JP6098053B2 - Photoreactive liquid crystal aligning agent, liquid crystal aligning element and method for producing the same - Google Patents

Description

  The present invention relates to a photoreactive liquid crystal aligning agent, a liquid crystal aligning element, and a method for producing the same.

The flat panel display (FPD) includes optically anisotropic optical anisotropic layers (alignment layers) such as polarizing plates and retardation plates as members. Such an optically anisotropic layer is generally formed by two methods. The method is first a method of forming an optically anisotropic layer by stretching a polymer, and secondly a method of forming an optically anisotropic layer from a coating film obtained by applying an alignment agent.
In particular, in the latter method, the optical anisotropic layer formed from the alignment agent can easily control the direction of the optical axis, and an optical film (liquid crystal formed by aligning and fixing a liquid crystal compound on the optical anisotropic layer). This is advantageous because the alignment element) is essentially a thin film and can be continuously produced by the Roll to Roll process.

For example, in Non-Patent Document 1, a solution containing a polymerizable liquid crystal compound (trade name: LC242, manufactured by BASF) represented by the following formula is applied on an alignment layer, and then the polymerizable liquid crystal compound is polymerized. A liquid crystal alignment element obtained by a production method for obtaining a polarizing layer is described. However, there is no known photo-alignment layer having the ability to form a polymerizable liquid crystal of the nematic phase and higher smectic phase, and a photo-alignment agent capable of forming the photo-alignment layer. .

Cordula Mock-Knoblauch, Olivier S. Enger, Ulrich D. Schalkowsky, “L-7 Novel Polymerisable Liquid Crystalline Acrylates for the Manufacturing of Ultrathin Optical Films”, SID Symposium Digest of Technical Papers, 2006, 37, p.1673

  A photo-alignment layer having an alignment ability in which a polymerizable liquid crystal compound becomes a polymerizable liquid crystal of a nematic phase and a higher-order smectic phase, and a novel photo-alignment agent (photo-reactive liquid crystal capable of forming the photo-alignment layer) There is a need for alignment agents.

［式（１−１）中、
ｎ及びｍはそれぞれ独立に、０又は１を表す。
ｖ及びｗはそれぞれ独立に、１〜３の整数を表す。
Ｓ^１及びＳ^２はそれぞれ独立に、フッ素原子又はシアノ基を有していてもよい炭素数１〜１２のアルカンジイル基を表す。
Ｓ^３は、フッ素原子又はシアノ基を有していてもよい炭素数１〜１２のアルキル基を表す。
Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４及びＸ^５はそれぞれ独立に、単結合、酸素原子、カルボニルオキシ基又はメチレン基を表す。
Ｙ^１及びＹ^２はそれぞれ独立に、単結合、酸素原子又はカルボニルオキシ基を表す。
Ｒ^１及びＲ^３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。
Ｒ^２及びＲ^４はそれぞれ独立に、炭素数１〜２のアルコキシ基、シアノ基又はハロゲン原子を表し、ｖが２又は３の場合、複数存在するＲ^２は、同一又は相異なり、ｗが２又は３の場合、複数存在するＲ^４は、同一又は相異なる。
Ｒ^５、Ｒ^６及びＲ^７はそれぞれ独立に、水素原子又はメチル基を表す。
ｐ、ｑ及びｒは、全構造単位に対する各構造単位のモル分率を表し、０．２５＜ｐ≦１、０≦ｑ＜０．７５及び０≦ｒ＜０．７５の関係を満たす。］
〔２〕前記ポリマーが、
前記式（１−１）のｑが０のポリマーである、前記〔１〕記載の光反応性液晶配向剤。
〔３〕前記ポリマーが、
前記式（１−１）のｒが０のポリマーである、前記〔１〕又は〔２〕記載の光反応性液晶配向剤。
〔４〕前記ポリマーが、
前記式（１−１）のＲ^１及びＲ^２がそれぞれ独立に、メトキシ基又はエトキシ基のポリマーである、前記〔１〕〜〔３〕のいずれか記載の光反応性液晶配向剤。
〔５〕前記ポリマーが、
前記式（１−１）のｎ及びｍがともに０のポリマーである、前記〔１〕〜〔４〕のいずれか記載の光反応性液晶配向剤。
〔６〕前記〔１〕〜〔５〕のいずれかに記載の光反応性液晶配向剤から塗布膜を形成し、該塗布膜を偏光照射してなる液晶配向層。
〔７〕前記〔６〕記載の液晶配向層と、偏光層とを有する液晶配向素子であり、
前記偏光層が、前記液晶配向層上に、重合性液晶化合物を含む組成物溶液を塗布して塗布膜を得、
前記塗布膜中に含まれる前記重合性液晶化合物を偏光照射によって重合することによって形成されたものである液晶配向素子。
〔８〕前記重合性液晶化合物が、スメクチック相の液晶状態を示す化合物である、前記〔７〕記載の液晶配向素子。
〔９〕前記重合性液晶化合物が、高次スメクチック相の液晶状態を示す化合物である、前記〔７〕記載の液晶配向素子。
〔１０〕前記重合性液晶化合物が、等方相の液晶状態から直接ネマチック相の液晶状態を示す化合物である、前記〔７〕記載の液晶配向素子。
〔１１〕前記重合性液晶化合物が、式（２）で表される、前記〔１０〕記載の液晶配向素子。

［式（２）中、
Ｑ^１は、置換もしくは非置換の多環式芳香族炭化水素基又は置換もしくは非置換の多環式芳香族複素環基を表す。
Ｄ^１及びＤ^２は、それぞれ独立に、単結合又は２価の連結基を表す。
Ｇ^１及びＧ^２は、それぞれ独立に、２価の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる水素原子は、ハロゲン原子、炭素数１〜４のアルキル基、炭素数１〜４のフルオロアルキル基、炭素数１〜４アルコキシ基、シアノ基又はニトロ基で置換されていてもよく、該脂環式炭化水素基を構成する−ＣＨ_２−は、−Ｏ−、−Ｓ−又は−ＮＨ−に置き換わっていてもよい。
Ｅ^１及びＥ^２は、それぞれ独立に、単結合又は２価の連結基を表す。
Ｂ^１及びＢ^２は、それぞれ独立に、単結合又は２価の連結基を表す。
Ａ^１及びＡ^２は、それぞれ独立に、２価の脂環式炭化水素基又は２価の芳香族炭化水素基を表し、該脂環式炭化水素基及び該芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、炭素数１〜４のアルキル基、炭素数１〜４アルコキシ基、シアノ基又はニトロ基で置換されていてもよい。該炭素数１〜４のアルキル基及び該炭素数１〜４アルコキシ基に含まれる水素原子は、フッ素原子で置換されていてもよい。
ｋ及びｌは、それぞれ独立に、０〜３の整数を表す。ｋが２以上の場合、複数存在するＡ^１は、互いに同一又は相異なり、複数存在するＢ^１は、互いに同一又は相異なる。ｌが２以上の場合、複数存在するＡ^２は、互いに同一又は相異なり、複数存在するＢ^２は、互いに同一又は相異なる。
Ｆ^１及びＦ^２は、それぞれ独立に、炭素数１〜１２のアルカンジイル基を表し、該アルカンジイル基に含まれる水素原子は、炭素数１〜５のアルコキシ基又はハロゲン原子で置換されていてもよく、該アルカンジイル基を構成する−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよい。
Ｐ^１及びＰ^２は、それぞれ独立に、水素原子、アクリロイルオキシ基又はメタクリロイルオキシ基を表すが、Ｐ^１及びＰ^２がともに水素原子であることはない。］
〔１２〕式（１−３）で表される化合物。

［式（１−３）中、
ｎは、０又は１を表す。ｖは、１〜３の整数を表す。
Ｓ^１は、フッ素原子又はシアノ基を有していてもよい炭素数１〜１２のアルカンジイル基を表す。
Ｘ^１及びＸ^３はそれぞれ独立に、単結合、酸素原子、カルボニルオキシ基又はメチレン基を表す。
Ｙ^１は、単結合、酸素原子又はカルボニルオキシ基を表す。
Ｒ^１は、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。
Ｒ^２は、炭素数１〜２のアルコキシ基、シアノ基又はハロゲン原子を表し、ｖが２又は３の場合、複数存在するＲ^２は、同一又は相異なる。
Ｒ^５は、水素原子又はメチル基を表す。］ The present invention comprises the following [1] to [12].
[1] A photoreactive liquid crystal aligning agent containing a polymer represented by the formula (1-1).

[In Formula (1-1),
n and m each independently represents 0 or 1.
v and w each independently represent an integer of 1 to 3.
S ¹ and S ² each independently represents a C 1-12 alkanediyl group which may have a fluorine atom or a cyano group.
S ³ represents a fluorine atom or an alkyl group having 1 to 12 carbon atoms which may have a cyano group.
X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a single bond, an oxygen atom, a carbonyloxy group or a methylene group.
Y ¹ and Y ² each independently represent a single bond, an oxygen atom or a carbonyloxy group.
R ¹ and R ³ 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.
R ² and R ⁴ each independently represents an alkoxy group having 1 to 2 carbon atoms, a cyano group or a halogen atom, and when v is 2 or 3, a plurality of R ² are the same or different and w is 2 Or, in the case of 3, a plurality of R ⁴ are the same or different.
R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom or a methyl group.
p, q, and r represent the mole fraction of each structural unit with respect to the total structural units, and satisfy the relationships of 0.25 <p ≦ 1, 0 ≦ q <0.75, and 0 ≦ r <0.75. ]
[2] The polymer is
The photoreactive liquid crystal aligning agent according to the above [1], wherein q in the formula (1-1) is a polymer having 0.
[3] The polymer is
The photoreactive liquid crystal aligning agent according to the above [1] or [2], wherein r in the formula (1-1) is a polymer of 0.
[4] The polymer is
The photoreactive liquid crystal aligning agent in any one of said [1]-[3] whose R < ¹ > and R < ² > of the said Formula (1-1) is a polymer of a methoxy group or an ethoxy group each independently.
[5] The polymer is
The photoreactive liquid crystal aligning agent according to any one of [1] to [4], wherein n and m in the formula (1-1) are both polymers having 0.
[6] A liquid crystal alignment layer formed by forming a coating film from the photoreactive liquid crystal aligning agent according to any one of [1] to [5] and irradiating the coating film with polarized light.
[7] A liquid crystal alignment element having the liquid crystal alignment layer according to [6] and a polarizing layer,
The polarizing layer obtains a coating film by applying a composition solution containing a polymerizable liquid crystal compound on the liquid crystal alignment layer,
A liquid crystal alignment element formed by polymerizing the polymerizable liquid crystal compound contained in the coating film by irradiation with polarized light.
[8] The liquid crystal alignment element according to [7], wherein the polymerizable liquid crystal compound is a compound exhibiting a smectic phase liquid crystal state.
[9] The liquid crystal alignment element according to [7], wherein the polymerizable liquid crystal compound is a compound exhibiting a liquid crystal state of a high-order smectic phase.
[10] The liquid crystal alignment element according to [7], wherein the polymerizable liquid crystal compound is a compound that directly exhibits a nematic liquid crystal state from an isotropic liquid crystal state.
[11] The liquid crystal alignment element according to [10], wherein the polymerizable liquid crystal compound is represented by the formula (2).

[In Formula (2),
Q ¹ represents a substituted or unsubstituted polycyclic aromatic hydrocarbon group or a substituted or unsubstituted polycyclic aromatic heterocyclic group.
D ¹ and D ² each independently represents a single bond or a divalent linking group.
G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group, and the hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, carbon The —CH ₂ — which may be substituted with a C 1-4 fluoroalkyl group, a C 1-4 alkoxy group, a cyano group or a nitro group, and which constitutes the alicyclic hydrocarbon group is —O—, -S- or -NH- may be substituted.
E ¹ and E ² each independently represents a single bond or a divalent linking group.
B ¹ and B ² each independently represent a single bond or a divalent linking group.
A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, and hydrogen contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group The atom may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. The hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a fluorine atom.
k and l each independently represents an integer of 0 to 3. When k is 2 or more, a plurality of A ¹ are the same or different from each other, and a plurality of B ¹ are the same or different from each other. When l is 2 or more, a plurality of A ² are the same or different from each other, and a plurality of B ² are the same or different from each other.
F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkanediyl group is substituted with an alkoxy group having 1 to 5 carbon atoms or a halogen atom. Alternatively, —CH ₂ — constituting the alkanediyl group may be replaced by —O— or —CO—.
P ¹ and P ² each independently represent a hydrogen atom, an acryloyloxy group or a methacryloyloxy group, but neither P ¹ nor P ² is a hydrogen atom. ]
[12] A compound represented by formula (1-3).

