JP2000281628A - Polymerizable compound, synthetic intermediate for the compound, polymerizable liquid crystal composition containing the polymerizable compound, optically anisotropic material composed of the composition and production of the optically anisotropic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new polymerizable compound having tolan skeleton, high birefringence, low crystal-nematic liquid crystal transition temperature and excellent compatibility with other liquid crystals and useful for a phase- difference film, etc. SOLUTION: The objective compound is expressed by formula I (Xa, xb and Xc are each F, Cl or methyl; (l), (m) and (n) are each 0-4; (q) and (t) are each 1-20, R1 and R2 are each a 1-18C bivalent hydrocarbon group; Y1 and y2 are each a linking group selected from single bond, O and S; Q1 and Q2 are each acryloyloxy, methacryloyloxy, acrylamido or the like), e.g. the compound of formula II. The compound can be produced by coupling a compound of formula III with a compound of formula IV (Z1 is Br or I) and converting the reactive functional group at the spacer terminal of the obtained synthetic intermediate into a polymerizable functional group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polymerizable liquid crystal compound used for a retardation film, a polarizing beam splitter, a polarizing prism, an optical low-pass filter, and the like, an intermediate for synthesizing the polymerizable liquid crystal compound, The present invention relates to a liquid crystal compound contained therein and an optically anisotropic body using the same.

[0002]

2. Description of the Related Art In recent years, it has been known that an optically anisotropic material formed by polymerizing a polymerizable liquid crystal is useful as a material for a retardation film, an optical low-pass filter, and the like. International Patent Publication No. 98/0047
5 and the like disclose polymerizable liquid crystals for use in optical element materials, but the polymerizable liquid crystals disclosed therein have a drawback that they have low birefringence for use in optical elements. In addition, the polymerizable liquid crystals or compositions disclosed in these patents have a drawback that the crystal-nematic liquid crystal transition temperature is not sufficiently low.

On the other hand, JP-A-8-3111 discloses a polymerizable liquid crystal composition which exhibits a liquid crystal at room temperature.
Since these liquid crystal compositions are monofunctional, they lack mechanical properties such as surface hardness, and furthermore, the optical anisotropic body obtained by polymerizing them has a drawback of insufficient transparency. there were. Japanese Patent Application Laid-Open No. Hei 11-80090 discloses a liquid crystal acrylate compound containing an ester or a liquid crystal-like compound, but has a drawback that the temperature range in which the liquid crystal is displayed is narrow.

Further, as a compound similar to the present invention, “Bu
lletin de la Societe Chemique de France ”(No. 603
(Page 2 No. 1973) discloses 4,4′-diacryloyloxytolan, but this compound has a drawback that it has a high temperature range showing liquid crystallinity and a small birefringence. Was.

[0005]

The first problem to be solved by the present invention is that it has high birefringence, low crystal-nematic liquid crystal transition temperature, and excellent compatibility with other liquid crystals. An object of the present invention is to provide a polymerizable liquid crystal compound. A second object of the present invention is to provide a polymerizable liquid crystal composition having a low crystal-nematic liquid crystal transition temperature and a high birefringence. Further, a third object to be solved by the present invention is to provide an optically anisotropic body obtained by polymerizing a polymerizable liquid crystal composition and having excellent transparency. Still another object of the present invention is to provide a synthetic intermediate of a polymerizable liquid crystal compound.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the use of a polymerizable liquid crystal compound having a trans skeleton among substituted biphenyl derivatives as a mesogen has been studied. The inventors have found that the above problems can be solved, and have completed the present invention.

That is, the present invention provides (I) a compound represented by the general formula (1-a)

[0008]

Embedded image

(Wherein X ^a , X ^b and X ^c each independently represent a fluorine atom, a chlorine atom or a methyl group;
l, m and n represent an integer of 0 to 4, and at least one of l, m and n represents an integer of 1 or more. q and t
Are, each independently, represent an integer of 1 to 20, R ¹
And R ² each independently represent a linear or branched divalent hydrocarbon group having 1 to 18 carbon atoms, and Y ¹ and Y ² each independently represent a single bond, —O -And -S
-Represents a linking group selected from the group consisting of Q ¹ and Q ²
Are each independently an acryloyloxy group, a methacryloyloxy group, ClCH = CHCOO-, an acrylamide group, a methacrylamide group, ClCH = CHCONH-,
It represents a reactive functional group selected from the group consisting of a vinyl group, CH ₂ ＣCCl—, CHCl ＝ CH—, an epoxy group, an ethynyl group, a mercapto group and CH ₂ ＝ CHO—. ) Is provided.

