JP5564773B2 - Polymerizable liquid crystal compound, polymerizable liquid crystal composition, liquid crystal polymer and optical anisotropic body - Google Patents

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 a constituent material of the liquid crystal polymer. It relates to an optical anisotropic body.

In recent years, a technique for producing a thin film optical anisotropic body using a liquid crystal compound has attracted attention.
In order to obtain a liquid crystal layer having optical performance as designed, it is necessary to form a good liquid crystal layer free from alignment defects. Therefore, in forming the liquid crystal layer, in order to form a liquid crystal layer having no alignment defect, very precise control is required for many items in the process from the previous step of liquid crystal coating.

More specifically, in the previous step, it is known that if the alignment film formed before applying the liquid crystal is not controlled to fit the liquid crystal compound to be applied, severe alignment defects will be experienced. .
In the liquid crystal coating process, the alignment temperature is an extremely important factor, and not only precise temperature control is required, but also the air layer in the heating furnace is disturbed, the temperature unevenness caused by it, and the transfer speed are various. It is necessary to control.

Thus, in the past, many of the measures for forming a liquid crystal layer free of alignment defects have mainly attempted to solve the problem in terms of process.
However, such attempts have many restrictions in terms of manufacturing facilities, and often have a disadvantage in terms of capital investment.
Therefore, there is a demand for the development of a new alignment improving additive that makes it difficult for alignment defects to appear only by adding a small amount to the liquid crystal composition to be applied.

As related to the present invention, Patent Document 1 includes a divalent chiral group, a monovalent group D and a monovalent group E bonded to two bonds of the chiral group, respectively. A chiral agent has been proposed in which the valent group D and the monovalent group E have the same number of rings having the same structure and satisfy the following (I) or (II).
(I) One of the monovalent group D and the monovalent group E has a carbon chain, and the other has no carbon chain.
(II) Both the monovalent group D and the monovalent group E have a carbon chain, and the carbon number of the carbon chain of the monovalent group D and the carbon chain of the monovalent group E The carbon number is different.
JP 2007-176870 A

When a cholesteric layer is formed using a liquid crystal compound, a linear alignment defect called an oily streak may appear.
This alignment defect is observed as turbidity in the cholesteric liquid crystal layer, and is known to greatly reduce the optical performance of the original liquid crystal layer.

  Therefore, the present invention provides a polymerizable liquid crystal compound that can greatly reduce or completely eliminate alignment defects by adding a very small amount, and a polymerizable liquid crystal compound containing the polymerizable liquid crystal compound and the polymerizable chiral compound. It is an object to provide a liquid crystal composition, a liquid crystalline polymer obtained by polymerizing these, and an optically anisotropic substance.

  As a result of diligent research to solve the above problems, the present inventors have found that the specific polymerizable liquid crystal compound represented by the formula (I) to be described later can add an extremely small amount of alignment defects in the liquid crystal layer to be formed. It has been found that it can be greatly reduced or completely eliminated, 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 ₁₀ 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 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
G _{1 to} G ₄ each independently represent a divalent aliphatic group having 1 to 20 carbon atoms, which 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- are 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 to} A ₄ each independently represents 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) —N ( R ³ ) R ⁴ or —O—C (═O) —N (R ³ ) R ⁴ is represented. Here, R < ³ >, R < ⁴ > represents a C1-C10 alkyl group which may have a hydrogen atom or a substituent each independently. When R ³ and / or R ⁴ 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) - is optionally interrupted (However, a case where two or more of -O- and S- are adjacent to each other is excluded.) Here, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
a and b are each independently 0 or 1, and c is an integer of 1 to 3. ]
A polymerizable liquid crystal compound represented by:

(2) In the formula (I), A _{1 to} A ₄ each independently represents a phenylene group which may have a substituent, a biphenylene group which may have a substituent, or a substituent. The polymerizable liquid crystal compound according to (1), which is a naphthylene group which may have.
(3) In the formula (I), 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 - The polymerizable liquid crystal compound according to (1) or (2), wherein CH═CH— or CH ₃ —CH═CH—CH ₂ —.

(4) In formula (I), Y _{1 to} Y ₁₀ are each independently —C (═O) —O—, —O—C (═O) —, or —O—,
G _{1 to} G ₄ are each independently — (CH ₂ ) ₆ — or — (CH ₂ ) ₄ —, and —O—, —C (═O) —O—, —O—C (= O)-or -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 to} A ₄ are each independently

The polymerizable liquid crystal compound according to (1), which is a group represented by:
(5) In formula (I), Y _{1 to} Y ₁₀ are each independently —C (═O) —O—, —O—C (═O) —, or —O—,
G _{1 to} G ₄ are each independently — (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 to} A ₄ are each independently

The polymerizable liquid crystal compound according to (1), which is a group represented by:
(6) Y _{1 to} Y ₁₀ are each independently —C (═O) —O—, —O—C (═O) —, or —O—,
G _{1 to} G ₄ are each independently — (CH ₂ ) ₆ — or — (CH ₂ ) ₄ —,
Z ₁ and Z ₂ are each independently CH ₂ ═CH—,
A _{1 to} A ₄ are each independently

The polymerizable liquid crystal compound according to (1), which is a group represented by:
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 containing the polymerizable liquid crystal compound according to any one of (1) to (6) and a polymerizable chiral 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.
.

  According to the present invention, a polymerizable liquid crystal compound that can greatly reduce or completely eliminate alignment defects by adding a very small amount, and a polymerizable liquid crystal compound containing this polymerizable liquid crystal compound and a polymerizable chiral compound. A liquid crystal composition, a liquid crystalline polymer obtained by polymerizing these, and an optical anisotropic body are provided.

  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 formula (I), Y _{1 to} Y ₁₀ 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 represents ^-NR 1 -O-.

R ¹ is a hydrogen atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, An alkyl group having 1 to 6 carbon atoms such as an n-hexyl group is represented. Among these, as R ¹ , a hydrogen atom or a methyl group is preferable.

G _{1 to} G ₄ are each independently an optionally substituted divalent aliphatic group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms optionally having a substituent. Represents a divalent aliphatic group.