[In Formula (1-3),
n represents 0 or 1. v represents an integer of 1 to 3.
S ¹ represents a fluorine atom or a alkanediyl group having 1 to 12 carbon atoms which may have a cyano group.
X ¹ and X ³ each independently represents a single bond, an oxygen atom, a carbonyloxy group or a methylene group.
Y ¹ represents a single bond, an oxygen atom or a carbonyloxy group.
R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
R ² represents an alkoxy group having 1 to 2 carbon atoms, a cyano group, or a halogen atom. When v is 2 or 3, a plurality of R ² are the same or different.
R ⁵ represents a hydrogen atom or a methyl group. ]

  According to the photoreactive liquid crystal aligning agent of the present invention, it is possible to form a photo-alignment layer having an alignment ability in which a polymerizable liquid crystal compound becomes a polymerizable liquid crystal of a nematic phase and a higher order smectic phase.

式（１−１）中、
ｎ及びｍはそれぞれ独立に、０又は１を表す。
ｖ及びｗはそれぞれ独立に、１〜３の整数を表す。
Ｓ^１及びＳ^２はそれぞれ独立に、フッ素原子又はシアノ基を有していてもよい炭素数１〜１２のアルカンジイル基を表す。
Ｓ^３は、フッ素原子又はシアノ基を有していてもよい炭素数１〜１２のアルキル基を表す。
Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４及びＸ^５はそれぞれ独立に、単結合、酸素原子、カルボニルオキシ基又はメチレン基を表す。
Ｙ^１及びＹ^２はそれぞれ独立に、単結合、酸素原子又はカルボニルオキシ基を表す。
Ｒ^１及びＲ^３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。
Ｒ^２及びＲ^４はそれぞれ独立に、炭素数１〜２のアルコキシ基、シアノ基又はハロゲン原子を表し、ｖが２又は３の場合、複数存在するＲ^２は、同一又は相異なり、ｗが２又は３の場合、複数存在するＲ^４は、同一又は相異なる。
Ｒ^５、Ｒ^６及びＲ^７はそれぞれ独立に、水素原子又はメチル基を表す。
ｐ、ｑ及びｒは、全構造単位に対する各構造単位のモル分率を表し、０．２５＜ｐ≦１、０≦ｑ＜０．７５及び０≦ｒ＜０．７５の関係を満たす。 <Photoreactive liquid crystal aligning agent>
The photoreactive liquid crystal aligning agent of this invention is a photoreactive liquid crystal aligning agent containing the polymer (henceforth "polymer (1-1)" depending on the case) represented by Formula (1-1).

In formula (1-1),
n and m each independently represents 0 or 1.
v and w each independently represent an integer of 1 to 3.
S ¹ and S ² each independently represents a C 1-12 alkanediyl group which may have a fluorine atom or a cyano group.
S ³ represents a fluorine atom or an alkyl group having 1 to 12 carbon atoms which may have a cyano group.
X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a single bond, an oxygen atom, a carbonyloxy group or a methylene group.
Y ¹ and Y ² each independently represent a single bond, an oxygen atom or a carbonyloxy group.
R ¹ and R ³ 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.
R ² and R ⁴ each independently represents an alkoxy group having 1 to 2 carbon atoms, a cyano group or a halogen atom, and when v is 2 or 3, a plurality of R ² are the same or different and w is 2 Or, in the case of 3, a plurality of R ⁴ are the same or different.
R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom or a methyl group.
p, q, and r represent the mole fraction of each structural unit with respect to the total structural units, and satisfy the relationships of 0.25 <p ≦ 1, 0 ≦ q <0.75, and 0 ≦ r <0.75.

  In the formula (1-1), the dotted line connecting each structural unit is not particularly limited to the copolymerization mode of each structural unit. Random copolymerization, block copolymerization, alternating copolymerization, and combinations thereof It means that there is.

The alkanediyl group having 1 to 12 carbon atoms which may have a fluorine atom or a cyano group of S ¹ and S ² is an alkanediyl group or a part of hydrogen atoms contained in the alkanediyl group is fluorine. It means a group substituted by an atom and / or a cyano group. Such alkanediyl groups may be linear or branched. S ¹ and S ² are preferably unsubstituted (having no fluorine atom or cyano group) and a linear alkanediyl group having 1 to 12 carbon atoms, more preferably an alkanediyl group having 2 to 11 carbon atoms. Preferred are ethanediyl group, butanediyl group, hexanediyl group and undecanediyl group.

The C 1-12 alkyl group optionally having a fluorine atom or a cyano group of S ³ is an alkyl group or a part of hydrogen atoms contained in the alkyl group is a fluorine atom and / or a cyano group. Means a group substituted by Such an alkyl group may be linear or branched. S ³ is preferably an unsubstituted group (having no fluorine atom or cyano group) and a linear alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, Octyl, decyl, undecyl and dodecyl groups are more preferred.

X ¹ , X ² , X ³ , X ⁴ and X ⁵ are each independently preferably a single bond or a carbonyloxy group, particularly preferably a carbonyloxy group.

Y ¹ and Y ² are each independently preferably an oxygen atom or a carbonyloxy group, and particularly preferably an oxygen atom.

R ¹ and R ³ are each independently more preferably a hydrogen atom, a methyl group or a methoxy group, and particularly preferably a hydrogen atom.

R ² and R ⁴ are each independently preferably a methoxy group, an ethoxy group, a cyano group or a fluorine atom, more preferably a methoxy group or an ethoxy group, and particularly preferably a methoxy group.

R ⁵ , R ⁶ and R ⁷ are particularly preferably methyl groups.

  n and m are preferably 0, and v and w are each independently preferably 1 or 2.

Each of p, q and r represents the mole fraction of each structural unit with respect to all the structural units of the polymer (1-1) as described above.
q preferably satisfies the relationship 0 ≦ q <0.25, and particularly preferably q = 0.
r preferably satisfies the relationship 0 ≦ r <0.25, and particularly preferably r = 0.

（式中の全ての符号はいずれも、前記と同義である。） p preferably satisfies the relationship of 0.75 <p ≦ 1, and p = 1 is particularly preferable because the photo-alignment layer formed has excellent solvent resistance. The polymer (1-1) satisfying the relationship of q = 0, r = 0 and p = 1 is substantially composed of a structural unit represented by the formula (1-2).

(All symbols in the formula are as defined above.)

（式中の全ての符号はいずれも、前記と同義である。） Here, the manufacturing method of the polymer (1-1) which consists of a structural unit substantially represented by Formula (1-2) is demonstrated. This polymer (1-1) can be produced by polymerizing a monomer represented by the formula (1-3) (hereinafter sometimes referred to as “monomer (1-3)”).

(All symbols in the formula are as defined above.)

  The monomer (1-3) is a novel and useful compound for the production of the polymer (1-1), and the present invention includes the invention according to the monomer (1-3).

Specific examples of the monomer (1-3) include compounds represented by the formula (M1-1-1) to the formula (M1-1-12).

この反応式において、Ｘは塩素原子及び臭素原子といったハロゲン原子を表し、その他の符号はいずれも前記と同義である。式（１−３Ｃ）で表される化合物は、所望のＳ^１、Ｒ^１、Ｒ^２及びＸ^３などに応じ、公知の製造方法により製造すればよい。式（１−３Ｂ）で表される化合物は例えば、（メタ）アクリル酸クロリド及び（メタ）アクリル酸ブロミドなどであり、これらは市場から容易に入手できる。
この反応は通常、溶媒中で実施される。かかる溶媒としては、この反応に対し不活性であり、式（１−３Ｂ）で表される化合物、及び式（１−３Ｃ）で表される化合物に対し、十分に溶解性を有するものであればよく、例えば、クロロホルム、ジクロロメタン、トルエン、キシレン、テトラヒドロフラン及びジメチルアセトアミドなどが用いられる。
また、この反応は、アルカリなどの脱酸剤の存在下に実施されることが好ましい。このアルカリとしては例えば、トリエチルアミン、ジイソプロピルエチルアミン、ピリジン及びジメチルアミノピリジンなどである。 One embodiment of a method for producing a monomer (1-3) is a monomer (1-3) in which X ¹ is a carbonyloxy group and Y ¹ is an oxygen atom [monomer represented by formula (1-3A) ( 1-3)] will be described as an example. This monomer (1-3) can be produced by reacting a compound represented by the formula (1-3B) with a compound represented by the formula (1-3C). Such a reaction is shown in the form of a reaction formula as follows.

In this reaction formula, X represents a halogen atom such as a chlorine atom and a bromine atom, and other symbols are as defined above. The compound represented by the formula (1-3C) may be produced by a known production method according to desired S ¹ , R ¹ , R ^2, X ³ and the like. Examples of the compound represented by the formula (1-3B) include (meth) acrylic acid chloride and (meth) acrylic acid bromide, which can be easily obtained from the market.
This reaction is usually carried out in a solvent. Such a solvent is inert to this reaction and has sufficient solubility with respect to the compound represented by the formula (1-3B) and the compound represented by the formula (1-3C). For example, chloroform, dichloromethane, toluene, xylene, tetrahydrofuran, dimethylacetamide and the like are used.
Further, this reaction is preferably carried out in the presence of a deoxidizing agent such as an alkali. Examples of the alkali include triethylamine, diisopropylethylamine, pyridine and dimethylaminopyridine.

Next, a method for producing the polymer (1-1) by polymerizing the monomer (1-3) will be described.
The polymerization for producing the polymer (1-1) from the monomer (1-3) employs an addition polymerization such as anionic polymerization or radical polymerization. The embodiment of radical polymerization may be any of solution polymerization, bulk polymerization, emulsion polymerization, and soap-free emulsion polymerization. However, solution polymerization is preferable in consideration of the stability and melting point of the monomer (1-3).

  As a polymerization solvent for solution polymerization, it is desirable to use a solvent that does not deactivate radical activity, such as benzene, dichloromethane, tetrahydrofuran, and diethyl ether. Among these, tetrahydrofuran is particularly preferable as a polymerization solvent from the viewpoint of solubility of the monomer (1-3).

  The polymerization temperature can be appropriately adjusted from the range of -20 ° C to 200 ° C depending on the type and amount of the polymerization initiator used, the stability of the monomer (1-3), etc., but the range of 20 ° C to 120 ° C is more. Preferably, the range of 30 ° C to 100 ° C is more preferable, and the range of 50 ° C to 75 ° C is particularly preferable.

  As the polymerization initiator, a thermal initiator such as a peroxide and an azo compound may be used, or a photoinitiator described later may be used. Thermal initiators are generally classified into low-temperature initiators, medium-temperature initiators, and high-temperature initiators depending on the radical generation temperature. For polymerization of the monomer (1-3), any of these initiators or a combination of these initiators can be used, but a polymer (1-1) having a high degree of polymerization is easily obtained. The intermediate temperature initiator is more preferable because side reactions hardly occur, and an azo compound is more preferable. Among these azo compounds, azobisisobutyronitrile (AIBN) is particularly preferable because it is easily available.

  By using the above azo compound as a polymerization initiator, a polymer (1-1) having a high degree of polymerization can be produced, but a polymer (1-1) having a desired molecular weight is produced, that is, the polymer (1 In order to control the molecular weight of -1), atom transfer radical polymerization may be employed by appropriately using a chain transfer agent.

  After the polymerization, reprecipitation purification is preferably performed in order to remove unreacted monomers and the like. Examples of the solvent used for reprecipitation purification include water, alcohol solvents, ether solvents, saturated hydrocarbon solvents, aromatic hydrocarbon solvents, or mixed solvents thereof. The type of polymerization solvent used for the polymerization, monomer (1 A suitable solvent can be appropriately selected according to the type of -3).

  Examples of the alcohol solvent include methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether, and methanol, ethanol, and isopropyl alcohol are more preferable. Examples of the ether solvent include tetrahydrofuran and dimethoxyethane, and tetrahydrofuran is more preferable. Examples of the saturated hydrocarbon solvent include n-pentane, n-heptane and cyclohexane, and n-heptane is more preferable. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene and chlorobenzene, with toluene and xylene being preferred. Such a solvent can be appropriately selected depending on its safety, etc., but methanol, ethanol, isopropyl alcohol, toluene, toluene / heptane mixed solvent, water / methanol mixed solvent, water / ethanol mixed solvent and water / ethanol mixed solvent A tetrahydrofuran mixed solvent is more preferable, and methanol, ethanol and isopropyl alcohol are particularly preferable.

The molecular weight of the polymer (1-1) 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, and it becomes difficult to prepare the photoreactive liquid crystal aligning agent of the present invention, and the sensitivity to light irradiation tends to decrease. The range of 1 × 10 ⁴ to 1 × 10 ⁶ is preferable. The analysis conditions for the GPC method for obtaining the molecular weight will be described in the examples of the present application.

