JP6724486B2 - Optically anisotropic substance in which polymerizable liquid crystal composition is spray-aligned - Google Patents

Description

The present invention relates to an optically anisotropic body obtained by splay alignment of a polymerizable liquid crystal composition. The present invention also relates to an optical compensation film, an optical element and a liquid crystal display device using this optically anisotropic body.

The polymerizable liquid crystal compound having a liquid crystal phase gives an optically anisotropic substance having a function such as optical compensation by polymerization. This is because the orientation of the polymerizable liquid crystal molecules is fixed by polymerization. Various polymerizable liquid crystal compounds having such an optically anisotropic function have been developed. One polymerizable liquid crystal compound may not sufficiently fulfill the function. Therefore, attempts have been made to prepare a composition using some polymerizable liquid crystal compounds, polymerize the composition, and satisfy the function.

An optical anisotropic body having a splay orientation can be applied to, for example, a viewing angle compensation plate in a TN (Twisted Nematic) mode (see Patent Document 1).

In the above applications, the liquid crystal material may be laminated on a supporting substrate such as a glass substrate or a plastic substrate. Examples of materials used as the plastic substrate are TAC (triacetyl cellulose), polycarbonate, PET (polyethylene terephthalate), and polymers of cycloolefin resins.

An optically anisotropic substance composed of a polymerizable liquid crystal composition in which a liquid crystal material exhibits a splay alignment is a polymerizable liquid crystal composition containing an acrylate derivative having a 9,9-dialkylfluorene skeleton as a main component (see Patent Document 2), polymerizable. A polymerizable liquid crystal composition composed of a monofunctional compound having a site bond in the center of a mesogenic skeleton and a polymerizable compound having a bisphenol skeleton (see Patent Document 3), and a monofunctional polymerizable liquid crystal compound having an alkyl ester terminal group are used. It can be obtained by using the polymerizable liquid crystal composition (see Patent Document 4). Further, as a method for controlling the average tilt angle of the splay alignment of the liquid crystal material, a method for producing an optically anisotropic body in which the number of carbon atoms of the spacer group of the polymerizable liquid crystal compound is controlled has been proposed (see Patent Document 5).
However, in the above-mentioned optical anisotropic body, it is difficult to develop a proper splay angle orientation, or when a monofunctional component is introduced to control the average tilt angle, the heat resistance may decrease. Further, when a polymerizable liquid crystal compound in which the number of carbon atoms of the spacer group is changed is applied, the number of intermediate raw materials in the manufacturing process may increase, and the manufacturing cost may increase.
On the other hand, a method has been disclosed in which a surfactant having a polymerizable group is mixed to control the average tilt angle of liquid crystal (see Patent Document 6). This method is different from the present application in that the expression of the average tilt angle of liquid crystal molecules is suppressed (horizontal alignment). As the mixture, a combination of a fluorine-based polymerizable compound and a polymerizable liquid crystal is disclosed (Patent Document 7). Patent Document 7 aims to increase the durability of a cured film containing a monofunctional liquid crystal, and is not intended to promote the development of the average tilt angle of the liquid crystal.
In view of the above background, there has been a demand for a spray-aligned optically anisotropic substance that can be easily manufactured at low cost because the average tilt angle of the liquid crystal material can be easily controlled.

JP 2001-55573 A JP, 2006-307150, A JP, 2008-138142, A JP, 2015-44974, A JP, 2008-134530, A US Publication 2004/0202799 JP-A-2007-177241

An object of the present invention is to provide an optical anisotropic body having a splay orientation, which can easily exhibit the splay orientation and can be manufactured at low cost. Further, it is an object of the present invention to provide an optical compensation film using the optically anisotropic substance having the splay orientation, and to provide an image display device such as a liquid crystal display device including the optical compensation film. Specifically, an optical anisotropic body having a splay orientation and an average tilt angle of 15 to 30 degrees has been required.

At least one polymerizable liquid crystal compound selected from the group of compounds represented by formulas (1-1), (1-2) and (1-3), which is a raw material of the liquid crystal material, has the formula (2-1) When the fluorine compound represented by the formula (2-2) is added, the average tilt angle of the liquid crystal material increases from 15 degrees to 30 degrees. This solves the problem.
The present invention is shown in the following items [1] to [11].

（ここに、Ｚ^１１は独立して、水素、フッ素、メチルまたはトリフルオロメチルであり；Ｗ^１は独立して水素、フッ素、またはメトキシであり；
Ｗ^２およびＷ^３は独立して水素またはメチルであり；
Ｘ^１は、独立して単結合または−ＣＨ_２ＣＨ_２−であり；
Ｚ^１２は独立して水素、フッ素、メチルまたはトリフルオロメチルであり；
Ｗ^４は水素、炭素数１〜７の直鎖アルキル、炭素数１〜７の分岐アルキル、−ＣＯＯＲ^ａ（ただし、Ｒ^ａは炭素数１〜７の直鎖アルキル）、または−ＣＯＲ^ｂ（ただし、Ｒ^ｂは炭
素数１〜１５の直鎖アルキル）であり；
Ｘ^２は、独立して−Ｏ−または式（ａ）で表される基であり；
ｍ１、ｍ２、ｎ１およびｎ２は独立して２〜１５の整数である。）

（ここに、ｐ１は５〜２０の整数であり；ｎは独立して１または２であり；Ｒ１は独立して式（２−ａ）、式（２−ｂ）または水素を表す。ただし、両方のＲ１が水素の場合を除く。）

（ここに、ｐ２およびｐ３は1以上の整数でありかつｐ２とｐ３の和は６〜２０であり；
ｎ^ａおよびｎ^ｂは独立して１または２である。）
［２］ 式（１−１）〜式（１−３）において、
Ｚ^１１は独立して、水素、またはメチルであり；
Ｗ^１は独立して水素、またはフッ素であり；
Ｚ^１２は独立して水素、またはメチルである［１］に記載の光学異方体。
［３］ 式（１−１）〜式（１−３）において、
Ｗ^２が水素、Ｗ^３がメチルである［２］記載の光学異方体。
［４］ 式（１−１）〜式（１−３）において、Ｗ^２およびＷ^３がメチルである［２］に記載の光学異方体。
［５］ 式（２−１）において、
ｐ１が２０であり；ｎが１であり；Ｒ１が式（２−ａ）または式（２−ｂ）である［１］〜［４］のいずれかに記載の光学異方体。
［６］ （Ａ）成分の全重量に対して（Ｂ）成分の重量比が０．０００１〜０．１０であ
る［１］〜［５］のいずれかに記載の光学異方体。
［７］ 式（２−１）および式（２−２）で表されるいずれかの化合物を用いることを特徴とする、光学異方体の製造時における重合性液晶化合物のスプレイ配向を促進する方法。

（ここに、ｐ１は５〜２０の整数であり；ｎは独立して１または２であり；Ｒ１は独立して式（２−ａ）、式（２−ｂ）または水素を表し、少なくとも一つのＲ１は（２−ａ）または（２−ｂ）である。）

（ここに、ｐ２およびｐ３は1以上の整数でありかつｐ２とｐ３の和は６〜２０であり；
ｎ^ａおよびｎ^ｂは独立して１または２である。）
［８］ ［６］に記載の光学異方体を有する光学補償素子。
［９］ ［６］に記載の光学異方体と偏光板とを有する光学素子。
［１０］ ［８］に記載の光学補償素子を液晶セルの内面または外面に有する液晶表示装置。
［１１］ ［９］に記載の光学素子を液晶セルの外面に有する液晶表示装置。 [1] Component (A) which is at least one compound selected from the group of compounds represented by formula (1-1), formula (1-2) and formula (1-3), and
The polymerizable liquid crystal composition containing the component (B), which is at least one compound selected from the group of compounds represented by formulas (2-1) and (2-2), is polymerized to form the above-mentioned (A). Optically anisotropic substance whose components are spray-oriented.

(Wherein Z ¹¹ is independently hydrogen, fluorine, methyl or trifluoromethyl; W ¹ is independently hydrogen, fluorine or methoxy;
W ² and W ³ are independently hydrogen or methyl;
X ¹ is independently a single bond or —CH ₂ CH ₂ —;
Z ¹² is independently hydrogen, fluorine, methyl or trifluoromethyl;
W ⁴ is hydrogen, linear alkyl having 1 to 7 carbons, branched alkyl having 1 to 7 carbons, —COOR ^a (provided that ^Ra is linear alkyl having 1 to 7 carbons), or —COR ^b (provided that. , R ^b is straight-chain alkyl having 1 to 15 carbon atoms);
X ² is independently -O- or a group represented by the formula (a);
m1, m2, n1 and n2 are each independently an integer of 2 to 15. )

(Here, p1 is an integer of 5 to 20; n is independently 1 or 2; R1 is independently formula (2-a), formula (2-b) or hydrogen. (Except when both R1 are hydrogen.)

(Here, p2 and p3 are integers of 1 or more, and the sum of p2 and p3 is 6 to 20;
n ^a and n ^b are independently 1 or 2. )
[2] In formulas (1-1) to (1-3),
Z ¹¹ is independently hydrogen or methyl;
W ¹ is independently hydrogen or fluorine;
Z ¹² is an optically anisotropic substance according to [1], which is independently hydrogen or methyl.
[3] In formulas (1-1) to (1-3),
The optically anisotropic substance according to [2], wherein W ² is hydrogen and W ³ is methyl.
[4] The optical anisotropic body according to [2], wherein in the formulas (1-1) to (1-3), W ² and W ³ are methyl.
[5] In formula (2-1),
p1 is 20; n is 1; The optical anisotropic body according to any one of [1] to [4], wherein R1 is formula (2-a) or formula (2-b).
[6] The optical anisotropic body according to any one of [1] to [5], wherein the weight ratio of the component (B) to the total weight of the component (A) is 0.0001 to 0.10.
[7] Promoting splay alignment of a polymerizable liquid crystal compound at the time of producing an optically anisotropic substance, which is characterized by using any of the compounds represented by the formula (2-1) and the formula (2-2). Method.

(Here, p1 is an integer of 5 to 20; n is independently 1 or 2; R1 is independently formula (2-a), formula (2-b) or hydrogen; One R1 is (2-a) or (2-b).)

(Here, p2 and p3 are integers of 1 or more, and the sum of p2 and p3 is 6 to 20;
n ^a and n ^b are independently 1 or 2. )
[8] An optical compensation element having the optically anisotropic body according to [6].
[9] An optical element having the optical anisotropic body according to [6] and a polarizing plate.
[10] A liquid crystal display device having the optical compensation element according to [8] on the inner surface or the outer surface of a liquid crystal cell.
[11] A liquid crystal display device having the optical element according to [9] on the outer surface of a liquid crystal cell.

By using the polymerizable liquid crystal composition used for producing the optical anisotropic body of the present invention, an optical anisotropic body having an appropriate average tilt angle can be easily obtained without using a monofunctional polymerizable liquid crystal compound. Therefore, it is possible to obtain a splay-oriented optically anisotropic body that is low in cost and excellent in heat resistance. Further, the optical anisotropic body of the present invention can be applied to various optical elements, and this optical element can be applied to a display device, particularly a liquid crystal display device.

It is a figure which shows the result of having measured the retardation of the optically anisotropic body which shows splay alignment. It is a figure which shows the result of having measured the retardation of the optically anisotropic body which shows homogeneous orientation.

The "liquid crystal phase" refers to a nematic phase, a smectic phase, a cholesteric phase, or another intermediate phase between a liquid and a solid exhibiting anisotropy.
The “liquid crystal composition” refers to a mixture having a liquid crystal phase.
“Liquid crystal compound” is a generic term for a compound having a liquid crystal phase and a compound having no liquid crystal phase but useful as a component of a liquid crystal composition.
"Polymerizable" refers to having the ability to polymerize by means of light, heat, a catalyst, or the like.
“(Meth)acrylate” refers to one or both of acrylate and methacrylate.
The “polymerizable liquid crystal composition” refers to a liquid crystal composition containing a compound having a polymerizability and a liquid crystal composition containing a compound having a polymerizability to which a solvent is added.
In the chemical formula, the substituent of the benzene ring, which is shown so that the bond is not bonded to any of the carbon atoms constituting the benzene ring, indicates that the bonding position is arbitrary.

The components of the polymerizable liquid crystal composition other than the solvent are represented based on the amount of the polymerizable liquid crystal composition excluding the solvent.

“Tilt angle” is the angle between the surface of a supporting substrate and the long axis of liquid crystal molecules.
The “homogeneous orientation” refers to a state in which the average tilt angle is 0° to 5°.
“Homeotropic alignment” refers to a state in which the average tilt angle is 85 degrees to 90 degrees.
What is "spray orientation"?
(1) A state in which the tilt angle is approximately 0 degrees near the base material but changes so as to approach 90 degrees as it moves away from the base material, or (2) the tilt angle is approximately 90 degrees near the base material, but the base material A state in which the distance changes from 0 to 0 as the distance from
The “average tilt angle” means the average value of tilt angles measured by scanning in the vertical direction from the surface of the base material.
The suitable average tilt angle in the present invention is in the range of 15 to 30 degrees in the splay alignment.
"Twist orientation" refers to a state in which the orientation state is such that the angle between the base surface and the major axis is approximately 0 degrees, but is twisted in a stepwise manner around a line vertically lowered from the base surface.
“Frontal phase difference” refers to a phase difference when an optically anisotropic body formed on the surface of a supporting base material is observed from a direction perpendicular to the base material surface.
The "maintenance ratio of the front phase difference" is a change ratio of the front phase difference before and after the heating test.
"The heat resistance is excellent" because the "maintenance ratio of front phase difference" after the heating test is high and the change in "average tilt angle" before the heating test and "average tilt angle" after the heating test is small. Say.