In order to solve the above problems, the present invention provides a compound represented by the general formula (2-a):

[0011]

Embedded image

(Wherein, X ^d , X ^e and X ^f each independently represent a fluorine atom, a chlorine atom or a methyl group;
l, m and n each independently represent an integer of 0 to 4, but at least one of l, m and n represents an integer of 1 or more, and q and t each independently represent 0 to 20 (1) When q is 1 or more, R ³ represents a linear or branched divalent hydrocarbon group having 1 to 18 carbon atoms, Y ³ represents a single bond, —COO -, -O-, -OCO
-, - CO- and represents a linking group selected from the group consisting of -S-, (2) when t is 1 or more, R ⁴ is a linear or branched divalent C1-18 atoms Represents a hydrocarbon group, Y ⁴ is a single bond, -COO-, -O-, -OCO-,
It represents a linking group selected from the group selected -CO- and from -S-, Q ³ and Q ⁴ are, each independently, a hydroxyl group,
A reactive functional group selected from the group consisting of an iodine atom, a bromine atom, a chlorine atom, an amino group and a carboxyl group, or a protected amino group, a protected hydroxyl group or a protected carboxyl group. ) Is provided. This compound has the general formula (Ia) of the above item (I)
Are useful as intermediates for the synthesis of the compound represented by

Further, the present invention provides (III) a polymerizable liquid crystal composition containing a polymerizable compound represented by the general formula (1-a) in the above item (I).

Further, the present invention provides (IV) an optically anisotropic substance comprising a polymer of the polymerizable liquid crystal composition described in the above (III) in order to solve the above problems.

Further, the present invention provides, in order to solve the above-mentioned problems, (V) production of an optically anisotropic body in which the polymerizable liquid crystal composition described in the above (III) is polymerized by light, electron beam or radiation. Provide a way.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Among the compounds represented by the general formula (1-a) of the present invention, those in which X ^a , X ^b and X ^c are fluorine atoms are preferred. And n
Are each independently an integer of 0 to 2, and more preferably a compound in which at least one of m and n is 1 or more. Among the compounds represented by the general formula (1-a) of the present invention, those represented by the general formula (1-b)

[0017]

Embedded image

(Wherein X ¹ , X ² and X ³ each independently represent a fluorine atom or a hydrogen atom, but X ¹ , X ²
And at least one of X ³ represents a fluorine atom, q and t each independently represent an integer of 1 to 10, and R ¹ and R ² each independently represent a carbon atom of 1 to 1. 18 represents an alkylene group or an alkenylene group having 2 to 18 carbon atoms, Y ¹ and Y ² each independently represent a single bond or —O—, and Q ¹ and Q ² each independently represent Represents an acryloyloxy group or a methacryloyloxy group. A) a polymerizable compound represented by general formula (1-c):

[0019]

Embedded image

Wherein q and t are each independently:
Represents an integer of 1 to 3, R ¹ and R ² each independently represent an alkylene group having 1 to 18 carbon atoms or an alkenylene group having 2 to 18 carbon atoms, and Y ¹ and Y ² are both- O- and Q ¹ and Q ² each independently represent an acryloyloxy group or a methacryloyloxy group. ) Are more preferred.