（式中の全ての符号はいずれも前記と同義である。） The polymer (1-1) can be produced by the polymerization of the monomer (1-3) described above. In the polymerization of the monomer (1-3), the copolymer polymer (1-1) can be produced by using the following monomers together. However, when the following monomers are used, the amount of each of the structural units of the polymer (1-1) satisfying the above relationship so that the amount of each of the monomers (1-3) and the monomers shown below is used. It needs to be adjusted.

(All symbols in the formula are as defined above.)

<Photoreactive liquid crystal aligning agent>
The photoreactive liquid crystal aligning agent of the present invention (hereinafter sometimes referred to as “the present liquid crystal aligning agent”) contains the polymer (1-1), and more preferably, light is formed by a photo alignment layer forming method described later. In order to form an alignment layer, the polymer (1-1) and a solvent are included. In order to prepare such a liquid crystal aligning agent, first, the polymer (1-1) is dissolved in a solvent. Such a solvent can be appropriately selected as long as the polymer (1-1) can be dissolved and the liquid crystal aligning agent having an appropriate viscosity can be obtained. For example, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, Alcohol solvents such as 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; acetone, methyl ethyl ketone Ketone solvents such as cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone; pentane, hexane, heptane, etc. Aliphatic hydrocarbon solvents; 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, N, N- Examples include amide solvents such as dimethylformamide, γ-butyrolactone, and dimethylacetamide. These solvents may be used alone or in combination of two or more.

  Although the density | concentration of the polymer (1-1) with respect to this liquid crystal aligning agent can also be adjusted suitably according to the kind and solubility of the said polymer (1-1), when expressed with solid content concentration, it is at least 0.2 mass%. The range of 0.3 to 10% by mass is particularly preferable. The liquid crystal aligning agent may contain a polymer material such as polyvinyl alcohol or polyimide, or a photosensitizer such as anthracene.

  The present liquid crystal aligning agent prepared by dissolving the polymer (1-1) in a solvent is used for forming a photo-alignment layer as it is or after being filtered as necessary.

<Photo alignment layer formation method>
A method for forming a photo-alignment layer (photo-alignment layer forming method) using the present liquid crystal aligning agent containing polymer (1-1) and a solvent will be described. First, this liquid crystal aligning agent is apply | coated on a predetermined | prescribed support base material. Such a supporting substrate is preferably a transparent supporting substrate. Examples of methods for applying the liquid crystal aligning agent on the transparent support substrate include spin coating methods, extrusion methods, gravure coating methods, die coating methods, bar coating methods, applicator methods, and flexo methods. A known method such as this printing method is employed.

  Next, the solvent is removed from the coating film formed by coating the liquid crystal aligning agent on the transparent support substrate to form a dry film. This solvent can be removed by heating at an appropriate temperature to remove the solvent by drying (heating method), or after sealing in an appropriate pressure-resistant container and then reducing the pressure in the container to reduce the solvent. It can be carried out by a method of drying and removing (pressure reduction method), ventilation drying (aeration method), natural drying, or a combination of these methods. The heating method is more preferable because it can be carried out in a continuous form of Roll to Roll.

The thickness of the dry film containing the polymer (1-1) formed on the transparent support substrate is, for example, in the range of 1 nm to 10000 nm, and preferably in the range of 10 nm to 1000 nm.
The thickness of the dry film can be controlled by adjusting the solid content concentration of the liquid crystal aligning agent (particularly, the solid content concentration of the polymer (1-1)) and the application conditions of the liquid crystal aligning agent to the transparent substrate. Thus, a laminate in which a dry film containing the polymer (1-1) is provided on the transparent support substrate is obtained.

  Subsequently, the polymer (1-1) is aligned by irradiating the dried coating film of the laminate with polarized UV (polarized ultraviolet light), thereby imparting liquid crystal alignment ability (hereinafter referred to as “photo-alignment operation” in some cases). Thus, a photo-alignment layer is formed. In the photo-alignment operation, in order to irradiate the laminated body with polarized UV, the transparent substrate side of the laminated body can be used even in the form of irradiating polarized UV directly from the dry film side of the laminated body (form (A)). The type (form (B)) which irradiates polarized UV to a dry film by irradiating polarized UV to this, and making polarized UV permeate | transmit through this transparent base material may be sufficient. 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 higher the transparency of the transparent substrate in the laminate to be used, the better.

  The polarized UV to be irradiated preferably has a wavelength region in which the photoreactive group (cinnamoyl group) of the polymer (1-1) contained in the dry film can absorb light energy. Specifically, 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. The light source used for the photo-alignment operation is more preferably a high-pressure mercury lamp or an ultra-high 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. When light from the light source passes through a suitable polarizer and is irradiated to the laminate, the laminate is irradiated with polarized UV light. As such a polarizer, a polarizing prism such as a polarizing filter, Glan-Thompson, or Granteller, or a wire grid type polarizer can be used.

  In irradiating polarized UV to the dry film of the laminate, it is not always necessary that the irradiation direction of polarized UV is substantially perpendicular to the surface direction of the laminate. The irradiation direction of the polarized UV may be oblique. The irradiation direction of polarized UV with respect to the plane direction of the laminate is determined so that the obtained photo-alignment layer has a desired absorption axis according to the type of light source and polarizer used in the photo-alignment operation.

  The photo-alignment layer formed from the present liquid crystal aligning agent by the above-described method or the like is applied to the photo-alignment layer with a composition containing a polymerizable liquid crystal compound, and the polymerizable liquid crystal compound is applied to the nematic phase or higher. The liquid crystal state of the following smectic phase (polymerizable liquid crystal) can be obtained. The photo-alignment layer obtained from the present liquid crystal aligning agent is a very useful liquid crystal aligning agent that can form a photo-alignment layer in such a liquid crystal state (polymerizable liquid crystal) with a polymerizable liquid crystal compound. The knowledge is unique to the inventors.

When a polymerizable smectic liquid crystal compound capable of forming a smectic liquid crystal state is used as the polymerizable liquid crystal compound, the polymerizable smectic liquid crystal compound mainly has a polarizing layer on the photo-alignment film by combining dichroic dyes. A liquid crystal alignment element formed can be obtained. Further, when a polymerizable nematic liquid crystal compound capable of forming a nematic liquid crystal state is used as the polymerizable liquid crystal compound, a liquid crystal alignment element formed by forming a retardation layer on the photo-alignment film can be obtained. Thus, when providing a polarizing layer or a phase difference layer on a photo-alignment layer, what is necessary is just to apply | coat and dry the solution containing a polymeric liquid crystal compound, and to photopolymerize. Hereinafter, these methods will be described separately for the case of using a polymerizable smectic liquid crystal compound and the case of using a polymerizable nematic liquid crystal compound. In this description, a solution containing a polymerizable smectic liquid crystal compound is referred to as a “polarizing layer forming composition”, and a solution containing a polymerizable nematic liquid crystal compound is referred to as a “retardation layer forming composition”.

<Liquid crystal alignment element using polymerizable smectic liquid crystal compound>
The polymerizable smectic liquid crystal compound is a compound having a polymerizable group and exhibiting a smectic liquid crystal phase. The polymerizable group means a group involved in the polymerization reaction of the polymerizable smectic liquid crystal compound.

  The liquid crystal phase 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. If the smectic liquid crystal phase exhibited by the polymerizable smectic liquid crystal compound is higher order, a polarizing layer with a higher degree of alignment order can be formed, and a polarizing layer with higher performance can be obtained.

As a preferable polymerizable smectic liquid crystal composition, for example, a compound represented by the formula (3-1) (hereinafter sometimes referred to as “compound (3-1)”) may be mentioned.

^{U 1 -V 1 -W 1 -E 1} -J 1 -E 2 -J 2 -E 3 -W 2 -V 2 -U 2 (3-1) [ in the formula (3-1),
E ¹ , E ² and E ³ 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 E ¹ , E ² and E ³ is a p-phenylene group which may have a substituent.
J ¹ and ^{J 2} are 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 (3-1), as described above, at least one of E ¹ , E ² and E ³ is a 1,4-phenylene group which may have a substituent. It is preferable that at least two are p-phenylene groups 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 more preferably unsubstituted.

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. Note that —CH ₂ — constituting the cyclohexane-1,4-diyl group may be replaced by —O—, —S—, or —NR ⁷ —. R ⁷ is an alkyl group having 1 to 6 carbon atoms or a phenyl group.

J ¹ of the compound (3-1) is preferably —CH ₂ CH ₂ —, —COO— or a single bond, and J ² 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 (3-1), 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 the compound (3-1) include compounds represented by any one of the formulas (3-1-1) to (3-1-24). When a specific example of the compound (3-1) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably a trans isomer.

  The exemplified compound (3-1) is hereinafter referred to as “compound (3-1-1)” or the like depending on the formula number.

  The exemplified compound (3-1) can be used alone or as a polymerizable smectic liquid crystal mixture in which two or more kinds are mixed. Further, two or more polymerizable smectic compounds may be used, and at least one of the two or more polymerizable smectic compounds may be a compound (3-1). 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 (3-1) is used in the composition for forming a polarizing layer, the phase transition temperature of the compound (3-1) is obtained in advance, and the compound (3-1) is obtained under a temperature condition lower than the phase transition temperature. Components other than the compound (3-1) [polymerizable smectic liquid crystal compound] of the composition for forming a polarizing layer are adjusted so as to allow polymerization. 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 the compound (3-1) can be controlled by appropriately adjusting these types and amounts. In addition, also when using the mixture of 2 or more types of compounds (3-1) [polymerizable smectic liquid crystal composition], ie, a polymerizable smectic liquid crystal composition, for the composition for forming a polarizing layer, the polymerizable smectic liquid crystal. After obtaining the phase transition temperature of the composition, the polymerization temperature is controlled in the same manner as in the case of the polymerizable smectic liquid crystal compound.

  Among the exemplified compounds (3-1), formula (3-1-3), formula (3-1-6), formula (3-1-7), formula (3-1-12), formula (3) The compound represented by any of (1-1-13) and formula (3-1-23) is preferred. These compounds (3-1) can be mixed or interacted with the photopolymerization initiator used together so that they can be easily converted into a liquid crystal having a higher order smectic phase under temperature conditions lower than the phase transition temperature. Since a supercooled state can be obtained while maintaining the state sufficiently, the compound (3-1) can be polymerized. More specifically, due to the interaction with the photopolymerization initiator, these compounds (3-1) have a liquid crystal state of a high-order smectic phase under a temperature condition of 70 ° C. or less, preferably 60 ° C. or less. Polymerization can be carried out with sufficient retention.

  As described above, the compound (3-1) may be a single species or a plurality of types, but is preferably a plurality of types. That is, it is preferable to use 2 or more types of polymerizable smectic liquid crystal compositions, and preferably 2 or more types of compounds (3-1) in the composition for forming a polarizing layer.

  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 (3-1) in the said composition for polarizing layer formation, 90-99.9 mass%. Is more preferable. If the content rate of a compound (3-1) is in the said range, there exists a tendency for the orientation of a compound (3-1) to become high. Here, solid content means the total amount of the component remove | excluding volatile components, such as a solvent, from the said composition for polarizing layer formation. In addition, when multiple types of compound (3-1) is contained in this composition for polarizing layer formation, the total content rate should just be the 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 liquid crystal composition and flattening a coating film obtained by coating the polarizing layer forming composition. Can be mentioned. 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 thereof is preferably 0.3 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the polymerizable smectic liquid crystal compound, and 0.5 parts by mass. More preferred is 3 parts by mass or less. 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 formed 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 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. Such a solvent is the same as that exemplified as the solvent for preparing the present liquid crystal aligning agent composition. Solvents for preparing the composition for forming a polarizing layer may be used alone or in combination of two or more.

  As for content of the solvent in the said composition for polarizing layer formation, 50-98 mass% is preferable with respect to the total amount of this composition for polarizing layer formation. On the other hand, when the solid content of the composition for forming a polarizing layer is 50% by mass or less, the viscosity of the composition becomes low, so that the thickness of the coating film becomes substantially uniform. The solid content can be determined so that the polarizing layer has a desired thickness.

  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 maintains a liquid crystal state of a higher order smectic phase. Polymerization can be performed as is.

  Moreover, when the said composition for polarizing layer formation contains a photoinitiator, this composition may contain the 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 polarizing layer forming composition contains a photopolymerization initiator and a photosensitizer, the polymerization reaction of the polymerizable smectic liquid crystal compound contained in the polarizing layer forming composition may be further promoted. it can. 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 the polymerization reaction of the polymerizable smectic liquid crystal compound can be promoted by including a photosensitizer in the composition for forming a polarizing layer. However, in order to make the polymerization reaction proceed stably, the polarizing layer 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 a liquid crystal state of a high-order smectic phase in good condition.

  The polarizing layer forming composition described above is applied onto the photo-alignment layer of the laminate (first laminate) provided with the transparent support substrate and the photo-alignment layer to obtain a coating film. By drying under the condition that the polymerizable smectic liquid crystal compound contained is not polymerized, a dry film for forming a polarizing layer is formed, and a second laminate is obtained.