Examples of the divalent aliphatic group having 1 to 20 carbon atoms of G _{1 to} G ₄ 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, and a methylene group. , An alkylene group having 1 to 12 carbon atoms such as ethylene group, trimethylene group, propylene group, tetramethylene group, pentamethylene group, hexamethylene group and octamethylene group is more preferable, and tetramethylene group [— (CH ₂ ) ₄ -], and hexamethylene group [- _{(CH 2) 6} -] it is particularly preferred.

Examples of the substituent for the aliphatic group of G _{1 to} G ₄ include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy Group, sec-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group and other C1-C6 alkoxy groups; and the like. Among these, a fluorine atom, a methoxy group, and an ethoxy group are preferable.

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 present (provided that —O— and —S -Except when two or more intervening each other.) Among these, —O—, —O—C (═O) —, and —C (═O) —O— are preferable.
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.

Specific examples of the aliphatic group mediated by these groups include —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —, —CH ₂ —CH ₂ —S—CH ₂ —CH ₂ —, —CH _{2. -CH 2 -O-C (= O} ) -CH 2 -CH 2 -, - CH 2 -CH 2 -C (= O) -O-CH 2 -, - CH 2 -O-C (= O) - _{O-CH 2 -CH 2 -,} - CH 2 -CH 2 -NR 2 -C (= O) -CH 2 -CH 2 -, - CH 2 -CH 2 -C (= O) -NR 2 -CH 2 ^{_{-, - CH 2 -NR 2 -CH}} 2 -CH 2 -, - CH 2 -C (= O) -CH 2 - and the like.

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 alkenyl group having 2 to 10 carbon atoms Z ₁ and _{Z 2,} preferably an alkenyl group having 2 to 6 carbon atoms. Moreover, as a halogen atom of a substituent, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned, A chlorine atom is preferable.

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

Among these, from the viewpoint of better express the desired effects of the present _{invention, 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 = CH-CH} 2 - is preferred.

A _{1 to} A ₄ each independently represents a divalent organic group A having 1 to 30 carbon atoms. Examples of the divalent organic group A of A _{1 to} A ₄ include a divalent aliphatic group and an aromatic group.

  The divalent aliphatic group includes a chain-like or cyclic saturated or unsaturated divalent aliphatic hydrocarbon group or alicyclic hydrocarbon group having 1 to 30 carbon atoms, preferably 2 carbon atoms. ~ 22. The unsaturated aliphatic group includes those having a double bond or a triple bond.

  Examples of the divalent aromatic group include a divalent hydrocarbon group derived from a monocyclic aromatic hydrocarbon having one benzene ring (benzene, toluene, xylene, etc.), and two or more, usually 2 to Examples thereof include a divalent hydrocarbon group derived from a polycyclic aromatic hydrocarbon having four benzene rings (naphthalene, biphenyl, terphenyl, etc.).

Among these, A _{1 to} A ₄ may each independently have a phenylene group which may have a substituent, a biphenylene group which may have a substituent, or a substituent. It is preferably a good naphthylene group, more preferably any group represented by the following (Ai), (A-ii), or (A-iii), represented by (Ai). It is particularly preferred that

In the above formula, * represents a bond, and X _{9 to} X ₂₆ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, a cyano group, or a nitro group. , —OR ⁶ , —O—C (═O) —R ⁶ , —C (═O) —OR ⁶ , —O—C (═O) —OR ⁶ , —NR ⁷ —C (═O) —R ⁶ , —C (═O) —N (R ⁶ ) R ⁷ , or —O—C (═O) —N (R ⁶ ) R ⁷ .

Here, R < ⁶ >, R < ⁷ > respectively independently represents a hydrogen atom; or the C1-C10 alkyl group which may have a substituent.
Examples of the alkyl group having 1 to 10 carbon atoms of X _{9 to} X ₂₆ , R ⁶ and R ⁷ which may have a substituent include a methyl group, an ethyl group, and n-propyl. Group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n- A decyl group etc. are mentioned, Preferably, they are a methyl group, an ethyl group, n-propyl group, and an isopropyl group.

  Examples of the substituent of the alkyl group having 1 to 10 carbon atoms which may have a substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methoxy group, ethoxy group, n-propoxy group, And an alkoxy group having 1 to 6 carbon atoms such as an isopropoxy group, an n-butoxy group, a sec-butoxy group, a t-butoxy group, an n-pentyloxy group and an n-hexyloxy group.

When R ⁶ and / or R ⁷ is an alkyl group, the alkyl group includes —O—, —S—, —O—C (═O) —, —C (═O) —O—, ^{-O-C (= O) -O} -, - NR 8 -C (= O) -, - C (= O) -NR 8 -, - NR 8 -, or, -C (= O) - is interposed You may do it.
However, the case where two or more of -O- and S- are adjacent to each other is excluded.
Wherein, ^{R 8} denotes a hydrogen atom or a similar alkyl group having 1 to 6 carbon atoms and the ^{R 1.}

R ⁶ , R ⁷ , —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C (═O) —O—, —NR ^{8 -C (= O) -,} - C (= O) -NR 8 -, - NR 8 -, or -C (= O) - are specific examples of the alkyl group _intervening, -CH 2 -CH ₂ —O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —S—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —O—C (═O) —CH ₃ , —CH ₂ —CH ₂ —C (═O) —O—CH ₃ , —CH ₂ —O—C (═O) —O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —NR ⁸ —C (═O) —CH ₃ , — CH ₂ —CH ₂ —C (═O) —NR ⁸ —CH ₃ , —CH ₂ —NR ⁸ —CH ₂ —CH ₃ , —CH ₂ —CH ₂ —C (═O) —CH _{3 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) —N ( R ³ ) R ⁴ or —O—C (═O) —N (R ³ ) R ⁴ is represented.

Here, R < ³ >, R < ⁴ > respectively independently represents the same C1-C10 alkyl group which may have a hydrogen atom; or the same substituent as said R < ⁶ >, R < ⁷ >.

