (a compound represented by the following formula (1-13)), a compound ( 1-14) (a compound represented by the following formula (1-14)) was synthesized by referring to the synthesis method of the compound (1-6).

Example 1
[Adjustment of composition for forming polarizing layer]
The following components were mixed and stirred at 80 ° C. for 1 hour to obtain a polarizing layer forming composition.

Polymerizable liquid crystal compound; Compound (1-6) 75 parts
Compound (1-7) 25 parts Dichroic dye; Azo dye (G205; manufactured by Hayashibara Biochemical Laboratories) 3.0 parts Polymerization initiator; 1-hydroxycyclohexyl phenyl ketone (Irgacure 184; manufactured by Ciba Specialty Chemicals) 6 Part leveling agent; polyacrylate compound (BYK-361N; manufactured by BYK-Chemie) 1.5 parts solvent; 250 parts of cyclopentanone

(Measurement of phase transition temperature)
The phase transition temperature was confirmed by texture observation with a polarizing microscope. The polymerizable liquid crystal compound contained in the composition for forming a polarizing layer is heated to 120 ° C., removed from the solvent, dried, then transitioned to a nematic phase at 110 ° C. and then to a smectic A phase at 104 ° C. Then, it was confirmed that the phase transition to the smectic B phase was performed at 83 ° C.

(Preparation of photo-alignment layer)
A solution (composition for forming a photo-alignment layer) in which a polymer having a photoreactive group (polymer 1 or polymer 2) is dissolved in cyclopentanone at a concentration of 5% by weight is bar-coated on a polyethylene terephthalate substrate (PET substrate). After applying by the method and drying at 60 ° C. for 1 minute, a first dry film having a thickness of 100 nm was formed. Subsequently, the surface of the obtained first dry film was subjected to polarized UV irradiation treatment to form a photo-alignment layer. The polarized UV treatment was performed using a UV irradiation apparatus (SPOT CURE SP-7; manufactured by USHIO INC.) Under the condition that the intensity measured at a wavelength of 365 nm was 100 mJ.

(Preparation of polarizing layer)
A composition for forming a polarizing layer was applied onto the photo-alignment film by a bar coating method, dried by heating in a drying oven at 120 ° C. for 1 minute, and then cooled to room temperature to obtain a second dry film. Using a UV irradiation apparatus (SPOT CURE SP-7; manufactured by USHIO INC.), The polarizing film is formed by irradiating the second dry film with ultraviolet rays having an exposure amount of 1200 mJ / cm ² (365 nm standard). A device was manufactured. When the film thickness of the polarizing layer at this time was measured with a laser microscope (OLS3000 manufactured by Olympus Corporation), it was 1.6 μm.

[X-ray diffraction measurement]
X-ray diffraction measurement was performed on the obtained polarizing layer using an X-ray diffractometer X′Pert PRO MPD (Spectris Co., Ltd.). Using Cu as a target, X-rays generated under conditions of an X-ray tube current of 40 mA and an X-ray tube voltage of 45 kV are incident from the rubbing direction through a fixed diverging slit 1/2 °, and the scanning range 2θ = 4.0 to 40 As a result of scanning and measuring in steps of 2θ = 0.01671 ° in a range of 0.0 °, a sharp diffraction peak (FWHM) = approximately 0.187 ° in the vicinity of 2θ = 20.22 ° ( Bragg peak) was obtained. In addition, the same result was obtained even when incident from the rubbing vertical direction. The order period (d) obtained from the peak position is about 4.4 cm, and it can be seen that a structure reflecting a high-order smectic phase is formed.