Further, in the chemical formula, when a group as shown in the following A is described, it means that the wavy line portion is a bonding position as a group.

The polymerizable liquid crystal composition used for producing the optically anisotropic substance of the present invention comprises a compound represented by the formula (1-1), the formula (1-2) and the formula (1-3) as the component (A). It contains at least one compound selected from the group.

In formula (1-1), formula (1-2) and formula (1-3),
Z ¹¹ is independently hydrogen, fluorine, methyl or trifluoromethyl; W ¹ is independently hydrogen, fluorine or methoxy;
W ² and W ³ are independently hydrogen or methyl;
X ¹ is independently a single bond or —CH ₂ CH ₂ —;
Z ¹² is independently hydrogen, fluorine, methyl or trifluoromethyl;
W ⁴ is hydrogen, linear alkyl having 1 to 7 carbons, preferably methyl, branched alkyl having 1 to 7 carbons, —COOR ^a (where R ^a is linear alkyl having 1 to 7 carbons), or — COR ^b (wherein R ^b is a straight-chain alkyl having 1 to 15 carbon atoms);
X ² is independently -O- or a group represented by the formula (a);
m1, m2, n1 and n2 are independently an integer of 2 to 15, preferably an integer of 2 to 11. )

The polymerizable liquid crystal composition used for producing the optically anisotropic substance of the present invention contains the component (B) which is at least one of the compounds represented by the formulas (2-1) and (2-2). ..

In formula (2-1),
p1 is an integer of 5 to 20, preferably 20;
n is independently 1 or 2, preferably 1.
R1 independently represents formula (2-a), formula (2-b) or hydrogen, at least one R1 is (2-a) or (2-b), preferably two R1 are formula (2- 2-a).
In formula (2-2),
p2+p3 is an integer of 6 to 20;
n ^a and n ^b are independently 1 or 2.
Since the component (B) has fluoroalkyl in the side chain, it gathers near the air interface. It is considered that the side chain or the polymerizable group contained in the polymerizable liquid crystal compound having a high affinity with the component (B) is also attracted to the vicinity of the air side interface where the component (B) gathers. As a result, it is estimated that the addition of the compound of the component (B) increased the tilt angle and facilitated the expression of splay alignment.
When the polymerizable liquid crystal composition of the invention is used for producing an optically anisotropic substance, the production becomes easy. This is because the structure of the component (A) is almost symmetrical.
When the polymerizable liquid crystal composition of the present invention is used for producing an optically anisotropic substance, an optically anisotropic substance having a splay alignment excellent in heat resistance can be obtained. This is because an appropriate average tilt angle can be obtained without using a monofunctional polymerizable liquid crystal compound.

The polymerizable liquid crystal composition used for producing the optically anisotropic substance of the present invention includes formula (3-1), formula (3-2), formula (3-3), formula (3-4), and formula (3-4). The component (C), which is at least one compound selected from the group of compounds represented by 3-5) and the formula (3-6), may be contained. It becomes easier to increase the average tilt angle by adding the component (C).

式（３−１）において、Ｌ^１ａおよびＬ^１ｂは独立して炭素数１〜４のアルキルである。Ｒ^１ａおよびＲ^１ｂは独立して炭素数２〜４のアルキレンであり、好ましくは炭素数２のアルキレン、即ちエチレンである。Ｚ^３１は独立して水素またはメチルであり、好ましくは水素である。ｋ１およびｋ２は独立して０〜４の整数であり、好ましくは０である。ｍ３１およびｎ３１は独立して０〜６の整数であり、好ましくは１〜４の整数であり、より好ましくは１である。

In formula (3-1), L ^1a and L ^1b are independently alkyl having 1 to 4 carbons. R ^1a and R ^1b are independently alkylene having 2 to 4 carbon atoms, preferably alkylene having 2 carbon atoms, that is, ethylene. Z ³¹ is independently hydrogen or methyl, preferably hydrogen. k1 and k2 are independently an integer of 0 to 4, preferably 0. m31 and n31 are each independently an integer of 0 to 6, preferably an integer of 1 to 4, and more preferably 1.

式（３−２）において、Ｚ^３２は独立して水素またはメチルであり、好ましくは水素である。ｍ３２およびｎ３２は独立して１〜３の整数であり、好ましくは１である。Ｌ^２ａおよびＬ^２ｂは独立して炭素数１〜６のアルキル、フェニル、またはフッ素であり、好ましくはメチル、フェニルまたはフッ素であり、より好ましくは、メチルまたはフェニルである。ｊ１およびｊ２は独立して０〜４の整数であり、好ましくは０〜２の整数であり、より好ましくは０である。

In formula (3-2), Z ³² is independently hydrogen or methyl, preferably hydrogen. m32 and n32 are each independently an integer of 1 to 3, and preferably 1. L ^2a and L ^2b are independently alkyl having 1 to 6 carbons, phenyl, or fluorine, preferably methyl, phenyl or fluorine, and more preferably methyl or phenyl. j1 and j2 are independently an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0.

式（３−３）において、Ｚ^３３は独立して水素またはメチルであり、好ましくは水素である。Ｒ^３ａおよびＲ^３ｂは独立して水素、メチルまたはエチルであり、好ましくは水素である。ｍ３３およびｎ３３は独立して０〜３の整数であり、好ましくは１〜３の整数である。

In formula (3-3), Z ³³ is independently hydrogen or methyl, preferably hydrogen. R ^3a and R ^3b are independently hydrogen, methyl or ethyl, preferably hydrogen. m33 and n33 are independently an integer of 0 to 3, and preferably an integer of 1 to 3.

式（３−４）において、Ｚ^３４は水素またはメチルであり、好ましくは水素である。Ｒ^４ａおよびＲ^４ｂは独立して水素、または炭素数１〜６のアルキルであり、好ましくは水素である。ｍ３４およびｎ３４は独立して０〜１０の整数であり、好ましくは０〜５の整数であり、より好ましくは０〜２の整数である。

In formula (3-4), Z ³⁴ is hydrogen or methyl, preferably hydrogen. R ^4a and R ^4b are independently hydrogen or alkyl having 1 to 6 carbons, preferably hydrogen. m34 and n34 are independently an integer of 0 to 10, preferably an integer of 0 to 5, and more preferably an integer of 0 to 2.

式（３−５）において、Ｚ^３５は独立して水素またはメチルであり、好ましくは水素である。

In formula (3-5), Z ³⁵ is independently hydrogen or methyl, preferably hydrogen.

式（３−６）において、Ｚ^３６は独立して水素またはメチルであり、好ましくは水素である。Ｒ^５ａおよびＲ^５ｂは独立して水素または炭素数１〜６のアルキルであり、好ましくは水素である。Ｌ^２ａおよびＬ^２ｂは独立して炭素数１〜６のアルキル、フェニル、またはフッ素であり、好ましくはメチル、フェニルまたはフッ素であり、より好ましくは、メチルまたはフェニルである。ｍ３５およびｎ３５は独立して１〜３の整数であり、好ましくは１である。ｍ３６およびｎ３６は独立して１〜３の整数であり、好ましくは１である。そして、ｊ１およびｊ２は独立して０〜４の整数であり、好ましくは０〜２の整数であり、より好ましくは０である。

In formula (3-6), Z ³⁶ is independently hydrogen or methyl, preferably hydrogen. R ^5a and R ^5b are independently hydrogen or alkyl having 1 to 6 carbons, preferably hydrogen. L ^2a and L ^2b are independently alkyl having 1 to 6 carbons, phenyl, or fluorine, preferably methyl, phenyl or fluorine, and more preferably methyl or phenyl. m35 and n35 are each independently an integer of 1 to 3, and preferably 1. m36 and n36 are each independently an integer of 1 to 3, and preferably 1. And, j1 and j2 are independently an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0.

The polymerizable liquid crystal composition used for producing the optically anisotropic substance of the present invention is at least one compound selected from the group of compounds represented by formula (4-1) and formula (4-2). You may contain a certain (D) component. The addition of the component (D) makes it easier to increase the average tilt angle.

In formula (4-1) and formula (4-2), Z ⁴¹ and Z ⁴² are independently hydrogen or methyl. Y ¹ and ^{Y 2} independently represents a single bond, - _{(CH 2) 2} - or -CH = CH-. W ⁷ and W ⁸ are independently hydrogen or fluorine. m5, m6, n5 and n6 are each independently an integer of 2 to 15, preferably an integer of 2 to 10, more preferably an integer of 2 to 8, and still more preferably an integer of 4 to 6. ..

The polymerizable liquid crystal composition used for producing the optically anisotropic substance of the present invention contains the component (E) which is at least one compound selected from the group of compounds represented by formula (5-1). You may. It becomes easy to adjust the melting point by adding the component (E).

In equation (5-1),
Z ⁵¹ is hydrogen or methyl;
R ⁵¹ is cyano, trifluoromethoxy, alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, —R ^d —COOR ^c , —R ^d —OCOR ^c or —R ^d —CH═CH—COOR ^c ( Provided that R ^c is linear alkyl having 1 to 20 carbons and R ^d is a single bond or linear alkylene having 1 to 10 carbons);
Ring E represents a benzene ring or a cyclohexane ring,
W ⁹ is independently hydrogen, fluorine or methoxy;
X ⁵² is independently a single bond, -COO -, - OCO -, - OCO-CH = CH -, - CH = CH-COO -, - OCO-CH 2 CH 2 - or _-CH 2 _CH 2 -COO - ^{wherein; X 51} is a single bond, -O -, - COO -, - OCO-, wherein (a), - OCO-CH = CH -, - CH = CH-COO-, or _-OCO-CH 2 _{CH 2-} is;
m7 is an integer of 2 to 15, preferably an integer of 2 to 12;
q7 is 0 to 2.

The polymerizable liquid crystal composition used for producing the optically anisotropic substance of the present invention is at least one compound selected from the group of compounds represented by formula (6-1) and formula (6-2). You may contain a certain (F) component. By adding the component (F), it becomes easy to adjust the birefringence (Δn) of the optically anisotropic body.

In equation (6-1),
R ⁶¹ is a polymerizable group represented by any of formulas (R ⁶¹ -A) to (R ⁶¹ -F), hydrogen, chlorine, fluorine, cyano, alkyl having 1 to 10 carbons, and 1 to 10 carbons. Is alkoxy, trifluoromethyl or trifluoromethoxy;
A ⁶¹ is independently 1,4-cyclohexylene, 1-cyclohexene-1,4-ylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2. , 7-diyl or bicyclo[2.2.2]octane-1,4-diyl, wherein one or two non-adjacent two —CH ₂ — in 1,4-cyclohexylene may be replaced by —O—. Well, one or two -CH= in 1,4-phenylene may be replaced by -N=, and at least one hydrogen in 1,4-phenylene is halogen, cyano, alkyl having 1 to 5 carbons, It may be replaced by alkoxy having 1 to 5 carbons or alkyl halide having 1 to 5 carbons;
X ⁶¹ _{is, -CO -, - COCH 2 -} , - CO (CH 2) 2 - or -COCH = CH- and is;
X ⁶² is independently a single bond or alkylene having 1 to 20 carbon atoms, and at least one —CH ₂ — in this alkylene is —O—, —CO—, —COO—, —OCO—, —CH═. CH-, -CF=CF- or -C[identical to]C-, in which at least one hydrogen may be replaced by halogen;
Q ⁶¹ is a single bond or alkylene having 1 to 20 carbon atoms, and at least one —CH ₂ — in this alkylene is —O—, —CO—, —COO—, —OCO—, —OCOO— or —CH. =CH- and at least one hydrogen in these groups may be replaced by halogen;
q61 is an integer of 1 to 5;
Z ⁶¹ is hydrogen, halogen, alkyl having 1 to 5 carbons or alkyl halide having 1 to 5 carbons.
In formulas (R ⁶¹ -A) to (R ⁶¹ -F), Z ^6a is independently hydrogen, halogen, alkyl having 1 to 5 carbons or alkyl halide having 1 to 5 carbons.
In the present invention, halogen refers to a Group 17 element, specifically fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.

In formula (6-2),
Z ⁶² is independently hydrogen, fluorine, methyl or trifluoromethyl;
W ⁶² is independently hydrogen, fluorine, or methoxy;
X ⁶³ is independently -O- or a group represented by formula (a);
X ⁶⁴ is independently -CH = CH- or _-CH 2 CH ₂ - and are;
W ⁶³ is hydrogen, linear alkyl having 1 to 7 carbons, preferably methyl, branched alkyl having 1 to 7 carbons, alkoxycarbonyl (-COOR ^a ; ^Ra is linear alkyl having 1 to 7 carbons), or Alkylcarbonyl (-COR ^b ; R ^b is a straight-chain alkyl having 1 to 15 carbon atoms);
m62 and n62 are independently an integer of 2 to 15.

In the present invention, room temperature refers to 0 to 40 degrees Celsius.
The polymerizable liquid crystal composition used for producing the optically anisotropic substance of the present invention has a nematic phase at room temperature in the state before photo-curing, and has a photo-alignment treatment or a rubbing alignment treatment on a plastic substrate. Splay alignment is performed on an alignment film such as polyimide that has been subjected to rubbing alignment treatment. When the polymerizable liquid crystal composition used for producing the optically anisotropic substance of the present invention contains the component (B), the tendency of splay alignment on the alignment film subjected to the alignment treatment becomes strong, and when it contains the component (A). Even when the arrangement of fluorene rings or benzene rings in the molecule is asymmetric, the splay orientation is likely to occur.