  The method for applying the composition for forming a polarizing layer to the first laminate (application method) and the drying method are the same as those described as the method for applying the liquid crystal aligning agent on the transparent support substrate. . The thickness of the coating film 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. The thickness of the coating film is determined so that the obtained polarizing layer has a desired thickness. The thickness of the polarizing layer is obtained by measurement with an interference film thickness meter, a laser microscope or a stylus thickness meter.

Furthermore, by performing photopolymerization on the polymerizable smectic liquid crystal compound contained in the dried film (dried film for forming the polarizing layer) of the second laminate, the polymerizable smectic liquid crystal compound has a smectic phase, preferably Polymerization is performed while maintaining the liquid crystal state of the higher-order smectic phase as exemplified above, and as a result, the dry film is converted into a polarizing layer.

<Liquid crystal alignment element using polymerizable nematic liquid crystal compound>
Next, a method for forming a retardation layer on a photo-alignment film formed from the present liquid crystal aligning agent using a retardation layer forming composition (a solution containing a polymerizable nematic liquid crystal compound) will be described.

  Examples of the polymerizable nematic liquid crystal compound contained in the composition for forming a retardation layer include a compound represented by the formula (20) (hereinafter sometimes referred to as “compound (20)”).

^{P 11 -E 11 - (B 11} -A 11) t -B 12 -G (20)
[In the formula (20),
A ¹¹ represents a divalent aromatic hydrocarbon group, a divalent alicyclic hydrocarbon group or a divalent heterocyclic group, the divalent aromatic hydrocarbon group, the divalent alicyclic carbonization. The hydrogen atom contained in the hydrogen group and the divalent heterocyclic group is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, It may be substituted with an N, N-dialkylamino group having 2 to 12 carbon atoms, a nitro group, a cyano group or a sulfanyl group.
B ¹¹ and ^{B 12} are each ^{independently, -CR 14 R 15 -, -} C≡C -, - CH = CH -, - CH 2 -CH 2 -, - O -, - S -, - C (= O)-, -C (= O) -O-, -O-C (= O)-, -O-C (= O) -O-, -C (= S)-, -C (= S). -O-, -OC (= S)-, -CH = N-, -N = CH-, -N = N-, -C (= O) -NR < ¹⁶ >-, -NR < ¹⁶ > -C (= O) —, —OCH ₂ —, —OCF ₂ —, —NR ¹⁶ —, —CH ₂ O—, —CF ₂ O—, —CH═CH—C (═O) —O—, —O—C ( = O) -CH = CH- or a single bond. R ¹⁴ and R ¹⁵ each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁴ and R ¹⁵ are connected to form an alkanediyl group having 4 to 7 carbon atoms. Also good. R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
E ¹¹ represents an alkanediyl group having 1 to 12 carbon atoms. The hydrogen atom contained in the alkanediyl group may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.
P ¹¹ represents a polymerizable group.
G is a hydrogen atom, a halogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a fluoroalkyl group having 1 to 13 carbon atoms, an N-alkylamino group having 1 to 13 carbon atoms, carbon A hydrogen atom contained in the alkanediyl group, which is a N, N-dialkylamino group having 2 to 26, a cyano group, or a nitro group, or a polymerizable group bonded via an alkanediyl group having 1 to 12 carbon atoms. The atom may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.
t represents an integer of 1 to 5. When t is an integer of 2 or more, the plurality of A ¹¹ are the same or different from each other, and the plurality of B ¹¹ are the same or different from each other. ]

As the polymerizable group in P ¹¹ and G, vinyl group, vinyloxy group, styryl group, p- (2-phenylethenyl) phenyl group, acryloyl group, acryloyloxy group, methacryloyl group, methacryloyloxy group, carboxy group, acetyl group Group, hydroxy group, carbamoyl group, amino group, N-alkylamino group having 1 to 4 carbon atoms, epoxy group, oxetanyl group, formyl group, -N = C = O and N = C = S. Among them, a radically polymerizable group or a cationically polymerizable group is preferable in terms of high photopolymerization reactivity, an acryloyloxy group, a methacryloyloxy group, or a group that is easy to handle and easy to produce a liquid crystal compound. A vinyloxy group is more preferable.

Moreover, divalent aromatic hydrocarbon group A ^11, respectively divalent carbon atoms in the alicyclic hydrocarbon group and a divalent heterocyclic group, for example in the range of 3 to 18, 5 to 12 range Is preferable, and 5 or 6 is particularly preferable.

  Examples of the compound (20) include a compound represented by the formula (20-1) and a compound represented by the formula (20-2).

^{P 11 -E 11 - (B 11} -A 11) t1 -B 12 -E 12 -P 12 (20-1)
^{P 11 -E 11 - (B 11} -A 11) t2 -B 12 -F 11 (20-2)
[In Formula (20-1) and Formula (20-2),
P ¹¹ , E ¹¹ , B ¹¹ , A ¹¹ and B ¹² are as defined above.
F ¹¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a fluoroalkyl group having 1 to 13 carbon atoms, an N-alkylamino group having 1 to 13 carbon atoms, An N, N-dialkylamino group, a cyano group or a nitro group having 2 to 26 carbon atoms is represented.
E ¹² represents an alkanediyl group having 1 to 12 carbon atoms, and the alkanediyl group may have an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.
P ¹² represents a polymerizable group.
t ¹ and t ² each independently represents an integer of 1 to 5. ]

Further, the compounds represented by the formulas (20-1) and (20-2) are represented by the formula (I), the formula (II), the formula (III), the formula (IV), or the formula (V). Compounds.
P ¹¹ -E ¹¹ -B ¹¹ -A ¹¹ -B ¹² -A ¹² -B ¹³ -A ¹³ -B ¹⁴ -A ¹⁴ -B ¹⁵ -A ¹⁵ -B ¹⁶ -E ¹² -P ¹² (I)
P ¹¹ -E ¹¹ -B ¹¹ -A ¹¹ -B ¹² -A ¹² -B ¹³ -A ¹³ -B ¹⁴ -A ¹⁴ -B ¹⁵ -E ¹² -P ¹² (II)
P ¹¹ -E ¹¹ -B ¹¹ -A ¹¹ -B ¹² -A ¹² -B ¹³ -A ¹³ -B ¹⁴ -E ¹² -P ¹² (III)
P ¹¹ -E ¹¹ -B ¹¹ -A ¹¹ -B ¹² -A ¹² -B ¹³ -A ¹³ -B ¹⁴ -F ¹¹ (IV)
P ¹¹ -E ¹¹ -B ¹¹ -A ¹¹ -B ¹² -A ¹² -B ¹³ -F ¹¹ (V)
[In Formula (I)-Formula (V),
A ^{12 to} A ¹⁵ are synonymous with A ¹¹ , and B ^{13 to} B ¹⁶ are synonymous with B ¹¹ . ]

In the compounds represented by formula (20-1), formula (20-2), formula (I), formula (II), formula (III), formula (IV), and formula (V), P ¹¹ and E ¹¹ is preferably bonded via an ether bond or an ester bond, and P ¹² and E ¹² are preferably bonded via an ether bond or an ester bond.

  Specific examples of the polymerizable nematic liquid crystal compound include compounds represented by formulas (I-1) to (I-5), formulas (B1) to (B20), and formulas (C1) to (C4). Compound represented by Formula (I); Compound represented by Formula (II) such as compounds represented by Formula (II-1) to Formula (II-6); Formula (III-1) to Formula (III-19) A compound represented by formula (III) such as a compound represented by formula (IV); a compound represented by formula (IV) such as a compound represented by formula (IV-1) to formula (IV-14); Examples thereof include compounds represented by formula (V) such as compounds represented by formula (V-5). In the formula, k represents an integer of 1 to 11, and * represents a bond. These polymerizable nematic liquid crystal compounds are preferable because they can be produced relatively easily or are easily available from the market.

（式（Ｂ１）中の２つの＊は、（Ｂ１−１）〜（Ｂ１−８）のいずれかの＊と結合している。）

(Two * in the formula (B1) are bonded to any one of (B1-1) to (B1-8).)

（式（Ｂ２）中の２つの＊は、（Ｂ２−１）〜（Ｂ２−８）のいずれかの＊と結合している。）

(Two * in the formula (B2) are bonded to any one of (B2-1) to (B2-8).)

（式（Ｂ３）中の２つの＊は、（Ｂ３−１）〜（Ｂ３−８）のいずれかの＊と結合している。）

(Two * in the formula (B3) are bonded to any one of (B3-1) to (B3-8).)

（式（Ｂ４）中の２つの＊は、（Ｂ４−１）〜（Ｂ４−８）のいずれかの＊と結合している。）

(Two * in the formula (B4) are bonded to any one of (B4-1) to (B4-8).)

（式（Ｂ５）中の２つの＊は、（Ｂ５−１）〜（Ｂ５−８）のいずれかの＊と結合している。）

(Two * in the formula (B5) are bonded to any one of (B5-1) to (B5-8).)

（式（Ｂ６）中の２つの＊は、（Ｂ６−１）〜（Ｂ６−８）のいずれかの＊と結合している。）

(Two * in the formula (B6) are bonded to any one of (B6-1) to (B6-8).)

（式（Ｂ７）中の２つの＊は、（Ｂ７−１）〜（Ｂ７−８）のいずれかの＊と結合している。）

(Two * in the formula (B7) are bonded to any one of (B7-1) to (B7-8).)

（式（Ｂ８）中の２つの＊は、（Ｂ８−１）〜（Ｂ８−８）のいずれかの＊と結合している。）

(Two * in the formula (B8) are bonded to any one of (B8-1) to (B8-8).)

（式（Ｂ９）中の２つの＊は、（Ｂ９−１）〜（Ｂ９−８）のいずれかの＊と結合している。）

(Two * s in the formula (B9) are bonded to any one of (B9-1) to (B9-8).)

（式（Ｂ１０）中の２つの＊は、（Ｂ１０−１）〜（Ｂ１０−８）のいずれかの＊と結合している。）

(Two * s in the formula (B10) are bonded to any one of (B10-1) to (B10-8).)

（式（Ｂ１１）中の２つの＊は、（Ｂ１１−１）〜（Ｂ１１−８）のいずれかの＊と結合している。）

(Two * in the formula (B11) are bonded to any one of (B11-1) to (B11-8).)

（式（Ｂ１２）中の２つの＊は、（Ｂ１２−１）〜（Ｂ１２−８）のいずれかの＊と結合している。）

(Two * in the formula (B12) are bonded to any one of (B12-1) to (B12-8).)

（式（Ｂ１３）中の２つの＊は、（Ｂ１３−１）〜（Ｂ１３−８）のいずれかの＊と結合している。）

(Two * in the formula (B13) are bonded to any one of (B13-1) to (B13-8).)

（式（Ｂ１４）中の２つの＊は、（Ｂ１４−１）〜（Ｂ１４−８）のいずれかの＊と結合している。）

(Two * in the formula (B14) are bonded to any one of (B14-1) to (B14-8).)

（式（Ｂ１５）中の２つの＊は、（Ｂ１５−１）〜（Ｂ１５−８）のいずれかの＊と結合している。）

(Two * in the formula (B15) are bonded to any one of (B15-1) to (B15-8).)

（式（Ｂ１６）中の２つの＊は、（Ｂ１６−１）〜（Ｂ１６−８）のいずれかの＊と結合している。）

(Two * in the formula (B16) are bonded to any one of (B16-1) to (B16-8).)

（式（Ｂ１７）中の２つの＊は、（Ｂ１７−１）〜（Ｂ１７−８）のいずれかの＊と結合している。）

(Two * in the formula (B17) are bonded to any one of (B17-1) to (B17-8).)

（式（Ｂ１８）中の２つの＊は、（Ｂ１８−１）〜（Ｂ１８−８）のいずれかの＊と結合している。）

(Two * in the formula (B18) are bonded to any one of (B18-1) to (B18-8).)

（式（Ｂ１９）中の２つの＊は、（Ｂ１９−１）〜（Ｂ１９−８）のいずれかの＊と結合している。）

(Two * s in the formula (B19) are bonded to any one of (B19-1) to (B19-8).)

（式（Ｂ２０）中の２つの＊は、（Ｂ２０−１）〜（Ｂ２０−８）のいずれかの＊と結合している。）

(Two * in the formula (B20) are bonded to any one of (B20-1) to (B20-8).)

（式（Ｃ１）中の２つの＊は、（Ｃ１−１）〜（Ｃ１−８）のいずれかの＊と結合している。）

(Two * in the formula (C1) are bonded to any one of (C1-1) to (C1-8).)

（式（Ｃ２）中の２つの＊は、（Ｃ２−１）〜（Ｃ２−８）のいずれかの＊と結合している。）

(Two * in the formula (C2) are bonded to any one of (C2-1) to (C2-8).)

