JP2009167378A - Polymerizable liquid crystal compound, polymerizable liquid crystal composition, liquid crystal polymer, and optically anisotropic substance - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable liquid crystal compound which has a wider temperature range in which it shows a liquid crystal phase, is chemically stable, is inexpensively producible, and exhibits a wide selective reflection wavelength band Δλ, a polymerizable liquid crystal composition containing this compound, liquid crystal polymers obtained by polymerizing these, and an optically anisotropic substance containing the liquid crystal polymer as a constituent material. <P>SOLUTION: Provided are a polymerizable liquid crystal compound represented by formula (I); a polymerizable liquid crystal composition containing the polymerizable liquid crystal compound and a polymerizable chiral compound polymerizable therewith; a liquid crystal polymer obtained by polymerizing the polymerizable liquid crystal compound or the polymerizable liquid crystal composition; and an optically anisotropic substance containing the liquid crystal polymer as a constituent material. In formula (I), Z<SB>1</SB>and Z<SB>2</SB>are each a 2-10C alkenyl group or the like; and a is 0 or 1. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polymerizable liquid crystal compound, a polymerizable liquid crystal composition containing the polymerizable liquid crystal compound and a polymerizable chiral compound, a liquid crystal polymer obtained by polymerizing these, and the liquid crystal polymer. The present invention relates to an optical anisotropic body as a material.

  In recent years, a liquid crystal alignment film obtained by aligning a liquid crystal polymer or a liquid crystal compound having a polymerizable functional group has been developed as an optical film such as an optical compensator used for a liquid crystal display. This film has been attracting attention as being capable of realizing a higher degree of orientation, that is, an orientation such as a tilt orientation and a twist orientation, which is impossible with a birefringent film utilizing a polymer film stretching technique.

  Also, cholesteric utilizing the selective reflection characteristics of a liquid crystal alignment film (selective reflection film) obtained by cholesteric alignment of a composition comprising a polymerizable liquid crystal compound such as a liquid crystal polymer or a liquid crystalline (meth) acrylate compound and a chiral compound. Polarizers have also been put into practical use.

  The selective reflection center wavelength λ of the selective reflection characteristic is represented by λ = n × P (where n is an average refractive index and P is a cholesteric pitch). The selective reflection wavelength band Δλ is Δλ = Δn × P (where Δn is (ne−no), ne is an extraordinary refractive index, and no is an ordinary refractive index). ] Is represented. Therefore, in order to widen the selective reflection wavelength band Δλ, a material having a large Δn, that is, optical anisotropy is required.

  Further, in order to use the selective reflection film as a cholesteric polarizer in a liquid crystal display, it is necessary that selective reflection occurs in the visible light region. Usually, since the selective reflection wavelength band Δλ in one layer of the selective reflection film is narrower than the visible light region, a plurality of selective reflection films are laminated in order to widen the selective reflection wavelength band Δλ. For this reason, the selective reflection film using a material having a narrow selective reflection wavelength band Δλ has a problem that the number of laminated layers increases and the productivity is low. Therefore, also from this point, a material having a wide selective reflection wavelength band Δλ, that is, a material having a large Δn (such as a polymerizable liquid crystal compound) is demanded.

  However, any of the conventionally known polymerizable compounds having a large Δn is poor in solubility, coating property, and orientation, and has selective orientation that can be used for use or when it cannot be uniformly formed into a film. In some cases, it was difficult to obtain a film.

On the other hand, as a liquid crystalline compound, the following formula (A)

In the formula, Ra represents an alkyl group, and Rb represents an alkyl group, a cyano group, a fluorine atom, a trifluoromethoxy group, or the like.
This compound is an excellent liquid crystal material having characteristics such as a wide temperature range exhibiting a liquid crystal phase, chemical stability and inexpensive production.

  However, these azines are not always satisfactory in compatibility with currently used liquid crystal compounds. Further, in the above formula (A), if the number of carbon atoms of the side chain alkyl group is increased, the compatibility can be improved somewhat, but there is also a problem that the temperature range showing the liquid crystal phase becomes narrow.

  In order to solve such a problem, Patent Document 1 discloses the following formula (B):

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and when R is an alkyl group, the double bond is in a trans configuration. P represents an integer of 1 to 10, and q represents 0. Or W, X and Y represent a fluorine atom, a chlorine atom, a methyl group, a cyano group or a hydrogen atom, Z represents a fluorine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms or Represents an alkoxyl group, an alkenyl group having 3 to 12 carbon atoms, or an alkenyloxy group, and one or more hydrogen atoms contained in these groups may be substituted with fluorine atoms). Liquid crystal compounds have been proposed.

This compound is chemically stable to heat, light, etc., has excellent liquid crystallinity, and can be easily produced industrially. Moreover, since it is excellent in compatibility with a conventional liquid crystal compound or liquid crystal composition, the response time of the obtained liquid crystal can be greatly improved by using this. Therefore, it is considered to be practical as a constituent component of a liquid crystal material for a liquid crystal display element capable of high-speed response over a wide temperature range.
However, liquid crystal display devices in recent years have been improved in performance, and there is a demand for the development of liquid crystal materials having a wide Δn range, a wide temperature range showing a liquid crystal phase, being chemically stable and inexpensive, and having a large Δn. Is the current situation.

JP-A-10-147562

  The present invention has been made in view of the above-described prior art, has a wider temperature range showing a liquid crystal phase, is chemically stable, can be manufactured at low cost, and has a wide selective reflection wavelength band Δλ. That is, a polymerizable liquid crystal compound having a large Δn, a polymerizable liquid crystal composition containing the compound, a liquid crystal polymer obtained by polymerizing these compounds, and an optical anisotropic body comprising the liquid crystal polymer as a constituent material The issue is to provide.

  As a result of diligent research to solve the above problems, the present inventor generally has a conjugated linear shape called a mesogenic group that imparts liquid crystal alignment properties, which is generally present at the center of a chain of a polymerizable liquid crystal compound having a chain structure. A predetermined compound having an azine skeleton as an atomic group is chemically stable to heat, light, etc., has excellent liquid crystallinity, can be easily manufactured industrially, and has a selective reflection wavelength band Δλ. It has been found that it is wide, that is, Δn is large and is particularly suitable as a material for forming a cholesteric liquid crystal layer, and the present invention has been completed.

Thus, according to the first aspect of the present invention, the following polymerizable liquid crystal compounds (1) to (6) are provided.
(1) The following formula (I)

[Wherein Y _{1 to} Y ₅ are each independently a chemical single bond, —O—, —S—, —O—C (═O) —, —C (═O) —O—, — O—C (═O) —O—, —NR ¹ —C (═O) —, —C (═O) —NR ¹ —, —O—C (═O) —NR ¹ —, —NR ¹ — It represents C (═O) —O—, —NR ¹ —C (═O) —NR ¹ —, —O—NR ¹ —, or —NR ¹ —O—. Here, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
G ₁ represents a divalent aliphatic group having 1 to 20 carbon atoms that may have a substituent. The aliphatic group includes —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C (═O) —O—, —NR ^2. -C (= O) -, - C (= O) -NR 2 -, - NR 2 -, or -C (= O) - may be interposed (but, -O- and -S- is Except when two or more adjacent to each other.) Here, R < ² > represents a hydrogen atom or a C1-C6 alkyl group.
Z ₁ and Z ₂ each independently represent an alkenyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom.
A ₁ and A ₂ each independently represent a divalent organic group A having 1 to 30 carbon atoms.
X _{1 to} X ₈ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, a cyano group, a nitro group, —OR ³ , —O—C ( ═O) —R ³ , —C (═O) —OR ³ , —O—C (═O) —OR ³ , —NR ⁴ —C (═O) —R ³ , —C (═O) —NR ³ , or —O—C (═O) —NR ³ . Here, R ³ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms, and in the case of an alkyl group, the alkyl group includes —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C (═O) —O—, —NR ⁵ —C (═O) —, —C (═O) — ^{NR 5 -, - NR 5 -} , or -C (= O) - is optionally interposed (unless However, the -O- and -S- is interposed adjacent 2 or more, respectively.). Here, R ⁴ and R ⁵ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
a is 0 or 1; ]
A polymerizable liquid crystal compound represented by:

(2) A ₁ and A ₂ are each independently a phenylene group that may have a substituent, a biphenylene group that may have a substituent, or a naphthylene that may have a substituent. The polymerizable liquid crystal compound according to (1), which is a group.
(3) Z ₁ and Z ₂ are each independently CH ₂ ═CH—, CH ₂ ═C (CH ₃ ) —, CH ₂ ═C (Cl) —, CH ₂ ═CH—CH ₂ —, CH _{2 = C (CH 3) -CH} 2 -, CH 2 = C (CH 3) -CH 2 CH 2 -, (CH 3) 2 C = CH-CH 2 -, CH 3 -CH = CH-, or CH The polymerizable liquid crystal compound according to (1) or (2), wherein ₃ -CH═CH—CH ₂ —.

(4) Y _{1 to} Y ₅ are each independently —C (═O) —O—, —O—C (═O) —, or —O—,
G ₁ is — (CH ₂ ) ₆ — or — (CH ₂ ) ₄ — (in these groups, —O—, —C (═O) —O—, or —O—C (═O) — May be interposed)
Z ₁ and Z ₂ are each independently CH ₂ ═CH—, CH ₂ ═C (CH ₃ ) —, or CH ₂ ═C (Cl) —,
A ₁ and A ₂ are each independently

Any of the groups represented by
X _{1 to} X ₈ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, —C (═O) —OR ³ , —O—C (═O) —R ³ , or — OR ³ [R ³ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms. When R ³ is an alkyl group, —O—, —C (═O) —O—, or —O—C (═O) — may be interposed in the alkyl group (provided that — Except when two or more O- are present adjacent to each other.) The polymerizable liquid crystal compound according to (1).