[Dichroic ratio measurement]
Using the apparatus which set the folder with a polarizer to the spectrophotometer (Shimadzu Corporation UV-3150) for the absorbance (A ¹ ) in the transmission axis direction and the absorbance (A ² ) in the absorption axis direction at the maximum absorption wavelength. Measured by the double beam method. The folder was provided with a mesh that cuts the light amount by 50% on the reference side. The ratio (A ² / A ¹ ) was calculated from the measured absorbance (A ¹ ) in the transmission axis direction and absorbance (A ² ) in the absorption axis direction to obtain a dichroic ratio. The results are shown in the table. It can be said that the higher the dichroic ratio, the more useful the polarizing layer. Table 1 shows the measurement results of the dichroic ratio.

(Observation of orientation state)
The alignment state of the obtained polarizing layer was confirmed by polarizing microscope observation. A sample was inserted in the direction of about 45 ° between the polarizing microscope crossed Nicols, and observation was carried out in a light-out state. In the case of being oriented in the vertical direction, a dark field state is observed without occurrence of light omission, and in the case of being oriented in the horizontal direction, light omission is caused and observed in a bright field state. The evaluation was based on two levels: “◯” when a bright field was obtained over the entire screen, and “X” when a dark field was obtained over the entire screen. The results are shown in Table 1.

[Measurement of Haze Value]
The haze value was measured with respect to the obtained polarizer using the haze meter (HZ-2; Suga Test Instruments Co., Ltd. product). The haze value is represented by the following formula.
Haze value (%) = scattering transmittance (%) / total light transmittance (%) × 100
If the alignment regulating force of the polarizing layer by the photo-alignment layer is insufficient, discontinuous defects occur in the polymerizable smectic liquid crystal that is the main component of the polarizing layer. Since light scattering occurs at this discontinuous defect interface, the haze value becomes a large value. That is, it can be said that the smaller the haze value, the better the orientation. Here, 3% or less was considered good. The results are shown in Table 1.

Example 2
A polarizing element was produced in the same manner as in Example 1, except that the dichroic dye was changed from an azo dye (G205; manufactured by Hayashibara Biochemical Laboratories) to an azo dye (NKX2029; manufactured by Hayashibara Biochemical Laboratories).

(Measurement of phase transition temperature)
In the same manner as in Example 1, the phase transition behavior of the polymerizable liquid crystal composition contained in the composition for forming a polarizing layer in Example 2 was measured. After heating to 120 ° C, removing the solvent and drying, at the time of cooling, it was confirmed that the phase transition to the nematic phase at 113 ° C, the phase transition to the smectic A phase at 107 ° C, and the phase transition to the smectic B phase at 83 ° C. did.

  As in Example 1, dichroic ratio measurement, orientation state observation, and haze value measurement of the manufactured polarizing element were performed. The results are shown in Table 1.

Example 3
The polymerizable liquid crystal compound contained in the composition for forming a polarizing layer is obtained by mixing 75 parts of compound (1-6) and 75 parts of compound (1-8) from a mixture of 75 parts of compound (1-6) and 25 parts of compound (1-7). ) A polarizing element was produced in the same manner as in Example 1 except that the mixture was changed to 25 parts.

(Measurement of phase transition temperature)
In the same manner as in Example 1, the phase transition behavior of the polymerizable liquid crystal composition contained in the composition for forming a polarizing layer in Example 3 was measured. After heating to 120 ° C., removing the solvent and drying, it was confirmed that the phase transitioned to the nematic phase at 111 ° C., to the smectic A phase at 105 ° C., and to the smectic B phase at 82 ° C. did.

  As in Example 1, dichroic ratio measurement, orientation state observation, and haze value measurement of the manufactured polarizing element were performed. The results are shown in Table 1.

Example 4
The polymerizable liquid crystal compound contained in the composition for forming a polarizing layer is obtained by mixing 75 parts of compound (1-6) and 75 parts of compound (1-13) from a mixture of 75 parts of compound (1-6) and 25 parts of compound (1-7). ) A polarizing element was produced in the same manner as in Example 1 except that the mixture was changed to 25 parts.