When R ³ and / or R ⁴ 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) — intervene. You may do it.
However, the case where two or more of -O- and S- are adjacent to each other is excluded.
Here, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms similar to R ¹ .

R ³ , R ⁴ , —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C (═O) —O—, —NR Specific examples of the alkyl group mediated by ^5- C (═O) —, —C (═O) —NR ⁵ —, —NR ⁵ —, or —C (═O) — include —CH ₂ —CH _2. —O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —S—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —O—C (═O) —CH ₃ , —CH ₂ —CH ₂ —C (═O) —O—CH ₃ , —CH ₂ —O—C (═O) —O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —NR ⁵ —C (═O) —CH ₃ , — CH ₂ —CH ₂ —C (═O) —NR ⁵ —CH ₃ , —CH ₂ —NR ⁵ —CH ₂ —CH ₃ , —CH ₂ —CH ₂ —C (═O) —CH _{3 and the} like can be mentioned. .

  a and b are each independently 0 or 1, and c is an integer of 1 to 3.

The polymerizable liquid crystal compound of the present invention is preferably the following (α), more preferably (β), and still more preferably (γ).
(Α) In the formula (I), Y _{1 to} Y ₁₀ are each independently —C (═O) —O—, —O—C (═O) —, —O—,
G _{1 to} G ₄ each independently represent — (CH ₂ ) ₆ —, — (CH ₂ ) ₄ —, and —O—, —C (═O) —O—, —O—C (= O)-, -C (= O)-may be present,
Z ₁ and Z ₂ are each independently CH ₂ ═CH—, CH ₂ ═C (CH ₃ ) —, or CH ₂ ═C (Cl) —,
A _{1 to} A ₄ are each independently

A polymerizable liquid crystal compound which is a group represented by:
(Β) Y _{1 to} Y ₁₀ are each independently —C (═O) —O—, —O—C (═O) —, or —O—,
G _{1 to} G ₄ are each independently — (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 to} A ₄ are each independently

A polymerizable liquid crystal compound which is a group represented by:
(Γ) Y _{1 to} Y ₁₀ are each independently —C (═O) —O—, —O—C (═O) —, or —O—,
G _{1 to} G ₄ are each independently — (CH ₂ ) ₆ — or — (CH ₂ ) ₄ —,
Z ₁ and Z ₂ are each independently CH ₂ ═CH—,
A _{1 to} A ₄ are each independently

A polymerizable liquid crystal compound which is a group represented by:

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

(Wherein X ₁ represents the same meaning as described above.)
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.
(I) A compound represented by the formula: Q1-X (X represents a halogen atom; the same applies hereinafter) and a formula: Q2-OM (M represents an alkali metal (mainly sodium). The same) is mixed and condensed. In the formula, Q1 and Q2 represent arbitrary organic groups (the same applies hereinafter). This reaction is generally called Williamson synthesis.
(Ii) A compound represented by the formula: Q1-X and a compound represented by the formula: Q2-OH are mixed and condensed in the presence of a base such as sodium hydroxide or potassium hydroxide.
(Iii) A compound represented by the formula: Q1-E (E represents an epoxy group) and a compound represented by the formula: Q2-OH in the presence of a base such as sodium hydroxide or potassium hydroxide, Mix and condense.
(Iv) A compound represented by the formula: Q1-OFN (OFN represents a group having an unsaturated bond) and a compound represented by the formula: Q2-OM are mixed with sodium hydroxide, potassium hydroxide or the like. In the presence of a base, they are mixed and subjected to an addition reaction.
(V) A compound represented by the formula: Q1-X and a compound represented by the formula: Q2-OM are mixed and condensed in the presence of copper or cuprous chloride. This reaction is generally called Ullmann condensation.

Formation of an ester bond and an amide bond can be performed as follows, for example.
(I) formula: and Q1-COOH represented by compounds of formula: and Q2-OH or Q2-NH is represented by ₂ compound, in the presence of a dehydrating condensing agent (N, N-dicyclohexylcarbodiimide, etc.) dehydration Allow to condense.
(Ii) Formula: by the action of a halogenating agent to the compound represented by Q1-COOH, wherein: obtain a compound represented by Q1-COX, the ones with the formula: in Q2-OH or Q2-NH ₂ The compound represented is reacted in the presence of a base.
(Iii) formula by the action of an acid anhydride to a compound represented by Q1-COOH, after obtaining a mixed acid anhydride, in this one, the formula: represented by Q2-OH or Q2-NH ₂ The compound is reacted.
(Iv) Formula: reacting 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 formed, for example, as follows.
(I) Phosphorus trichloride or phosphorus pentachloride is allowed to act on the compound represented by the formula: Q1-COOH.
(Ii) Thionyl chloride is allowed to act on the compound represented by the formula: Q1-COOH.
(Iii) Oxalyl chloride is allowed to act on the compound represented by the formula: Q1-COOH.
(Iv) Chlorine is allowed to act on the compound represented by the formula: Q1-COOAg (Ag: silver element).
(V) A carbon tetrachloride solution of red mercuric oxide is allowed to act on the compound represented by the formula: Q1-COOH.

  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).

The hydroxyl group can be protected as follows, for example.
(I) A compound represented by the formula: Q1Q2Q3-Si-X (X represents a halogen atom; the same shall apply hereinafter) and a compound represented by the formula: Q4-OH are bases such as imidazole and pyridine. React in the presence. In the formula, Q3 and Q4 represent arbitrary organic groups (the same applies hereinafter).
(Ii) Reaction of a vinyl ether such as 3,4-dihydro-2H-pyran with a compound represented by the formula: Q2-OH in the presence of an acid such as paratoluenesulfonic acid, paratoluenesulfonic acid pyridine salt, hydrogen chloride or the like. Let

(Iii) A compound represented by the formula: Q1-C (= O) -X and a compound represented by the formula: Q2-OH are reacted in the presence of a base such as triethylamine or pyridine.
(Iv) An acid anhydride represented by the formula: Q1-C (= O) -O-C (= O) -Q2 and a compound represented by the formula: Q3-OH are optionally hydroxylated. The reaction is carried out in the presence of a base such as sodium or triethylamine.
(V) A compound represented by the formula: Q1-X and a compound represented by the formula: Q2-OH are reacted in the presence of a base such as sodium hydroxide or triethylamine.