（式（Ｃ３）中の２つの＊は、（Ｃ３−１）〜（Ｃ３−８）のいずれかの＊と結合している。）

(Two * in the formula (C3) are bonded to any one of (C3-1) to (C3-8).)

（式（Ｃ４）中の２つの＊は、（Ｃ４−１）〜（Ｃ４−８）のいずれかの＊と結合している。）

(Two * s in formula (C4) are bonded to any one of (C4-1) to (C4-8)).

［式（２）中、
Ｑ^１は、置換もしくは非置換の多環式芳香族炭化水素基又は置換もしくは非置換の多環式芳香族複素環基を表す。
Ｄ^１及びＤ^２は、それぞれ独立に、単結合又は２価の連結基を表す。
Ｇ^１及びＧ^２は、それぞれ独立に、２価の脂環式炭化水素基を表し、該脂環式炭化水素基に含まれる水素原子は、ハロゲン原子、炭素数１〜４のアルキル基、炭素数１〜４のフルオロアルキル基、炭素数１〜４アルコキシ基、シアノ基又はニトロ基で置換されていてもよく、該脂環式炭化水素基を構成する−ＣＨ_２−は、−Ｏ−、−Ｓ−又は−ＮＨ−に置き換わっていてもよい。
Ｅ^１及びＥ^２は、それぞれ独立に、単結合又は２価の連結基を表す。
Ｂ^１及びＢ^２は、それぞれ独立に、単結合又は２価の連結基を表す。
Ａ^１及びＡ^２は、それぞれ独立に、２価の脂環式炭化水素基又は２価の芳香族炭化水素基を表し、該脂環式炭化水素基及び該芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、炭素数１〜４のアルキル基、炭素数１〜４アルコキシ基、シアノ基又はニトロ基で置換されていてもよい。該炭素数１〜４のアルキル基及び該炭素数１〜４アルコキシ基に含まれる水素原子は、フッ素原子で置換されていてもよい。
ｋ及びｌは、それぞれ独立に、０〜３の整数を表す。ｋが２以上の場合、複数存在するＡ^１は、互いに同一又は相異なり、複数存在するＢ^１は、互いに同一又は相異なる。ｌが２以上の場合、複数存在するＡ^２は、互いに同一又は相異なり、複数存在するＢ^２は、互いに同一又は相異なる。
Ｆ^１及びＦ^２は、それぞれ独立に、炭素数１〜１２のアルカンジイル基を表し、該アルカンジイル基に含まれる水素原子は、炭素数１〜５のアルコキシ基又はハロゲン原子で置換されていてもよく、該アルカンジイル基を構成する−ＣＨ_２−は、−Ｏ−又は−ＣＯ−に置き換わっていてもよい。
Ｐ^１及びＰ^２は、それぞれ独立に、水素原子、アクリロイルオキシ基又はメタクリロイルオキシ基を表すが、Ｐ^１及びＰ^２がともに水素原子であることはない。］ Similarly to the compound (20), a polymerizable nematic liquid crystal compound represented by the formula (2) (hereinafter, sometimes referred to as “compound (2)”) is also used as a composition for forming a retardation layer. Thus, a retardation layer can be formed on the photo-alignment layer.

[In Formula (2),
Q ¹ represents a substituted or unsubstituted polycyclic aromatic hydrocarbon group or a substituted or unsubstituted polycyclic aromatic heterocyclic group.
D ¹ and D ² each independently represents a single bond or a divalent linking group.
G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group, and the hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, carbon The —CH ₂ — which may be substituted with a C 1-4 fluoroalkyl group, a C 1-4 alkoxy group, a cyano group or a nitro group, and which constitutes the alicyclic hydrocarbon group is —O—, -S- or -NH- may be substituted.
E ¹ and E ² each independently represents a single bond or a divalent linking group.
B ¹ and B ² each independently represent a single bond or a divalent linking group.
A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, and hydrogen contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group The atom may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. The hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a fluorine atom.
k and l each independently represents an integer of 0 to 3. When k is 2 or more, a plurality of A ¹ are the same or different from each other, and a plurality of B ¹ are the same or different from each other. When l is 2 or more, a plurality of A ² are the same or different from each other, and a plurality of B ² are the same or different from each other.
F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkanediyl group is substituted with an alkoxy group having 1 to 5 carbon atoms or a halogen atom. Alternatively, —CH ₂ — constituting the alkanediyl group may be replaced by —O— or —CO—.
P ¹ and P ² each independently represent a hydrogen atom, an acryloyloxy group or a methacryloyloxy group, but neither P ¹ nor P ² is a hydrogen atom. ]

Specific examples of Q ¹ include a group represented by any one of formulas (ar-1) to (ar-840). In the following groups, Me represents a methyl group, Et represents an ethyl group, and * represents a bond.

で示される基の＊の一方に対する結合手を表す。Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基であることが好ましく、水素原子、メチル基又はエチル基であることがより好ましい。Ｒ^８は、水素原子、メチル基又はエチル基であることが好ましい。 In formula (2), D ¹ and D ² each independently represents a single bond or a divalent linking group. Examples of the divalent linking group include —CO—O—, —O—CO—, —C (═S) —O—, —O—C (═S) —, —CR ⁴ R ⁵ —, — ^{CR 4 R 5 -CR 6 R 7} -, - O-CR 4 R 5 -, - CR 4 R 5 -O -, - CR 4 R 5 -O-CR 6 R 7 -, - CR 4 R 5 -O ^{-CO -, - O-CO-} CR 4 R 5 -, - CR 4 R 5 -O-CO-CR 6 R 7 -, - CR 4 R 5 -CO-O-CR 6 R 7 -, - NR 8 ^{-CR 4 R 5 -, - CR} 4 R 5 -NR 8 -, - CO-NR 8 -, - NR 8 -CO -, - O -, - S -, - NR 8 - , and ^-CR 4 = CR ⁵ -Etc. are mentioned. Here, R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group) Group). R ⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group).
Among these, D ¹ and D ² are each independently * —O—CO—, * —O—C (═S) —, * —O—CR ⁴ R ⁵ —, * —NR ⁸ —CR ⁴ R. ⁵ - or ^* is preferably -NR 8 -CO-, * - O- CO -, * - O-C (= S) - or ^* is more preferably -NR 8 -CO- is. Here, * indicates the compound (2)

Represents a bond to one of the * of the group represented by R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, a methyl group or an ethyl group. R ⁸ is preferably a hydrogen atom, a methyl group or an ethyl group.

（式中、＊は結合手を表す。） The divalent alicyclic hydrocarbon group of G ¹ and G ² is preferably a group having a range of 3 to 10 as the number of atoms (ring constituting atoms) constituting the ring. When a ring atom contains a hetero atom, the number of the hetero atom is 2 or less. Specific examples of such alicyclic hydrocarbon groups are those represented by any one of formula (g-1) to formula (g-10). Among these, the divalent alicyclic hydrocarbon group of G ¹ and G ² is more preferably a 5-membered or 6-membered alicyclic hydrocarbon group.

(In the formula, * represents a bond.)

  The hydrogen atom contained in the group represented by any one of the formulas (g-1) to (g-10) is an alkyl having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, and a tert-butyl group. A C 1-4 alkoxy group such as a methoxy group and an ethoxy group; a C 1-4 fluoroalkyl group such as a trifluoromethyl group; a C 1-4 fluoroalkoxy group such as a trifluoromethoxy group; Cyano group; nitro group; optionally substituted by halogen atoms such as fluorine atom, chlorine atom and bromine atom.

G ¹ and G ² are preferably a group represented by the formula (g-1), more preferably a 1,4-cyclohexanediyl group, and a trans-1,4-cyclohexanediyl group. It is particularly preferred.

Examples of the divalent linking group of E ¹ and ^{E 2,} for _{^{example, -CR 9 R 10 -, -}} CH 2 -CH 2 -, - O -, - S -, - CO-O -, - O-CO- , —O—CO—O—, —C (═S) —O—, —O—C (═S) —, —O—C (═S) —O—, —CO—NR ¹¹ —, —NR _{^{11 -CO -, - O-CH}} 2 -, - CH 2 -O -, - S-CH 2 -, - CH 2 -S -, - NR 11 - and ^-CR 9 = ^{CR 10} -, and the like. R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

E ¹ and E ² are —CO—O—, —O—CO—, —O—CO—O—, —CO—NR ¹¹ —, —NR ¹¹ —CO—, —CH ₂ —O—, —CH. ₂ -S- or a single bond is preferable, and -CO-O- is more preferable.

Examples of the divalent linking group for B ¹ and ^{B 2,} for _{^{example, -CR 9 R 10 -, -}} CH 2 -CH 2 -, - O -, - S -, - CO-O -, - O-CO- , —O—CO—O—, —C (═S) —O—, —O—C (═S) —, —O—C (═S) —O—, —CO—NR ¹¹ —, —NR _{^{11 -CO -, - O-CH}} 2 -, - CH 2 -O -, - S-CH 2 -, - CH 2 -S -, - NR 11 - and ^-CR 9 = ^{CR 10} -, and the like.

From the viewpoint of easier production, B ¹ and B ² are each independently —CH ₂ —CH ₂ —, —CO—O—, —O—CO—, —CO—NH—, —NH—. CO—, —O—CH ₂ —, —CH ₂ —O— or a single bond is preferable, and —CO—O— or —O—CO is preferable in that the compound (2) exhibits particularly high liquid crystallinity. -Is preferred.
From the viewpoint that can be produced more easily compound (2), it is preferable and B ¹ and B ² are identical.

Specific examples of the divalent alicyclic hydrocarbon group or the divalent aromatic hydrocarbon group in A ¹ and A ² include the formulas (g-1) to (g) described in the description of G ¹ and G ^2. -10) and a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by any of the following formulas (a-1) to (a-8): Is mentioned.

  The hydrogen atoms contained in the groups represented by the formulas (a-1) to (a-8) are alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, and a tert-butyl group; A C1-C4 alkoxy group such as a methoxy group and an ethoxy group; a C1-C4 fluoroalkyl group such as a trifluoromethyl group; a C1-C4 fluoroalkoxy group such as a trifluoromethoxy group; a cyano group A nitro group; optionally substituted with a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

Among them, as A ¹ and A ² , a 1,4-phenylene group or a 1,4-cyclohexanediyl group is preferable, and a 1,4-phenylene group is more preferable in terms of easy production of the compound (2). preferable. Furthermore, in terms of production of the compound (2) is easier, it is preferable A ¹ and A ² are the same.

From the viewpoint of liquid crystallinity of the compound (2), k and l are preferably 0, 1 or 2.
The sum of k and l is preferably 5 or less, and more preferably 4 or less.

The alkanediyl group having 1 to 12 carbon atoms in F ¹ and F ² is — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —, — (CH ₂ ) ₆ —, — (CH ₂ ) ₇ -,-(CH ₂ ) ₈ -,-(CH ₂ ) ₉ -,-(CH ₂ ) ₁₀ -,-(CF ₂ ) ₄ -,-(CF ₂ ) ₆ -,-(CF ₂ ) ₈ -is preferable, and-(CH ₂ ) _4- and-(CH ₂ ) ₆ -are more preferable.
B ¹ and B ² are each independently —O—, —CO—O—, —O—CO—, —O—CO—O—, —CO—NH—, —NH—CO— or a single bond. It is preferable.

P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group, but both are not hydrogen atoms. That is, at least one of P ¹ and P ² is a polymerizable group. It is more preferable that both P ¹ and P ² are polymerizable groups in that the retardation layer obtained from the compound (2) tends to have excellent hardness.

The polymerizable group may be any group that can participate in the polymerization reaction of the compound (2). Although it overlaps with the polymerizable groups of U ¹ and U ² of the compound (3-1), specific examples of the polymerizable group include vinyl group, vinyloxy group, styryl group, p- (2-phenylethenyl). ) Phenyl group, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, carboxy group, acetyl group, hydroxy group, carbamoyl group, C1-C4 N-alkylamino group, amino group, epoxy group, oxetanyl group , Formyl group, isocyanato group and isothiocyanato group. Among them, a radical polymerizable group and a cationic polymerizable group are preferable in that they are suitable for photopolymerization, and an acryloyloxy group or a methacryloyloxy group is more preferable in terms of easy handling and easy production of the compound (2). An acryloyloxy group is particularly preferred.
The polymerizable group may be directly bonded to F ¹ and F ² , but is bonded through one or more divalent linking groups (for example, the divalent linking group in B ¹ and B ² above). It is preferable.

で表される基の＊の一方との結合手を表す。 ^{-D 1 -G 1 -E 1 - (} A 1 -B 1) k -F 1 -P 1 and ^{-D 2 -G 2 -E 2 - (} A 2 -B 2) of l ^-F 2 -P ² Specific examples include groups represented by formula (R-1) to formula (R-134). *

Represents a bond to one of the * of the group represented by

（式（Ａ１）中の２つの＊は、（Ａ１−１）〜（Ａ１−８）のいずれかの＊と結合している。）

(Two * in the formula (A1) are bonded to any one of (A1-1) to (A1-8).)