Among the compounds represented by the general formulas (1-a), (1-b) and (1-c), R ¹ and R ² each independently represent a group having 1 to 1 carbon atoms. Preferred are compounds having 18 linear or branched alkylene groups or alkenylene groups, and more preferred are compounds having alkylene groups. In addition, the general formula (1-a) and the general formula (1-
Among the compounds represented by b) and the general formula (1-c), Y ¹ and Y ² are each independently a single bond or -O-
Is preferred, and a compound represented by —O— is more preferred. Among the compounds represented by the general formulas (1-a), (1-b) and (1-c), q and t
Are each independently preferably a compound having an integer of 1 to 10, particularly preferably a compound having an integer of 1 to 5.
Compounds having an integer of from 1 to 3 are more preferable, and compounds having an integer of 1 are most preferable. General formula (1-a), General formula (1-
Among the compounds represented by b) and the general formula (1-c), Q ¹ and Q ² are each independently an acryloyloxy group, a methacryloyloxy group, a vinyl group, an epoxy group, an ethynyl group or a mercapto group. Compound is preferred, acryloyloxy group, methacryloyloxy group,
A compound that is a vinyl group or an ethynyl group is more preferable, an acryloyloxy group, a compound that is a methacryloyloxy group or a vinyl group is more preferable, a compound that is an acryloyloxy group or a methacryloyloxy group is more preferable, and a compound that is an acryloyloxy group is Most preferred. Among the compounds represented by the general formulas (1-a), (1-b) and (1-c), Q ¹
Is a vinyl group or a vinyl ether, and a compound in which Q ² is a mercapto group is preferable. A compound in which Q ² is a vinyl group or a vinyl ether and Q ¹ is a mercapto group is preferable.

Among the compounds represented by the general formula (2-a) of the present invention, a compound wherein X ^d , X ^e and X ^f are all fluorine atoms is preferred. Further, among the compounds represented by the general formula (2-a) of the present invention, l is 0, and m and n are
Each is independently an integer of 0 to 2, but a compound in which at least one of m and n is 1 or more is preferable, and a compound in which m and n are an integer of 0 or 1 is more preferable. Has the general formula (2-b)

[0023]

Embedded image

(Where q and t are each independently:
Represents an integer of 0 to 3, and (1) when q is 1 or more, R ³
Represents an alkylene group having 1 to 18 carbon atoms or an alkenylene group having 2 to 18 carbon atoms, and Y ³ represents -COO
-Or -O-, and (2) when t is 1 or more, R ⁴
Represents an alkylene group having 1 to 18 carbon atoms or an alkenylene group having 2 to 18 carbon atoms, Y ⁴ represents —O— or —OCO—, and Q ³ and Q ⁴ each independently. Hydroxyl group, iodine atom, bromine atom, chlorine atom, reactive functional group selected from the group consisting of amino group and carboxyl group or protected amino group, protected hydroxyl group,
Represents a protected carboxyl group. The compounds characterized by the formula (1) are most preferred.

The general formula (2-a) and the general formula (2) of the present invention
Among the compounds represented by -b), R ³ is a linear or branched alkylene group or alkenylene group is 1 to 18 carbon atoms are preferred, the compound is an alkylene group is more preferable. Further, among the compounds represented by the general formulas (2-a) and (2-b) of the present invention, Y ³ is a single bond, —OCO—, —O— or —S—.
Is preferable, a single bond, -OCO- or -O
Is more preferable, a compound which is a single bond or -O- is more preferable, and a compound which is -O- is particularly preferable. The general formulas (2-a) and (2) of the present invention
Among the compounds represented by -b), compounds wherein q is an integer of 0 to 10 are preferable, compounds having an integer of 1 to 5 are more preferable, compounds having an integer of 1 to 3 are more preferable, and 1 is preferable. Compounds are particularly preferred. Among the compounds represented by formulas (2-a) and (2-b) of the present invention, compounds wherein Q ³ is a hydroxyl group, a bromine atom, a chlorine atom, a carboxyl group, a protected carboxyl group or a hydroxyl group Preferably, a hydroxyl group, a bromine atom, a carboxyl group, a compound that is a protected carboxyl group or a hydroxyl group is more preferable, a hydroxyl group, a compound that is a protected hydroxyl group or a bromine atom is more preferable, and a compound that is a hydroxyl group or a protected hydroxyl group is More preferred.