(Vi) formula: _Q1-O-CH 2 compound represented by -X the formula: and Q2-OH are represented by compounds, sodium hydride, the reaction of sodium hydroxide, triethylamine, in the presence of a base such as pyridine Let
(Vii) formula: and _{Q1-O-CH 2 -C (} = O) represented by -X compounds of the formula: and Q2-OH are represented by compounds, potassium carbonate, the presence of a base such as sodium hydroxide To react.
(Viii) A compound represented by the formula: Q1-OC (= O) -X and a compound represented by the formula: Q2-OH are reacted in the presence of a base such as triethylamine or pyridine.

The method for deprotecting the hydroxyl-protecting group is not particularly limited, and examples thereof include the following known methods.
(I) A fluorine ion such as tetrabutylammonium fluoride is mixed to be deprotected.
(Ii) Deprotection by mixing in the presence of an acid such as paratoluenesulfonic acid, paratoluenesulfonic acid pyridine salt, hydrogen chloride, acetic acid and the like.
(Iii) Deprotection by mixing in the presence of a base such as sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, pyridine.
(Iv) Deprotection is carried out by hydrogenation in the presence of a catalyst such as Pd-C.
These methods can be appropriately selected and adopted depending on the structure and type of the protecting group.

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.

  According to the polymerizable liquid crystal compound of the present invention, by adding a small amount, alignment defects that deteriorate the optical performance of the liquid crystal layer can be greatly reduced or eliminated, and the optical performance of the liquid crystal layer as designed can be brought out. Is possible. Also, in the manufacturing process for aligning liquid crystals, the temperature and time tolerances are greatly widened, making it possible to manufacture with general manufacturing equipment, reducing capital investment, and improving the product yield. Can contribute.

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.

  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, JP-T-2002-533742, JP-A-2002-308832, JP-A-2002-265421, JP-A-62-070406, JP-A-11-10055, etc., or Japanese Patent Application No. 2008-92093, Other polymerizable liquid crystal compounds described in Japanese Patent Application Nos. 2008-92162 and 2008-170835 (hereinafter sometimes referred to as “other polymerizable liquid crystal compounds”) may be arbitrarily used.

  The content of the other polymerizable liquid crystal compound 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 capable of (co) polymerizing with the polymerizable liquid crystal compound of the present invention, and the polymerizable liquid crystal of the present invention. There is no particular limitation as long as it does not disturb the orientation of the compound.
Here, "(co) polymerization" means a chemical reaction in a broad sense including a (co) crosslinking reaction in addition to a normal (co) polymerization reaction.

In the composition of the present invention, the polymerizable chiral compound can be used alone or in combination of two or more.
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.

  As the polymerizable chiral compound, for example, known compounds described in JP-A-11-193287 can be used. Examples of such chiral compounds include, but are not limited to, compounds represented by the following three general formulas.

In the above formula, examples of R ⁹ and R ¹⁰ include a hydrogen atom, a methyl group, and a methoxy group. Examples of Y ¹¹ and Y ¹² include —O—, —O—C (═O) —, —O—C (═O) —O—, and the like. M ¹ and m ² are each independently ² , 4 or 6.
Specific examples of the compounds represented by these general formulas include the 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. .

  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 anionically polymerizable group, and a cationic polymerization initiator is used if it is a cationically polymerizable group. Good.

  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-dichloroacetophenone Acetophenones such as 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one and N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 1 -Anthraquinones such as chloroanthraquinone and 2-amylanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc. Thioxanthone; 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; Examples include 4,6-trimethylbenzoyldiphenylphosphine oxide.

  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 include alkyl lithium compounds; monolithium salts or monosodium salts such as biphenyl, naphthalene and pyrene; polyfunctional initiators such as dilithium salts and trilithium salts; and the like.

Examples of the cationic polymerization initiator 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; A combined system of a group onium salt or an aromatic onium salt and a reducing agent.
These polymerization initiators can be used singly or in combination of two or more.

  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.

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

  The polymerizable liquid crystal composition of the present invention preferably contains a surfactant in order to adjust the surface tension. The surfactant is not particularly limited, but a nonionic surfactant is usually 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. 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, metal oxides, such as a titanium oxide. In the polymerizable liquid crystal composition of the present invention, the blending ratio of other additives is preferably 0.1 to 20 parts by weight with respect to 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.

  Examples of the organic solvent 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; 1,2-dimethoxyethane, 1 , 4-dioxane, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, and other ethers;

  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 of the present invention is a liquid crystalline 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 comprising two or more of the polymerizable liquid crystal compound of the present invention, a copolymer of the polymerizable liquid crystal compound of the present invention and another polymerizable liquid crystal compound, or the polymerizable liquid crystal compound of the present invention, Examples thereof include copolymers with other copolymerizable monomers (excluding the above-described polymerizable chiral compounds).

  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′-sia 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 However, it is preferably 50% by weight or more, more preferably 70% by weight or more based on the total structural units. Within such a range, a liquid crystalline polymer having a high glass transition temperature (Tg) and high film hardness can be obtained.

  (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 anionically polymerizable group, and a cationic polymerization initiator is used if it is a cationically polymerizable group. Good.
Specific examples thereof include those listed in the section of the polymerizable liquid crystal composition of the present invention.

  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. For example, aromatic hydrocarbons such as toluene, xylene, mesitylene; 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 obtained 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.

  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 substrate made of a commonly used material can be used regardless of organic or inorganic. Examples of the material of the substrate include polycycloolefins [for example, ZEONEX (registered trademark; manufactured by ZEON CORPORATION), ZEONOR (registered trademark; manufactured by ZEON CORPORATION), ARTON (registered trademark; manufactured by JSR Corporation), 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 Etc. The shape of the substrate may be a curved surface in addition to 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, it does not specifically limit as a method of apply | coating the solution for polymerization reaction to a support body in the method of said (b), A well-known method is employable. Examples thereof include the same ones listed as methods for applying the above-mentioned liquid crystalline polymer solution on the support.