(5) Y _{1 to} Y ₅ are each independently —C (═O) —O—, —O—C (═O) —, or —O—,
G ₁ is — (CH ₂ ) ₆ — or — (CH ₂ ) ₄ —,
Z ₁ and Z ₂ are each independently CH ₂ ═CH— or CH ₂ ═C (CH ₃ ) —,
A ₁ and A ₂ are of the formula

A group represented by
X _{1 to} X ₈ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, —C (═O) —OR ³ , —O—C (═O) —R ³ , or — OR ³ [R ³ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms. When R ³ is an alkyl group, —O—, —C (═O) —O—, or —O—C (═O) — may be interposed in the alkyl group (provided that — Except when two or more O- are present adjacent to each other.) The polymerizable liquid crystal compound according to (1).

(6) Y _{1 to} Y ₅ are each independently —C (═O) —O—, —O—C (═O) —, or —O—,
G ₁ is — (CH ₂ ) ₆ — or — (CH ₂ ) ₄ —,
Z ₁ and Z ₂ are CH ₂ ═CH—
A ₁ and A ₂ are of the formula

A group represented by
X _{1 to} X ₈ are each independently a hydrogen atom, —C (═O) —OR ^3, or —OR ³ (R ³ is a hydrogen atom or an optionally substituted carbon atom having 1 to 10 carbon atoms. The polymerizable liquid crystal compound according to (1).

According to the second aspect of the present invention, there is provided a polymerizable liquid crystal composition of the following (7).
(7) A polymerizable liquid crystal composition comprising the polymerizable liquid crystal compound according to any one of (1) to (6) and a polymerizable chiral compound polymerizable with the polymerizable liquid crystal compound.
According to the third aspect of the present invention, the following liquid crystalline polymer (8) is provided.
(8) A liquid crystalline polymer obtained by polymerizing the polymerizable liquid crystal compound according to any one of (1) to (6) or the polymerizable liquid crystal composition according to (7).
According to the fourth aspect of the present invention, the following optical anisotropic body (9) is provided.
(9) An optical anisotropic body comprising the liquid crystalline polymer according to (8) as a constituent material.

The polymerizable liquid crystal compound of the present invention is a liquid crystal material that has a wide temperature range showing a liquid crystal phase, is chemically stable, can be produced at low cost, and has a wide selective reflection wavelength band Δλ, that is, a large Δn.
According to the polymerizable liquid crystal composition of the present invention, a liquid crystal layer having a wide temperature range showing a liquid crystal phase and a wide selective reflection wavelength band Δλ, that is, a large Δn can be formed.
Since the liquid crystalline polymer of the present invention has excellent orientation and high optical anisotropy (Δn), it is a retardation plate, an alignment film for liquid crystal display elements, a polarizing plate, a viewing angle widening plate, a color filter, and a low-pass filter. It is useful as a raw material for producing optical anisotropic bodies such as light polarizing prisms and various optical filters. In addition, since the optical anisotropic body of the present invention is produced using the polymerizable liquid crystal compound of the present invention, it has uniform and high-quality liquid crystal alignment.

  Hereinafter, the present invention will be described in detail by dividing it into 1) a polymerizable liquid crystal compound, 2) a polymerizable liquid crystal composition, 3) a liquid crystal polymer, and 4) an optical anisotropic body.

1) Polymerizable liquid crystal compound The polymerizable liquid crystal compound of the present invention is a compound represented by the formula (I).

In the formula (I), Y _{1 to} Y ₅ are each independently a chemical single bond, —O—, —S—, —O—C (═O) —, —C (═O ) —O—, —O—C (═O) —O—, —NR ¹ —C (═O) —, —C (═O) —NR ¹ —, —O—C (═O) —NR ¹ —, —NR ¹ —C (═O) —O—, —NR ¹ —C (═O) —NR ¹ —, —O—NR ¹ —, or —NR ¹ —O— is represented.

Here, R ¹ is a hydrogen atom; or methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n -An alkyl group having 1 to 6 carbon atoms such as a hexyl group. Among these, R ¹ is preferably a hydrogen atom or a methyl group.

Particularly preferred as a combination of Y is Y ₁ and Y ₃ are —C (═O) —O— from the viewpoint of easy synthesis and better expression of the desired effect of the present invention. ₄ and Y ₅ are —O—C (═O) —, and Y ₂ is —O—.

G ₁ is an optionally substituted divalent aliphatic group having 1 to 20 carbon atoms, preferably a divalent aliphatic group having 1 to 12 carbon atoms.
Examples of the divalent aliphatic group having 1 to 20 carbon atoms of G ₁ include a chain aliphatic group and an aliphatic group having an alicyclic structure. Among these, a chain aliphatic group such as an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 20 carbon atoms is preferable from the viewpoint of better expressing the desired effect of the present invention, a methylene group, C1-C12 alkylene groups, such as ethylene group, trimethylene group, propylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, etc. are more preferable.

Examples of the substituent of the aliphatic group of G ₁ include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and an isopropoxy group; Can be mentioned.

In addition, the aliphatic group of G ₁ includes —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C (═O) —O. —, —NR ² —C (═O) —, —C (═O) —NR ² —, —NR ² —, or —C (═O) — may be present. However, the case where two or more of —O— and —S— are adjacent to each other is excluded.

Wherein, ^{R 2} represents the same hydrogen atom or an alkyl group having 1 to 6 carbon atoms and the ^{R 1.} R ² is preferably a hydrogen atom or a methyl group.

Z ₁ and Z ₂ each independently represent an alkenyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom.

The number of carbon atoms of the alkenyl group of the _{Z 1} and _{Z 2,} 2 to 6 are preferred. As the halogen atom is a substituent of alkenyl groups Z ₁ and Z _2, a chlorine atom is preferable.

Preferable specific examples of the alkenyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom in Z ₁ and Z ₂ include CH ₂ ═CH—, CH ₂ ═C (CH ₃ ) —, CH _{2. = C (Cl) -, CH} 2 = CH-CH 2 -, CH 2 = C (CH 3) -CH 2 -, CH 2 = C (CH 3) -CH 2 -CH 2 -, (CH 3) 2 C═CH—CH ₂ —, CH ₃ —CH═CH—, CH ₃ —CH═CH—CH ₂ — and the like can be mentioned.

X _{1 to} X ₈ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, a cyano group, a nitro group, —OR ³ , —O—C ( ═O) —R ³ , —C (═O) —OR ³ , —O—C (═O) —OR ³ , —NR ⁴ —C (═O) —R ³ , —C (═O) —NR ³ , or —O—C (═O) —NR ³ .

Here, R < ³ > represents a C1-C10 alkyl group which may have a hydrogen atom or a substituent. The alkyl group having 1 to 10 carbon atoms of the alkyl group having 1 to 10 carbon atoms which may have a substituent of R ³ includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. , S-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group and the like.

Examples of the substituent of the alkyl group having 1 to 10 carbon atoms which may have a substituent of R ³ include a halogen atom such as a fluorine atom and a chlorine atom; an alkoxy group such as a methoxy group and an ethoxy group, a phenyl group, 4 -Phenyl group which may have a substituent such as methylphenyl group; and the like.

In addition, when R ³ is an alkyl group, the alkyl group includes —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C ( ═O) —O—, —NR ⁵ —C (═O) —, —C (═O) —NR ⁵ —, —NR ⁵ —, or —C (═O) — may be present.
However, the case where two or more of —O— and —S— are adjacent to each other is excluded.
Here, R ⁴ and R ⁵ represent the same hydrogen atom or alkyl group having 1 to 6 carbon atoms as R ¹ .

In the polymerizable liquid crystal compound of the present invention, from the viewpoint of easy availability of raw materials, (a) any of X _{1 to} X ₈ is a hydrogen atom, or (b) any of X _{1 to} X ₅ and X ₇ Or X ₆ and X ₈ are —OCH ₃ , —OCH ₂ CH ₃ , or —CH ₃ , or (c) X _{1 to} X ₅ , X ₇ and X ₈ are all hydrogen atoms. X ₆ is —C (═O) —OR ³ , —OCH ₃ , —OCH ₂ CH ₃ , —CH ₃ , —CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₃ or a fluorine atom. Or (d) X _{1 to} X ₄ and X _{6 to} X ₈ are all hydrogen atoms, and X ₅ is —C (═O) —OR ³ , —OCH ₃ , —OCH ₂ CH ₃ , —CH. _{3, -CH 2 CH 3, -CH} 2 CH 2 CH 3 or fluorine atom It is preferable that.

a is the number of repetitions of (G ₁ -Y ₁ ) units. a is 0 or 1, and is preferably 1 from the viewpoint of ease of synthesis and better expression of the desired effect of the present invention.

Specific examples of the group represented by the formula: —Y ₂ — (G ₁ —Y ₁ ) _a —Z ₁ , which are bonded to A ₁ and A ₂ in the formula (I), include the following. It is done.
First, the legend of a = 1, that is, the structure represented by the following formula (α) will be mentioned.

（α）

(Α)

In the formula (α), Y ₂ is —C (═O) —O—, G ₁ is a hexamethylene group (— (CH ₂ ) ₆ —), Y ₁ is —O—C (═O) —, Z ₁ corresponds to a vinyl group.
Specific examples of the structure similar to the structure represented by the above formula (α) are shown below.