The general formula (2-a) and the general formula (2)
Among the compounds represented by -b), compounds wherein R ⁴ is a linear or branched alkylene group or alkenylene group is 1 to 18 carbon atoms are preferred, the compound is an alkylene group is more preferable. Further, among the compounds represented by the general formulas (2-a) and (2-b) of the present invention, Y ⁴ is a single bond, —OCO—, —O— or —S—.
Is preferable, a single bond, -OCO- or -O
Is more preferable, a compound which is a single bond or -O- is more preferable, and a compound which is -O- is particularly preferable. The general formulas (2-a) and (2) of the present invention
Among the compounds represented by -b), compounds wherein t is an integer of 0 to 10 are preferred, compounds having an integer of 1 to 5 are more preferred, compounds having an integer of 1 to 3 are more preferred, and 1 is preferred. Compounds are particularly preferred. Among the compounds represented by the general formulas (2-a) and (2-b) of the present invention, compounds wherein Q ⁴ is a hydroxyl group, a bromine atom, a chlorine atom, a carboxyl group, a protected carboxyl group or a hydroxyl group, Preferably, a hydroxyl group, a bromine atom, a carboxyl group, a compound that is a protected carboxyl group or a hydroxyl group is more preferable, a hydroxyl group, a compound that is a protected hydroxyl group or a bromine atom is more preferable, and a compound that is a hydroxyl group or a protected hydroxyl group is More preferred.

Examples of the hydroxyl-protecting group include a tetrahydropyranyloxy group (THP), an acetoxy group, a methoxy group, a t-butoxy group, a trityloxy group, a benzyloxy group, a p-methoxybenzyloxy group and a t-dimethyl group. Silyloxy group, triethylsilyloxy group, t-
Examples include a diphenylsilyloxy group, a methanesulfonyloxy group, a pivaloyloxy group, a 2,2,2-trichloroethoxycarbonyloxy group, an allyloxycarbonyloxy group, and among them, a tetrahydropyranyloxy group is particularly preferable.

As the amino-protecting group, any of those usually used in polypeptide synthesis can be suitably used. For example, a t-butoxycarbonyl group,
Examples include an acetamidomethyl group, a benzyloxymethyl group, a benzyloxycarbonyl group, a parachlorobenzyloxycarbonyl group, and the like. Among them, a parachlorobenzyloxycarbonyl group, a t-butoxycarbonyl group, and a benzyloxycarbonyl group are particularly preferable. .

Examples of the carboxyl-protecting group include methyl ester, benzyl ester, allyl ester, tertiary butyl ester, cyclohexyl ester, ethyl ester, phenacyl ester, silyl ester, and oxazolidine. Methyl ester, benzyl ester and ethyl ester are preferred, and methyl ester and benzyl ester are particularly preferred.

The compound represented by the general formula (2-a) is
For example, it can be manufactured according to the following manufacturing method. That is, the general formula (6-a)

[0031]

Embedded image

(Wherein Q ³ , R ³ , Y ³ , X ^d , q and l
Has the same meaning as in formula (2-a). And a compound represented by the general formula (6-b)

[0033]

Embedded image

(Wherein Q ⁴ , R ⁴ , Y ⁴ , X ^e , X ^f , t,
m and n represent the same meaning as in the general formula (2-a);
¹ represents a bromine atom or an iodine atom. Or a method of coupling the compound represented by the general formula (7-a)

[0035]

Embedded image

(Where Q ⁴ , R ⁴ , Y ⁴ , X ^e , X ^f , t,
m and n have the same meaning as in formula (2-a). )
And a compound represented by the general formula (7-b)

[0037]

Embedded image

Wherein Q ³ , R ³ , Y ³ , X ^d , q and l
Has the same meaning as in formula (2-a), and Z ² represents a bromine atom or an iodine atom. ) Can be produced by a method of coupling with the compound represented by the formula:

The compound represented by formula (6-a) or (7-b) can be produced, for example, according to the following production method. That is, the reaction formula (8)

[0040]

Embedded image

As shown in the above, by reacting the compound (i) represented by the formula (I) with the compound represented by the formula (ii) in the presence of potassium carbonate,
The compound represented by is synthesized. Reaction formula (9)

[0042]

Embedded image

As shown in the above, by reacting the compound represented by the formula (iii) with the compound represented by the formula (iv) in the presence of a zero-valent palladium catalyst and a monovalent copper catalyst, The compound represented by (v) is synthesized. Further, the reaction formula (10)

[0044]

Embedded image

As shown in the above, the compound represented by the formula (vi) is synthesized by reacting the compound represented by the formula (v) with acrylic acid chloride in the presence of a base such as pyridine. Furthermore, equation (11)

[0046]

Embedded image

As shown in the above, the compound represented by the formula (vi) is treated with tetrabutylammonium fluoride to synthesize the compound represented by the formula (vii).