(Measurement of phase transition temperature)
In the same manner as in Example 1, the phase transition behavior of the polymerizable liquid crystal composition contained in the composition for forming a polarizing layer in Example 4 was measured. After heating to 130 ° C., removing the solvent and drying, it was confirmed that the phase transitioned to 119 ° C. to nematic phase, to 111 ° C. to smectic A phase, and to 82 ° C. to smectic B phase. did.

  As in Example 1, dichroic ratio measurement, orientation state observation, and haze value measurement of the manufactured polarizing element were performed. The results are shown in Table 1.

Example 5
The polymerizable liquid crystal compound contained in the composition for forming a polarizing layer is obtained by mixing 75 parts of compound (1-6) and 75 parts of compound (1-14) from a mixture of 75 parts of compound (1-6) and 25 parts of compound (1-7). ) A polarizing element was produced in the same manner as in Example 1 except that the mixture was changed to 25 parts.

(Measurement of phase transition temperature)
In the same manner as in Example 1, the phase transition behavior of the polymerizable liquid crystal composition contained in the composition for forming a polarizing layer in Example 5 was measured. After heating to 130 ° C., removing the solvent and drying, at the time of cooling, it was confirmed that the phase transitioned to the nematic phase at 118 ° C., the phase transition to the smectic A phase at 109 ° C., and the phase transition to the smectic B phase at 79 ° C. did.

  As in Example 1, dichroic ratio measurement, orientation state observation, and haze value measurement of the manufactured polarizing element were performed. The results are shown in Table 1.

Example 6
A polarizing element was produced in the same manner as in Example 1 except that the polymer having a photoreactive group contained in the composition for forming a photo-alignment layer was changed from polymer 1 to polymer 2.

  As in Example 1, dichroic ratio measurement, orientation state observation, and haze value measurement of the manufactured polarizing element were performed. The results are shown in Table 1.

  The polarizing element and the circularly polarizing plate of the present invention are useful for producing a liquid crystal display device, an (organic) EL display device, and a projection type liquid crystal display device.

DESCRIPTION OF SYMBOLS 1 Transparent base material 2 Photo-alignment layer 3 Polarizing layer 100 This polarizing element 110 This circularly polarizing plate 101 1st laminated body 102 2nd laminated body 103 3rd laminated body 210 1st roll 210A core 220 2nd roll 220A core 211A , 211B Coating device 212A, 212B Drying furnace 213A Polarized UV irradiation device 213B Light irradiation device 300 Auxiliary roll 10 Liquid crystal display device 12a, 12b Polarizer (this polarizing element)
13a, 13b retardation layer (retardation film)
14a, 14b Substrate 15 Color filter 16 Transparent electrode 17 Liquid crystal layer 18 Interlayer insulating film 20 Black matrix 21 Thin film transistor 22 Pixel electrode 23 Spacer 24 Liquid crystal display device 30 EL display device 31 Circularly polarizing plate 33 Substrate 34 Interlayer insulating film 35 Pixel electrode 36 Light emission Layer 37 Cathode electrode 38 Desiccant 39 Sealing lid 40 Thin film transistor 41 Rib 42 Thin film plate 44 EL display device 111 Light source 112 First lens array 112a Lens 113 Second lens array 114 Polarization conversion element 115 Superposed lenses 121, 123, 132 Dichroic mirror 122 Reflection mirrors 140R, 140G, 140B Liquid crystal panels 142, 143 Polarizer 150 Cross dichroic prism 170 Projection lens 180 Screen

Claims (17)