  Next, the legend of a = 0, that is, the structure represented by the following formula (β) will be mentioned.

（β）

(Β)

In the above formula (β), Y ₂ corresponds to —C (═O) —O—, and Z ₁ corresponds to a vinyl group.
Specific examples of the structure similar to the structure represented by the above formula (β) are shown below.

A ₁ and A ₂ each independently represent a divalent organic group A having 1 to 30 carbon atoms. As carbon number of the organic group A, 6-20 are preferable. The organic group A of A ₁ and A _2, is not particularly limited, those having an aromatic ring are preferred.
Specific examples of A ₁ and A ₂ include the following.

The organic groups mentioned as specific examples of A ₁ and A ₂ may have a substituent at any position. Examples of the substituent include a halogen atom, a cyano group, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, and a —C (C═O) —OR group; It is done. Here, R is an alkyl group having 1 to 6 carbon atoms. Among these, a halogen atom, an alkyl group, and an alkoxy group are preferable, a fluorine atom as the halogen atom, a methyl group, an ethyl group, and a propyl group as the alkyl group, and a methoxy group and an ethoxy group as the alkoxy group. preferable.

As A ₁ and A ₂ , any one of groups represented by the following formulas (A ₁₁ ), (A ₂₁ ), and (A ₃₁ ) is preferable from the viewpoint of better expressing the desired effect of the present invention. And a group represented by the following formula (A ₁₁ ) is more preferable. In addition, the groups represented by the following formulas (A ₁₁ ), (A ₂₁ ) and (A ₃₁ ) may have a substituent at an arbitrary position.

Among these, as the polymerizable liquid crystal product of the present invention, in the formula (I), Y _{1 to} Y ₅ are each independently —C (═O) —O—, —O—C (═O). -, Or -O-,
G ₁ is — (CH ₂ ) ₆ — or — (CH ₂ ) ₄ — (in these groups, —O—, —C (═O) —O—, or —O—C (═O) — May be interposed)
Z ₁ and Z ₂ are each independently CH ₂ ═CH—, CH ₂ ═C (CH ₃ ) —, or CH ₂ ═C (Cl) —,
A ₁ and A ₂ are each independently

Any of the groups represented by
X _{1 to} X ₈ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, —C (═O) —OR ³ , —O—C (═O) —R ³ , or — OR ³ [R ³ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms. When R ³ is an alkyl group, —O—, —C (═O) —O—, or —O—C (═O) — may be interposed in the alkyl group (provided that — Except when two or more O- are present adjacent to each other.) It is preferable that the compound is

Y _{1 to} Y ₅ are each independently —C (═O) —O—, —O—C (═O) —, or —O—,
G ₁ is — (CH ₂ ) ₆ — or — (CH ₂ ) ₄ —,
Z ₁ and Z ₂ are each independently CH ₂ ═CH— or CH ₂ ═C (CH ₃ ) —,
A ₁ and A ₂ are of the formula

A group represented by
X _{1 to} X ₈ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, —C (═O) —OR ³ , —O—C (═O) —R ³ , or — OR ³ [R ³ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms. When R ³ is an alkyl group, —O—, —C (═O) —O—, or —O—C (═O) — may be interposed in the alkyl group (provided that — Except when two or more O- are present adjacent to each other.) It is more preferable that the compound is

Y _{1 to} Y ₅ are each independently —C (═O) —O—, —O—C (═O) —, or —O—,
G ₁ is — (CH ₂ ) ₆ — or — (CH ₂ ) ₄ —,
Z ₁ and Z ₂ are CH ₂ ═CH—
A ₁ and A ₂ are of the formula

A group represented by
X _{1 to} X ₈ are each independently a hydrogen atom, —C (═O) —OR ^3, or —OR ³ (R ³ is a hydrogen atom or an optionally substituted carbon atom having 1 to 10 carbon atoms. It is more preferable that it is a compound represented by the following formula:

  Preferable specific examples of the polymerizable liquid crystal compound of the present invention represented by the formula (I) include the following, but the polymerizable liquid crystal compound of the present invention is not limited to the following compounds.

  All of the polymerizable liquid crystal compounds of the present invention are —O—, —S—, —NH—C (═O) —, —C (═O) NH—, —NHC (═O) NH—, —O—. Known methods for forming various chemical bonds such as C (= O)-and -C (= O) -O- (for example, organic compound synthesis method [I], [II] Sasakawa Shoten by Sandler Caro functional group) , Published in 1976).

  The polymerizable liquid crystal compound of the present invention typically has an ether bond (—O—), an ester bond (—C (═O) —O—), an amide bond (—C (═O) NH—), and It can be produced by appropriately combining and modifying a plurality of known compounds having a desired structure by arbitrarily combining acid chloride (—COCl) formation reactions.

The ether bond can be formed, for example, as follows.
1) A compound represented by the formula: Q1-X (X represents a halogen atom) and a compound represented by the formula: Q2-OM (M: alkali metal (mainly sodium)) are mixed and condensed. Let In the formula, Q1 and Q2 represent an arbitrary organic group B (the same applies hereinafter). This reaction is generally called Williamson synthesis.
2) A compound represented by the formula: Q1-X (X represents a halogen atom) and a compound represented by the formula: Q2-OH were mixed in the presence of a base such as sodium hydroxide or potassium hydroxide. To condense.
3) A compound represented by the formula: Q1-E (E represents an epoxy group) and a compound represented by the formula: Q2-OH were mixed in the presence of a base such as sodium hydroxide or potassium hydroxide. To condense.
4) A compound represented by the formula: Q1-OFN (OFN represents a group having an unsaturated bond) and a formula: Q2-OM (M: alkali metal (mainly sodium)) are mixed with sodium hydroxide and hydroxylated. In the presence of a base such as potassium, they are mixed and subjected to an addition reaction.
5) A compound represented by the formula: Q1-X (X represents a halogen atom) and a compound represented by the formula: Q2-OM (M: alkali metal (mainly sodium)) are mixed with copper or chloride. Mix and condense in the presence of monocopper. This reaction is generally called Ullmann condensation.

Formation of an ester bond and an amide bond can be performed as follows, for example.
6): and Q1-COOH represented by compounds formula: Q2-OH or a compound represented by Q2-NH _2, dehydrated in the presence of a dehydrating condensing agent (N, N-dicyclohexylcarbodiimide, etc.) condensation Let
7) A halogenating agent is allowed to act on the compound represented by the formula: Q1-COOH to obtain the formula: Q1-COX (X represents a halogen atom), which is combined with the formula: Q2-OH or Q2- The compound represented by NH ₂ is reacted in the presence of a base.
8): a compound represented by Q1-COOH, by the action of an acid anhydride, after obtaining a mixed acid anhydride, in this one, the formula: represented by Q2-OH or Q2-NH ₂ The compound is reacted.
9): with a compound represented by Q1-COOH, wherein: the Q2-OH or the compound represented by Q2-NH _2, dehydration condensation in the presence of an acid catalyst or base catalyst.

The acid chloride can be produced by a known method. For example,
(Α) Formula: a method in which a halogenating agent such as phosphorus trichloride, phosphorus pentachloride, thionyl chloride, oxalyl chloride is allowed to act on a carboxylic acid represented by Q1-COOH; (β) formula: represented by Q1-COOAg A method in which chlorine or bromine is allowed to act on a silver salt of carboxylic acid; a method in which (γ) a compound represented by the formula: Q1-COOH is allowed to act on a carbon tetrachloride solution of red mercuric oxide;

  In the synthesis of the polymerizable liquid crystal compound of the present invention, the yield can be improved by protecting the hydroxyl group present in the intermediate. As a method for protecting a hydroxyl group, it can be produced by using a known method (for example, see Green's Protective Groups in Organic Synthesis 3rd edition published by Wiley-Interscience, 1999).

More specifically, the protection of the hydroxyl group can be performed as follows.
a) A compound represented by the formula: Q1Q2Q3-Si-X (X represents a halogen atom) and a compound represented by the formula: Q4-OH are reacted in the presence of a base such as imidazole or pyridine. In the formula, Q1 to Q4 represent an arbitrary organic group B (the same applies hereinafter).
b) A vinyl ether such as 3,4-dihydro-2H-pyran and a compound represented by Q2-OH are reacted in the presence of an acid such as paratoluenesulfonic acid, paratoluenesulfonic acid pyridine salt, hydrogen chloride or the like.
c) A compound represented by the formula: Q1-C (= O) -X (X represents a halogen atom) and a compound represented by the formula: Q4-OH in the presence of a base such as triethylamine or pyridine. React.
d) An acid anhydride compound represented by the formula: Q1-C (= O) -OC (= O) -Q2 is reacted with a compound represented by the formula: Q3-OH. In this case, a base such as sodium hydroxide or triethylamine may be present if desired.
e) A compound represented by Q1-X (X represents a halogen atom) is reacted with a compound represented by the formula: Q2-OH in the presence of a base such as sodium hydroxide or triethylamine.
f) A compound represented by the formula: Q1-O—CH ₂ —X (X represents a halogen atom) and a compound represented by the formula: Q2-OH are mixed with sodium hydride, sodium hydroxide, triethylamine, The reaction is carried out in the presence of a base such as pyridine.
_{g) Q1-O-CH 2} -C (= O) -X (X represents a halogen atom the compounds represented by) the formula:. a compound represented by Q4-OH, potassium carbonate, sodium hydroxide In the presence of a base such as
H) A compound represented by the formula: Q1-O—C (═O) —X (X represents a halogen atom) and a compound represented by the formula: Q2-OH are present in a base such as triethylamine or pyridine. React below.