In the reaction formula (10), methacrylate or chloroacrylate can be produced by using methacrylic acid chloride or 3-chloroacrylic acid chloride instead of acrylic acid chloride. In the reaction formula (8), the compound represented by the formula (viii) synthesized from polyethylene glycol and tosylate chloride in the presence of a base instead of the compound represented by the formula (ii)

[0049]

Embedded image

By using the compound represented by the formula, instead of the compound (iiv), the compound of the formula (ix)

[0051]

Embedded image

Compound (ix) having an ether bond in the spacer represented by the formula (ix) can be synthesized.

The reaction formula (12)

[0054]

Embedded image

According to the above, a compound represented by the formula (x) can be synthesized. This compound is combined with a compound of formula (xi), which is one of the inexpensively available compounds as a raw material for acrylic resin and methacrylic resin.

[0056]

Embedded image

Is reacted in the presence of a catalyst, and further treated with tetrabutylammonium fluoride in the same manner as in the reaction formula (11).
Equation (xii)

[0058]

Embedded image

A compound having an ester bond in the spacer portion represented by the following formula can be synthesized. Further, by using maleic anhydride instead of the compound represented by the formula (xi), the compound represented by the formula (xiii)

[0060]

Embedded image

A compound having a double bond in the spacer represented by the following formula can be synthesized.

Further, the reaction formula (13)

[0063]

Embedded image

As shown in the above, by treating the compound represented by the formula (v) with carbon tetrachloride in the presence of triphenylphosphine, a compound having a hydroxyl group substituted with a chlorine atom can be obtained. By treating with carbon tetrabromide instead of carbon chloride, a compound in which a hydroxyl group has been substituted with a bromine atom can be obtained. By further treating the bromide with sodium iodide, a compound substituted with an iodine atom can be obtained.

Reaction formula (14)

[0066]

Embedded image

As shown in the above, by reacting the compound represented by the formula (iii) with epichlorohydrin in the presence of a base, a compound having an epoxy group introduced into the terminal of the spacer can be obtained.

An intermediate having an epoxy group at the terminal can be obtained by carrying out a reaction similar to the reaction formula (9) and the subsequent steps using this compound.

Reaction formula (15)

[0070]

Embedded image

As shown in the above, instead of compound (ii),
By using the compound (xvi), a compound having a terminal carboxyl group represented by the formula (xvii) can be obtained. After protecting the carboxyl group with methanol or the like, an intermediate having a carboxyl group at a terminal can be produced by carrying out the same operation as in the reaction after the reaction formula (9).

Further, the reaction formula (16)

[0073]

Embedded image

As shown in the above, by using the compound represented by the formula (xviii) instead of the compound represented by the formula (ii), a compound having a terminal nitro group represented by the formula (xix) is obtained. be able to. By using this compound and performing the same operation as in Reaction formula (9) and thereafter,
Expression (xx)

[0075]

Embedded image

The compound represented by the following formula can be obtained.
The nitro group is reduced with palladium carbon and sodium borohydride or tin chloride, and the same operation as in the reaction formula (11) is carried out to obtain the compound of the formula (xxi)

[0077]

Embedded image

The compound having an amino group at the terminal represented by the formula (1) can be obtained. Further, a compound having an acrylamide group or a methacrylamide group at a terminal can be obtained by reacting this compound with acrylic acid chloride or methacrylic acid chloride in the presence of a base.

Further, the compound represented by the formula (xiv) is treated with a suitable sulfurizing agent, and then reduced with a reducing agent such as lithium aluminum hydride, whereby
The corresponding thiol can be obtained. Compound (xiv)
Can obtain a similar compound.