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 subjected to an alignment treatment in advance 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, from the viewpoint of performing the polymerization reaction more efficiently, it is preferable to use a polymerization initiator as described above, particularly a photopolymerization initiator.

Hereinafter, an embodiment using such a polymerizable liquid crystal composition will be described.
The polymerizable liquid crystal composition of the present invention is applied onto a support having an alignment function, obtained, for example, according to the method for performing the alignment treatment, and the polymerizable liquid crystal compound in the polymerizable liquid crystal composition of the present invention, The liquid crystalline polymer of the present invention can be obtained by uniformly aligning and polymerizing 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.

  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 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, drying under reduced pressure, drying under reduced pressure, 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. . The temperature of the heat treatment is usually 50 to 150 ° C., preferably 70 to 120 ° C., and the time of the heat treatment is usually 0.5 to 15 minutes and preferably 2 to 10 minutes.

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 the 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 by ultraviolet irradiation using a mask, 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).

  Further, instead of such a multilayer polarizer, it can be used as a so-called broad-band polarizer in combination with appropriate 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 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, and the like, 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.

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

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 ratio of the developing solvent used in the column chromatography (solvent ratio shown in parentheses) is a volume ratio.

Example 1 Synthesis of polymerizable liquid crystal compound T

Step 1: Synthesis of Intermediate A

  To a four-necked reactor equipped with a cooler and a thermometer, in a nitrogen stream, 600 g of 20% by weight potassium hydroxide aqueous solution and 100 g (0.72 mmol) of 4-hydroxybenzoic acid were added, and then 198 g of chlorohexanol ( 1.45 mmol) was added, and the whole was heated to reflux for 3 hours under vigorous stirring. To the reaction solution, 100 g of a 20 wt% aqueous potassium hydroxide solution was added, and the mixture was further heated to reflux for 4 hours. After cooling to room temperature, 600 g of water and 300 g of 2-propanol were added, and 600 g of concentrated hydrochloric acid was added dropwise over about 30 minutes to precipitate a white powder. This was collected by filtration and washed with water to obtain 147 g of intermediate A (yield 85.7%).

⁽¹ H-NMR data of intermediate A)
¹ H-NMR (500 MHz, THF-d8, TMS, δ ppm): 12.0-10.5 (bs, 1H), 8.10 (d, 2H, J = 8.5 Hz), 7.09 (d, 2H, J = 8.5 Hz), 4.19 (t, 2H, J = 6.5 Hz), 3.67 (t, 2H, J = 6.5 Hz), 1.98-1.95 (m, 2H) ) 1.70-1.60 (m, 6H).

Step 2: Synthesis of Intermediate B

  In a four-necked reactor equipped with a condenser, a thermometer, and a dropping funnel, 52.2 g (0.22 mol) of Intermediate A was added to 760 g of tetrahydrofuran (hereinafter abbreviated as “THF”) in a nitrogen stream, Stir to dissolve. After cooling to 2 ° C. in an ice bath, 36.7 g (0.24 mol) of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) was slowly added. Thereafter, 30.0 g (0.24 mol) of 2-methoxyethoxymethyl chloride diluted with 40 g of THF was gradually added dropwise over 20 minutes. After completion of dropping, the mixture was stirred as it was at 2 ° C. for 1 hour. After completion of the reaction, 10 liters of water was added to the reaction solution, and extraction was performed with 2 liters of ethyl acetate. The aqueous layer was removed by a liquid separation operation, and the obtained ethyl acetate layer was dried over anhydrous sodium sulfate and then filtered to remove sodium sulfate. The ethyl acetate layer as the filtrate was concentrated under reduced pressure using a rotary evaporator to obtain a pale yellow oil. This pale yellow oil was purified by silica gel column chromatography (gradient from n-hexane: THF = 2: 1 to 3: 2). As a white solid, 57.0 g (yield 79.7%) of Intermediate B was obtained.

⁽¹ H-NMR data of the intermediates B)
¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 8.00 (d, 2H, J = 8.8 Hz), 6.89 (d, 2H, J = 8.8 Hz), 5.54 (s , 2H), 4.00 (t, 2H, J = 6.4 Hz), 3.87-3.82 (m, 2H), 3.65 (t, 2H, J = 6.4 Hz), 3.58 -3.54 (m, 2H), 3.37 (s, 3H), 1.85-1.77 (m, 2H), 1.63-1.56 (m, 2H), 1.53-1 .41 (m, 4H).

Step 3: Synthesis of Intermediate C

  In a four-necked reactor equipped with a condenser, a thermometer and a dropping funnel, 55.0 g (0.17 mol) of the intermediate B was dissolved in 400 ml of N-methylpyrrolidone in a nitrogen stream, and 4- (6-acryloyl-hex -1-yloxy) benzoic acid (manufactured by Nippon Shibel Heguna) 73.9 g (0.25 mol) and 4- (dimethylamino) pyridine 30.9 g (0.25 mol) were further added and dissolved. 48.5 g (0.25 mol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC) was slowly added. Then, reaction was performed at 24 degreeC for 13 hours. After the reaction, 1.3 liters of ethyl acetate, 7.0 liters of water, and 0.8 liters of saturated saline were added to the reaction solution for extraction. The aqueous layer was removed by a liquid separation operation, and the obtained ethyl acetate layer was dried over anhydrous magnesium sulfate, and the magnesium sulfate was filtered off by filtration. The ethyl acetate layer was concentrated under reduced pressure using a rotary evaporator to obtain a pale yellow oil. The pale yellow oil was purified by silica gel column chromatography (n-hexane: THF = 2: 1). As a white solid, 52.8 g (yield 52.2%) of Intermediate C was obtained.