The compound used in the polymerizable liquid crystal composition used for producing the optically anisotropic substance of the present invention will be described.
The compounds represented by formula (1-1), formula (1-2) and formula (1-3) have two polymerizable groups. Since the polymer of the polymerizable liquid crystal compound can have a three-dimensional structure, it gives a harder polymer as compared with a compound having one polymerizable group. The compounds represented by the formulas (1-1), (1-2) and (1-3) show a liquid crystal phase in a wide temperature range. Further, these compounds tend to be in a homogeneous orientation, and depending on the state of the additive and the supporting base material, they tend to be in the splay orientation when the fluorene ring or benzene ring in the molecule is asymmetric.

The compound (2) is a general term for compounds represented by formula (2-1) to formula (2-2). The compound (2) has a fluoroalkyl side chain. Since the compound represented by the formula (2-1) has at least one polymerizable group, it is integrated with the optically anisotropic substance when the polymerizable liquid crystal compound is cured. The compound represented by formula (2-2) does not have a polymerizable group. Since it has a hydroxyl group, the polarity of the compound (2-2) is considered to be larger than that of the compound (2-1), so that the concentration of the compound (2) near the air interface side can be finely adjusted.

The compound (3) is a general term for compounds represented by the formulas (3-1) to (3-6). The compound (3) is not a liquid crystal compound. The compound (3) is a compound having a fluorene structure and a phenoxide structure in one molecule. The compound (3) has an effect of aligning the liquid crystal compound homeotropically.

The compound (4) is a general term for compounds represented by the formula (4-1) and the formula (4-2). The compound (4) has a bisphenol skeleton and two polymerizable groups. Since the polymer of the compound (4) can have a three-dimensional structure, the polymer becomes harder than the polymer of the compound having one polymerizable group. The compound (4) may or may not exhibit liquid crystallinity. The compound (4) has a function of lowering the melting point of the polymerizable liquid crystal composition. Although it depends on the conditions such as a supporting base material and additives, when the compound (4) is used in combination with another polymerizable liquid crystal compound, homeotropic alignment is likely to occur.

The compounds represented by formula (5-1), formula (6-1) and formula (6-2) may be used in combination for controlling the birefringence (Δn) of the polymerizable liquid crystal composition. The compounds represented by the formulas (5-1) and (6-1) can be adjusted to have a low Δn, and the compounds represented by the formula (6-2) have a high Δn when selecting a cinnamate bond. Can be adjusted.

The polymerizable liquid crystal composition used for producing the optically anisotropic substance of the present invention has formulas (1-1) to (1-3), formulas (2-1) to (2-2) and formula (3-). 1) to Formula (3-6), Formula (4-1) to Formula (4-2), Formula (5-1), Formula (6-1) and Formula (6-2) May contain other polymerizable compound (hereinafter, also referred to as "other polymerizable compound") different from each other. This composition further contains an additive such as a surfactant in order to form a coating film having a uniform thickness and to suppress alignment defects, which is a phenomenon in which the rising directions of the tilt angle of the polymerizable liquid crystal are different. Good. This composition may contain additives such as a polymerization initiator and a photosensitizer suitable for the polymerization reaction.
This composition may contain additives such as an ultraviolet absorber, an antioxidant, a radical scavenger, and a light stabilizer in order to improve the properties of the polymer. This composition may contain an organic solvent capable of sufficiently dissolving the polymerizable liquid crystal composition without damaging the supporting substrate. Organic solvents are useful for producing paint films of uniform thickness. Further, a dichroic dye may be contained in order to impart polarization characteristics to the optically anisotropic body.

The use ratio of each component in the polymerizable liquid crystal composition used for producing the optically anisotropic substance of the present invention will be described.
The amount of the compound (1-1) and the compound (1-3) in the component (A) is 15 to 85% by weight based on the total weight of the component (A). A more preferable ratio is 30 to 70% by weight.
The content of the component (A) in the polymerizable liquid crystal composition used for producing the optically anisotropic substance of the present invention is 5 to 100% by weight based on the total amount of the polymerizable liquid crystal composition. However, it is preferably 10 to 100% by weight.
A preferable ratio of the component (B) is 0.0001 to 0.10. by weight ratio with respect to the total weight of the component (A). A more preferable weight ratio range is 0.0005 to 0.05.

A preferable ratio when the component (C) is used is 0.01 to 0.20 in terms of a weight ratio with respect to the total weight of the component (A). A more preferable weight ratio range is 0.03 to 0.15.
When using the component (D), a preferable ratio is 0.01 to 0.25 in terms of a weight ratio with respect to the total weight of the component (A). A more preferable ratio is 0.03 to 0.15.
When the component (E) is used, the preferable ratio is 0.01 to 1.00 in terms of weight ratio to the total weight of the component (A). A more preferable ratio is 0.03 to 0.50. When the component (E) is used in combination, it is preferable to use the minimum amount as long as the heat resistance is not affected.
When using the component (F), the preferable ratio is 0.01 to 1.00 in terms of weight ratio to the total weight of the component (A) and the component (B). A more preferable ratio is 0.03 to 0.50.

When using other polymerizable compounds, the preferable addition amount is 0.01 to 0.40, and preferably 0.03 to 0.25 in terms of weight ratio to the total weight of the component (A). When additives such as surfactants and polymerization initiators are used, the amount used may be the minimum amount that achieves the purpose.

It is preferable to prepare an optically anisotropic body by combining the components (A) and (B).
In order to adjust the average tilt angle, it is preferable to add the (C) component, the (D) component or both the (C) component and the (D) component in addition to the (A) component and the (B) component. In addition to the above mixture, the component (E), the component (F) and other polymerizable compounds may be further combined.

Next, a method for synthesizing the compound will be described. The compounds used in the present invention include Houben Wyle (Methoden der Organischen Chemie, Georg Thieme Verlag, Stuttgart), Organic Reactions (John Wily & Sons Inc.), Organic Syntheses, John. Wily & Sons, Inc.), Comprehensive Organic Synthesis (Pergamon Press), New Experimental Chemistry Course (Maruzen), etc. ..

The method for synthesizing the compound represented by formula (1-1) is described in JP-A-2003-238491 and JP-A-2006-307150. The method for synthesizing the compound represented by the formula (1-2) is described in Makromol. Chem., 190, 3201-3215 (1998), WO 97/00600 and the like. Regarding the method for synthesizing the compound represented by the formula (1-3), the method described in US Pat. No. 5,770,107 or JP 2012-177087 A can be referred to.
The alpha-fluoro acryloyloxy _(CH 2 = CF-COO-) of introduction method, alpha-fluoro acrylic acid, can also be used alpha-fluoro acrylic acid chloride, alpha-fluoro acrylic acid fluoride _(CH 2 = CFCOOF ) Is effective. J. Org. Chem., 1989, 54, 5640, JP-A-60-158137, JP-A-61-8534.
No. 5, etc. describe methods for synthesizing ?-fluoroacrylic acid fluoride, and the synthesis can be performed according to those methods. By utilizing these compounds as starting materials, the compounds represented by formula (1-1) and formula (1-2) can be synthesized.
The synthesis method of the compound represented by the formula (5) is described in Macromolecules, 26, 6132-6134 (1993), Makromol. Chem., 183, 2311-2321 (1982), German Patent No. 195022424, DE 2722589. It can be synthesized by the method described in the specification, WO 1997/00600, US Pat. No. 4,952,334, US Pat. No. 4,842,754 and the like.

The method for synthesizing the compound represented by the formula (3) is described in the following document.
Formula (3-1): International Publication No. 2005/33061 Formula (3-2) to Formula (3-4): JP 2005-338550 A (3-4): JP 2002-293762 A ( 3-5): JP 2005-272485 A precursor of formula (3-6) (epoxy acrylate precursor): JP 2002-348357 A table of formula (4-1) and formula (4-2). The method for synthesizing the compound described above is described in JP2007-16213A.
The method for synthesizing the compound represented by formula (6-1) is described in JP 2011-246365 A. The method for synthesizing the compound represented by formula (6-2) is described in US Pat. No. 5,770,107.

Next, the component compounds will be exemplified. Preferred examples of the compound represented by formula (1-1) are shown below.

In formulas (1-1-A) to (1-1-D), Z ¹¹ is independently hydrogen, fluorine, methyl or trifluoromethyl, and m1 and n1 are each independently 2 to 15. It is an integer, preferably an integer of 2-11.

Preferred examples of the compound represented by formula (1-2) are shown below.

In formulas (1-2-A) to (1-2-L), Z ¹² is independently hydrogen, fluorine, methyl or trifluoromethyl, and m 2 and n 2 are each independently 2 to 15 It is an integer, preferably an integer of 2-11.

Preferred examples of the compound represented by formula (1-3) are shown below.

In formulas (1-3-A) to (1-3-B), Z ¹¹ is independently hydrogen, fluorine, methyl or trifluoromethyl, W ¹ is independently hydrogen or fluorine, m1 and n1 are each independently an integer of 2 to 15, preferably an integer of 2 to 11. formula(
The compounds represented by 1-3-A) to (1-3-B) are preferably trans-forms, and it is more preferable that both -CH=CH- are in trans form.

ここに、Ｚ^３１は独立して水素またはメチルであり、Ｒ^１aおよびＲ^１ｂは独立して炭素
数２〜４のアルキレンであり、そしてｍ３１およびｎ３１は独立して０〜６の整数である。 Preferred examples of the compounds represented by formula (3-1) to formula (3-6) are shown below.

Here, Z ³¹ is independently hydrogen or methyl, R ^1a and R ^1b are independently alkylene having 2 to 4 carbon atoms, and m31 and n31 are independently integers of 0 to 6.

ここに、Ｚ^３２は独立して水素またはメチルであり、そしてｍ３２およびｎ３２は独立して１〜３の整数である。

Where Z ³² is independently hydrogen or methyl, and m 32 and n 32 are independently integers from 1 to 3.

ここに、Ｚ^３３は独立して水素またはメチルであり、そしてｍ３３およびｎ３３は独立して０〜３の整数である。

Where Z ³³ is independently hydrogen or methyl, and m33 and n33 are independently integers from 0-3.

ここに、Ｚ^３４は水素またはメチルであり、そしてｍ３４およびｎ３４は独立して０〜１
０の整数である。

Where Z ³⁴ is hydrogen or methyl, and m34 and n34 are independently 0-1
It is an integer of 0.

ここに、Ｚ^３５は独立して水素またはメチルである。

Wherein Z ³⁵ is independently hydrogen or methyl.

ここに、Ｚ^３６は独立して水素またはメチルであり、ｍ３５およびｎ３５は独立して１〜３の整数であり、ｍ３６およびｎ３６は独立して１〜３の整数である。

Here, Z ³⁶ is independently hydrogen or methyl, m35 and n35 are independently integers of 1 to 3, and m36 and n36 are independently integers of 1 to 3.

Preferred examples of the compounds represented by formula (4-1) and formula (4-2) are shown below.

In formulas (4-1-A) to (4-1-C), Z ⁴¹ is independently hydrogen or methyl, W ⁷ is independently hydrogen or fluorine, and m5 and n5 are independently. And is an integer of 2 to 15. In formulas (4-2-A) to (4-2-C), Z ⁴² is independently hydrogen or methyl, W ⁸ is independently hydrogen or fluorine, and m6 and n6 are independently. And is an integer of 2 to 15. In Formula (4-1-B) and Formula (4-2-B), the trans form is preferable, and it is more preferable that both —CH═CH— are in the trans form.

Preferred examples of the compound represented by formula (5-1) are shown below.

In formula (5-1-A) to formula (5-1-Q),
Z ⁵¹ is hydrogen or methyl,
W ⁹ is hydrogen or fluorine,
R ⁵¹ is cyano, trifluoromethoxy, —Rd—COORc, —Rd—OCORc or —Rd—CH═CH—COORc (wherein, in these groups, Rc is linear alkyl having 1 to 20 carbon atoms, Rd is a single bond or a linear alkylene having 1 to 10 carbon atoms), alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons,
m7 is an integer of 2 to 15, preferably 2 to 12.
In Formula (5-1-G) to Formula (5-1-J), the trans form is more preferable.

Preferred examples of the compound represented by formula (6-1) are shown below.

式（６−１−１）〜式（６−１−１９）において、Ｒは水素、炭素数１〜１０のアルキル、炭素数１〜１０のアルコキシ、トリフルオロメチルまたはトリフルオロメトキシである。また、式（６−１−９）、式（６−１−１６）および式（６−１−１８）において、トランス体がより好ましい。

In formulas (6-1-1) to (6-1-19), R represents hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, trifluoromethyl or trifluoromethoxy. Further, in the formula (6-1-9), the formula (6-1-16) and the formula (6-1-18), the trans form is more preferable.

式（６−１−２８）、式（６−１−３２）および式（６−１−３７）で表される化合物は、トランス体であることが好ましい。式（６−１−３３）で表される化合物はトランス体であることが好ましく、両方の−ＣＨ＝ＣＨ−がトランス型をとることがより好ましい。

The compounds represented by formula (6-1-28), formula (6-1-32) and formula (6-1-37) are preferably trans isomers. The compound represented by the formula (6-1-33) is preferably a trans isomer, and it is more preferable that both —CH═CH— have a trans form.

Preferred examples of the compound represented by formula (6-2) are shown below.