In the reaction formula (8), instead of the compound (i), a corresponding thiophenol derivative, for example, a compound of the formula (xx)
iv)

[0081]

Embedded image

The compound represented by the following formula can also be used. By using this compound, the compound represented by the formula (xxv) corresponding to the compound (vii) represented by the formula (vii)

[0083]

Embedded image

A thioether compound (xxv) represented by
Can be obtained. A thiophenol such as a compound represented by the formula (xxiv) is converted from a corresponding sulfonic acid into a compound represented by the formula (18).

[0085]

Embedded image

Can be obtained by the following reaction.

The other intermediate can be synthesized in a manner generally similar to the above intermediate. That is, the reaction formula (8)
Wherein, in place of the compound represented by the formula (I), for example, a compound represented by the formula (xxvii)

[0088]

Embedded image

Using a compound such as the compound represented by the following formula, the reaction formula (19) corresponding to the reaction formula (14)

[0090]

Embedded image

The compound represented by the formula (xxviii) can be obtained by the method shown in the above. In this reaction, it is necessary to raise the reaction temperature as compared with the reaction formula (14).
Can be synthesized without any problems.

Compound (xxvii) can be produced as follows. That is, the reaction formula (20)

[0093]

Embedded image

As shown in the above, a commercially available compound represented by the formula (xxix) was treated with aluminum chloride and acetyl chloride, and further treated with a reaction formula (21).

[0095]

Embedded image

As shown in the above, it can be produced by oxidizing this with hydrogen peroxide / formic acid and then hydrolyzing it.

The spacer and the functional group corresponding to the compound represented by the general formula (21) can be produced by the same procedure as the method for synthesizing the compound represented by the general formula (18).

The polymerizable compound represented by the general formula (1) of the present invention can be produced, for example, as follows.

That is, there is a method of converting the reactive functional group at the terminal of the spacer of the synthetic intermediate represented by the general formula (2-a) into a polymerizable functional group. For example, reaction formula (22)

[0100]

Embedded image

As described above, a compound having an acrylate group can be synthesized. A compound having methacrylate can be synthesized in the same manner as in this method.

The reaction formula (23)

[0103]

Embedded image

As shown in the above formula, a compound having a methacrylamide group can be synthesized. A compound having acrylamide can be similarly synthesized.

The reaction formula (24)

[0106]

Embedded image

As shown in the above formula, a compound having an epoxy group can be synthesized by oxidizing a terminal double bond with a peroxide such as perbenzoic acid.

The reaction formula (25)

[0109]

Embedded image

As shown in the above formula, a compound having a triple bond at a terminal can also be synthesized.

The starting material for the spacer portion can be easily synthesized by tosylating an alcohol having an ethynyl group at the terminal.

The present invention further relates to a compound represented by the general formula (1-
A liquid crystal composition containing the polymerizable compound represented by a) is also provided. As the liquid crystal phase of the liquid crystal composition of the present invention, any phase can be used without particular limitation as long as it is generally recognized as a liquid crystal phase in this technical field. Among them, a nematic phase, a chiral nematic phase, a smectic A phase, a smectic phase C phase, chiral smectic C phase (hereinafter, (chiral)
Abbreviated as smectic C phase. ), Those which express a cholesteric phase are particularly preferred. Further, when a smectic C phase (or a chiral smectic C phase) is shown, a smectic A phase is shown in a temperature range above the smectic C phase (or a chiral smectic C phase), and when a smectic A phase is shown, the smectic A phase is shown. It is preferable to exhibit a nematic phase in a temperature range above the smectic A phase, because good uniaxial orientation characteristics can be obtained. As the temperature range of the liquid crystal phase of the polymerizable liquid crystal composition, those which exhibit a liquid crystal phase at 50 ° C. or lower are preferable, and more preferably around room temperature, for example, 20 ° C.
Those exhibiting a liquid crystal phase in a temperature range of from about to 30 ° C are preferred, and those exhibiting a liquid crystal phase at least at 25 ° C are particularly preferred. For example, in the case where the liquid crystal composition of the present invention is actually polymerized in a smectic C phase (or a chiral smectic C phase), it is preferable that the smectic C phase (or the chiral smectic C phase) be expressed at around room temperature.