⁽¹ H-NMR data of intermediate C)
¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 8.01-7.95 (m, 4H), 6.91-6.87 (m, 4H), 6.39 (dd, 1H, J = 1.4 Hz, J = 17.4 Hz), 6.11 (dd, 1 H, J = 10.1 Hz, J = 17.4 Hz), 5.81 (dd, 1 H, J = 1.4 Hz, J = 10 .1 Hz), 5.55 (s, 2H), 4.29 (t, 2H, J = 6.7 Hz), 4.16 (t, 2H, J = 6.7 Hz), 4.03-3.98 (M, 4H), 3.88-3.85 (m, 2H), 3.58-3.56 (m, 2H), 3.38 (s, 3H), 1.86-1.67 (m , 8H), 1.54-1.40 (m, 8H).

Step 3: Synthesis of Intermediate D

  In a four-necked reactor equipped with a condenser, a thermometer and a dropping funnel, 50.0 g (0.083 mol) of Intermediate C was dissolved in THF in a nitrogen stream. After this solution was cooled to 18 ° C. in a cold water bath, a separately prepared mixed solution of 183.3 g of 12N aqueous hydrochloric acid and 83.3 g of methanol was slowly added dropwise over 35 minutes. After completion of the dropwise addition, the reaction was further carried out by stirring at 23 ° C. for 1 hour. After completion of the reaction, extraction was performed with 11.2 liters of water and 2.0 liters of ethyl acetate. The aqueous layer was removed by a liquid separation operation, and the obtained ethyl acetate layer was dried over anhydrous sodium sulfate, and then sodium sulfate was separated by filtration. The ethyl acetate layer was concentrated under reduced pressure using a rotary evaporator, and the resulting pale yellow oil was purified by silica gel column chromatography (n-hexane: THF = 2: 1). As a white solid, 25.9 g (yield 60.7%) of Intermediate D was obtained.

⁽¹ H-NMR data of intermediate D)
¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 8.04 (d, 2H, J = 8.7 Hz), 7.96 (d, 2H, J = 8.7 Hz), 6.92-6 .86 (m, 4H), 6.39 (dd, 1H, J = 1.4 Hz, J = 17.4 Hz), 6.11 (dd, 1H, J = 10.5 Hz, J = 17.4 Hz), 5.81 (dd, 1H, J = 1.4 Hz, 10.5 Hz), 4.30 (t, 2H, J = 6.6 Hz), 4.17 (t, 2H, J = 6.6 Hz), 4 .04-3.98 (m, 4H), 1.86-1.67 (m, 8H), 1.55-1.42 (m, 8H).

Step 4: Synthesis of Intermediate E

In a 4-necked reactor equipped with a condenser, thermometer and dropping funnel, 90 g (0.54 mol) of 5-formylsalicylic acid, 87 g (2.7 mol) of methanol and 4- (dimethylamino) pyridine in 1 liter of THF were added in a nitrogen stream. Dissolved. To this solution, 224 g (1.09 mol) of N, N-dicyclohexylcarbodiimide dissolved in 500 ml of THF was slowly added with a dropping funnel at room temperature. Then, reaction was performed at room temperature for 6 hours. After completion of the reaction, the reaction mixture was filtered under reduced pressure, and then THF was removed by distillation under reduced pressure using a rotary evaporator to obtain a yellow oil. This yellow oil was purified by silica gel column chromatography (n-hexane: THF = 9: 1) to obtain a white solid 80.4 (yield: 82.4%). The structure was identified by ¹ H-NMR.

⁽¹ H-NMR data of intermediate E)
¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 11.36 (s, 1H), 9.88 (s, 1H), 8.39 (s, 1H), 8.00 (d, 1H, J = 9.0 Hz), 7.11 (d, 1H, J = 9.0 Hz), 4.01 (s, 3H).

Step 5: Synthesis of Intermediate F

In a four-necked reactor equipped with a condenser, a thermometer and a dropping funnel, 100 g (0.72 mol) of 4-hydroxybenzoic acid and 126 g (0.84 mol) of t-butyldimethylsilyl chloride were added to N, N in a nitrogen stream. -Dissolved in 1.2 liters of dimethylformamide (hereinafter abbreviated as "DMF"). To this solution, 120 g (1.8 mol) of imidazole dissolved in 700 ml of DMF was slowly added 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 10 liter of saturated aqueous sodium hydrogen carbonate solution and extracted three times with 1 liter of n-hexane. The aqueous layer was removed by a liquid separation operation, and the obtained n-hexane layer was dried over anhydrous magnesium sulfate, followed by filtration to remove magnesium sulfate. The n-hexane layer was concentrated with a rotary evaporator to obtain a pale yellow oil. This pale yellow oil was purified by silica gel column chromatography (n-hexane: ethyl acetate = 9: 1) to obtain 100 g of intermediate F as a colorless oil (yield: 58.4%). The structure was identified by ¹ H-NMR.

⁽¹ H-NMR data of intermediate F)
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) .8 Hz), 0.98 (s, 9H), 0.23 (s, 6H).

Step 6: Synthesis of Intermediate G

In a four-necked reactor equipped with a condenser, a thermometer, and a dropping funnel, 106 g (2.1 mol) of hydrazine monohydrate was added to 500 ml of THF in a nitrogen stream. To this solution, 100 g (0.42 mol) of Intermediate F dissolved in 500 ml of 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 until the reaction solution reached about 200 ml. To this solution was added 2 liters of chloroform and washed twice with 5 liters of a saturated aqueous sodium bicarbonate solution. The aqueous layer was removed by liquid separation operation, and 50 ml of triethylamine was added to the resulting chloroform layer, followed by drying over anhydrous magnesium sulfate. Thereafter, filtration was performed to remove magnesium sulfate. The chloroform layer was concentrated with a rotary evaporator to obtain a pale yellow oil. This yellow oil was dissolved in 500 ml of THF, and 30 ml of triethylamine was added. Intermediate solution E72g (0.4mol) melt | dissolved in THF500ml was slowly added to this solution with the dropping funnel at room temperature. Then, reaction was performed at room temperature for 12 hours. After completion of the reaction, the reaction mixture was filtered under reduced pressure and then 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) to obtain 107.6 g of Intermediate G as a yellow solid (yield: 61.7%). The structure was identified by ¹ H-NMR.