In formula (6-2-A) to formula (6-2-F),
Z ⁶² is independently hydrogen, fluorine, methyl or trifluoromethyl,
W ⁶³ is hydrogen, linear alkyl having 1 to 7 carbons, preferably methyl, branched alkyl having 1 to 7 carbons,
^Ra is linear alkyl having 1 to 7 carbons,
R ^b is linear alkyl having 1 to 15 carbon atoms,
m62 and n62 are independently an integer of 2 to 15.
In formula (6-2-A), formula (6-2-C) and formula (6-2-E), the trans form is preferable, and it is more preferable that both —CH═CH— are in the trans form.

Furthermore, formula (1-1) to formula (1-3), formula (2-1) to formula (2-2), formula (3-1) to formula (3-6), formula (4-1). Specific examples of preferred compounds represented by Formula (4-2), Formula (5-1), Formula (6-1) and Formula (6-2) are shown below.

式（１−３−Ａ−１）〜式（１−３−Ａ−４）、式（１−３−Ｂ−１）〜式（１−３−Ｂ−４）において、トランス体が好ましく、両方の−ＣＨ＝ＣＨ−がトランス型をとることがより好ましい。

In formula (1-3-A-1) to formula (1-3-A-4) and formula (1-3-B-1) to formula (1-3-B-4), a trans form is preferable, More preferably, both -CH=CH- are in the trans form.

As a commercially available product containing a compound represented by the formula (2-1) or the formula (2-2) as the component (B), PolyFox (registered trademark) PF-3305 (diacrylate type, fluoro side chain) manufactured by OMNOVA. N is 1, p1 is 20), PF-3510 (monoacrylate type, n of fluoro side chain is 2, p1 is 10), PF-3320 (diacrylate type, n of fluoro side chain is 1, p1 is 20) ), PF-636 (p2 + p3 is 6, fluoro-side chain ^{n a} and ^{n b} is 1), PF-6320 (p2 + p3 is 20, the fluoro side-chain ^{n a} and ^{n b} is 1), the PF-656 (p2 + p3 6, ^{n a} and ^{n b} of the fluoro side chain 2), PF-6520 (p2 + p3 is 20, ^{n a} and ^{n b} of the fluoro side chain 2), and the like. You may use these commercial items.

これらの式において、ｎは独立してそれぞれ独立して、１〜４の整数である。 Specific examples of the compound represented by the formula (3) are shown below.

In these formulas, n is independently and independently an integer of 1 to 4.

これらの式において、ｎは独立してそれぞれ独立して、１〜３の整数である。

In these formulas, n is independently an integer of 1 to 3.

これらの式において、ｎは独立して、１〜３の整数である。

In these formulas, n is independently an integer of 1 to 3.

これらの式において、ｎは独立して、０〜２の整数である。

In these formulas, n is independently an integer of 0-2.

As a commercial product containing a compound represented by formula (3-1-1), formula (3-2-1), formula (3-3-1) or formula (3-6-1), manufactured by Osaka Gas Chemicals OGSOL (registered trademark) EA-0250T, OGSOL EA-0500, OGSOL EA-1000, CA-0400, CA-0450T, ONF-1, BPEFA, GA-1000, Nippon Steel & Sumitomo Metal's ASF-
400 etc. are mentioned. You may use these commercial items.

式（４−１−２）〜式（４−１−４）において、トランス体が好ましく、両方の−ＣＨ＝ＣＨ−がトランス型をとることがより好ましい。 Specific examples of the compound represented by the formula (4) are shown below.

In the formulas (4-1-2) to (4-1-4), the trans form is preferable, and it is more preferable that both —CH═CH— are in the trans form.

式（４−２−５）〜式（４−２−７）において、トランス体が好ましく、両方の−ＣＨ＝ＣＨ−がトランス型をとることがより好ましい。

In Formulas (4-2-5) to (4-2-7), trans isomers are preferable, and it is more preferable that both —CH═CH— are in trans form.

Next, preferable examples of the compound represented by the formula (5-1) are shown.

式（５−１−１６）〜式（５−１−２３）において、トランス体がより好ましい。

In Formula (5-1-16) to Formula (5-1-23), the trans form is more preferable.

式（５−１−６５）および式（５−１−６６）において、トランス体がより好ましい。

In Formula (5-1-65) and Formula (5-1-66), the trans form is more preferable.

式（５−１−８０）および式（５−１−８１）において、トランス体がより好ましい。

In Formula (5-1-80) and Formula (5-1-81), the trans form is more preferable.

式（６−１−１６−１）において、トランス体がより好ましい。

In Formula (6-1-16-1), the trans form is more preferable.

式（６−２−Ａ−１）〜式（６−２−Ａ−４）において、トランス体が好ましく、両方の−ＣＨ＝ＣＨ−がトランス型をとることがより好ましい。

In formulas (6-2-A-1) to (6-2-A-4), a trans form is preferable, and it is more preferable that both —CH═CH— are in a trans form.

式（６−２−Ｃ−１）〜式（６−２−Ｃ−３）において、トランス体が好ましく、両方の−ＣＨ＝ＣＨ−がトランス型をとることがより好ましい。

In formulas (6-2-C-1) to (6-2-C-3), a trans form is preferable, and it is more preferable that both —CH═CH— are in a trans form.

式（６−２−Ｅ−１）〜式（６−２−Ｅ−３）において、トランス体がより好ましく、両方の−ＣＨ＝ＣＨ−がトランス型をとることがより好ましい。

In Formulas (6-2-E-1) to (6-2-E-3), trans-forms are more preferable, and both —CH═CH— are more preferably trans-forms.

Next, other polymerizable compounds, additives and organic solvents will be exemplified. These compounds may be commercially available products. Examples of the other polymerizable compound include a compound having one polymerizable group, a compound having two polymerizable groups, a compound having three or more polymerizable groups, and a functional group containing a hydroxyl group in one compound, A non-liquid crystalline polymerizable compound having acryloyl or methacryloyl, a polymerizable compound having a carboxyl, and a polymerizable compound having a phosphoric acid group.

Examples of compounds having one polymerizable group but no functional group containing a hydroxyl group are styrene, nucleus-substituted styrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl pyridine, N-vinyl pyrrolidone, vinyl sulfonic acid, and fatty acid vinyl. (Example: vinyl acetate), α,β-ethylenically unsaturated carboxylic acid (eg: acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.), alkyl ester of (meth)acrylic acid (carbon number of alkyl) 1-18), a hydroxyalkyl ester of (meth)acrylic acid (hydroxyalkyl having 1 to 1 carbon atoms)
8), aminoalkyl ester of (meth)acrylic acid (aminoalkyl having 1 to 18 carbon atoms), ether oxygen-containing alkyl ester of (meth)acrylic acid (ether oxygen containing alkyl having 3 to 18 carbon atoms, for example, methoxyethyl) Ester, ethoxyethyl ester, methoxypropyl ester, methylcarbyl ester, ethylcarbyl ester, and butylcarbyl ester), N-vinylacetamide, vinyl p-t-butylbenzoate, vinyl N,N-dimethylaminobenzoate, benzoic acid Vinyl, vinyl pivalate, vinyl 2,2-dimethylbutanoate, vinyl 2,2-dimethylpentanoate, vinyl 2-methyl-2-butanoate, vinyl propionate, vinyl stearate, 2-ethyl-2-methylbutanoic acid Vinyl, dicyclopentanyloxylethyl (meth)acrylate, isobornyloxylethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dimethyladamantyl (meth)acrylate, dicyclopentanyl (meth)acrylate , Dicyclopentenyl (meth) acrylate, polyethylene glycol capped with alkyl having 1 to 6 carbon atoms (the number of repeating units (degree of polymerization) is 2 to 20), mono (meth) acrylate ester, carbon terminated Poly(meth)acrylic acid ester of polypropylene glycol (having 2 to 20 repeating units (degree of polymerization)) capped with alkyl having 1 to 6 atoms, and capped with alkyl having 1 to 6 carbon atoms Mono(meth)acrylic acid ester of polyalkylene glycol such as a copolymer of ethylene oxide and propylene oxide (polymerization degree: 2 to 20) described in JP-A-2008-138142. 17-p. 31 is a monofunctional compound (2-1-1) to (2-1-81) in which the bond of the polymerizable site is at the center of the mesogen skeleton.

Examples of compounds having two polymerizable groups but no functional group containing a hydroxyl group are 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neo. Pentyl glycol diacrylate, dimethylol tricyclodecane diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, bisphenol A EO addition diacrylate, bisphenol A glycidyl diacrylate ( Viscoat V#700), polyethylene glycol diacrylate, and methacrylate compounds of these compounds. These compounds are suitable for further enhancing the film-forming ability of the polymer.

Examples of compounds having three or more polymerizable groups but no functional group containing a hydroxyl group are trimethylolpropane tri(meth)acrylate, trimethylolEO-added tri(meth)acrylate, tris(meth)acryloyloxyethylphosphine. Fate, tris((meth)acryloyloxyethyl)isocyanurate, alkyl-modified dipentaerythritol tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tetra (Meth)acrylate, alkyl-modified dipentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, alkyl-modified dipentaerythritol penta(meth)acrylate, biscoat V#802( The number of functional groups=8) and VISCOAT V#1000 (the number of functional groups=14 on average). "Viscoat" is a product name of Osaka Organic Chemical Co., Ltd. Those having 16 or more functional groups can be obtained by acrylating them using Boltron H20 (16-functional), Boltorn H30 (32-functional), and Boltorn H40 (64-functional) sold by Perstorp Specialty Chemicals.

The non-liquid crystal polymerizable compound having a functional group containing a hydroxyl group in one compound and having acryloyl or methacryloyl may be a commercially available product. Preferred examples include butanediol monoacrylate, a reaction product of butylglycidyl ether and (meth)acrylic acid (Denacol (registered trademark) DA-151 manufactured by Nagase & Co., Ltd.), 3-chloro-2-hydroxypropyl methacrylate, glycerol monomethacrylate (NOF BREMMER (registered trademark) GLM), glycerol monoacrylate, glycerin dimethacrylate (NOF BREMMER GMR series), glycerol triacrylate (Nagase Chemtex EX-314), 2-hydroxyethyl acrylate (Nippon Shokubai BHEA) ), 2-hydroxyethyl methacrylate (HEMA manufactured by Nippon Shokubai), 2-hydroxypropyl acrylate (HPA manufactured by Nippon Shokubai), 2-hydroxypropyl methacrylate (HPMA manufactured by Nippon Shokubai), caprolactone-modified 2-hydroxyethyl acrylate, caprolactone-modified 2- Hydroxyethyl methacrylate, phenoxyhydroxypropyl acrylate (M-600A manufactured by Kyoeisha Chemical), 2-hydroxy-3-acryloyloxypropyl methacrylate (G-201P manufactured by Kyoeisha Chemical), Kayarad (registered trademark) R-167 manufactured by Nippon Kayaku. , Triglycerol diacrylate (Kyoeisha Chemical's epoxy ester 80MFA), pentaerythritol tri(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydro. Phthalic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-methacryloyl Roxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, 4-(2-acryloyloxyethi-1-yloxy)benzoic acid, 4 -(3-acryloyloxy-n-prop-1-yloxy)benzoic acid, 4-(2-methacryloyloxyethyl-1-yloxy)benzoic acid, 4-(4-acryloyloxy-n-but-1-yloxy) ) Benzoic acid, 4-(6-acryloyloxy-n-hex-1-yloxy)benzoic acid, 4-(6-acryloyloxy-n-hex-1-yloxy) )-2-Methylbenzoic acid, 4-(6-methacryloyloxy-n-hex-1-yloxy)benzoic acid, 4-(10-acryloyloxy-n-dec-1-yloxy)benzoic acid, 2 -Acryloyloxyethyl acid phosphate and 2-methacryloyloxyethyl acid phosphate can be mentioned.

Except where otherwise described in the text, n _u and m _u represent the average number of constitutional units in the compound group.
As examples of mono-methacrylic acid esters of polyethylene glycol having a degree of polymerization of 2 to 20 is exemplified in the following formula (7-1), made by NOF Blemmer _{PE-90 (n u = 2} ), PE-200 (n u =4.5) and PE-350 ( _nu =8). Here, the number of repeating units (degree of polymerization) of the polyethylene glycol chain is more preferably 2 to 10.

As examples of mono-acrylic acid esters of polyethylene glycol having a degree of polymerization of 2 to 20 is exemplified in the following formula (7-2), made by NOF Blemmer _{AE-90 (n u = 2} ), AE-200 (n u = 4.5) and AE-400 ( _nu =10). Here, the number of repeating units (degree of polymerization) of the polyethylene glycol chain is more preferably 2 to 10.

Mono-methacrylic acid esters of polypropylene glycol having a polymerization degree of 2 to 20, as exemplified in the following formula (7-3), made by NOF Blemmer _{PP-1000 (n u = 4~6} ), PP-500 (N _u =9) and PP-800 (n _u =13). Here, the number of repeating units (degree of polymerization) of the polypropylene glycol chain is more preferably 3 to 13.

The monoacrylate of polypropylene glycol having a polymerization degree of 2 to 20, as exemplified in the following formula (7-4), made by NOF Blemmer _{AP-150 (n u = 3} ), AP-400 (n u =6), AP-550 ( _nu =9), AP-800 ( _nu =13). Here, the number of repeating units (degree of polymerization) of the polypropylene glycol chain is more preferably 3 to 13.

Examples of poly(ethylene glycol-propylene glycol) monomethacrylic acid ester include BLEMMER 50PEP-300 manufactured by NOF Corporation, as exemplified by the following formula (7-5). However, the compound is a random copolymer of ethylene glycol and propylene glycol. The average numbers of ethyleneoxy and propyleneoxy structures in one molecule are 2.5 and 3.5, respectively.