A polarizer in which a photo-alignment layer and a polarizing layer are provided in this order on a transparent substrate,
The photo-alignment layer has a photoreactive group that causes a dimerization reaction, and a main chain is represented by a (meth) acrylate unit represented by the following formula (M-1), represented by the formula (M-2). (Meth) acrylic acid ester unit, (meth) acrylic acid amide unit represented by formula (M-3), (meth) acrylamide unit represented by formula (M-4), represented by formula (M-5) Vinyl ether unit, vinyl ether unit represented by formula (M-6), (methyl) styrene unit represented by formula (M-7), (methyl) styrene unit represented by formula (M-8), formula ( Formed from a polymer selected from the group consisting of vinyl ester units represented by M-9) and vinyl ester units represented by formula (M-10),
The polarizing layer is
Der those formed from a composition containing a polymerizable smectic liquid crystal compound and dichroic dye is,
The dichroic dye has the formula (2)
^{_{A 1 (-N = N-A}} 2) p -N = N-A 3 (2)
[In Formula (2),
A ¹ and A ³ are each independently a phenyl group that may have a substituent, a naphthyl group that may have a substituent, or a monovalent heterocyclic group that may have a substituent. Represents. A ² represents a p-phenylene group which may have a substituent, a naphthalene-1,4-diyl group which may have a substituent, or a divalent heterocyclic ring which may have a substituent. Represents a group. p represents an integer of 1 to 4. When p is 2 or more, the plurality of A ² may be the same as or different from each other. ]
Compound der Ru polarizing element shown in.

  The polarizing element according to claim 1, wherein the polarizing layer is a polarizing layer capable of obtaining a Bragg peak in X-ray diffraction measurement.   The polarizing element according to claim 1, wherein the composition contains two or more polymerizable smectic liquid crystal compounds. The polarizing element according to claim 1, wherein the polymer having the photoreactive group is a polymer containing a group represented by the formula (A ′).