（式（Ａ２）中の２つの＊は、（Ａ２−１）〜（Ａ２−８）のいずれかの＊と結合している。）

(Two * s in the formula (A2) are bonded to any one of (A2-1) to (A2-8).)

（式（Ａ３）中の２つの＊は、（Ａ３−１）〜（Ａ３−８）のいずれかの＊と結合している。）

(Two * in the formula (A3) are bonded to any one of (A3-1) to (A3-8).)

（式（Ａ４）中の２つの＊は、（Ａ４−１）〜（Ａ４−８）のいずれかの＊と結合している。）

(Two * in the formula (A4) are bonded to any one of (A4-1) to (A4-8).)

（式（Ａ５）中の２つの＊は、（Ａ５−１）〜（Ａ５−８）のいずれかの＊と結合している。）

(Two * in the formula (A5) are bonded to any one of (A5-1) to (A5-8).)

（式（Ａ６）中の２つの＊は、（Ａ６−１）〜（Ａ６−８）のいずれかの＊と結合している。）

(Two * s in formula (A6) are bonded to any one of (A6-1) to (A6-8).)

（式（Ａ７）中の２つの＊は、（Ａ７−１）〜（Ａ７−８）のいずれかの＊と結合している。）

(Two * in the formula (A7) are bonded to any one of (A7-1) to (A7-8).)

（式（Ａ８）中の２つの＊は、（Ａ８−１）〜（Ａ８−８）のいずれかの＊と結合している。）

(Two * in the formula (A8) are bonded to any one of (A8-1) to (A8-8).)

（式（Ａ９）中の２つの＊は、（Ａ９−１）〜（Ａ９−８）のいずれかの＊と結合している。）

(Two * in the formula (A9) are bonded to any one of (A9-1) to (A9-8).)

（式（Ａ１０）中の２つの＊は、（Ａ１０−１）〜（Ａ１０−８）のいずれかの＊と結合している。）

(Two * in the formula (A10) are bonded to any one of (A10-1) to (A10-8).)

（式（Ａ１１）中の２つの＊は、（Ａ１１−１）〜（Ａ１１−８）のいずれかの＊と結合している。）

(Two * in the formula (A11) are bonded to any one of (A11-1) to (A11-8).)

（式（Ａ１２）中の２つの＊は、（Ａ１２−１）〜（Ａ１２−８）のいずれかの＊と結合している。）

(Two * s in formula (A12) are bonded to any one of (A12-1) to (A12-8).)

（式（Ａ１３）中の２つの＊は、（Ａ１３−１）〜（Ａ１３−８）のいずれかの＊と結合している。）

(Two * in the formula (A13) are bonded to any one of (A13-1) to (A13-8).)

（式（Ａ１４）中の２つの＊は、（Ａ１４−１）〜（Ａ１４−８）のいずれかの＊と結合している。）

(Two * in the formula (A14) are bonded to any one of (A14-1) to (A14-8).)

（式（Ａ１５）中の２つの＊は、（Ａ１５−１）〜（Ａ１５−８）のいずれかの＊と結合している。）

(Two * in the formula (A15) are bonded to any one of (A15-1) to (A15-8).)

（式（Ａ１６）中の２つの＊は、（Ａ１６−１）〜（Ａ１６−８）のいずれかの＊と結合している。）

(Two * in the formula (A16) are bonded to any one of (A16-1) to (A16-8).)

（式（Ａ１７）中の２つの＊は、（Ａ１７−１）〜（Ａ１７−８）のいずれかの＊と結合している。）

(Two * in the formula (A17) are bonded to any one of (A17-1) to (A17-8).)

（式（Ａ１８）中の２つの＊は、（Ａ１８−１）〜（Ａ１８−８）のいずれかの＊と結合している。）

(Two * in the formula (A18) are bonded to any one of (A18-1) to (A18-8).)

（式（Ａ１９）中の２つの＊は、（Ａ１９−１）〜（Ａ１９−８）のいずれかの＊と結合している。）

(Two * s in formula (A19) are bonded to any one of (A19-1) to (A19-8).)

（式（Ａ２０）中の２つの＊は、（Ａ２０−１）〜（Ａ２０−８）のいずれかの＊と結合している。）

(Two * in the formula (A20) are bonded to any one of (A20-1) to (A20-8).)

（式（Ａ２１）中の２つの＊は、（Ａ２１−１）〜（Ａ２１−８）のいずれかの＊と結合している。）

(Two * s in formula (A21) are bonded to any one of (A21-1) to (A21-8).)

（式（Ａ２２）中の２つの＊は、（Ａ２２−１）〜（Ａ２２−８）のいずれかの＊と結合している。）

(Two * in the formula (A22) are bonded to any one of (A22-1) to (A22-8).)

（式（Ａ２３）中の２つの＊は、（Ａ２３−１）〜（Ａ２３−８）のいずれかの＊と結合している。）

(Two * s in the formula (A23) are bonded to any one of (A23-1) to (A23-8).)

（式（Ａ２４）中の２つの＊は、（Ａ２４−１）〜（Ａ２４−８）のいずれかの＊と結合している。）

(Two * s in the formula (A24) are bonded to any one of (A24-1) to (A24-8).)

（式（Ａ２５）中の２つの＊は、（Ａ２５−１）〜（Ａ２５−８）のいずれかの＊と結合している。）

(Two * in the formula (A25) are bonded to any one of (A25-1) to (A25-8).)

（式（Ａ２６）中の２つの＊は、（Ａ２６−１）〜（Ａ２６−８）のいずれかの＊と結合している。）

(Two * in the formula (A26) are bonded to any one of (A26-1) to (A26-8).)

（式（Ａ２７）中の２つの＊は、（Ａ２７−１）〜（Ａ２７−８）のいずれかの＊と結合している。）

(Two * in the formula (A27) are bonded to any one of (A27-1) to (A27-8).)

（式（Ａ２８）中の２つの＊は、（Ａ２８−１）〜（Ａ２８−８）のいずれかの＊と結合している。）

(Two * s in formula (A28) are bonded to any one of (A28-1) to (A28-8).)

（式（Ａ２９）中の２つの＊は、（Ａ２９−１）〜（Ａ２９−８）のいずれかの＊と結合している。）

(Two * s in the formula (A29) are bonded to any one of (A29-1) to (A29-8).)

（式（Ａ３０）中の２つの＊は、（Ａ３０−１）〜（Ａ３０−８）のいずれかの＊と結合している。）

(Two * in the formula (A30) are bonded to any one of (A30-1) to (A30-8).)

（式（Ａ３１）中の２つの＊は、（Ａ３１−１）〜（Ａ３１−８）のいずれかの＊と結合している。）

(Two * in the formula (A31) are bonded to any one of (A31-1) to (A31-8).)

（式（Ａ３２）中の２つの＊は、（Ａ３２−１）〜（Ａ３２−８）のいずれかの＊と結合している。）

(Two * s in formula (A32) are bonded to any one of (A32-1) to (A32-8).)

（式（Ａ３３）中の２つの＊は、（Ａ３３−１）〜（Ａ３３−８）のいずれかの＊と結合している。）

(Two * in the formula (A33) are bonded to any one of (A33-1) to (A33-8).)

（式（Ａ３４）中の２つの＊は、（Ａ３４−１）〜（Ａ３４−８）のいずれかの＊と結合している。）

(Two * in the formula (A34) are bonded to any one of (A34-1) to (A34-8).)

（式（Ａ３５）中の２つの＊は、（Ａ３５−１）〜（Ａ３５−８）のいずれかの＊と結合している。）

(Two * in the formula (A35) are bonded to any one of (A35-1) to (A35-8).)

（式（Ａ３６）中の２つの＊は、（Ａ３６−１）〜（Ａ３６−８）のいずれかの＊と結合している。）

(Two * in the formula (A36) are bonded to any one of (A36-1) to (A36-8).)

（式（Ａ３７）中の２つの＊は、（Ａ３７−１）〜（Ａ３７−８）のいずれかの＊と結合している。）

(Two * s in formula (A37) are bonded to any one of (A37-1) to (A37-8).)

（式（Ａ３８）中の２つの＊は、（Ａ３８−１）〜（Ａ３８−８）のいずれかの＊と結合している。）

(Two * s in the formula (A38) are bonded to any one of (A38-1) to (A38-8).)

（式（Ａ３９）中の２つの＊は、（Ａ３９−１）〜（Ａ３９−８）のいずれかの＊と結合している。）

(Two * s in formula (A39) are bonded to any one of (A39-1) to (A39-8).)

（式（Ａ４０）中の２つの＊は、（Ａ４０−１）〜（Ａ４０−８）のいずれかの＊と結合している。）

(Two * s in formula (A40) are bonded to any one of (A40-1) to (A40-8).)

（式（Ａ４１）中の２つの＊は、（Ａ４１−１）〜（Ａ４１−８）のいずれかの＊と結合している。）

(Two * in the formula (A41) are bonded to any one of (A41-1) to (A41-8).)

（式（Ａ４２）中の２つの＊は、（Ａ４２−１）〜（Ａ４２−８）のいずれかの＊と結合している。）

(Two * in the formula (A42) are bonded to any one of (A42-1) to (A42-8).)

（式（Ａ４３）中の２つの＊は、（Ａ４３−１）〜（Ａ４３−８）のいずれかの＊と結合している。）

(Two * in the formula (A43) are bonded to any one of (A43-1) to (A43-8).)

（式（Ａ４４）中の２つの＊は、（Ａ４４−１）〜（Ａ４４−８）のいずれかの＊と結合している。）

(Two * in the formula (A44) are bonded to any one of (A44-1) to (A44-8).)

（式（Ａ４５）中の２つの＊は、（Ａ４５−１）〜（Ａ４５−８）のいずれかの＊と結合している。）

(Two * in the formula (A45) are bonded to any one of (A45-1) to (A45-8).)

（式（Ａ４６）中の２つの＊は、（Ａ４６−１）〜（Ａ４６−８）のいずれかの＊と結合している。）

(Two * in the formula (A46) are bonded to any one of (A46-1) to (A46-8).)

（式（Ａ４７）中の２つの＊は、（Ａ４７−１）〜（Ａ４７−８）のいずれかの＊と結合している。）

(Two * in the formula (A47) are bonded to any one of (A47-1) to (A47-8).)

（式（Ａ４８）中の２つの＊は、（Ａ４８−１）〜（Ａ４８−８）のいずれかの＊と結合している。）

(Two * s in the formula (A48) are bonded to any one of (A48-1) to (A48-8).)

（式（Ａ４９）中の２つの＊は、（Ａ４９−１）〜（Ａ４９−８）のいずれかの＊と結合している。）

(Two * in the formula (A49) are bonded to any one of (A49-1) to (A49-8).)

（式（Ａ５０）中の２つの＊は、（Ａ５０−１）〜（Ａ５０−８）のいずれかの＊と結合している。）

(Two * s in the formula (A50) are bonded to any one of (A50-1) to (A50-8).)

（式（Ａ５１）中の２つの＊は、（Ａ５１−１）〜（Ａ５１−８）のいずれかの＊と結合している。）

(Two * in the formula (A51) are bonded to any one of (A51-1) to (A51-8).)

（式（Ａ５２）中の２つの＊は、（Ａ５２−１）〜（Ａ５２−８）のいずれかの＊と結合している。）

(Two * s in formula (A52) are bonded to any one of (A52-1) to (A52-8).)

（式（Ａ５３）中の２つの＊は、（Ａ５３−１）〜（Ａ５３−８）のいずれかの＊と結合している。）

(Two * in the formula (A53) are bonded to any one of (A53-1) to (A53-8).)

（式（Ａ５４）中の２つの＊は、（Ａ５４−１）〜（Ａ５４−８）のいずれかの＊と結合している。）

(Two * in the formula (A54) are bonded to any one of (A54-1) to (A54-8).)

（式（Ａ５５）中の２つの＊は、（Ａ５５−１）〜（Ａ５５−８）のいずれかの＊と結合している。）

(Two * s in formula (A55) are bonded to any one of (A55-1) to (A55-8).)

（式（Ａ５６）中の２つの＊は、（Ａ５６−１）〜（Ａ５６−８）のいずれかの＊と結合している。）

(Two * s in formula (A56) are bonded to any one of (A56-1) to (A56-8).)

（式（Ａ５７）中の２つの＊は、（Ａ５７−１）〜（Ａ５７−８）のいずれかの＊と結合している。）

(Two * in the formula (A57) are bonded to any one of (A57-1) to (A57-8).)