⁽¹ H-NMR data of intermediate G)
¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 11.08 (s, 1H), 8.61 (s, 1H), 8.58 (s, 1H), 8.26 (d, 1H, J = 2.0), 8.01 (dd, 1H, J = 2.0 Hz, J = 8.8 Hz), 7.73 (d, 1H, J = 8.8 Hz), 7.06 (d, 1H) , J = 8.4 Hz), 6.90 (d, 3H, J = 8.4 Hz), 4.00 (s, 3H), 0.98 (s, 9H), 0.24 (s, 6H).

Step 7: Synthesis of Intermediate H

To a four-necked reactor equipped with a condenser, a thermometer, and a dropping funnel, 240 ml of a THF solution of tetrabutylammonium fluoride having a concentration of 1 mol / L was added in a nitrogen stream. To this solution, 100 g (0.24 mol) of Intermediate G dissolved in 500 ml of THF was slowly added through 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 poured into water, and 1% citric acid aqueous solution was added to make it weakly acidic. This solution was extracted twice with 2 liters of chloroform. The aqueous layer was removed by a liquid separation operation, and the resulting chloroform layer was dried over anhydrous sodium sulfate, followed by filtration to remove sodium sulfate. The chloroform layer 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) to obtain 63 g of intermediate H as a yellow solid (yield: 87.1%). The structure was identified by ¹ H-NMR.

⁽¹ H-NMR data of intermediate H)
¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 11.10 (s, 1H), 8.61 (s, 1H), 8.58 (s, 1H), 8.27 (d, 1H, J = 2.2 Hz), 8.01 (dd, 1H, J = 2.0 Hz, J = 8.6 Hz), 7.75 (d, 2H, J = 8.6 Hz), 7.06 (d, 1H) , J = 8.4 Hz), 6.90 (d, 2H, J = 8.4 Hz), 5.21 (s, 1H), 4.00 (s, 3H).

Step 8: Synthesis of Intermediate I

  In a four-necked reactor equipped with a condenser, a thermometer and a dropping funnel, 49.0 g of 4- (6-acryloyl-hex-1-yloxy) benzoic acid (manufactured by Nippon Shibel Heguna) in a nitrogen stream (0 .17 mol) was dissolved in 700 ml of THF. To this solution, 32.0 g (0.17 mol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC) was added and stirred at 23 ° C. for 90 minutes to form an active form. . Separately, a solution in which 50.0 g (0.17 mol) of intermediate H was dissolved in 900 ml of THF was prepared, and a solution containing the previously prepared active substance was slowly added dropwise to this solution over 80 minutes. After completion of dropping, the reaction was carried out at 23 ° C. for 7 hours. Thereafter, the reaction solution was concentrated on a rotary evaporator to 200 ml as a reaction solution. To this reaction solution, 1.6 liters of water, 200 ml of saturated saline, and 200 ml of chloroform were sequentially added, and extraction operation was performed. The chloroform layer was washed twice with 1.2 liters of 4.5% saline. The aqueous layer was removed by a liquid separation operation, and the resulting chloroform layer was dried over anhydrous magnesium sulfate, followed by filtration to remove magnesium sulfate. The chloroform layer was concentrated with a rotary evaporator to obtain a yellow oil. The obtained yellow oil was purified by silica gel column chromatography (toluene: ethyl acetate = 20: 1) to obtain 20.4 g (yield 21.3%) of intermediate I as a pale yellow solid.

⁽¹ H-NMR data of the intermediates I)
¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 11.10 (s, 1H), 8.66 (s, 1H), 8.60 (s, 1H), 8.28 (d, 1H, J = 1.8 Hz), 8.14 (d, 2H, J = 8.7 Hz), 8.02 (dd, 1H, J = 1.8 Hz, J = 8.7 Hz), 7.90 (d, 2H) , J = 8.7 Hz), 7.30 (d, 2H, J = 8.7 Hz), 7.07 (d, 1H, J = 8.7 Hz), 6.97 (d, 2H, J = 8. 7 Hz), 6.40 (dd, 1 H, J = 1.4 Hz, J = 17.4 Hz), 6.12 (dd, 1 H, J = 10.6 Hz, J = 17.4 Hz), 5.82 (dd , 1H, J = 1.4 Hz, J = 10.6 Hz), 4.18 (t, 2H, J = 6.4 Hz), 4.05 (t, 2H, J = 6.4 Hz), .00 (s, 3H), 1.88-1.81 (m, 2H), 1.76-1.69 (m, 2H), 1.56-1.44 (m, 4H).

Step 9: Synthesis of polymerizable liquid crystal compound T In a four-necked reactor equipped with a condenser, a thermometer and a dropping funnel, in a nitrogen stream, 193 g of N-methylpyrrolidone, 19.3 g of intermediate I (0.034 mol), intermediate Form D 25.9 g (0.051 mol) and 4- (dimethylamino) pyridine 0.62 g (5.1 mmol) were added and dissolved. Next, 9.70 g (0.051 mol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC) was slowly added and reacted at 24 ° C. for 12 hours. After the reaction, extraction was performed using 2.5 liters of ethyl acetate, 2.5 liters of water, and 1.7 liters of saturated brine, the aqueous layer was removed by liquid separation, and the resulting ethyl acetate layer was treated with anhydrous sodium sulfate. Dried. After sodium sulfate was filtered off, the filtrate was concentrated with a rotary evaporator to obtain a yellow oil. The obtained yellow oil was purified by silica gel column chromatography (toluene: ethyl acetate = 10: 1) to obtain 5.4 g (yield 15.0%) of a polymerizable liquid crystal compound T as a pale yellow solid.