Examples of the polyethylene glycol-polypropylene glycol monomethacrylic acid ester include BLEMMER 70PEP-350B manufactured by NOF CORPORATION, as exemplified by the following formula (7-6). However, the compound is a random copolymer of ethylene glycol and propylene glycol. The average number of ethyleneoxy and propyleneoxy structures in one molecule is 5 and 2, respectively.

Examples of polyethylene glycol-polybutylene glycol monoacrylic acid ester include Blemmer AEP series.
Examples of the poly(ethylene glycol-butylene glycol) monomethacrylic acid ester include BLEMMER 55PET-400, 30PET-800 and 55PET-800 manufactured by NOF CORPORATION, as exemplified by the following formula (7-7). Here, the number of repeating units of the poly(ethylene glycol-tetramethylene glycol) chain is more preferably 2 to 10, provided that the compound is a random copolymer of ethylene glycol and propylene glycol. Average structural unit number of ethyleneoxy and butylene oxy _{(m u)} are each a 55PET-400 in 5 and 2 are a 10 30PET-800 In 6, a 5 and 10, 55PET-800.

Examples of the poly(ethylene glycol-butylene glycol) monoacrylic acid ester include NOF BREMMER AET series.
Examples of the poly(propylene glycol-tetramethylene glycol) monomethacrylic acid ester include BLEMMER 30PPT-800, 50PPT-800 and 70PPT-800 manufactured by NOF CORPORATION, as exemplified by the following formula (7-8). Here, the number of repeating units of the poly(propylene glycol-tetramethylene glycol) chain is more preferably 3 to 10, provided that the compound is a random copolymer of ethylene glycol and propylene glycol. Propyleneoxy and average structural unit number of butylene oxy _{(m u),} respectively, is a 30 ppt-800 in 4 8 is a 7, 50 ppt-800 6, a 70PPT-800 in 10 and 3.

Examples of poly(propylene glycol-tetramethylene glycol) monoacrylic acid ester include BLEMMER APT series manufactured by NOF.
The propylene glycol polybutylene glycol mono ((meth) acrylic acid ester), made by NOF Blemmer _{10PPB-500B (n u = 6} ) are exemplified by the following formula _{(7-9), 10APB-500B (} n u = 6 ) Is exemplified by the following formula (7-10). Here, it is more preferable that the number of repeating units of the propylene glycol polybutylene glycol chain is 6.

The preferred specific examples of the polymerizable compound having a carboxyl group are as follows, and a commercially available product may be used.
2-methacryloyloxyethyl succinic acid (Kyoeisha Chemical's light ester HO-MS (N), 2-methacryloyloxyethyl hexahydrophthalic acid (Kyoeisha Chemical's light ester HO-HH(N), 2-acryloyloxyethyl Succinic acid (Kyoeisha Chemical's light acrylate HOA-MS(N), 2-acryloyloxyethylhexahydrophthalic acid (Kyoeisha Chemical's light acrylate HOA-HH(N), 2-acryloyloxyethylphthalic acid (Kyoeisha's chemical Light acrylate HOA-MPL(N), 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid (Kyoeisha Chemical's light acrylate HOA-MPE(N),
4-(2-acryloyloxyethyl-1-yloxy)benzoic acid (ST01630 manufactured by Synthon Chemicals),
4-(3-acryloyloxy-n-prop-1-yloxy)benzoic acid (ST02453 manufactured by Synthon Chemicals),
4-(2-methacryloyloxyethyl-1-yloxy)benzoic acid (ST01889 manufactured by Synthon Chemicals),
4-(4-acryloyloxy-n-but-1-yloxy)benzoic acid (ST01680 manufactured by Synthon Chemicals),
4-(6-acryloyloxy-n-hex-1-yloxy)benzoic acid (ST00902 manufactured by Synthon Chemicals),
4-(6-acryloyloxy-n-hex-1-yloxy)-2-methylbenzoic acid (ST03606 manufactured by Synthon Chemicals),
4-(6-methacryloyloxy-n-hex-1-yloxy)benzoic acid (ST01618 manufactured by Synthon Chemicals),
4-(10-acryloyloxy-n-dec-1-yloxy)benzoic acid (ST03604 manufactured by Synthon Chemicals) and the like can be mentioned.
The preferred specific examples of the polymerizable compound having a phosphoric acid group are as follows, and a commercially available product may be used. 2-acryloyloxyethyl acid phosphate (Kyoeisha chemical light acrylate P-1A(N)), 2-methacryloyloxyethyl acid phosphate (Kyoeisha chemical light ester P-1M), Kyoeisha chemical light ester P-2M, Nippon Kayaku KAYAMER (registered trademark) PM-2) and the like can be mentioned.

Examples of the surfactant that can be used in combination include a cationic surfactant, an anionic surfactant and a nonionic surfactant.
Examples of the ionic surfactant include titanate compounds, imidazoline, quaternary ammonium salts, alkylamine oxides, polyamine derivatives, polyoxyethylene-polyoxypropylene condensates, polyethylene glycol and its esters, sodium lauryl sulfate, ammonium lauryl sulfate, lauryl. Amine sulfates, alkyl-substituted aromatic sulfonates, alkyl phosphates, aliphatic or aromatic sulfonic acid formalin condensates, laurylamidopropyl betaine, laurylaminoacetic acid betaine, polyethylene glycol fatty acid esters, polyoxyethylene alkylamines, Examples thereof include compounds such as perfluoroalkyl sulfonates and perfluoroalkyl carboxylates.

Examples of the type of nonionic surfactant include vinyl type, silicone type, fluorine type, and hydrocarbon type.
Examples of the vinyl type include one or more selected from polyalkyl acrylate, polyalkyl methacrylate, polyalkyl vinyl ether, polybutadiene, polyolefin, polyvinyl ether and the like.
Examples of silicone-based materials include polydimethylsiloxane, polyphenylsiloxane, specially modified siloxane, fluorine-modified siloxane, and surface-treated siloxane.
Examples of fluorine-based polymers include fluorine-based polymers.
Examples of hydrocarbons include polyethylene, polypropylene, polyisobutylene, paraffin, liquid paraffin, chlorinated polypropylene, chlorinated paraffin, and chlorinated liquid paraffin.
As specific examples, silicone-based nonionic surfactants described in paragraph 0196 of JP2011-246365A, fluorine-based nonionic surfactants described in paragraph 0197 of the publication, paragraphs of the publication. The nonionic surfactant containing the acrylic polymer as the main component described in 0199, and the fluorine-based nonionic surfactant and the silicone nonionic interface described in paragraph 0019 of JP2009-242563A. Activators or vinyl-based nonionic surfactants such as TEGO Flow 300, TEGO Flow 370 and TEGO Flow ZFS460 (above manufactured by Evonik), Polyflow series (Polyflow No. 7, No. 50E, No. 50EHF, No. 54N, No. 75, No. 77, No. 85, No. 85HF, No. 90, No. 90D-50, No. 95, or No. 99C (manufactured by Kyoeisha Chemical Co., Ltd.), BYK series (BYK350). , 352, 354, 355, 356, 358N, 361N, 381, 392, 394, 3441, or 3440) (manufactured by BYK Japan KK) and the like.
When a surfactant is used in combination, two or more may be mixed and used.

In order to optimize the wettability to the base material, a surfactant classified as a (base material) wetting agent may be used in combination within a range that does not affect the spray orientation. The wetting agent has the effect of lowering the surface tension of the polymerizable liquid crystal solution and improving the wettability on the coated substrate. Examples of such a wetting agent include polyflow series (KL-100, KL-700, LE-604, 605, 606), TEGO Twin series (4000) (manufactured by Evonik), TEGO Wet series (KL245, 250, 260). 265, 270, 280, 500, 505, 510, 520) (manufactured by Evonik), and the like.
The surfactant may have a polymerizable group in order to integrate it with the polymerizable liquid crystal compound. Examples of the polymerizable group introduced into the surfactant include a UV-reactive functional group and a thermally polymerizable functional group. From the viewpoint of reactivity with the polymerizable liquid crystal compound, a UV-reactive functional group is preferable. The preferable ratio of the surfactant varies depending on the kind of the surfactant, the composition ratio of the composition and the like, but is 0.0001 to 0.05 by weight ratio to the total weight of the component (A), and more preferably 0. It is 0003 to 0.03.

A known photopolymerization initiator may be used in order to optimize the polymerization rate of the polymerizable liquid crystal composition. The preferred addition amount of the photopolymerization initiator is 0.0001 to 0.20 in terms of weight ratio to the total weight of the component (A). A more preferable range of this weight ratio is 0.001 to 0.15. A more preferable range is 0.01 to 0.15.
Examples of the photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur (registered trademark) 1173), 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-. Diphenylethan-1-one (Irgacure (registered trademark) 651), 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184), Irgacure 127, Irgacure 500 (mixture of Irgacure 184 and benzophenone), Irgacure 2959, Irgacure 907, Irgacure. 369, IRGACURE 379, IRGACURE 754, IRGACURE 1300, IRGACURE 819, IRGACURE 1700, IRGACURE 1800, IRGACURE 1850, IRGACURE 1870, DAROCURE 4265, DAROCURE MBF, DAROCURE 02C, OGACURE OX, OGACURE 750E, IRGACURE 750E NCI-831, ADEKA ARKUL'S NCI-930 and ADEKA Optomer N-1919. The photopolymerization initiator may be used alone or in combination of two or more. Both Darocur and Irgacure are names of products sold by BASF Japan Ltd. Both ADEKA ARKULZ and ADEKA OPTOMER are names of products sold by ADEKA Corporation. Known sensitizers (isopropylthioxanthone, diethylthioxanthone, ethyl-4 dimethylaminobenzoate (Darocur EDB), 2-ethylhexyl-4-dimethylaminobenzoate (Darocur EHA), etc.) may be added to these.

Other examples of the photo-radical polymerization initiator include p-methoxyphenyl-2,4-bis(trichloromethyl)triazine and 2-(p-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole. , 9-phenylacridine, 9,10-dimethylbenzo[a]phenazine, benzophenone/Michler's ketone mixture, hexaarylbiimidazole/mercaptobenzimidazole mixture, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane- 1-one, benzyl dimethyl ketal, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,4-diethylxanthone/methyl p-dimethylaminobenzoate mixture, benzophenone/ Such as a mixture of methyltriethanolamine.

When using the compound represented by the formula (6), when it has (R ⁶¹ -B) to (R ⁶¹ -F) as a polymerizable group, a known photocationic polymerization initiator may be used. The preferable addition amount of the cationic photopolymerization initiator is 0.0001 to 0.1 based on the total weight of the cationically polymerizable compound. A more preferable weight ratio is 0.001 to 0.07.

Examples of specific trade names of the photo-cationic polymerization initiator are CPI series (CPI-100P, 200K, etc.) manufactured by San-Apro Co., Ltd., UCC product Cylacure UVI-6990, Cylacure UVI-6974 and Cylacure. UVI-6992, ADEKA ADEKA OPTOMER SP series (SP-150, SP-170, SP-171, SP-056, SP-066, SP-130, SP-140, SP-082, SP-). 103, SP-601, SP-606 and SP-701), PHOTOINITIATOR 2074 manufactured by Rhodia Co., Ltd., Irgacure 250, 270, 290 manufactured by BASF Japan Ltd., WPI series manufactured by Wako Pure Chemical Industries, Ltd., WPAG series, GE Silicones product UV-9380C, as well as TPS series, TAZ series, DPI series, BPI series, MDS series, DTS series, SI series, PI series, NDI series, PAI series from Midori Kagaku Co., Ltd. Many products such as NAI series, NI series, DAM series, MBZ series, PYR series, DNB series, and NB series are on sale.

When a salt is generated and polymerization inhibition is expected to occur when the radical polymerization initiator and the photo-acid generator are used in combination, the photo-acid generator may be changed to a photo-base generator. Examples of specific trade names of the photobase generator are WPBG series (WPBG-018, WPBG-027, WPBG-082, WPBG-140, WPBG-165, WPBG-166, manufactured by Wako Pure Chemical Industries, Ltd.). WPBG-167, WPBG-168, WPBG-172, WPBG-266, etc.).

A thermal polymerization initiator may be used in the present invention. Examples of specific product names are Adeka Opton series (CP-66) manufactured by ADEKA Co., Ltd., San-Aid (main ingredient) manufactured by Sanshin Chemical Industry Co., Ltd.
SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-160, SI-180, and San-Aid (auxiliary agent) SI. These may be used together with a photo radical initiator and a photo cationic polymerization initiator, or may be used together with a photo radical initiator.

It is possible to add one or more chain transfer agents to the polymerizable liquid crystal composition to control the mechanical properties of the optically anisotropic substance. The chain transfer agent can be used to control the length of the polymer chain or the length of two crosslinked polymer chains in the polymer film. It is also possible to control these lengths simultaneously. Increasing the amount of chain transfer agent decreases the polymer chain length. Preferred chain transfer agents are thiol compounds and styrene dimers.
Examples of monofunctional thiols are dodecanethiol, 2-ethylhexyl-(3-mercaptopropionate. Examples of polyfunctional thiols are trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis. (3-mercaptopropionate), 1,4-bis(3-mercaptobutyryloxy)butane (Karenz MT BD1), pentaerythritol tetrakis (3-mercaptobutyrate) (Karenz MT PE1), and 1,3,3. 5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (Karen's MT NR1) "Karenzu" is Showa Denko KK Examples of thiol compounds other than the above are the thiol compounds described in paragraphs 0042 to 0043 of International Publication No. 2013/080855, and line 11 to line 24 of page 23 of International Publication No. 2008/077261. No. 27, line 27. Examples of the styrene dimer are α-methylstyrene dimer (2,4-diphenyl-4-methyl-1-pentene) and 1,1-diphenylethylene. Kino Exter QE-2014 can also be used, "Kino Exter" is a product name of Kawasaki Kasei Kogyo Co., Ltd.