The deprotection of the protecting group for the hydroxyl group can be deprotected by using a known method depending on the structure and type of the protecting group. For example, the following method is mentioned.
(I) Deprotection method using a fluoride such as tetrabutylammonium fluoride (ii) Deprotection method using an acid such as paratoluenesulfonic acid, paratoluenesulfonic acid pyridine salt, hydrogen chloride, acetic acid (iii) ) Method of deprotection using a base such as sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, pyridine, etc. (iv) Deprotection by hydrogenation in the presence of a catalyst such as Pd-C How to protect

In any reaction, after the completion of the reaction, the usual post-treatment operation in organic synthetic chemistry is performed, and if desired, by applying known separation / purification means such as column chromatography, recrystallization method, distillation method, etc. Product can be isolated.
The structure of the target product can be identified by measurement of NMR spectrum, IR spectrum, mass spectrum, etc., elemental analysis or the like.

2) Polymerizable liquid crystal composition The second aspect of the present invention is a polymerizable liquid crystal composition containing the polymerizable liquid crystal compound of the present invention and a polymerizable chiral compound polymerizable with the polymerizable liquid crystal compound.

  The composition of the present invention contains one or more of the polymerizable liquid crystal compounds of the present invention described above as essential components. The composition of the present invention includes, in addition to the polymerizable liquid crystal compound of the present invention, JP-A-11-130729, JP-A-8-104870, JP-A-2005-309255, JP-A-2005-263789, Other publicly known others such as those described in JP-T-2002-533742, JP-A-2002-308832, JP-A-2002-265421, JP-A-62-070406, JP-A-11-10055, etc. One or two or more of the polymerizable liquid crystal compounds can be used.

  The content of other known polymerizable liquid crystal compounds is not particularly limited, but is preferably 50% by weight or less and more preferably 30% by weight or less in the total amount of the polymerizable liquid crystal compound used in the present invention.

The polymerizable chiral compound used in the composition of the present invention is a compound having a chiral carbon atom in the molecule and polymerizable with the polymerizable liquid crystal compound of the present invention, and the orientation of the polymerizable liquid crystal compound of the present invention. If it does not disturb, there is no particular limitation.
Here, “polymerization” means a chemical reaction in a broad sense including a crosslinking reaction in addition to a normal polymerization reaction.

  The polymerizable liquid crystal compound of the present invention constituting the polymerizable liquid crystal composition of the present invention can develop a cholesteric phase by mixing with the polymerizable chiral compound.

In the composition of the present invention, the polymerizable chiral compound can be used alone or in combination of two or more.
Examples of the polymerizable chiral compound to be used include known compounds as described in JP-A No. 11-193287.

  Specific examples of the polymerizable chiral compound used in the present invention include, but are not limited to, compounds represented by the following three general formulas.

In the above formula, examples of R ⁶ and R ⁷ include a hydrogen atom, a methyl group, and a methoxy group. Examples of Y ⁹ and Y ¹⁰ include —O—, —O—C (═O) —, —O—C (═O) —O—, and the like. M ¹ and m ² are each independently ² , 4 or 6. More specifically, examples of the compounds represented by these general formulas include compounds shown below.

  In the polymerizable liquid crystal composition of the present invention, the mixing ratio of the polymerizable chiral compound is usually 0.1 to 100 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the polymerizable liquid crystal compound. .

  In general, a polymerization initiator, particularly a photopolymerization initiator, is preferably added to the polymerizable liquid crystal composition of the present invention from the viewpoint of performing a polymerization reaction more efficiently. Examples of the polymerization initiator include polymerization initiators described in the section “3) Liquid crystalline polymer” described later.

  In the polymerizable liquid crystal composition of the present invention, the blending ratio of the polymerization initiator is usually 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the polymerizable liquid crystal compound. It is.

  The polymerizable liquid crystal composition of the present invention preferably contains a surfactant in order to adjust the surface tension. Although there is no limitation in particular as this surfactant, Usually, a nonionic surfactant is preferable. A commercially available product may be used as the nonionic surfactant, and examples thereof include a nonionic surfactant that is an oligomer having a molecular weight of about several thousand, such as KH-40 manufactured by Seimi Chemical Co., Ltd. In the polymerizable liquid crystal composition of the present invention, the blending ratio of the surfactant is usually 0.01 to 10 parts by weight, preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the polymerizable liquid crystal compound.

  When the polymerizable liquid crystal composition of the present invention is used for a polarizing film or a raw material for an alignment film, or for printing inks, paints, protective films, etc., other than the above components, other components described below are used depending on the purpose. Copolymerizable monomers, metals, metal complexes, dyes, pigments, fluorescent materials, phosphorescent materials, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange You may mix | blend other additives, such as resin and metal oxides, such as a titanium oxide. In the polymerizable liquid crystal composition of the present invention, the blending ratio of other additives is usually 0.1 to 20 parts by weight per 100 parts by weight of the polymerizable liquid crystal compound.

  The polymerizable liquid crystal composition of the present invention usually contains a predetermined amount of the polymerizable liquid crystal compound of the present invention, a polymerizable chiral compound, a photopolymerization initiator, a nonionic surfactant, and other additives as appropriate. It can be prepared by dissolving in a solvent.

  Organic solvents to be used include ketones such as cyclopentanone, cyclohexanone and methyl ethyl ketone; acetates such as butyl acetate and amyl acetate; halogenated hydrocarbons such as chloroform, dichloromethane and dichloroethane; 1,4-dioxane and cyclopentylmethyl And ethers such as ether, tetrahydrofuran and tetrahydropyran;

  The polymerizable liquid crystal composition obtained as described above is useful as a raw material for producing a cholesteric liquid crystal layer or a cholesteric liquid crystal polymer as described later.

3) Liquid Crystalline Polymer The third aspect of the present invention is a liquid crystal polymer obtained by polymerizing the polymerizable liquid crystal compound of the present invention or the polymerizable liquid crystal composition of the present invention.
Here, “polymerization” means a chemical reaction in a broad sense including a crosslinking reaction in addition to a normal polymerization reaction.

  Specifically, the liquid crystalline polymer of the present invention is obtained by polymerizing (1) a liquid crystalline polymer obtained by polymerizing the polymerizable liquid crystal compound of the present invention, or (2) polymerizing the polymerizable liquid crystal composition of the present invention. It is a liquid crystalline polymer obtained as described above.

(1) Liquid crystalline polymer obtained by polymerizing the polymerizable liquid crystal compound of the present invention The liquid crystalline polymer obtained by polymerizing the polymerizable liquid crystal compound of the present invention includes a single weight of the polymerizable liquid crystal compound of the present invention. A copolymer composed of two or more of the polymerizable liquid crystal compounds of the present invention, a copolymer of the polymerizable liquid crystal compound of the present invention and other known polymerizable liquid crystal compounds, or the polymerizable liquid crystal compound of the present invention And other copolymerizable monomers.

  Examples of the other known polymerizable liquid crystal compounds include JP-A-11-130729, JP-A-8-104870, JP-A-2005-309255, JP-A-2005-263789, and JP-T-2002-533742. Examples thereof include polymerizable liquid crystal compounds as described in JP-A No. 2002-308832, JP-A No. 2002-265421, JP-A No. 62-070406, JP-A No. 11-10055 and the like.

  The other copolymerizable monomer is not particularly limited, and examples thereof include 4- (2-methacryloyloxyethyloxy) benzoic acid-4′-methoxyphenyl, 4- (6-methacryloyloxyhexyl). Oxy) benzoic acid biphenyl, 4- (2-acryloyloxyethyloxy) benzoic acid-4′-cyanobiphenyl, 4- (2-methacrylolyloxyethyloxy) benzoic acid-4′-cyanobiphenyl, 4- (2 -Methacryloyloxyethyloxy) benzoic acid-3 ', 4'-difluorophenyl, 4- (2-methacryloyloxyethyloxy) benzoic acid naphthyl, 4-acryloyloxy-4'-decylbiphenyl, 4-acryloyloxy- 4′-cyanobiphenyl, 4- (2-acryloyloxyethyloxy) -4′-si Nobiphenyl, 4- (2-methacryloyloxyethyloxy) -4'-methoxybiphenyl, 4- (2-methacryloyloxyethyloxy) -4 '-(4 "-fluorobenzyloxy) -biphenyl, 4-acryloyloxy- 4′-propylcyclohexylphenyl, 4-methacryloyl-4′-butylbicyclohexyl, 4-acryloyl-4′-amyltran, 4-acryloyl-4 ′-(3,4-difluorophenyl) bicyclohexyl, 4- (2- And acryloyloxyethyl) benzoic acid (4-amylphenyl), 4- (2-acryloyloxyethyl) benzoic acid (4- (4′-propylcyclohexyl) phenyl), and the like.

  When the liquid crystalline polymer of the present invention is a copolymer of the polymerizable liquid crystal compound of the present invention and another polymerizable liquid crystal compound, the content of the polymerizable liquid crystal compound unit of the present invention is particularly limited. Although it is not a thing, 50 weight% or more is preferable with respect to all the structural units, and 70 weight% or more is more preferable. If it exists in this range, since the glass transition temperature (Tg) of liquid crystalline polymer is high and high film | membrane hardness is obtained, it is preferable.

  (Co) polymerization of the polymerizable liquid crystal compound of the present invention and other copolymerizable monomers used as necessary can be carried out in the presence of a suitable polymerization initiator. The proportion of the polymerization initiator used may be the same as the proportion of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition.