( ¹ H-NMR data of polymerizable liquid crystal compound T)
¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 8.68 (s, 2H), 8.48 (d, 1H, J = 2.3 Hz), 8.17-8.09 (m, 5H) ), 7.98 (d, 2H, J = 8.7 Hz), 7.92 (d, 2H, J = 8.7 Hz), 7.34-7.31 (m, 3H), 6.99-6 .96 (m, 4H), 6.89 (d, 2H, J = 9.2 Hz), 6.40 (dd, 1H, J = 1.4 Hz, J = 17.4 Hz), 6.39 (dd, 1H, J = 1.4 Hz, J = 17.4 Hz), 6.12 (dd, 1H, J = 10.5 Hz, J = 17.4 Hz), 6.11 (dd, 1H, J = 10.5 Hz) J = 17.4 Hz), 5.81 (dd, 1 H, J = 1.4 Hz, J = 10.5 Hz), 5.80 (dd, 1 H, J = 1.4 Hz, J 10.5 Hz), 4.31 (t, 2H, J = 6.4 Hz), 4.20-4.15 (m, 4H), 4.07-3.98 (m, 6H), 3.78 ( s, 3H), 1.88-1.67 (m, 12H), 1.60-1.44 (m, 12H).

(Evaluation of orientation)
Example 1
A solution was prepared by dissolving 153 parts by weight of cyclopentanone with respect to 100 parts by weight of the polymerizable liquid crystal compound T obtained above. To this, 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) 11 A solution was prepared by adding 6 parts by weight. A test solution was obtained using LC756 (manufactured by BASF) as a chiral agent and KH-40 manufactured by Seimi Chemical Co., Ltd. as a surfactant.

This test solution was 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), and then hot plate It was dried 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. This cured film was observed with a polarizing microscope, and the amount of orientation defect called oily streak was visually confirmed and judged. The observation photograph figure of a polarizing microscope is shown in FIGS. In the figure, alignment defects called oily streaks are observed as black lines. Evaluation is made in 5 stages, 5 when no alignment defects are observed (FIG. 1), 3 when alignment defects are partially observed (FIG. 2), and when alignment defects exist over the entire surface ( 3) was determined to be 1, respectively. Therefore, a larger value indicates a better result. Moreover, about the evaluation 2 and 4 which are not shown by the figure, it was set as the evaluation, when it judged visually from the result of the micrograph to the middle of a figure.

(Examples 2-3, Comparative Example 1)
As shown in Table 1, a part or all of 100 parts by weight of the polymerizable liquid crystal compound T in the test solution described above is prepared in the following compound U (another polymerizable liquid crystal compound) produced by the method described in Japanese Patent Application No. 2008-92093. The test was carried out with the ratio changed. In Table 1, “%” is “wt%”.

(Evaluation results)

  From the results in Table 1, it can be seen that the orientation is improved as the blending ratio of the polymerizable liquid crystal compound of the present invention is increased.

It is an observation photograph figure of the polarizing film of a cured film, and is a case where an orientation defect is not seen at all. It is an observation photograph figure of the polarizing microscope of a cured film, and is a case where an orientation defect is seen partially. It is an observation photograph figure of the polarizing microscope of a cured film, and is a case where an orientation defect exists over the whole surface.

Claims (8)

Formula (I)

[Wherein, Y _{1 to} Y ₁₀ each independently represent —O—, —O—C (═O) —, or —C (═O) —O—.
G _{1 to} G ₄ each independently represents an alkylene group having 1 to 20 carbon atoms which may have a substituent selected from a halogen atom and an alkoxy group having 1 to 6 carbon atoms .
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 to} A ₄ each independently represent any of the following (A-i), (A-ii), or (A-iii).

(In the above formula, * represents a bond, and X _{9 to} X ₂₆ each independently have a substituent selected from a hydrogen atom ; a halogen atom ; a halogen atom; and a C 1-6 alkoxy group. A good alkyl group having 1 to 10 carbon atoms ; a cyano group ; a nitro group ; —OR ⁶ ; —O—C (═O) —R ⁶ ; —C (═O) —OR ⁶ ; —O—C (═O) ^{-OR 6; -NR 7 -C (=} O) -R 6; -C (= O) -N (R 6) R 7; or, -O-C (= O) -N (R 6) R 7 ; represented here, R ^6, R ⁷ each independently represent a hydrogen atom;. or the number halogen atoms and carbon may have a substituent group selected from an alkoxy group having 1 to 6 carbon atoms to 10 Represents an alkyl group of
X _{1 to} X ₈ are each independently a hydrogen atom, a halogen atom , an 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) —N (R ³ ) R ⁴ , or —O—C (═O) —N (R ³ ) R ⁴ is represented. Here, R < ³ >, R < ⁴ > is respectively independently a hydrogen atom ; or a C1- C10 alkyl group which may have a substituent chosen from a halogen atom and a C1-C6 alkoxy group ; Represents.
a and b are each independently 0 or 1, and c is an integer of 1 to 3. ]
A polymerizable liquid crystal compound represented by: In the formula (I), 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 The polymerizable liquid crystal compound according to claim 1, wherein — or CH ₃ —CH═CH—CH ₂ —. In the formula (I), G _{1 to} G ₄ are each independently — (CH ₂ ) ₆ — or — (CH ₂ ) ₄ —, —O—, —C (C═O). -O-, -O-C (= O)-, or -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 to} A ₄ are each independently

The polymerizable liquid crystal compound according to claim 1, which is a group represented by the formula: In the formula (I), G _{1 to} G ₄ are each independently — (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 to} A ₄ are each independently

The polymerizable liquid crystal compound according to claim 1, which is a group represented by the formula: In the formula (I), G _{1 to} G ₄ are each independently — (CH ₂ ) ₆ — or — (CH ₂ ) ₄ —,
Z ₁ and Z ₂ are each independently CH ₂ ═CH—,
A _{1 to} A ₄ are each independently

The polymerizable liquid crystal compound according to claim 1, which is a group represented by the formula:   A polymerizable liquid crystal composition comprising the polymerizable liquid crystal compound according to claim 1 and a polymerizable chiral compound.   A liquid crystal polymer obtained by polymerizing the polymerizable liquid crystal compound according to claim 1 or the polymerizable liquid crystal composition according to claim 6.   An optical anisotropic body comprising the liquid crystalline polymer according to claim 7 as a constituent material.

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