A polymerization inhibitor may be added to the polymerizable liquid crystal composition in order to prevent the initiation of polymerization during storage. Although known polymerization inhibitors can be used, preferred examples thereof are 2,5-di(t-butyl)hydroxytoluene (BHT), hydroquinone, methyl blue, diphenylpicric acid hydrazide (DPPH), benzothiazine and 4-nitrosodimethyl. Examples include aniline (NIDI) and o-hydroxybenzophenone. The polymerization inhibitors may be used alone or in combination of two or more.

An oxygen inhibitor may be added in order to improve the storage stability of the polymerizable liquid crystal composition. The radicals generated in the composition react with oxygen in the atmosphere to give peroxide radicals, which promotes an unfavorable reaction with the polymerizable compound. It is preferable to add an oxygen inhibitor for the purpose of preventing this. Examples of oxygen inhibitors are phosphoric acid esters.

In order to further improve the weather resistance of the polymerizable liquid crystal composition, an ultraviolet absorber, a light stabilizer (radical scavenger), an antioxidant and the like may be added. These may be used alone or in combination of two or more. Examples of ultraviolet absorbers are Tinuvin PS, Tinuvin P, Tinuvin 99-2, Tinuvin 109, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 328, Tinuvin 329, Tinuvin 384-2, Tinuvin 571, Tinuvin 900, Tinuvin 928, and Tinuvin 928. TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479, TINUVIN 5236, ADK STAB LA-32, ADK STAB LA-34, ADK STAB LA-36, ADK STAB LA-31, ADK STAB 1413, and ADK STAB LA-51. "Tinuvin (registered trademark)" is a registered trademark of Ciba Holding, Inc., and is a product name of BASF Japan Ltd. "Adeka Stub (registered trademark)" is a product name of ADEKA Corporation.

Examples of light stabilizers are TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 622, TINUVIN 770, TINUVIN 765, TINUVIN 780, TINUVIN 905, TINUVIN 5100, TINUVIN 5050, 5060, TINUVIN 5151, CHIMASORB 119FL. , Kimasorb 944FL, Kimasorb 944LD, Adeka Stab LA-52, Adeka Stab LA-57, Adeka Stab LA-62, Adeka Stab LA-67, Adeka Stab LA-63P, Adeka Stab LA-68LD, Adeka Stab LA-82, Adeka Stab LA-82-Adeka Stab LA-82, Adeka Stab LA-82 87, Cythorb UV-3346, Uvinul 4050H, Uvinul 4077H, Uvinul 4092H, Uvinul 5050H, Uvinul 5062H manufactured by Cytec, and Goodlight UV-3034 manufactured by Goodrich. "Kimasorb (registered trademark)" and Uvinul are trade names of BASF Japan Ltd.

Examples of the antioxidant include ADEKA CORPORATION ADEKA STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and Sumilizer (registered) from Sumitomo Chemical Co., Ltd. Trademark) BHT, Sumilizer BBM-S, and Sumilizer GA-80, and Irganox (registered trademark) 1076, Irganox1010, Irganox3114, and Irganox245 sold by BASF Japan Ltd. You may use these commercial items. Alternatively, the antioxidants described in paragraphs 0008 to 0014 of JP 2008-44989 A may be used.

A silane coupling agent may be further added to the polymerizable liquid crystal composition in order to control the adhesion to the supporting substrate. Specifically, vinyltrialkoxysilane, 3-aminopropyltrialkoxysilane, N-(2-aminoethyl)3-aminopropyltrialkoxysilane, N-(1,3-dimethylbutylidene)-3-tri Ethoxysilyl-1-propanamine, 3-triethoxysilyl-N-(1,3-dimethylbutylidene), 3-glycidoxypropyltrialkoxysilane, 3-chlorotrialkoxysilane, 3-methacryloxypropyltrialkoxy For example, silane. Another example is dialkoxymethylsilane in which in these compounds one of the alkoxys (three) is replaced by methyl. The preferred silane coupling agent is 3-aminopropyltriethoxysilane. The silane coupling agent may be used alone or in combination of two or more.

A dichroic dye or a fluorescent dye may be further added to the polymerizable liquid crystal composition in order to impart polarization properties or fluorescence properties. As the dichroic dye, (1) one having a high dichroic ratio, (2) one having a high extinction coefficient in the direction parallel to the molecular long axis, or (3) compatibility or solubility with the polymerizable liquid crystal composition The dyes used in a guest-host liquid crystal display device such as anthraquinones and azos can be used alone or in combination. Moreover, the dichroic dye may have a polymerizable group.
The preferred addition amount of the dichroic dye is 0.01 to 0.50 as a weight ratio with respect to the total weight of the component (A). A more preferable range of this weight ratio is 0.01 to 0.40. A more preferable range is 0.01 to 0.30. Examples of dichroic dyes include SI-486, SI-426, SI-483, SI-412, and SI-42 sold by Mitsui Chemicals Fine.
8. G-205, G-206, G-207, G-241, G-472, LSB-278, LSB-335, etc. sold by Nagase & Co. You may use these commercial items.

The polymerizable liquid crystal composition used for producing the optically anisotropic substance of the present invention can be directly applied to the surface of the supporting substrate. However, in order to facilitate the coating, the polymerizable liquid crystal composition may be diluted with the solvent as long as the solvent does not attack the supporting substrate. This solvent may be used alone or in combination of two or more. Examples of the solvent are ester solvents, amide solvents, alcohol solvents, ether solvents, glycol monoalkyl ether solvents, aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, These are halogenated aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, ketone solvents, and acetate solvents.

Preferred examples of the ester solvent include alkyl acetate (eg, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, 3-methoxybutyl acetate, isobutyl acetate, pentyl acetate and isopentyl acetate), cyclohexyl acetate, trifluoroacetic acid. Ethyl, alkyl propionate (eg methyl propionate, methyl 3-methoxypropionate, ethyl propionate, propyl propionate and butyl propionate), alkyl butyrate (eg methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate and butyrate) Propyl), dialkyl malonate (eg: diethyl malonate), alkyl glycolate (eg: methyl glycolate and ethyl glycolate), alkyl lactate (eg: methyl lactate, ethyl lactate, isopropyl lactate, n-propyl lactate, butyl lactate) And ethylhexyl lactate), monoacetin, γ-butyrolactone and γ-valerolactone.

Preferred examples of the amide solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N-methylpropionamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-diethylacetamide, N,N-dimethylacetamide dimethylacetal, N-methylcaprolactam and dimethylimidazolidinone.

Preferable examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, diacetone alcohol, t-butyl alcohol, sec-butyl alcohol, butanol, 2-ethylbutanol, n. -Hexanol, n-heptanol, n-octanol, 1-dodecanol, ethylhexanol, 3,5,5-trimethylhexanol, n-amyl alcohol, hexafluoro-2-propanol, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, Tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, hexylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2,4 -Pentanediol, 2,5-hexanediol, 3-methyl-3-methoxybutanol, cyclohexanol and methylcyclohexanol.

Preferred examples of ether solvents are ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, bis(2-propyl) ether, 1,3-dioxolane, 1,4-dioxane, cyclopentyl methyl ether and tetrahydrofuran (THF).

Preferred examples of the glycol monoalkyl ether solvent include ethylene glycol monoalkyl ether (eg, ethylene glycol monomethyl ether and ethylene glycol monobutyl ether), diethylene glycol monoalkyl ether (eg: diethylene glycol monoethyl ether), triethylene glycol monoalkyl ether, Propylene glycol monoalkyl ether (eg propylene glycol monobutyl ether),
Dipropylene glycol monoalkyl ether (eg: dipropylene glycol monomethyl ether), ethylene glycol monoalkyl ether acetate (eg: ethylene glycol monobutyl ether acetate), diethylene glycol monoalkyl ether acetate (eg: diethylene glycol monoethyl ether acetate), triethylene glycol Monoalkyl ether acetate, propylene glycol monoalkyl ether acetate (eg propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate), dipropylene glycol monoalkyl ether acetate (eg dipropylene glycol monomethyl ether acetate) ), and diethylene glycol methyl ethyl ether.

Preferred examples of aromatic hydrocarbon solvents are benzene, toluene, xylene, anisole, mesitylene, ethylbenzene, diethylbenzene, i-propylbenzene, n-propylbenzene, t-butylbenzene, s-butylbenzene, n-butylbenzene, Terpene derivatives (p-cymene, 1,4-cineole, 1,8-cineole, D-limonene, D-limonene oxide, p-menthane, α-pinene, β-pinene, γ-terpinene, terpinolene and tetralin. Preferred examples of halogenated aromatic hydrocarbon solvents are chlorobenzene, preferred examples of aliphatic hydrocarbon solvents are hexane and heptane, preferred examples of halogenated aliphatic hydrocarbon solvents are chloroform, dichloromethane, Carbon tetrachloride, dichloroethane, trichloroethylene and tetrachloroethylene, Preferred examples of alicyclic hydrocarbon solvents are cyclohexane, methylcyclohexane and decalin.

Preferred examples of the ketone solvent are acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, cyclohexanone, cyclopentanone, and methyl propyl ketone.

Preferred examples of the acetate solvent include ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl acetoacetate, 1-methoxy-2-propyl acetate, propylene glycol diacetate and 1,4-butane. These are diol diacetate and 1,3-butylene glycol diacetate.

From the viewpoint of the solubility of the polymerizable liquid crystal compound, it is preferable to use an amide-based solvent, an aromatic hydrocarbon-based solvent, and a ketone-based solvent. Considering the boiling point of the solvent, an ester-based solvent, an alcohol-based solvent, an ether-based solvent, glycol A combined use of a monoalkyl ether-based solvent is also preferable. There is no particular limitation on the selection of the solvent, but when a plastic substrate is used as the supporting substrate, it is necessary to lower the drying temperature in order to prevent the deformation of the substrate and prevent the solvent from eroding the substrate. Solvents preferably used in such a case are aromatic hydrocarbon solvents, ketone solvents, ester solvents, ether solvents, alcohol solvents, acetate solvents, glycol monoalkyl ether solvents.

The proportion of the solvent in the solution of the polymerizable liquid crystal composition is usually 0 to 95% based on the total weight of the solution. The lower limit of this range is a numerical value in consideration of the case where the supporting substrate is eroded by the solvent. Then, the upper limit is a numerical value in consideration of productivity such as solution viscosity, solvent cost, time and amount of heat when the solvent is evaporated. The preferred range of this ratio is 0 to 90%, and the more preferred range is 0 to 85%.

In the following description, the liquid crystal film obtained by curing the polymerizable liquid crystal composition may be referred to as an optically anisotropic body. The optically anisotropic body can be formed as follows. First, a polymerizable liquid crystal composition or a solution thereof is applied on a supporting substrate and heated and dried to form a coating film. Next, the coating film is irradiated with light to polymerize the polymerizable liquid crystal composition to fix the nematic orientation formed by the composition in the coating film in the liquid crystal state.
Supporting substrates that can be used are glass and plastic films. Examples of the plastic film are polyimide, polyamideimide, polyamide, polyetherimide, polyetheretherketone, polyetherketone, polyketone sulfide, polyethersulfone, polysulfone, polyphenylene sulfide, polyphenylene oxide, polyethylene terephthalate (PET), polybutylene. Such as terephthalate, polyethylene naphthalate, polyacetal, polycarbonate, polyarylate, acrylic resin, polyvinyl alcohol, polypropylene, cellulose, cellulose nanofiber film, triacetyl cellulose and its partial saponification product, epoxy resin, phenol resin, or cycloolefin resin It is a film.

Examples of the cycloolefin-based resin include, but are not limited to, norbornene-based resin and dicyclopentadiene-based resin. Among these, those not having an unsaturated bond or having an unsaturated bond hydrogenated are preferably used. For example, a hydrogenated product of a ring-opening (co)polymer of one or more norbornene-based monomers, an addition (co)polymer of one or more norbornene-based monomers, a norbornene-based monomer and an olefin-based monomer (Ethylene, α-olefin, etc.), addition copolymer with norbornene-based monomer and cycloolefin-based monomer (cyclopentene, cyclooctene, 5,6-dihydrodicyclopentadiene, etc.), and these Examples include modified products. Specifically, ZEONEX (registered trademark), ZEONOR (registered trademark, manufactured by Zeon Corporation), ARTON (manufactured by JSR Corporation), TOPAS (registered trademark, manufactured by Chicona Corporation), APEL (registered trademark, manufactured by Mitsui Chemicals, Inc.), Examples include ESCINA (registered trademark, manufactured by Sekisui Chemical Co., Ltd.) and OPTOREZ (manufactured by Hitachi Chemical Co., Ltd.).