  As the polymerization initiator to be used, an appropriate one may be selected and used depending on the type of polymerizable group present in the polymerizable liquid crystal compound to be used. For example, a radical polymerization initiator is used if the polymerizable group is radically polymerizable, an anionic polymerization initiator is used if it is an anionic polymerizable group, and a cationic polymerization initiator is used if it is a cationically polymerizable group. That's fine. As the radical polymerization initiator, either a thermal radical generator or a photo radical generator can be used, but it is preferable to use a photo radical generator.

  Examples of the photo radical generator include benzoin such as benzoin, benzoin methyl ether, and benzoin propyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloro Acetophenones such as acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one and N, N-dimethylaminoacetophenone; 2-methylanthraquinone, Anthraquinones such as 1-chloroanthraquinone and 2-amylanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthio Thioxanthones such as Sandton; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, methylbenzophenone, 4,4-dichlorobenzophenone, 4,4-bisdiethylaminobenzophenone, Michler's ketone and 4-benzoyl-4-methyldiphenyl sulfide 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

  Specific examples of the photo radical polymerization initiator include, for example, trade name Irgacure 907, trade name Irgacure 184, trade name Irgacure 369, and trade name Irgacure 651 manufactured by Ciba Specialty Chemicals.

  Examples of the anionic polymerization initiator to be used include alkyl lithium compounds; monolithium salts or monosodium salts such as biphenyl, naphthalene, and pyrene; polyfunctional initiators such as dilithium salts and trilithium salts;

Examples of the cationic polymerization initiator used include proton acids such as sulfuric acid, phosphoric acid, perchloric acid, and trifluoromethanesulfonic acid; Lewis acids such as boron trifluoride, aluminum chloride, titanium tetrachloride, and tin tetrachloride. An aromatic onium salt or a combination system of an aromatic onium salt and a reducing agent.
These polymerization initiators can be used alone or in combination of two or more.

  Further, when performing (co) polymerization with the polymerizable liquid crystal compound and other copolymerizable monomers used as necessary, an ultraviolet absorber, an infrared absorber, an oxidizer are optionally added. Functional compounds such as inhibitors may be present.

  More specifically, the liquid crystalline polymer of the present invention includes (A) the polymerizable liquid crystal compound in the presence of a suitable polymerization initiator, and other copolymerizable monomers used as necessary. And (B) the polymerizable liquid crystal compound, and other copolymerizable monomers used as necessary, together with a polymerization initiator, in an organic solvent. After the solution dissolved in is coated on a support by a known coating method, the solvent can be removed with the monomer oriented and then heated or irradiated with active energy rays.

  The organic solvent used in the method (A) is not particularly limited as long as it is inert, and examples thereof include aromatic hydrocarbons such as toluene, xylene, mesitylene, etc .; ketones such as cyclohexanone, cyclopentanone, and methyl ethyl ketone. Acetic esters such as butyl acetate and amyl acetate; Halogenated hydrocarbons such as chloroform, dichloromethane and dichloroethane; Ethers such as cyclopentyl methyl ether, tetrahydrofuran and tetrahydropyran; Among these, from the viewpoint of excellent handleability, those having a boiling point of 60 to 250 ° C are preferable, and those having a boiling point of 60 to 150 ° C are more preferable.

  In the case of the method (A), for example, the target liquid crystalline polymer is isolated from the polymerization reaction liquid after the reaction is performed according to the polymerization reaction conditions described later, and the resulting liquid crystalline polymer is appropriately used. Prepare a solution by dissolving in an organic solvent, dry the coating film obtained by coating this solution on a suitable support, heat it to a temperature that shows liquid crystallinity, and slowly cool it. The liquid crystal state can be fixed.

  Examples of organic solvents for dissolving the liquid crystalline polymer include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; ester solvents such as butyl acetate and amyl acetate; dichloromethane, chloroform, dichloroethane, and the like. And halogenated hydrocarbon solvents such as tetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1,4-dioxane, cyclopentyl methyl ether, and the like.

  As the support, a known and commonly used substrate can be used regardless of whether it is organic or inorganic. Examples of the material of the substrate include polycycloolefins (for example, ZEONEX, ZEONOR (registered trademark; manufactured by Nippon Zeon), ARTON (registered trademark; manufactured by JSR), and APPEL (registered trademark; manufactured by Mitsui Chemicals)). , Polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, cellulose, cellulose triacetate, polyethersulfone, silicon, glass, calcite and the like. The shape of the substrate may be a curved surface other than a flat plate. These substrates may have an electrode layer, an antireflection function, and a reflection function as necessary.

  As a method of applying the liquid crystalline polymer solution to the support, a known method can be used. For example, a curtain coating method, an extrusion coating method, a roll coating method, a spin coating method, a dip coating method, a bar coating method, Examples thereof include a spray coating method, a slide coating method, and a printing coating method.

  Examples of the organic solvent used in the method (B) include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; ester solvents such as butyl acetate and amyl acetate; dichloromethane, chloroform, dichloroethane, and the like. Halogenated hydrocarbon solvents; ether solvents such as tetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1,4-dioxane, cyclopentyl methyl ether;

  Although it does not specifically limit as a support body to be used, For example, the thing similar to what was listed as what can be used for coating the solution of the liquid crystalline polymer mentioned above is mentioned.

  Moreover, as a method for applying the polymerization reaction solution to the support in the method (B), a known method can be used. For example, the above-mentioned liquid crystalline polymer solution is coated on the support. Examples of the method to do are the same as those listed.

In the method (B), it is preferable to align the polymerizable liquid crystal compound coated on the support. As a method for aligning the polymerizable liquid crystal compound, for example, a method in which the above-mentioned support is previously subjected to an alignment treatment can be mentioned. As a preferable method of performing an alignment treatment on the support, a method of performing a treatment such as rubbing by providing a liquid crystal alignment layer composed of various polyimide alignment films, polyvinyl alcohol alignment films, etc. on the support, SiO _{2 on} the support A method of irradiating polarized or non-polarized light to an organic thin film having a functional group that undergoes photodimerization reaction in the molecule or an organic thin film having a functional group that is isomerized by light, etc. A well-known method is mentioned. Polymerization of the polymerizable liquid crystal compound may be performed according to polymerization reaction conditions as described later.

(2) Liquid crystalline polymer obtained by polymerizing the polymerizable liquid crystal composition of the present invention By polymerizing the polymerizable liquid crystal composition of the present invention in the presence of a polymerization initiator, the liquid crystalline polymer of the present invention is obtained. Can be easily obtained. The obtained liquid crystalline polymer is a cholesteric liquid crystalline polymer. In the present invention, it is preferable to use a polymerizable liquid crystal composition containing a polymerization initiator as described above, particularly a photopolymerization initiator and a polymerizable chiral compound, from the viewpoint of performing a polymerization reaction more efficiently. Hereinafter, an embodiment using such a polymerizable liquid crystal composition will be described.

  Specifically, for example, the polymerizable liquid crystal composition of the present invention is applied on a support having an alignment function obtained according to the method for performing the alignment treatment, and polymerization in the polymerizable liquid crystal composition of the present invention is performed. The liquid crystalline polymer of the present invention can be obtained by uniformly aligning and polymerizing the liquid crystalline compound while maintaining the cholesteric phase. As the support, those described above can be used.

  In the above method, in order to form a uniform alignment state, a polyimide thin film that gives a pretilt angle used in a normal twisted nematic (TN) element or a super twisted nematic (STN) element is used. Control of the alignment state of the polymerizable liquid crystal compound can be facilitated.

Generally, when a liquid crystal composition is brought into contact with a support having an alignment function, the liquid crystal compound is aligned along the direction in which the support is aligned on the support surface. Whether the liquid crystal compound is aligned horizontally with respect to the support surface or inclined or perpendicular is greatly influenced by the alignment treatment method on the support surface.
For example, when an alignment film having a very small pretilt angle as used in an in-plane switching (IPS) type liquid crystal display element is provided on a support, a polymerizable liquid crystal layer aligned almost horizontally can be obtained.

  In addition, when an alignment film used for a TN type liquid crystal display element is provided on a support, a polymerizable liquid crystal layer having a slightly inclined alignment is obtained, and an alignment used for an STN type liquid crystal display element is obtained. When a film is used, a polymerizable liquid crystal layer having a large alignment can be obtained.

  In addition, when the polymerizable liquid crystal composition of the present invention is brought into contact with a support having a pre-tilt angle and having a horizontal alignment function, the angle is uniformly or continuously changed from the support surface to the vicinity of the air interface and tilted. An oriented optical anisotropic body can be obtained.

  In addition, an organic thin film having a functional group that undergoes photodimerization reaction in a molecule or an organic thin film having a functional group that is isomerized by light (hereinafter abbreviated as “photo-alignment film”) is irradiated with polarized light or non-polarized light, etc. If the photo-alignment method is used, a substrate in which regions having different orientation directions are distributed in a pattern can be produced.

  First, a support having a uniform orientation is prepared by irradiating light having a wavelength in the absorption band of the photo-alignment film onto the support on which the photo-alignment film is installed. Thereafter, the support is covered with a mask and irradiated with light having a different state from the first irradiation at the absorption wavelength of the photo-alignment film, for example, light having a different polarization state or light having a different irradiation angle and direction from above the mask. Only the irradiated portion has an orientation function different from that of the portion obtained by the first irradiation.

  If the polymerizable liquid crystal composition is brought into contact with the support in which regions having different alignment functions are distributed in the pattern obtained as described above, regions having different alignment directions are formed in a pattern according to the alignment function of the support. Distributed. If polymerization by light irradiation is performed in this state, a liquid crystalline polymer film having an alignment pattern can be obtained.