[In the formula (A ′),
n represents 0 or 1.
X ¹ represents a single bond, —O—, —COO—, —OCO—, —N═N—, —CH═CH— or —CH ₂ —.
Y ¹ represents a single bond or —O—.
R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
* Represents a bond to the polymer main chain. ] It is a manufacturing method of the polarizing element in any one of Claims 1-4,
On the transparent substrate,
Applying a composition containing a polymer having a photoreactive group and a solvent to form a first coating film on the transparent substrate;
Forming the first dry film on the transparent substrate by drying and removing the solvent from the first coating film to obtain a first laminate;
Irradiating the first dry film with polarized UV to form a photo-alignment layer from the first dry film to obtain a second laminate;
A step of applying a composition containing a polymerizable smectic liquid crystal compound, a dichroic dye and a solvent on the photo-alignment layer in the second laminate to form a second coating film on the photo-alignment layer When,
The second coating film is dried under a condition in which the polymerizable smectic liquid crystal compound contained in the second coating film is not polymerized, thereby forming a second dry film on the photo-alignment layer to form a third laminate. Obtaining
The polymerizable smectic liquid crystal compound in the second dry film is changed to a smectic liquid crystal state, and then the polymerizable smectic liquid crystal compound is polymerized while the smectic liquid crystal state is maintained, whereby a polarizing layer is formed from the second dry film. The manufacturing method which has a process of forming.   The polarizing element according to claim 1, wherein the shape is a film and a long shape. It is a manufacturing method of the polarizing element according to claim 6.
Preparing a first roll in which a transparent substrate is wound around a first core;
Continuously feeding the transparent substrate from the first roll;
Applying a composition containing a polymer having a photoreactive group and a solvent, and continuously forming a first coating film on the transparent substrate;
Forming the first dry film on the transparent substrate by drying and removing the solvent from the first coating film, and continuously obtaining the first laminate;
By irradiating the first dry film with polarized UV, a photo-alignment layer having an orientation direction at an angle of about 45 ° with respect to the transport direction of the first laminate is formed, and the second laminate is continuously formed. And the process of obtaining
Applying a composition containing a polymerizable smectic liquid crystal compound, a dichroic dye and a solvent on the photo-alignment layer, and continuously forming a second coating film on the photo-alignment layer; The coating film is dried under the condition that the polymerizable smectic liquid crystal compound contained in the second coating film is not polymerized to form a second dry film on the photo-alignment layer, thereby continuously forming the third laminate. A process of obtaining
The polymerizable smectic liquid crystal compound contained in the second dry film is changed to a smectic liquid crystal state, and then the polymerizable smectic liquid crystal compound is polymerized while maintaining the smectic liquid crystal state. Forming a polarizing layer having an absorption axis at an angle of 45 ° with respect to the transport direction to obtain a polarizing element continuously;
The manufacturing method which has the process of winding up the polarizing element obtained continuously on the 2nd core, and obtaining the 2nd roll.   A liquid crystal display device comprising the polarizing element according to claim 1.   A liquid crystal display device comprising the polarizing element according to claim 1 disposed inside a liquid crystal cell. A circle obtained by laminating the polarizing element according to any one of claims 1 to 4 and a retardation film so that an angle formed by an absorption axis of the polarizing layer and a slow axis of the retardation film is approximately 45 °. A polarizing plate,
The ellipticity value measured with light having a wavelength of 550 nm is 80% or more,
A circularly polarizing plate in which the retardation film is a film having a front retardation value of 100 to 150 nm measured with light having a wavelength of 550 nm.   The circularly polarizing plate according to claim 10, wherein the retardation film has a property that a value of front retardation with respect to visible light becomes smaller as a wavelength becomes shorter.   The circularly polarizing plate according to claim 10 or 11, wherein the shape is a film and a long shape. A method for producing a circularly polarizing plate according to claim 12,
Preparing a third roll in which a retardation film is wound around a third core;
Preparing a second roll in which the polarizing element is wound around a second core;
A step of continuously unwinding the polarizing element from the second roll and unwinding the retardation film from the third roll;
The manufacturing method which has the process of bonding the polarizing layer of the polarizing element unwound continuously, and the retardation film unwound continuously. The transparent substrate contained in the polarizing element according to any one of claims 1 to 4 is replaced with a retardation film having retardation, and an angle formed by a slow axis of the retardation film and an absorption axis of the polarizing layer. Is a circularly polarizing plate formed by laminating at approximately 45 °,
The ellipticity value measured with light having a wavelength of 550 nm is 80% or more,
A circularly polarizing plate in which the retardation film is a film having a front retardation value of 100 to 150 nm measured with light having a wavelength of 550 nm.   The circularly polarizing plate according to claim 14, wherein the shape is a film and a long shape. A method for producing a circularly polarizing plate according to claim 15,
Preparing a first roll in which a phase difference film is wound around a first core;
A step of continuously feeding out the retardation film from the first roll;
Applying a composition containing a polymer having a photoreactive group and a solvent, and continuously forming a first coating film on the retardation film;
A step of drying and removing the solvent from the first coating film to form a first dry film on the transparent substrate to obtain a first laminate continuously;
By irradiating the first dry film with polarized UV, a photo-alignment layer having an orientation direction at an angle of about 45 ° with respect to the transport direction of the first laminate is formed, and the second laminate is continuously formed. And the process of obtaining
A step of coating a composition containing a polymerizable smectic liquid crystal compound, a dichroic dye, a polymerization initiator and a solvent on the photo-alignment layer, and continuously forming a second coating film on the photo-alignment layer. And the second coating film is dried under a condition in which the polymerizable smectic liquid crystal compound contained in the second coating film is not polymerized, thereby forming a second dry film on the photo-alignment layer to form a third laminate. Obtaining a body continuously;
The polymerizable smectic liquid crystal compound contained in the second dry film is changed to a smectic liquid crystal state, and then the polymerizable smectic liquid crystal compound is polymerized while maintaining the smectic liquid crystal state. Forming a polarizing layer having an absorption axis at an angle of 45 ° with respect to the transport direction to obtain a circularly polarizing plate continuously;
The manufacturing method which has the process of winding up the circularly-polarizing plate obtained continuously on the 2nd core, and obtaining the 2nd roll.   An organic EL display device comprising the circularly polarizing plate according to claim 10, and an organic EL element.

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