（式（Ａ５８）中の２つの＊は、（Ａ５８−１）〜（Ａ５８−８）のいずれかの＊と結合している。）

(Two * in the formula (A58) are bonded to any one of (A58-1) to (A58-8).)

（式（Ａ５９）中の２つの＊は、（Ａ５９−１）〜（Ａ５９−８）のいずれかの＊と結合している。）

(Two * in the formula (A59) are bonded to any one of (A59-1) to (A59-8).)

（式（Ａ６０）中の２つの＊は、（Ａ６０−１）〜（Ａ６０−８）のいずれかの＊と結合している。）

(Two * s in formula (A60) are bonded to any one of (A60-1) to (A60-8).)

（式（Ａ６１）中の２つの＊は、（Ａ６１−１）〜（Ａ６１−８）のいずれかの＊と結合している。）

(Two * in the formula (A61) are bonded to any one of (A61-1) to (A61-8).)

（式（Ａ６２）中の２つの＊は、（Ａ６２−１）〜（Ａ６２−８）のいずれかの＊と結合している。）

(Two * in the formula (A62) are bonded to any one of (A62-1) to (A62-8).)

（式（Ａ６３）中の２つの＊は、（Ａ６３−１）〜（Ａ６３−８）のいずれかの＊と結合している。）

(Two * s in formula (A63) are bonded to any one of (A63-1) to (A63-8).)

（式（Ａ６４）中の２つの＊は、（Ａ６４−１）〜（Ａ６４−８）のいずれかの＊と結合している。）

(Two * in the formula (A64) are bonded to any one of (A64-1) to (A64-8).)

（式（Ａ６６）中の２つの＊は、（Ａ６６−１）〜（Ａ６６−８）のいずれかの＊と結合している。）

(Two * in the formula (A66) are bonded to any one of (A66-1) to (A66-8).)

（式（Ａ６７）中の２つの＊は、（Ａ６７−１）〜（Ａ６７−８）のいずれかの＊と結合している。）

(Two * in the formula (A67) are bonded to any one of (A67-1) to (A67-8).)

（式（Ａ６８）中の２つの＊は、（Ａ６８−１）〜（Ａ６８−８）のいずれかの＊と結合している。）

(Two * s in formula (A68) are bonded to any one of (A68-1) to (A68-8).)

（式（Ａ６９）中の２つの＊は、（Ａ６９−１）〜（Ａ６９−８）のいずれかの＊と結合している。）

(Two * in the formula (A69) are bonded to any one of (A69-1) to (A69-8).)

（式（Ａ７０）中の２つの＊は、（Ａ７０−１）〜（Ａ７０−８）のいずれかの＊と結合している。）

(Two * s in formula (A70) are bonded to any one of (A70-1) to (A70-8).)

（式（Ａ７１）中の２つの＊は、（Ａ７１−１）〜（Ａ７１−８）のいずれかの＊と結合している。）

(Two * s in formula (A71) are bonded to any one of (A71-1) to (A71-8).)

（式（Ａ７２）中の２つの＊は、（Ａ７２−１）〜（Ａ７２−８）のいずれかの＊と結合している。）

(Two * in the formula (A72) are bonded to any one of (A72-1) to (A72-8).)

（式（Ａ７３）中の２つの＊は、（Ａ７３−１）〜（Ａ７３−８）のいずれかの＊と結合している。）

(Two * in the formula (A73) are bonded to any one of (A73-1) to (A73-8).)

  As the polymerizable nematic liquid crystal compound used for forming the retardation layer, the exemplified compound (2) may be used alone, or two or more kinds may be appropriately mixed. In particular, the use of a compound represented by any one of formulas (A1) to (A73) is more preferable because the obtained retardation layer becomes an inverse wavelength dispersion retardation layer. These compounds (2) are also preferable from the viewpoint that the wavelength dispersion exhibits more ideal reverse wavelength dispersion.

  The retardation layer forming composition preferably further contains a polymerization initiator. Suitable polymerization initiators are the same as those exemplified as preferred polymerization initiators optionally contained in the composition for forming a polarizing layer. Further, the retardation layer forming composition includes a photosensitizer and a polymerization agent for further promoting the polymerization of a polymerizable liquid crystal compound (polymerizable nematic liquid crystal compound), as in the polarizing layer forming composition. It may contain a polymerization inhibitor for controlling the viscosity. The photosensitizer and the polymerization inhibitor are also as described in the polarizing layer forming composition. Further, the retardation layer forming composition may contain a leveling agent as in the polarizing layer forming composition.

  The composition for forming a retardation layer preferably contains a solvent, particularly an organic solvent, in terms of fluidity. The organic solvent can be appropriately selected according to the type and amount of the polymerizable nematic liquid crystal compound used in the composition for forming a retardation layer. Specifically, methanol, ethanol, ethylene glycol, isopropyl Alcohol solvents such as alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, ethyl lactate; acetone, methyl ethyl ketone Ketone solvents such as cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone; non-chlorinated aliphatic hydrocarbon solvents such as pentane, hexane and heptane; toluene Non-chlorinated aromatic hydrocarbon solvents such as xylene and phenol; Nitrile solvents such as acetonitrile; Ether solvents such as propylene glycol monomethyl ether, tetrahydrofuran and dimethoxyethane; Chlorinated hydrocarbon solvents such as chloroform and chlorobenzene; Phenol; It is done. These organic solvents may be used alone or in combination. In particular, alcohol solvents, ester solvents, ketone solvents, non-chlorinated aliphatic hydrocarbon solvents and non-chlorinated aromatic hydrocarbon solvents are preferred.

  When an organic solvent is used in the composition for forming a retardation layer, the content thereof is 10 to 10,000 parts by mass, preferably 100 to 5,000 parts by mass with respect to 100 parts by mass of the polymerizable nematic liquid crystal compound. Part. The viscosity of the composition for forming a retardation layer is from 0.1 to 10 mPa · s, preferably from 0.1 to 7 mPa · s, in that the thickness of the retardation layer to be formed tends not to be uneven. s. Therefore, the kind and amount (content) of the organic solvent used for the retardation layer forming composition can be determined so as to have such a suitable viscosity.

  Moreover, the solid content concentration in the said composition for phase difference layer formation is the range of 2-50 mass%, and the range of 5-50 mass% is preferable. When the solid content concentration is 2% by mass or more, the retardation layer does not become too thin, and a retardation layer having a birefringence index necessary for optical compensation as a liquid crystal panel of a liquid crystal display device tends to be obtained. There is. In addition, when the solid content concentration is 50% by mass or less, the viscosity of the retardation layer forming composition does not become too small, and the above-described appropriate viscosity is obtained, so that unevenness in the thickness of the retardation layer is hardly generated. Tend to be. In addition, solid content means the component remove | excluding volatile components, such as an organic solvent, from the said composition for phase difference layer formation.

  The retardation layer is used for converting linearly polarized light into circularly polarized light or elliptically polarized light, or conversely converting circularly polarized light or elliptically polarized light into linearly polarized light.

  The retardation layer is obtained by polymerizing a polymerizable nematic liquid crystal compound contained in the retardation layer forming composition.

An unpolymerized film (dried film for forming a retardation layer) is obtained by applying the composition for forming a retardation layer on a photo-alignment layer formed from the liquid crystal aligning agent and drying the composition. The coating method and the drying method are the same as those described in the method for obtaining the polarizing layer forming coating film and the dry coating from the polarizing layer forming coating film.
A retardation layer obtained by polymerizing a polymerizable nematic liquid crystal in an unpolymerized film after making it into a nematic liquid crystal state exhibits birefringence due to monodomain alignment.

By appropriately adjusting the solid content concentration of the retardation layer forming composition and the content of the organic solvent, and the coating amount of the retardation layer forming composition on the support substrate, a retardation layer film is prepared. Thickness can be controlled. When the content of the polymerizable nematic liquid crystal compound contained in the composition for forming a retardation layer is constant, the retardation value (retardation value, Re (λ)) of the obtained retardation layer is represented by the formula (7)
Re (λ) = d × Δn (λ) (7)
(In the formula, Re (λ) represents a retardation value at a wavelength λnm, d represents a film thickness, and Δn (λ) represents a birefringence at a wavelength λnm.)
Therefore, in order to obtain a desired Re (λ), the film thickness d and Δn (λ) may be adjusted.

The method for polymerizing the polymerizable nematic liquid crystal compound in the unpolymerized film may be appropriately determined according to the type of the polymerizable nematic liquid crystal compound. When the polymerizable nematic liquid crystal compound has a photopolymerizable group as a polymerizable group, a photopolymerization method is used, and when the polymerizable group is a thermopolymerizable group, a thermal polymerization method is used. It is done. According to the photopolymerization method, the polymerizable nematic liquid crystal compound can be polymerized at a low temperature, and the range of heat resistance of the supporting substrate is widened, and the photopolymerizability is easy in terms of industrial production. It is preferable to use a polymerizable nematic liquid crystal compound having a polymerizable group. Photopolymerization is also preferred from the viewpoint of film formability.
The polymerization reaction according to the photopolymerization method is performed by irradiating an unpolymerized film with visible light, ultraviolet light, or laser light. In view of easy handling, ultraviolet light is particularly preferable. The light irradiation may be performed at a temperature at which the compound of the present invention takes a liquid crystal phase. At this time, the polymerized film can be patterned by masking or the like.
The birefringence Δn (λ) can be adjusted so as to give a desired phase difference by appropriately adjusting the exposure amount, the heating temperature, and the heating time during polymerization.

  The retardation layer thus obtained has a smaller film thickness than a stretched film that gives a retardation by stretching a polymer. Furthermore, by combining with the photo-alignment layer formed from this liquid crystal aligning agent, patterning and the direction of a fast axis (slow axis) can be controlled freely.

  Furthermore, the retardation layer is excellent in transparency, and the thickness of the retardation layer used as various display films varies depending on the retardation value of the optical film as described above, but is 0.1 to 10 μm. In terms of reducing photoelasticity, it is more preferably 0.2 to 5 μm, and particularly preferably 0.5 to 3 μm.

  The retardation value of the retardation layer exhibiting birefringence is about 50 to 500 nm, preferably 100 to 300 nm.

  Such a retardation layer is capable of uniform polarization conversion in a wider wavelength range. Therefore, the liquid crystal alignment element combined with the photo-alignment layer formed from this liquid crystal aligning agent can be used as an optical compensation film in all liquid crystal panels and FPDs such as organic EL.

  The retardation layer can be used as a broadband λ / 4 plate or λ / 2 plate. When used as a broadband λ / 4 plate or λ / 2 plate, the content of the polymer formed from the polymerizable nematic liquid crystal compound in the retardation layer may be appropriately selected. In the case of a λ / 4 plate, the film thickness may be adjusted so that Re (550) of the obtained liquid crystal alignment element is 113 to 163 nm, preferably 135 to 140 nm, particularly preferably about 137.5 nm. In the case of a plate, the film thickness may be adjusted so that Re (550) of the obtained liquid crystal alignment element is 250 to 300 nm, preferably 273 to 277 nm, particularly preferably about 275 nm.

  The retardation layer can also be used as an optical film for a VA (Vertical Alignment) mode. When used as an optical film for VA mode, the content in the retardation layer of the polymer formed from the polymerizable nematic liquid crystal compound may be appropriately selected. The film thickness may be adjusted so that Re (550) of the obtained optical film is preferably 40 to 100 nm, more preferably 60 to 80 nm.

  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.

Example 1: Synthesis of Compound (M1-1-1) Compound (1-1-1) was synthesized according to the following scheme.

[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 Compound (M1-1-1) (Alternative Method)]
27.46 g (93 mmol) of the compound (c1-1-1) was dissolved in 280 g of chloroform. While adding 8.00 g of BHT (di-t-butyl-hydroxytoluene), 11.16 g of paratoluenesulfonic acid and 44.63 g of methacrylic acid as a polymerization inhibitor to the obtained solution, water was removed by azeotropic dehydration. , Reacted for 8 hours. After cooling the reaction solution to 5 ° C. or lower, 200 g of water was added, and the organic layer was recovered by stirring, standing and liquid separation. To the obtained organic layer, 5.7 g of dimethylaminopyridine and 190 g of water were added and stirred at room temperature for 12 hours. The organic layer of the obtained reaction liquid was collected, and this organic layer was washed twice with 100 g of 2N aqueous hydrochloric acid. The organic layer was recovered, 300 g of n-heptane was added, and the precipitated crystals were collected by filtration. After washing twice with a mixed solvent consisting of 100 g of water and 80 g of methanol, it was vacuum dried to obtain 18.3 g of compound (M1-1-1). The yield was 54% based on the compound (c1-1-1).