  In particular, when a support having a substantially horizontal alignment function in which regions having different alignment directions are distributed in a pattern is used as the support, a liquid crystalline polymer film particularly useful as a retardation film can be obtained. .

  In addition, as a method for obtaining an alignment pattern, a method that does not use a photo-alignment film, such as a method of rubbing the alignment film with an AFM (atomic force microscope) stylus or a method of edging an optical anisotropic body, can be employed. A method using a photo-alignment film is simple and preferable.

  Examples of a method for applying the polymerizable liquid crystal composition of the present invention on a support include known and usual coating methods such as bar coating, spin coating, roll coating, gravure coating, spray coating, die coating, cap coating, and dipping. Can be mentioned. At this time, in order to improve coatability, a known and commonly used organic solvent may be added to the polymerizable liquid crystal composition of the present invention. In this case, it is preferable to remove the organic solvent by natural drying, heat drying, reduced pressure drying, reduced pressure heat drying or the like after coating the polymerizable liquid crystal composition of the present invention on the support.

  After coating, the liquid crystal compound in the polymerizable liquid crystal composition of the present invention is preferably uniformly aligned while maintaining the cholesteric phase. Specifically, the alignment can be further promoted by performing a heat treatment that promotes the alignment of the liquid crystal.

  As the heat treatment method, for example, the polymerizable liquid crystal composition of the present invention is coated on a support, and then the C (solid phase) -N (nematic phase) transition temperature (hereinafter referred to as “CN transition temperature”) of the liquid crystal composition. The aforesaid polymerizable liquid crystal composition is brought into a liquid crystal phase or an isotropic phase liquid state. From there, it is gradually cooled as necessary to develop a cholesteric phase. At this time, it is desirable to maintain the temperature at which the liquid crystal phase is once exhibited, and to sufficiently grow the liquid crystal phase domain into a mono domain.

  In addition, after applying the polymerizable liquid crystal composition of the present invention on a support, a heat treatment may be performed so that the temperature is maintained for a certain time within a temperature range in which the cholesteric phase of the polymerizable liquid crystal composition of the present invention is expressed. .

If the heating temperature is too high, the polymerizable liquid crystal compound may deteriorate due to an undesirable polymerization reaction. Moreover, when it cools too much, a polymeric liquid crystal composition raise | generates a phase-separation, expresses a high-order liquid crystal phase like crystal precipitation and a smectic phase, and an alignment process may become impossible.
By performing such heat treatment, a homogeneous liquid crystalline polymer film with few alignment defects can be produced as compared with a coating method in which coating is simply performed.

  In addition, after the homogeneous alignment treatment is performed in this manner, the liquid crystal phase is cooled to the lowest temperature at which phase separation does not occur, that is, is brought into a supercooled state, and the liquid crystal phase is aligned at the temperature and polymerized. Thus, a liquid crystalline polymer film having high alignment order and excellent transparency can be obtained.

  Examples of the method for polymerizing the polymerizable liquid crystal compound or the polymerizable liquid crystal composition of the present invention include a method of irradiating active energy rays and a thermal polymerization method, but the reaction proceeds at room temperature without requiring heating. The method of irradiating active energy rays is preferable. Among these, a method of irradiating light such as ultraviolet rays is preferable because the operation is simple.

The temperature at the time of irradiation is set to a temperature at which the polymerizable liquid crystal compound or polymerizable liquid crystal composition of the present invention can maintain a liquid crystal phase, and in order to avoid induction of thermal polymerization of the polymerizable liquid crystal compound or polymerizable liquid crystal composition, as much as possible. It is preferable to set it at 30 degrees C or less. In addition, the polymerizable liquid crystal compound or the polymerizable liquid crystal composition usually has a N (nematic phase) -I (isotropic liquid phase) transition temperature (hereinafter referred to as “N— Abbreviated as “I transition temperature”). On the other hand, in the temperature lowering process, a non-equilibrium state is taken thermodynamically, so that the liquid crystal state may be maintained without being solidified even at a temperature lower than the CN transition temperature. This state is called a supercooled state. In the present invention, a polymerizable liquid crystal compound or a polymerizable liquid crystal composition in a supercooled state is also included in the state in which the liquid crystal phase is maintained. The ultraviolet irradiation intensity is usually in the range of 1 W / m ^{2 to} 10 kW / m ² , preferably in the range of 5 W / m ^{2 to 2} kW / m ² .

  In addition, after polymerizing only a specific part using a mask by ultraviolet irradiation, the orientation state of the unpolymerized part is changed by applying an electric field, a magnetic field or temperature, and then the unpolymerized part is polymerized. A liquid crystalline polymer film having a plurality of regions having different orientation directions can be obtained.

  In addition, when only a specific part is polymerized by ultraviolet irradiation using a mask, the orientation is regulated by applying an electric field, a magnetic field or a temperature to a polymerizable liquid crystal compound or a polymerizable liquid crystal composition in an unpolymerized state in advance. A liquid crystalline polymer film having a plurality of regions having different orientation directions can also be obtained by irradiating light from above the mask and polymerizing it while maintaining this state.

  The liquid crystalline polymer obtained by polymerizing the polymerizable liquid crystal compound or the polymerizable liquid crystal composition of the present invention can be used alone as it is peeled from the support, or it can be used as it is without being peeled from the support. It can also be used as

  In particular, the liquid crystalline polymer film obtained by polymerizing the polymerizable liquid crystal composition of the present invention is a cholesteric liquid crystal film and has an extremely high reflectance, and thus is suitable as a polarizer in a liquid crystal display element.

  In addition to this, a multilayer that covers all light in the visible spectrum by laminating a plurality of such liquid crystalline polymer films by a laminating method and appropriately selecting the selection wavelength of the selected liquid crystalline polymer film A polarizer can also be obtained (see EP07720041).

  Also, instead of such a multilayer polarizer, it can also be used as a so-called broad-band polarizer in combination with suitable compounds and processing conditions. As an implementation method for this purpose, for example, the methods described in WO98 / 08135 pamphlet, EP0606940 gazette, GB23125029 gazette, WO96 / 02016 pamphlet and the like can be mentioned.

  Furthermore, a color filter can also be produced using the polymerizable liquid crystal compound or polymerizable liquid crystal composition of the present invention. For this purpose, the required wavelengths can be applied appropriately by the application methods customary for those skilled in the art.

  Furthermore, the thermochromic property of cholesteric liquid crystal can also be used. By adjusting the temperature, the color of the cholesteric layer changes from red to blue via green. A specific zone can be polymerized at a defined temperature using a mask.

  The number average molecular weight of the liquid crystalline polymer of the present invention obtained as described above is preferably 500 to 500,000, more preferably 5,000 to 300,000. If the number average molecular weight is within such a range, a high film hardness can be obtained and handleability is excellent, which is desirable. The number average molecular weight of the liquid crystalline polymer can be measured by gel permeation chromatography (GPC) using monodispersed polystyrene as a standard sample and tetrahydrofuran (THF) as an eluent.

  In the liquid crystalline polymer of the present invention, it is presumed that the crosslinking points are present uniformly in the molecule. Since it is obtained by polymerizing the polymerizable liquid crystal compound of the present invention, the crosslinking efficiency is high and the hardness is excellent.

  The liquid crystalline polymer of the present invention utilizes the orientation and the anisotropy of physical properties such as refractive index, dielectric constant, magnetic susceptibility, etc., and a retardation plate, an alignment film for liquid crystal display elements, a polarizing plate, It can be used as a constituent material of an optical anisotropic body such as a viewing angle widening plate, a color filter, a low-pass filter, a light polarizing prism, and various optical filters.

4) Optical anisotropic body The fourth aspect of the present invention is an optical anisotropic body comprising the liquid crystalline polymer of the present invention as a constituent material.
Examples of the optical anisotropic body of the present invention include a retardation plate, an alignment film for liquid crystal display elements, a polarizing plate, a viewing angle widening plate, a color filter, a low-pass filter, a light polarizing prism, and various optical filters.

  Since the optical anisotropic body of the present invention uses a liquid crystalline polymer obtained by polymerizing the polymerizable liquid crystal compound of the present invention as a constituent material, it has a uniform and high-quality liquid crystal alignment.

The production method of the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. Parts and% are based on weight unless otherwise specified.
The test methods performed in this example are as follows.

Example 1 Synthesis of Compound 1

(Step 1) Synthesis of Intermediate A

In a four-necked reactor equipped with a condenser, a thermometer and a dropping funnel, 30 g (0.25 mol) of 4-hydroxybenzoic acid and 44.4 g (0.29 mol) of t-butyldimethylsilyl chloride were added in a nitrogen stream. , N-dimethylformamide (hereinafter abbreviated as “DMF”) was dissolved in 400 ml. A solution obtained by dissolving 41.8 g (0.61 mol) of imidazole in 200 ml of DMF was slowly added to this solution with a dropping funnel in a water bath. Then, reaction was performed at room temperature for 4 hours. After completion of the reaction, the reaction solution was poured into 3 L of saturated aqueous sodium hydrogen carbonate solution and extracted three times with 500 ml of n-hexane. The n-hexane layer was dried over anhydrous magnesium sulfate, and then magnesium sulfate was filtered off. The filtrate was concentrated with a rotary evaporator to obtain a pale yellow oil. The pale yellow oil was purified by silica gel column chromatography (n-hexane: ethyl acetate = 9: 1 (volume ratio)) to obtain 30 g of colorless oil (yield: 50.8%).
The structure of the target product was identified by ¹ H-NMR.

¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 9.87 (s, 1H), 7.78 (d, 2H, J = 7.8 Hz), 6.93 (d, 2H, J = 7) .8Hz), 0.98 (s, 9H), 0.23 (s, 6H)

(Step 2) Synthesis of Intermediate B

  In a four-necked reactor equipped with a condenser, a thermometer and a dropping funnel, 10.6 g (0.21 mol) of hydrazine monohydrate was dissolved in 50 ml of ethanol in a nitrogen stream. To this solution, a solution prepared by dissolving 10.0 g (0.042 mol) of Intermediate A in 50 ml of tetrahydrofuran (hereinafter abbreviated as “THF”) was slowly added with a dropping funnel at room temperature. Then, reaction was performed at room temperature for 3 hours. After completion of the reaction, the reaction solution was concentrated on a rotary evaporator to obtain a yellow oil. This yellow oil was dissolved in 200 ml of chloroform, and the chloroform layer was washed twice with 500 ml of saturated aqueous sodium bicarbonate. Next, 6 ml of triethylamine was added to the chloroform layer and then dried over anhydrous magnesium sulfate, and magnesium sulfate was filtered off. The filtrate was concentrated with a rotary evaporator to obtain a pale yellow oil.

This yellow oil was dissolved in 50 ml of THF, and 6 ml of triethylamine was added. To this solution, a solution prepared by dissolving 6.3 g (0.038 mol) of ethyl vanillin (3-ethoxy-4-hydroxybenzaldehyde) in 50 ml of THF was slowly added with a dropping funnel at room temperature. Then, reaction was performed at room temperature for 12 hours. After completion of the reaction, insoluble matters were filtered off, and the obtained filtrate was concentrated under reduced pressure using a rotary evaporator to obtain a yellow oil. The obtained yellow oil was purified by silica gel column chromatography (n-hexane: THF = 2: 1 (volume ratio)) to obtain 10.76 g of a yellow solid (yield: 60.3%).
The structure of the target product was identified by ¹ H-NMR.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 8.59 (s, 1H), 8.56 (s, 1H), 7.73 (s, 1H), 7.71 (s, 1H) 7.50 (s, 1H), 7.21 (d, 1H, J = 8.0 Hz), 7.00-6.89 (m, 3H), 4.23 (t, 2H, J = 6. 8Hz), 1.49 (t, 3H, J = 6.8Hz), 1.00 (s, 9H), 0.23 (s, 6H)

(Step 3) Synthesis of Intermediate C

In a four-necked reactor equipped with a condenser, a thermometer and a dropping funnel, in a nitrogen stream, intermediate B 5.0 g (0.0125 mol), 4- (6-acryloyl-n-hexyloxy) benzoic acid (Nippon Siebel) 4.0 g (0.014 mol) of Hegner was dissolved in 80 ml of DMF. To this solution, 2.6 g (0.014 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC) was added at room temperature. Then, reaction was performed at room temperature for 12 hours. After completion of the reaction, the reaction solution was poured into water and extracted twice with 200 ml of chloroform. The chloroform layer was dried over anhydrous magnesium sulfate, and magnesium sulfate was filtered off. The filtrate was concentrated with a rotary evaporator to obtain a yellow oil. This yellow oil was purified by silica gel column chromatography (n-hexane: THF = 85: 15 (volume ratio)) to obtain 4.8 g of a light yellow solid (yield: 57.1%).
The structure of the target product was identified by ¹ H-NMR.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 8.41 (s, 2H), 7.97-7.95 (m, 2H), 7.55-7.53 (m, 2H), 7.06-6.98 (m, 3H), 6.78-6.70 (m, 4H), 6.21 (d, 1H, J = 17.2 Hz), 5.93 (dd, 1H, J = 10.4 Hz, J = 17.2 Hz), 5.62 (d, 1H, J = 10.4 Hz), 4.00-3.92 (m, 4H), 3.86-3.83 (m, 2H), 1.66-1.63 (m, 2H), 1.54-1.51 (m, 2H), 1.34-1.28 (m, 4H), 1.13 (t, 3H, J = 6.2 Hz), 0.81 (s, 9H), 0.21 (s, 6H)

(Step 4) Synthesis of Intermediate D

To a four-necked reactor equipped with a condenser, a thermometer and a dropping funnel, 30 ml of 1M tetrabutylammonium fluoride in THF was added in a nitrogen stream. A solution prepared by dissolving 4.0 g (0.0059 mol) of Intermediate C in 50 ml of THF was slowly added thereto at room temperature using a dropping funnel. After completion of the dropping, the reaction was performed at room temperature for 3 hours. After completion of the reaction, the reaction solution was poured into water and made acidic by adding 50 ml of 1% aqueous citric acid solution. This solution was extracted twice with 300 ml of chloroform. The chloroform layer was dried over anhydrous sodium sulfate, and then sodium sulfate was filtered off. The filtrate was concentrated with a rotary evaporator to obtain a yellow oil. This yellow oil was purified by silica gel column chromatography (n-hexane: THF = 2: 1 (volume ratio)) to obtain 2.2 g of a yellow solid (yield: 66.8%).
The structure of the target product was identified by ¹ H-NMR.

¹ H-NMR (400 MHz, CDCl ₃ / CD ₃ OD, TMS, δ ppm): 8.60 (s, 1H), 8.57 (s, 1H), 8.14 (d, 2H, J = 8.4 Hz) ), 7.72 (d, 2H, J = 8.4 Hz), 7.54 (s, 1H), 6.70-6.95 (m, 4H), 6.84 (d, 2H, J = 8) .4 Hz), 6.39 (d, 1 H, J = 17.2 Hz), 6.11 (dd, 1 H, J = 10.0 Hz, J = 17.2 Hz), 5.81 (d, 1 H, J = 10.0 Hz), 4.18-4.02 (m, 6H), 1.85-1.82 (m, 8H), 1.30 (t, 3H, J = 6.8 Hz)

(Step 5) Synthesis of Intermediate E

  In a four-necked reactor equipped with a condenser, thermometer and dropping funnel, in a nitrogen stream, THF 200 ml, 4-hydroxybenzoic acid 12.0 g (0.087 mol), and N, N-dimethylaniline 22.1 g (0 .18 mol) was added to make a uniform solution. Thereafter, a solution obtained by dissolving 8.66 g (0.1 mol) of acrylic acid chloride in 40 ml of THF was added dropwise over 15 minutes in a water bath, and then the reaction was further performed for 5 hours.

After completion of the reaction, the reaction solution was poured into 1500 ml of 1.2N aqueous hydrochloric acid and extracted twice with 300 ml of chloroform. The chloroform layer was dried over anhydrous magnesium sulfate, and then magnesium sulfate was filtered off. The filtrate was concentrated with a rotary evaporator to obtain a yellow solid. This yellow solid was purified by silica gel column chromatography (n-hexane: THF = 75: 25 (volume ratio)) to obtain 6.2 g of a white solid (yield: 37.1%).
The structure of the target product was identified by ¹ H-NMR.

¹ H-NMR (400 MHz, CD ₃ OD, TMS, δ ppm): 8.08 (d, 2H, J = 8.8 Hz), 7.22 (d, 2H, J = 8.8 Hz), 6.61 ( d, 1H, J = 17.6 Hz), 6.33 (dd, 1H, J = 10.6 Hz, J = 17.6 Hz), 6.04 (d, 1H, J = 10.6 Hz)

(Step 6) Synthesis of Compound 1 In a four-necked reactor equipped with a condenser, a thermometer and a dropping funnel, 2.0 g (0.0036 mol) of Intermediate D and 0.76 g of Intermediate E (0. 004 mol), 49 mg (0.0004 mol) of N, N-dimethylaminopyridine was dissolved in 50 ml of DMF. To this solution, 0.77 g (0.004 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC) was added at room temperature. Then, reaction was performed at room temperature for 9 hours. After completion of the reaction, the reaction solution was poured into water and extracted twice with 200 ml of chloroform. The chloroform layer was dried over anhydrous magnesium sulfate and then filtered to remove magnesium sulfate. The filtrate was concentrated with a rotary evaporator to obtain a yellow solid. This yellow solid was purified by silica gel column chromatography (changed from toluene: ethyl acetate = 90: 10 (volume ratio) to toluene: ethyl acetate = 85: 15 (volume ratio)) to obtain Compound 1 as a pale yellow solid. 1.85 g was obtained (yield: 70.1%).
The structure of the target product was identified by ¹ H-NMR.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 8.67 (s, 1H), 8.62 (s, 1H), 8.25 (d, 2H, J = 8.4 Hz), 8. 15 (d, 2H, J = 8.8 Hz), 7.91 (d, 2H, J = 8.4 Hz), 7.61 (s, 1H), 7.37-7.27 (m, 5H), 6.97-6.95 (m, 3H), 6.65 (d, 1H, J = 17.6 Hz), 6.41-6.30 (m, 2H), 6.14-6.05 (m , 2H), 5.81 (dd, 1H, J = 1.2 Hz, J = 10.4 Hz), 4.19-4.12 (m, 4H), 4.06-4.02 (m, 2H) 1.85-1.80 (m, 2H), 1.75-1.68 (m, 2H), 1.55-1.49 (m, 4H), 1.32 (t, 3H, J = 7.0Hz)

<Evaluation of compound>
(1) Measurement of phase transition temperature 10 mg of compound 1 (test compound) was weighed and sandwiched between two glass substrates with a polyimide alignment film that had been rubbed in the solid state. The substrate was heated from 30 ° C. to 250 ° C. on a hot plate, and then lowered to 30 ° C. again. Changes in the structure of the structure when the temperature was raised and lowered were observed with a deflecting optical microscope (ECLIPSE LV100POL type manufactured by Nikon Corporation), and the phase transition temperature was measured. The measured phase transition temperatures are shown in Table 1.