These plastic films may be uniaxially stretched films or biaxially stretched films. These plastic films may be subjected to surface treatment such as hydrophilic treatment such as corona treatment or plasma treatment or hydrophobic treatment. The hydrophilic treatment method is not particularly limited, but corona treatment or plasma treatment is preferable, and particularly preferable method is plasma treatment. For the plasma treatment, the methods described in JP-A-2002-226616, JP-A-2002-121648 and the like may be used.
Alternatively, the optical anisotropic body may be formed on a different substrate and transferred to a plastic film. At that time, an anchor coat layer may be formed to improve the adhesion between the optical anisotropic body and the plastic film. Good. Such an anchor coat layer may be made of any inorganic or organic material as long as it enhances the adhesion between the optically anisotropic body and the plastic film. Further, the plastic film may be a laminated film. Instead of a plastic film, use a metal substrate such as aluminum, iron, or copper that has slit-like grooves on the surface, or a glass substrate such as alkali glass, borosilicate glass, or flint glass whose surface is etched into a slit shape. You can also

The supporting base material such as glass or plastic film may be subjected to physical or mechanical surface treatment by rubbing prior to forming a coating film of the polymerizable liquid crystal composition. Alternatively, a photo-alignment process using polarized UV may be performed. When forming the splay alignment, the surface treatment by rubbing may be directly applied to the supporting base material, or an alignment film may be previously provided on the supporting base material and the rubbing treatment may be applied to the alignment film. When performing the photo-alignment treatment, a photo-alignment film may be provided on the supporting substrate in advance and the photo-alignment treatment by polarized UV may be performed.
Examples of the alignment film are polyimide, polyamide, polyvinyl alcohol and the like. A particularly preferred alignment film is polyimide. An alignment film in which a side chain component is introduced into polyimide may be used to increase the average tilt angle of splay alignment. Although any method can be adopted for the rubbing treatment, usually, a rubbing cloth made of a material such as rayon, cotton, or polyamide is wrapped around a metal roll or the like, and the roll is rotated while being in contact with the supporting base material or the alignment film. A method of moving, a method of moving the supporting base material side with the roll fixed, and the like are adopted.
Examples of the photo-alignment film include a photo-isomerization type that uses azobenzene and the like, a photo-dimerization type that uses cinnamate groups and the like, and a photo-decomposition type that uses decomposition of cyclobutane and the like. These photo-alignment films are of oligomer type or polymer type.
When forming a tilted alignment, if the substrate or the exposure device is tilted when the polarized UV is irradiated, the alignment defect tends to be suppressed. Depending on the type of the supporting base material, it is possible to directly provide the orientation ability by obliquely depositing silicon oxide on the surface of the supporting base material.

When applying the polymerizable liquid crystal composition or a solution thereof, examples of the coating method for obtaining a uniform film thickness are spin coating, micro gravure coating, gravure coating, wire bar coating, dip coating, The spray coating method, the meniscus coating method, and the die coating method. In particular, a wire bar coating method or the like in which a shear stress is applied to the polymerizable liquid crystal composition at the time of application may be used when controlling the alignment of the liquid crystal material without performing the surface treatment of the substrate by rubbing or the like.

When preparing a solution of the polymerizable liquid crystal composition, it has the ability to dissolve the polymerizable liquid crystal composition, and further, a liquid crystal layer obtained from the polymerizable liquid crystal composition used for preparing the optically anisotropic substance of the present invention. The solvent is selected from the solvents that maintain the uniform orientation of the solvent and minimize the solvent damage to the supporting substrate. Examples of such a solvent are the above-mentioned solvents used when preparing a solution of the polymerizable liquid crystal composition. The amount used is also set within a range that maintains the uniform alignment of the polymerizable liquid crystal composition and minimizes solvent damage to the supporting substrate.

When a polymerizable liquid crystal composition or a solution thereof used for producing the optically anisotropic substance of the present invention is coated, if a solvent is contained, the solvent is removed after coating, and a uniform film thickness is formed on the supporting substrate. Liquid crystal layer, that is, a layer of a polymerizable liquid crystal composition is formed. The conditions for removing the solvent are not particularly limited. It may be dried until the solvent is almost removed and the fluidity of the coating film of the polymerizable liquid crystal composition disappears. The solvent can be removed by air-drying at room temperature, hot-plate drying, drying in a drying oven, blowing hot air or hot air.
Depending on the type and composition ratio of the compound used in the polymerizable liquid crystal composition, nematic alignment of the polymerizable liquid crystal composition in the coating film may be completed in the process of drying the coating film. Therefore, the coating film that has undergone the drying step can be subjected to the polymerization step without passing through the heat treatment step described below.

The temperature and time for heat treatment of the coating film, the wavelength of light used for light irradiation, the amount of light emitted from the light source, etc., are the kind and composition ratio of the compound used in the polymerizable liquid crystal composition, addition of a photopolymerization initiator. The preferred range varies depending on the presence or absence of the compound, the amount added, and the like. Therefore, the conditions for the temperature and time of heat treatment of the coating film, the wavelength of light used for light irradiation, and the amount of light emitted from the light source, which will be described below, are only in the approximate range.

The heat treatment of the coating film is preferably performed under the condition that the solvent is removed and uniform alignment of the polymerizable liquid crystal composition is obtained. An example of the heat treatment method is a method in which the coating film is heated to a temperature at which the polymerizable liquid crystal composition exhibits a nematic liquid crystal phase to form a nematic alignment in the polymerizable liquid crystal composition in the coating film. Nematic alignment may be formed by changing the temperature of the coating film within a temperature range in which the polymerizable liquid crystal composition exhibits a nematic liquid crystal phase. This method is a method in which the nematic orientation is almost completed in the coating film by heating the coating film to a high temperature range of the above temperature range, and then the temperature is lowered to obtain a more ordered orientation. Depending on the conditions under which uniform alignment of the polymerizable liquid crystal composition is obtained, the polymerization may be performed at a transition temperature (clearing point temperature) or more from the liquid crystal phase to the isotropic phase of the polymerizable liquid crystal composition. This method heats the coating film to a temperature at which it becomes an isotropic phase,
After that, it is a method of further ordered alignment by cooling to a temperature at which nematic alignment is achieved.
Regardless of which of the above heat treatment methods is adopted, the heat treatment temperature is usually room temperature to 150°C. The preferred range of this temperature is room temperature to 140°C, the more preferred range is room temperature to 130°C, and the still more preferred range is room temperature to 120°C.
The heat treatment time is usually 5 seconds to 2 hours. The preferred range of this time is 10 seconds to 40 minutes, and the more preferred range is 20 seconds to 20 minutes. In order to raise the temperature of the layer made of the polymerizable liquid crystal composition to a predetermined temperature, the heat treatment time is preferably 5 seconds or longer. In order not to reduce the productivity, the heat treatment time is preferably within 2 hours. Thus, the tilt-aligned polymerizable liquid crystal layer of the present invention is obtained.

The nematic alignment state of the polymerizable liquid crystal compound formed in the polymerizable liquid crystal layer is fixed by being polymerized by light irradiation. The wavelength of light used for light irradiation is not particularly limited. Electron rays, ultraviolet rays, visible rays, infrared rays (heat rays), etc. can be used. Usually, ultraviolet rays or visible rays may be used. The wavelength range is usually 150 to 500 nm. A preferred range is 250 to 450 nm, and a more preferred range is 300 to 400 nm. Examples of light sources include low pressure mercury lamps (sterilization lamps, fluorescent chemical lamps, black lights), high pressure discharge lamps (high pressure mercury lamps, metal halide lamps), short arc discharge lamps (ultra high pressure mercury lamps, xenon lamps, mercury xenon lamps), etc. Is. Preferred examples of the light source are a metal halide lamp, a xenon lamp, an ultrahigh pressure mercury lamp and a high pressure mercury lamp. The wavelength range of the irradiation light source may be selected by providing a filter or the like between the light source and the polymerizable liquid crystal layer and passing only a specific wavelength range.
The amount of light emitted from the light source is usually ² to 5000 mJ/cm ² . A preferred range of light intensity is 10~3000mJ / cm ^2, and more preferred range is 100 to 2000 mJ / cm ^2. The temperature condition during light irradiation is preferably set in the same manner as the above heat treatment temperature.
The atmosphere of the polymerization environment may be any of a nitrogen atmosphere, an inert gas atmosphere and an air atmosphere, but a nitrogen atmosphere or an inert gas atmosphere is preferable from the viewpoint of improving the curability.

When the polymerizable liquid crystal layer of the present invention and the optically anisotropic substance obtained by polymerizing the polymerizable liquid crystal layer with light or heat are used for various optical elements or when applied as an optical compensation element used for a liquid crystal display device, The control of the tilt angle distribution is extremely important.

One of the methods of controlling the average tilt angle is a method of adjusting the type or composition ratio of the liquid crystal compound used in the polymerizable liquid crystal composition. The average tilt angle can also be controlled by adding another component to the polymerizable liquid crystal compound. The average tilt angle of the optically anisotropic substance can also be controlled by the kind of solvent and solute concentration in the polymerizable liquid crystal composition, the kind and amount of a surfactant added as one of the other components, and the like.
The average tilt angle of the optically anisotropic substance can be controlled also by the kind and rubbing condition of the supporting substrate or the polymer coating, the drying condition and the heat treatment condition of the coating film of the polymerizable liquid crystal composition. When glass is used as the supporting substrate and a polyimide rubbing alignment film is used as the alignment film, the drying temperature should be near the temperature at which the polymerizable liquid crystal changes to the isotropic phase (clearing point) or above the clearing point temperature. In some cases, alignment defects can be reduced. Further, the irradiation atmosphere in the photopolymerization step after orientation, the temperature at the time of irradiation, and the like also affect the average tilt angle of the optically anisotropic body. That is, it can be considered that almost all the conditions in the manufacturing process of the optically anisotropic body have some influence on the average tilt angle.
Therefore, the tilt angle can be set to an arbitrary value by optimizing the polymerizable liquid crystal composition and appropriately selecting various conditions of the process for producing the optically anisotropic body.

The optical anisotropic body of the present invention is used for producing the optical anisotropic body of the present invention in which the component (A) and the component (B) are combined on an alignment film subjected to a surface treatment such as a rubbing treatment or a photo-alignment treatment. It is obtained by forming a coating film of the polymerizable liquid crystal composition on the surface of the supporting substrate.
In order to control the average tilt angle preferable in the present invention, when the compound represented by the formula (1-1) and/or the compound represented by the formula (1-3) is used as the component (A), It is preferred to use 9-methylfluorene as the structure (ie one of W ² and W ³ is methyl and the other is hydrogen). Further, m1 and n1 are preferably 4 to 6.
When the compound represented by the formula (1-2) is used, W ⁴ is preferably methyl, X ² is preferably —O—, and m 2 and n 2 are preferably 4 to 6.
As the component (B), a plurality of compounds represented by formulas (2-1) and (2-2) may be used in combination. From the viewpoint of being integrated with the polymerizable liquid crystal compound, R1 is preferably the formula (2-a) or the formula (2-b).
In the production of the optical anisotropic body of the present invention, the polymerizable liquid crystal composition contains at least one of the compounds represented by formula (2-1) and formula (2-2) which is the component (B), The splay alignment of the polymerizable liquid crystal compound is promoted. The use of the compounds represented by formula (2-1) and formula (2-2) is effective in promoting the splay alignment of the polymerizable liquid crystal compound during the production of the optically anisotropic substance. In the prior art, there is no example in which the compounds represented by the formulas (2-1) and (2-2) are used to promote splay alignment.
In order to promote the splay alignment, one of the compounds represented by formulas (2-1) and (2-2) may be contained in the polymerizable liquid crystal composition. The procedure and conditions for orientation are as described above.

A surfactant may be added to reduce alignment defects in the spray alignment. Further, in order to increase the average tilt angle, the compound represented by the formula (3) and the compound represented by the formula (4) may be used in combination.

The thickness of the optically anisotropic body varies depending on the retardation according to the target element and the birefringence of the optically anisotropic body. Therefore, although the range cannot be strictly determined, the preferable thickness of the optically anisotropic body is 0.05 to 50 μm. And a more preferable range is 0.1 to 20 μm, and a further preferable range is 0.5 to 10 μm. The preferable haze value of the optically anisotropic substance is 1.5% or less, and the preferable transmittance is 80% or more. A more preferable haze value is 1.0% or less, and a more preferable transmittance is 95% or more. It is preferable that the transmittance satisfies these conditions in the visible light region.

The optically anisotropic substance is effective as an optical compensation element applied to liquid crystal display elements (particularly active matrix type and passive matrix type liquid crystal display elements). Examples of types of liquid crystal display elements suitable for using this optically anisotropic body as an optical compensation film are IPS type (in-plane switching), OCB type (optically compensated birefringence), TN. Type (twisted nematic), STN type (super twisted nematic), ECB type (electrically controlled birefringence), HAN type (hybrid aligned nematic), DAP type (deformation effect of aligned phase), CSH type (color super homeotropic), VAN/VAC type (vertically aligned nematic/cholesteric), OMI type (optical mode interference), SBE type (super birefringence effect) and the like. Further, this optical anisotropic body can be used as a phase retarder for display devices of guest-host type, ferroelectric type, antiferroelectric type and the like. The optimum values of parameters such as the distribution of the tilt angle in the thickness direction and the thickness required for the optically anisotropic body strongly depend on the type of liquid crystal display element to be compensated and its optical parameters, and thus differ depending on the element type.