シュレンク管中に、化合物（Ｍ１−１−１）１．００ｇ（２．７６ｍｍｏｌ）、及び１０ｇのテトラヒドロフランを加えて、脱酸素後、窒素を流しながらアゾビスイソブチロニトリル（ＡＩＢＮ）２．２７ｍｇを加え、６０℃で７２時間攪拌させた。得られた反応溶液をトルエン２００ｇに加えた。析出物を濾取し、ヘプタンで洗浄後、真空乾燥させることにより、０．７５ｇのポリマー１を得た。収率は化合物（Ｍ１−１−１）を基準として７５％であった。ＧＰＣ測定より、得られたポリマーの分子量はポリスチレン標準で数平均分子量２８２００、Ｍｗ／Ｍｎ１．８２を示し、モノマー含有量は０．５％であった。
このポリマーをポリマー（１−１−１）とする。 Example 2 (Production of a polymer having a photoreactive group)
Production of a polymer having a photoreactive group from the compound (M1-1-1) was carried out as follows.

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 molecular weight of the obtained polymer was a polystyrene standard, showing a number average molecular weight of 28200, Mw / Mn1.82, and the monomer content was 0.5%.
This polymer is referred to as a polymer (1-1-1).

In addition, the GPC analysis which calculated | required the number average molecular weight with the polystyrene standard of the polymer (1-1-1) was measured on condition of the following.
Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation)
Guard column: TSK guard column MP (XL) (trade name)
Column; TSK-gel MultiporeH _XL- M (trade name)
TSK-gel MultiporeH _XL- M (trade name)
TSK-gel MultiporeH _XL- M (trade name)
(The above columns were connected in series.)
Column temperature: 40 ° C
Solvent: THF
Flow rate: 1.0 mL / min
Injection volume: 50 μL
Detector: IR, UV
Measurement sample concentration: 0.6% by mass (solvent: THF)
Reference material for calibration; TSK STANDARD POLYSTYRENE
A-500, A-1000, A-2500, A-5000,
F-1, F-2, F-4, F-10, F-20, F-40,
F-80, F-128, F-288, F-380
(Product name, manufactured by Tosoh Corporation)

Example 3: Production of photoreactive liquid crystal aligning agent The polymer (1-1-1) was dissolved in cyclopentanone so as to have a concentration of 5% by mass to produce a photoreactive liquid crystal aligning agent.

Evaluation 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 polymerizable liquid crystal composition.

Polymerizable liquid crystal compound; Compound (3-1-6) 75 parts
Compound (3-1-7) 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 parts 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)
The photoreactive liquid crystal aligning agent obtained in Example 3 was coated on a polyethylene terephthalate substrate (PET substrate) by a bar coating method, dried at 60 ° C. for 1 minute, and then formed a dry film having a thickness of 100 nm. Subsequently, the surface of the obtained dried 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)
On the photo-alignment film, the polarizing layer forming composition was applied by a bar coating method, dried by heating in a drying oven at 120 ° C. for 1 minute, and then cooled to room temperature. By irradiating a layer formed from the composition for forming a polarizing layer with an ultraviolet ray having an exposure amount of 1200 mJ / cm ² (365 nm standard) using a UV irradiation device (SPOT CURE SP-7; manufactured by USHIO INC.) A polarizing layer was formed to produce a liquid crystal alignment element. 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. When the bright field was obtained over the entire screen, “◯” was evaluated, and when the dark field was obtained over the entire screen, “x” was evaluated. 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.

Evaluation example 2
A liquid crystal alignment element was produced in the same manner as in Evaluation 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 Research Laboratories).

(Measurement of phase transition temperature)
In the same manner as in Evaluation Example 1, the phase transition behavior of the polymerizable liquid crystal composition contained in the composition for forming a polarizing layer in Evaluation 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 Evaluation Example 1, dichroic ratio measurement, alignment state observation, and haze value measurement of the produced liquid crystal alignment element were performed. The results are shown in Table 1.

Evaluation Example 3
A polymerizable liquid crystal compound contained in the composition for forming a polarizing layer is obtained by mixing 75 parts of the compound (3-1-6) and 75 parts of the compound (3-1-7) and 75 parts of the compound (3-1-6). And the liquid crystal aligning element was produced like the evaluation example 1 except having changed into the mixture of 25 parts of compounds (3-1-8).

(Measurement of phase transition temperature)
In the same manner as in Evaluation Example 1, the phase transition behavior of the polymerizable liquid crystal composition contained in the composition for forming a polarizing layer in Evaluation 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 Evaluation Example 1, dichroic ratio measurement, alignment state observation, and haze value measurement of the produced liquid crystal alignment element were performed. The results are shown in Table 1.

Evaluation Example 4
A polymerizable liquid crystal compound contained in the composition for forming a polarizing layer is obtained by mixing 75 parts of the compound (3-1-6) and 75 parts of the compound (3-1-7) and 75 parts of the compound (3-1-6). And the liquid crystal aligning element was produced like the evaluation example 1 except having changed into the mixture of 25 parts of compounds (3-1-13).

(Measurement of phase transition temperature)
In the same manner as in Evaluation Example 1, the phase transition behavior of the polymerizable liquid crystal composition contained in the polarizing layer forming composition of 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 Evaluation 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.

Evaluation Example 5
A polymerizable liquid crystal compound contained in the composition for forming a polarizing layer is obtained by mixing 75 parts of the compound (3-1-6) and 75 parts of the compound (3-1-7) and 75 parts of the compound (3-1-6). And the liquid crystal aligning element was produced like the evaluation example 1 except having changed into the mixture of 25 parts of compounds (3-1-14).

(Measurement of phase transition temperature)
In the same manner as in Evaluation Example 1, the phase transition behavior of the polymerizable liquid crystal composition contained in the polarizing layer forming composition of 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 Evaluation Example 1, dichroic ratio measurement, alignment state observation, and haze value measurement of the produced liquid crystal alignment element were performed. The results are shown in Table 1.

Evaluation Example 6
A polymerizable nematic liquid crystal compound (for example, A1-1, A5-1, A6-1) that can be aligned on a rubbing film of polyvinyl alcohol instead of the polymerizable liquid crystals (1-6) and (1-7) of Evaluation Example 1. A7-1, A9-1, A10-1, A11-1, A15-1, A21-1, A25-1, A63-1, A69-1, A70-1, A71-1, A72-1, or A73 1) and a composition for forming a retardation layer without using a dichroic dye was applied on the photo-alignment layer shown in Evaluation Example 1, heated to a nematic phase transition temperature, and then polymerized. By polymerizing the nematic liquid crystal compound, a liquid crystal alignment element having a nematic liquid crystal phase can be produced on the photo-alignment layer. The liquid crystal alignment element functions as a retardation layer if the thickness is adjusted so that the liquid crystal phase has a desired retardation.

  According to the photoreactive liquid crystal aligning agent of the present invention, a liquid crystal alignment element (for example, a polarizing layer or a retardation layer) using a nematic liquid crystal or a smectic liquid crystal can be formed. The alignment layer obtained by the photoreactive liquid crystal aligning agent of the present invention has advantages such as less dust and easy patterning using a mask because the alignment layer is formed in a non-contact system. The alignment layer obtained by the process is superior.

Claims (11)

An alignment layer comprising a photoreactive liquid crystal aligning agent containing a polymer represented by formula (1-1) , wherein the polymer is aligned;
A polarizing layer,
The said polarizing layer is a liquid crystal aligning element which is a layer formed on the said alignment layer and the said polymeric liquid crystal compound in the composition for polarizing layer formation containing a polymeric liquid crystal compound superposes | polymerizes .

[In Formula (1-1),
n and m each independently represents 0 or 1.
v and w each independently represent an integer of 1 to 3.
S ¹ and S ² each independently represents a C 1-12 alkanediyl group which may have a fluorine atom or a cyano group.
S ³ represents a fluorine atom or an alkyl group having 1 to 12 carbon atoms which may have a cyano group.
X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a single bond, an oxygen atom, a carbonyloxy group or a methylene group.
Y ¹ and Y ² each independently represent a single bond, an oxygen atom or a carbonyloxy group.
R ¹ and R ³ 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.
R ² and R ⁴ each independently represents an alkoxy group having 1 to 2 carbon atoms, a cyano group or a halogen atom, and when v is 2 or 3, a plurality of R ² are the same or different and w is 2 Or, in the case of 3, a plurality of R ⁴ are the same or different.
R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom or a methyl group.
p, q, and r represent the mole fraction of each structural unit with respect to the total structural units, and satisfy the relationships of 0.25 <p ≦ 1, 0 ≦ q <0.75, and 0 ≦ r <0.75. ] The polymer is
Liquid crystal alignment element q is claim 1 wherein the polymer of 0 in the formula (1-1). The polymer is
Formula (1-1) according to claim 1 or 2, wherein the liquid crystal orientation element r is a polymer of 0. The polymer is
Formula (1-1) R ¹ and R ² are each independently of the liquid crystal alignment device according to any one of claims 1 to 3 is a polymer of a methoxy group or an ethoxy group. The polymer is
Formula liquid crystal alignment device according to claim 1 to 4 n and m are both polymer 0 (1-1). The liquid crystal alignment element according to claim 1, wherein the polymerizable liquid crystal compound is a compound that exhibits a liquid crystal state of a smectic phase. The liquid crystal alignment element according to claim 1, wherein the polymerizable liquid crystal compound is a compound exhibiting a liquid crystal state of a high-order smectic phase. A method for producing the liquid crystal alignment element according to claim 1,
A coating film is formed from the photoreactive liquid crystal aligning agent, and the alignment layer is formed by aligning the polymer by irradiating the coating film with polarized ultraviolet rays.
On the formed alignment layer, a polarizing layer containing a polymerizable liquid crystal compound is applied to obtain a coating film,
A polarizing layer is formed by polymerizing the polymerizable liquid crystal compound contained in the coating film.
A method for producing the liquid crystal alignment element. An alignment layer comprising a photoreactive liquid crystal aligning agent containing a polymer represented by formula (1-1), wherein the polymer is aligned;
A retardation layer,

[In Formula (1-1),
n and m each independently represents 0 or 1.
v and w each independently represent an integer of 1 to 3.
S ¹ and S ² each independently represents a C 1-12 alkanediyl group which may have a fluorine atom or a cyano group.
S ³ represents a fluorine atom or an alkyl group having 1 to 12 carbon atoms which may have a cyano group.
X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a single bond, an oxygen atom, a carbonyloxy group or a methylene group.
Y ¹ and Y ² each independently represent a single bond, an oxygen atom or a carbonyloxy group.
R ¹ and R ³ 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.
R ² and R ⁴ each independently represents an alkoxy group having 1 to 2 carbon atoms, a cyano group or a halogen atom, and when v is 2 or 3, a plurality of R ² are the same or different and w is 2 Or, in the case of 3, a plurality of R ⁴ are the same or different.
R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom or a methyl group.
p, q, and r represent the mole fraction of each structural unit with respect to the total structural units, and satisfy the relationships of 0.25 <p ≦ 1, 0 ≦ q <0.75, and 0 ≦ r <0.75. ] The liquid crystal aligning element of Claim 9 with which the said polymeric liquid crystal compound is represented by Formula (2).

[In Formula (2),
Q ¹ represents a substituted or unsubstituted polycyclic aromatic hydrocarbon group or a substituted or unsubstituted polycyclic aromatic heterocyclic group.
D ¹ and D ² each independently represents a single bond or a divalent linking group.
G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group, and the hydrogen atom contained in the alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, carbon The —CH ₂ — which may be substituted with a C 1-4 fluoroalkyl group, a C 1-4 alkoxy group, a cyano group or a nitro group, and which constitutes the alicyclic hydrocarbon group is —O—, -S- or -NH- may be substituted.
E ¹ and E ² each independently represents a single bond or a divalent linking group.
B ¹ and B ² each independently represent a single bond or a divalent linking group.
A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, and hydrogen contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group The atom may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. The hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with a fluorine atom.
k and l each independently represents an integer of 0 to 3. When k is 2 or more, a plurality of A ¹ are the same or different from each other, and a plurality of B ¹ are the same or different from each other. When l is 2 or more, a plurality of A ² are the same or different from each other, and a plurality of B ² are the same or different from each other.
F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkanediyl group is substituted with an alkoxy group having 1 to 5 carbon atoms or a halogen atom. Alternatively, —CH ₂ — constituting the alkanediyl group may be replaced by —O— or —CO—.
P ¹ and P ² each independently represent a hydrogen atom, an acryloyloxy group or a methacryloyloxy group, but neither P ¹ nor P ² is a hydrogen atom. ] A method for producing the liquid crystal alignment element according to claim 9,
A coating film is formed from the photoreactive liquid crystal aligning agent, and the alignment layer is formed by aligning the polymer by irradiating the coating film with polarized ultraviolet rays.
On the formed alignment layer, a composition for forming a retardation layer containing a polymerizable liquid crystal compound is applied to obtain a coating film,
A retardation layer is formed by polymerizing the polymerizable liquid crystal compound contained in the coating film.
A method for producing the liquid crystal alignment element.