  In Table 1, “C” represents Crystal, “N” represents Nematic, and “I” represents Isotropic. “Crystal” indicates that the test compound is in the solid phase, “Nematic” indicates that the test compound is in the nematic liquid crystal phase, and “Isotropic” indicates that the test compound is in the isotropic liquid phase.

(2) Measurement of optical anisotropy (Δn value) 100 parts by weight of Compound 1 was dissolved in 233 parts by weight of cyclopentanone. A solution obtained by adding 2.7 parts by weight of a photopolymerization initiator (Ciba Specialty Chemicals, Irgacure 907) to this solution and dissolving it was used as a sample. The prepared solution was applied to a glass substrate having a rubbed polyvinyl alcohol film using a bar coater (manufactured by Tester Sangyo Co., Ltd .: bar coater Rod No. 4 shaft diameter 12.7 mm), and then on a hot plate. Dry at 100 ° C. for 2 minutes. The resulting film was irradiated with ultraviolet rays corresponding to 700 mJ / cm ² with a mercury lamp to obtain a cured polymer film having a thickness of 1.5 μm. The cured film was measured for retardation (Re) at a wavelength of 545.3 nm using an ellipsometer (XLS-100 type, manufactured by JA Woollam). Thereafter, Δn was calculated from the thickness (d) of the liquid crystal layer obtained separately by the calculation formula Δn = Re / d. The calculation results are shown in Table 1.

(3) Formation of Cholesteric Phase 100 parts by weight of Compound 1 was dissolved in 153 parts by weight of cyclopentanone. To this solution, 3.3 parts by weight of a photopolymerization initiator (manufactured by Ciba Specialty Chemicals, Irgacure 1919), 6.0 parts by weight of a chiral agent, and a surfactant (used as a 1% by weight cyclopentanone solution) A solution obtained by adding 11.6 parts by weight and dissolving was used as a sample. A compound represented by the formula (X) was used as a chiral agent, and KH-40 manufactured by Seimi Chemical Co., Ltd. was used as a surfactant.

The solution prepared as described above is applied to a glass substrate with a polyimide alignment film subjected to rubbing treatment using a bar coater (manufactured by Tester Sangyo Co., Ltd .: SA-203 bar coater Rod No. 8 shaft diameter 12.7 mm). Then, it was dried on a hot plate at 100 ° C. for 3 minutes. The obtained film was irradiated with ultraviolet rays corresponding to 1000 mJ / cm ² with a mercury lamp to obtain a cured film having a thickness of 4 μm. The transmission spectrum of this cured film was measured using a spectrophotometer (manufactured by Otsuka Electronics Co., Ltd., instantaneous multi-photometry system MCPD-3000). When a cholesteric phase was formed, a selective reflection region (a region where the transmittance was about 50%) was observed, and the bandwidth was about 50-100 nm. The evaluation results are shown in Table 1.

  Further, when a cured film of the test compound was obtained, the compatibility of the test compound was evaluated by visual observation at 23 ° C. as “◯” when there was no turbidity, and “X” when turbidity occurred. The evaluation results are shown in Table 1. Furthermore, when a solution having a test compound concentration of 40% by weight was obtained, the solubility of the test compound was also evaluated. When the test compound was dissolved in cyclopentanone at 60 ° C., “◯” was given, and when it was not, “X” was given. The evaluation results are shown in Table 1.

  The evaluation results are summarized below. It was confirmed that Compound 1 not only exhibits high solubility in a solvent, but also has excellent compatibility with additives such as a polymerization initiator and a chiral agent, and excellent handling properties. All the compounds showed good liquid crystallinity over a wide temperature range and formed a cholesteric phase. The obtained cured film was a good liquid crystal film exhibiting high optical anisotropy (Δn).

(Comparative Example 1)
A liquid crystal compound (manufactured by BASF, LC242) was evaluated in the same manner as in the methods (1) to (3) of the compound shown in Example 1. The results are summarized in Table 2.

(Comparative Example 2)
Further, the phase transition temperatures of conventional azine liquid crystal compounds are extracted from the description in JP-A-10-147562 and shown in Table 2.

The structures of the compounds shown in Comparative Examples 1 and 2 are shown below.
Known polymerizable liquid crystal compound: LC242 manufactured by BASF

Azine liquid crystal compounds described in JP-A-10-147562:

Claims (9)

Formula (I)

[Wherein Y _{1 to} Y ₅ are each independently a chemical single bond, —O—, —S—, —O—C (═O) —, —C (═O) —O—, — O—C (═O) —O—, —NR ¹ —C (═O) —, —C (═O) —NR ¹ —, —O—C (═O) —NR ¹ —, —NR ¹ — It represents C (═O) —O—, —NR ¹ —C (═O) —NR ¹ —, —O—NR ¹ —, or —NR ¹ —O—. Here, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
G ₁ represents a divalent aliphatic group having 1 to 20 carbon atoms that may have a substituent. The aliphatic group includes —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C (═O) —O—, —NR ^2. -C (= O) -, - C (= O) -NR 2 -, - NR 2 -, or -C (= O) - may be interposed (but, -O- and -S- is Except when two or more adjacent to each other.) Here, R < ² > represents a hydrogen atom or a C1-C6 alkyl group.
Z ₁ and Z ₂ each independently represent an alkenyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom.
A ₁ and A ₂ each independently represent a divalent organic group A having 1 to 30 carbon atoms.
X _{1 to} X ₈ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, a cyano group, a nitro group, —OR ³ , —O—C ( ═O) —R ³ , —C (═O) —OR ³ , —O—C (═O) —OR ³ , —NR ⁴ —C (═O) —R ³ , —C (═O) —NR ³ , or —O—C (═O) —NR ³ .
R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. When R ³ is an alkyl group, the alkyl group includes —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C (═O ) —O—, —NR ⁵ —C (═O) —, —C (═O) —NR ⁵ —, —NR ⁵ —, or —C (═O) — may be present (provided that Except when two or more of —O— and —S— are adjacent to each other.)
R ⁴ and R ⁵ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
a is 0 or 1; ]
A polymerizable liquid crystal compound represented by: A ₁ and A ₂ are each independently a phenylene group that may have a substituent, a biphenylene group that may have a substituent, or a naphthylene group that may have a substituent. The polymerizable liquid crystal compound according to claim 1. Z ₁ and Z ₂ are each independently CH ₂ ═CH—, CH ₂ ═C (CH ₃ ) —, CH ₂ ═C (Cl) —, CH ₂ ═CH—CH ₂ —, CH ₂ ═C. _{(CH 3) -CH 2 -,} CH 2 = C (CH 3) -CH 2 CH 2 -, (CH 3) 2 C = CH-CH 2 -, CH 3 -CH = CH-, or _CH 3 -CH The polymerizable liquid crystal compound according to claim 1, wherein = CH—CH ₂ —. Y _{1 to} Y ₅ are each independently —C (═O) —O—, —O—C (═O) —, or —O—,
G ₁ is — (CH ₂ ) ₆ — or — (CH ₂ ) ₄ — (in these groups, —O—, —C (═O) —O—, or —O—C (═O) — May be interposed)
Z ₁ and Z ₂ are each independently CH ₂ ═CH—, CH ₂ ═C (CH ₃ ) —, or CH ₂ ═C (Cl) —,
A ₁ and A ₂ are each independently

Any of the groups represented by
X _{1 to} X ₈ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, —C (═O) —OR ³ , —O—C (═O) —R ³ , or — OR ³ [R ³ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms. When R ³ is an alkyl group, —O—, —C (═O) —O—, or —O—C (═O) — may be interposed in the alkyl group (provided that — Except when two or more O- are present adjacent to each other.) The polymerizable liquid crystal compound according to claim 1. Y _{1 to} Y ₅ are each independently —C (═O) —O—, —O—C (═O) —, or —O—,
G ₁ is — (CH ₂ ) ₆ — or — (CH ₂ ) ₄ —,
Z ₁ and Z ₂ are each independently CH ₂ ═CH— or CH ₂ ═C (CH ₃ ) —,
A ₁ and A ₂ are of the formula

A group represented by
X _{1 to} X ₈ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, —C (═O) —OR ³ , —O—C (═O) —R ³ , or — OR ³ [R ³ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms. When R ³ is an alkyl group, —O—, —C (═O) —O—, or —O—C (═O) — may be interposed in the alkyl group (provided that — Except when two or more O- are present adjacent to each other.) The polymerizable liquid crystal compound according to claim 1. Y _{1 to} Y ₅ are each independently —C (═O) —O—, —O—C (═O) —, or —O—,
G ₁ is — (CH ₂ ) ₆ — or — (CH ₂ ) ₄ —,
Z ₁ and Z ₂ are CH ₂ ═CH—
A ₁ and A ₂ are of the formula

A group represented by
X _{1 to} X ₈ are each independently a hydrogen atom, —C (═O) —OR ^3, or —OR ³ (R ³ is a hydrogen atom or an optionally substituted carbon atom having 1 to 10 carbon atoms. The polymerizable liquid crystal compound according to claim 1, which represents an alkyl group of   A polymerizable liquid crystal composition comprising the polymerizable liquid crystal compound according to claim 1 and a polymerizable chiral compound polymerizable with the polymerizable liquid crystal compound.   A liquid crystalline polymer obtained by polymerizing the polymerizable liquid crystal compound according to claim 1 or the polymerizable liquid crystal composition according to claim 7.   An optical anisotropic body comprising the liquid crystalline polymer according to claim 8 as a constituent material.