The optically anisotropic substance can also be used as an optical element integrated with an absorption type polarizing plate or the like, and in this case, it is arranged on the outer surface of the liquid crystal cell. However, since the optically anisotropic substance as the optical compensation element has little or no elution of impurities into the liquid crystal filled in the cell, it can be arranged on the inner surface of the liquid crystal cell. For example, Japanese Patent No. 4899828 (Japanese Patent Laid-Open No.
By applying the method disclosed in JP-A 08-134530), a liquid crystal display composition in which an optical compensation layer is formed in a liquid crystal cell can be obtained. Since the optically anisotropic substance to which the dichroic dye is added has a polarization property, for example, Japanese Patent No. 4778192 (Japanese Patent Publication No. 2004-535483), Japanese Patent Application Laid-Open No. 11-337898, Japanese Patent Application Laid-Open No. 11-101964, International A visible angle control member can be obtained by applying the method disclosed in Japanese Patent Laid-Open No. 2005-45485.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples. The evaluation methods in the examples are shown below.
<Polymerization conditions>
Irradiation with light having an intensity of 20 mW/cm ² (365 nm) for 25 seconds in the air at room temperature (25° C.) using a 250 W ultra-high pressure mercury lamp (manufactured by Ushio Inc.).
<Confirmation of liquid crystal alignment state>
The optical anisotropic body obtained was sandwiched between two polarizing plates arranged in crossed nicols, and light was irradiated onto the optical anisotropic plane in the vertical direction (tilt angle was 0 degree). A change in transmitted light was observed while increasing the irradiation inclination angle from 0 degree to, for example, 50 degrees. The direction of tilting the irradiation was made to coincide with the rubbing alignment treatment direction (long-axis direction of liquid crystal). When it was confirmed that the transmitted light from the vertical direction was the maximum and the transmitted light intensity was symmetrical on the left and right of the rubbing direction with the vertical direction as the center, it was determined to be homogeneous alignment (see FIG. 2 ). This is because in the homogeneous alignment, the alignment vector of the liquid crystal is parallel to the supporting substrate. On the other hand, when it is confirmed that the change is asymmetrical in the right and left of the rubbing direction around the vertical direction, it indicates that the alignment vector of the liquid crystal molecules is tilted with respect to the supporting substrate (glass). It was judged to be oriented (see FIG. 1).

<Measurement using a polarization analyzer>
Using an ellipsometer (trade name: OPTIPRO) manufactured by Shintech Co., Ltd., an optically anisotropic substance is irradiated with light having a wavelength of 550 nm, and the incident angle of this light is inclined from the direction perpendicular to the film surface to the rubbing direction. The retardation was measured while the above was performed. Retardation is represented by Δn×d. Δn is the optical anisotropy, and d is the thickness of the optical anisotropic body.
<Calculation of average tilt angle>
It was obtained by a simulation assuming that the tilt angle changes linearly using the retardation value in steps of 10° from −50° to 50°.

The compounds used are shown below.

The compounds represented by formula (1-1-2) and formula (1-1-3) were synthesized by the method described in JP-A-2003-238491 (JP-A-4036076).
Compound (1-2-6) to compound (1-2-7) were synthesized according to the method described in Makromol. Chem., 190, 2255-268 (1989).
The compound represented by the formula (5-1-71) was synthesized by a method similar to that described in DE 2722589.

Polymers for photo-alignment films are disclosed in JP-A-2013-177561, p. The homopolymer (molecular weight 60,000) of the compound (1-3) described in 52 was dissolved in cyclopentanone.

[Example 1]
[Preparation of Solution of Polymerizable Liquid Crystal Composition (1)]
These compounds were mixed in a weight ratio of compound (1-1-3): compound (1-2-6): compound (1-2-7)=60:20:20. The polymerization initiator NCI-930 (manufactured by ADEKA) at a weight ratio of 0.05 to the total weight of this mixture, 0.001 of Irganox (registered trademark) 1076 and 0.003 of PolyFox (registered trademark) PF-3320. (Diacrylate type, n of fluoro side chain is 1, p1 is 20) was added as the component (B). Then, cyclohexanone was added to obtain a solution of the polymerizable liquid crystal composition (1) in which the concentration of the mixture of the polymerizable liquid crystal compounds was 20% by weight.

A polyamic acid for high pretilt angle (OCB orientation mode) (Rixon Aligner: PIA-5580 JNC Co., Ltd.) is applied on a glass substrate (Matsunami slide glass: S-1112), dried at 80° C. for 3 minutes, and then dried. It was baked at 30° C. for 30 minutes and rubbed with a rubbing cloth made of rayon (alignment film having been rubbed). Next, the solution of the polymerizable liquid crystal composition (1) was applied on the rubbing-treated glass substrate with an alignment film by spin coating. This substrate was heated at 80° C. for 1 minute and cooled at room temperature for 1 minute, and the coating film from which the solvent was removed was polymerized in the air with ultraviolet rays to obtain a liquid crystal film (optically anisotropic body). The obtained optically anisotropic substance was put between two polarizing plates arranged in crossed nicols, and when the substrate was placed in a dark field state, it was confirmed that there was no light leakage, and it was judged that the orientation was uniform. When the retardation of this optically anisotropic substance was measured, the results were as shown in FIG. 1 and it was found that the splay orientation was obtained due to the asymmetry and the average tilt angle was 22°. At this time, the front phase difference was 138 nm, and the thickness of the optically anisotropic body was about 0.8 μm.

[Example 2]
In the polymerizable liquid crystal composition (1) described in Example 1, the weight ratio of compound (1-1-2): compound (1-2-6): compound (5-1-71)=60:20:20. Then, a solution of the polymerizable liquid crystal composition (2) was obtained in the same manner as in the method described in Example 1 except that these compounds were mixed to form an optically anisotropic body. When the retardation of the obtained optically anisotropic body was measured, it was found that the same tendency as in FIG. 1 was obtained and the average tilt angle was 18°. At this time, the front phase difference was 138 nm and the thickness of the optically anisotropic body was about 0.9 μm. Further, when the obtained optically anisotropic substance was put between two polarizing plates arranged in crossed nicols and the substrate was placed in a dark field state, it was confirmed that there was no light leakage, and it was judged that the orientation was uniform.

[Example 3]
These compounds were mixed in a weight ratio of compound (1-1-3): compound (1-2-7)=60:40. The weight ratio of the compound to the total weight of this mixture was 0.03 (3-2-1, n=1), the same polymerization initiator NCI-930 (manufactured by ADEKA), the same 0.001 irganox (the same). (Registered trademark) 1076 and 0.003 of PolyFox (registered trademark) PF-3320 (diacrylate type, n of fluoro side chain is 1, p1 is 20) were added as the component (B). Then, cyclohexanone was added to obtain a solution of the polymerizable liquid crystal composition (3) in which the concentration of the mixture of the polymerizable liquid crystal compounds was 20% by weight.

A polymer for photo-alignment film (dimerization type) was formed on a glass substrate (Matsunami slide glass: S-1112), and alignment treatment was carried out by polarized light exposure of 313 nm. At this time, the glass substrate was tilted by 30° from the perpendicular direction. Next, the solution of the polymerizable liquid crystal composition (3) was applied by spin coating on the glass substrate with a photo-alignment-treated alignment film. This substrate was heated at 120° C. for 1 minute and cooled at room temperature for 1 minute, and the solvent-free coating film was polymerized in the air with ultraviolet rays to obtain a liquid crystal film (optically anisotropic substance). The obtained optically anisotropic substance was put between two polarizing plates arranged in crossed nicols, and when the substrate was placed in a dark field state, it was confirmed that there was no light leakage, and it was judged that the orientation was uniform. When the retardation of this optical anisotropic body was measured, it was found that the tendency was the same as in FIG. 1 and the average tilt angle was 25°. At this time, the front phase difference was 138 nm and the thickness of the optically anisotropic body was about 0.9 μm.

[Example 4]
Example 1 Polymerizable liquid crystal composition described in (1), except that instead of PolyFox (R) PF-3320, PF-6320 (n a and ^{n b} is 1, p2 + p3 is 20) were mixed, A solution of the polymerizable liquid crystal composition (4) was obtained in the same manner as in Example 1 to form an optically anisotropic body. When the retardation of the obtained optical anisotropic body was measured, it was found that the same tendency as in FIG. 1 was obtained and the average tilt angle was 20°. At this time, the front phase difference was 138 nm and the thickness of the optically anisotropic body was about 0.9 μm. Further, when the obtained optically anisotropic substance was put between two polarizing plates arranged in crossed nicols and the substrate was placed in a dark field state, it was confirmed that there was no light leakage, and it was judged that the orientation was uniform.

[Comparative Example 1]
In the polymerizable liquid crystal composition (1) described in Example 1, TEGOFLOW (registered trademark) 370 (vinyl-based surfactant) was mixed in place of PolyFox (registered trademark) PF-3320, A solution of the polymerizable liquid crystal composition (5) was obtained in the same manner as the method described in 1, and an optically anisotropic body was formed. When the retardation of the obtained optical anisotropic body was measured, the result was as shown in FIG. 2, and it was found that the average tilt angle was about 4° and the state was close to horizontal alignment because the results were as shown in FIG. .. At this time, the front phase difference was 140 nm, and the thickness of the optically anisotropic body was about 0.8 μm.

[Comparative example 2]
In the polymerizable liquid crystal composition (2) described in Example 2, TEGOFLOW (registered trademark) 370 (vinyl-based surfactant) was mixed in place of PolyFox (registered trademark) PF-3320, A solution of the polymerizable liquid crystal composition (6) was obtained in the same manner as the method described in 1, to form an optically anisotropic body. When the retardation of the obtained optical anisotropic body was measured, the tendency was the same as in FIG. 2 and it was found that the average tilt angle was about 4° and the state was close to horizontal alignment because the tendency was similar to that of FIG. .. At this time, the front phase difference was 140 nm, and the thickness of the optically anisotropic body was about 0.9 μm.

[Heat resistance evaluation]
The splay-oriented optically anisotropic substance obtained above was placed in an oven at 200° C. for 30 minutes, and the changes in retardation and average tilt angle were evaluated.
The front phase difference maintenance rate of Example 1 was 85%, and the average tilt angle was 22°, which was unchanged.
In Example 2, the front phase difference maintenance ratio was 80%, and the average tilt angle was 15°, which was slightly changed.
In Example 3, the front phase difference maintenance ratio was 80%, and the average tilt angle was slightly changed to 20°.
The front phase difference maintenance ratio of Example 4 was 80%, and the average tilt angle was 21°, which was slightly changed.

From the above results, it is understood that the splay alignment of the polymerizable liquid crystal can be easily promoted, that is, controlled by using the component (B) containing the compound represented by the formula (2-1) or (2-2). Further, it is understood that the heat resistance of the optically anisotropic substance in which the component (B) is contained in the polymerizable liquid crystal compound (1) and spray-aligned is excellent.

The polymerizable liquid crystal composition used in the splay-aligned optically anisotropic substance of the present invention is expected to be a raw material of a member for liquid crystal display devices and the like.

Claims (11)

Component (A), which is at least one compound selected from the group of compounds represented by formula (1-1), formula (1-2) and formula (1-3), and
The polymerizable liquid crystal composition containing the component (B), which is at least one compound selected from the group of compounds represented by formulas (2-1) and (2-2), is polymerized to form the above-mentioned (A). Optically anisotropic substance whose components are spray-oriented.

(Wherein Z ¹¹ is independently hydrogen, fluorine, methyl or trifluoromethyl; W ¹ is independently hydrogen, fluorine or methoxy;
W ² and W ³ are independently hydrogen or methyl;
X ¹ is independently a single bond or —CH ₂ CH ₂ —;
Z ¹² is independently hydrogen, fluorine, methyl or trifluoromethyl;
W ⁴ is hydrogen, linear alkyl having 1 to 7 carbons, branched alkyl having 1 to 7 carbons, —COOR ^a (provided that ^Ra is linear alkyl having 1 to 7 carbons), or —COR ^b (provided that. , R ^b is straight-chain alkyl having 1 to 15 carbon atoms);
X ² is independently -O- or a group represented by the formula (a);
m1, m2, n1 and n2 are each independently an integer of 2 to 15. )

(Here, p1 is an integer of 5 to 20; n is independently 1 or 2; R1 is independently formula (2-a), formula (2-b) or hydrogen. (Except when both R1 are hydrogen.)

(Here, p2 and p3 are integers of 1 or more, and the sum of p2 and p3 is 6 to 20;
n ^a and n ^b are independently 1 or 2. ) In formulas (1-1) to (1-3),
Z ¹¹ is independently hydrogen or methyl;
W ¹ is independently hydrogen or fluorine;
The optical anisotropic body according to claim 1, wherein Z ¹² is independently hydrogen or methyl. In formula (1-1) and formula (1-3),
The optically anisotropic substance according to claim ² , wherein W ² is hydrogen and W ³ is methyl.

The optical anisotropic body according to claim 2, wherein in the formulas (1-1) and (1-3), W ² and W ³ are methyl. In formula (2-1),
The optical anisotropic body according to any one of claims 1 to 4, wherein p1 is 20; n is 1; and R1 is formula (2-a) or formula (2-b). The weight ratio of (B) component with respect to the total weight of (A) component is 0.0001-0.10, The optically anisotropic body as described in any one of Claims 1-5. A method for promoting splay alignment of a polymerizable liquid crystal compound at the time of production of an optically anisotropic substance, which comprises using one of the compounds represented by formula (2-1) and formula (2-2).

(Here, p1 is an integer of 5 to 20; n is independently 1 or 2; R1 is independently formula (2-a), formula (2-b) or hydrogen; One R1 is (2-a) or (2-b).)

(Here, p2 + p3 is an 6-20 integer; ^{n a} and ^{n b} are independently 1 or 2.) An optical compensation element comprising the optically anisotropic body according to claim 6. An optical element comprising the optically anisotropic body according to claim 6 and a polarizing plate. A liquid crystal display device comprising the optical compensation element according to claim 8 on an inner surface or an outer surface of a liquid crystal cell. A liquid crystal display device comprising the optical element according to claim 9 on the outer surface of a liquid crystal cell.

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