In order to ensure a large birefringence in the liquid crystal composition of the present invention, the compound represented by the general formula (1-
The content of the polymerizable compound represented by a) is 3% by weight.
It is preferable that it is above.

Further, the liquid crystal composition of the present invention contains a compound other than the polymerizable compound represented by the general formula (1-a) and a skeleton which is generally recognized as a liquid crystal skeleton in this technical field. A polymerizable liquid crystal compound having a functional group at the same time can be added without particular limitation in a range of 97% by weight or less. The liquid crystal skeleton particularly preferably has at least two or three six-membered rings. Examples of the polymerizable functional group include an acryloyloxy group, a methacryloyloxy group, an epoxy group, a vinyloxy group, a cinnamoyl group, a vinyl group, an ethynyl group, and the like. Groups are particularly preferred. In the case of a compound having a plurality of polymerizable functional groups in one molecule, the types of the polymerizable functional groups may be different. For example, in the case of a compound having two polymerizable functional groups, one may be a methacryloyl group and the other may be a vinyl ether group. A large number of liquid crystal compounds having two polymerizable functional groups in one molecule are known. Generally, when these compounds are polymerized, good heat resistance and strength characteristics can be obtained. it can. Examples of such a liquid crystal compound having two polymerizable functional groups in one molecule include compounds represented by the following formulas (xxxii) to (xlii), but are not limited to these compounds. Not something.

[0115]

Embedded image

(Wherein the cyclohexane ring is in a trans configuration, X represents a halogen atom, a cyano group or a methyl group, and s each independently represents an integer of 2 to 12.)

Further, a liquid crystal compound having one polymerizable functional group in one molecule can be added to the liquid crystal composition of the present invention. Examples of such a liquid crystal compound having one polymerizable functional group in one molecule include the following formulas (xlii) to (xlii).
Compounds represented by (lxxxvii) and the like are not limited to these compounds.

[0118]

Embedded image

[0119]

Embedded image

[0120]

Embedded image

[0121]

Embedded image

(Wherein the cyclohexane ring is in a trans configuration, and Y is a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkyl group via an ether bond, an alkenyl group, Or an alkyl group or an alkenyl group via an ester bond (these may have an ether group or an ester group interposed between arbitrary C-C), and s independently represents an integer of 2 to 12. .)

Further, the liquid crystal composition of the present invention contains at least 2 molecules in the molecule for the purpose of facilitating the development of a liquid crystal phase near room temperature, for example, at a temperature in the range of 20 to 30 ° C.
A monofunctional acrylate or methacrylate of a cyclic alcohol, phenol or aromatic hydroxy compound having a liquid crystal skeleton having two six-membered rings as a partial structure can be contained. Such monofunctional acrylates and methacrylates have the general formula (19)

[0124]

Embedded image

(Wherein, X ⁴ represents a hydrogen atom or a methyl group, u represents an integer of 0 or 1, and the 6-membered rings A, B and C each independently represent

[0126]

Embedded image

Wherein p is an integer of 1 to 4;
⁷ and Y ⁸ are each independently a single bond, -CH ₂ CH
_{2 -, - CH 2 O -} , - OCH 2 -, - CF 2 O -, - OC
F ₂ —, —COO—, —OCO—, —C≡C—, —CH
= CH -, - CF = CF -, - (CH 2) 4 -, - CH 2
_{CH 2 CH 2 O -, -} OCH 2 CH 2 CH 2 -, - CH = C
A connecting chain selected from the group consisting of H—CH ₂ CH ₂ — and —CH ₂ CH ₂ CH ₂ O—, wherein Y ⁹ is a single bond, —O
—, —COO— or —OCO—, and Z ⁷ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an alkenyl group having 1 to 20 carbon atoms. )) Are preferred.

As such a monofunctional acrylate or methacrylate, for example, the following formula (lxxxviii)
To (cvii), but the monofunctional acrylate and methacrylate that can be used in the liquid crystal composition of the present invention are not limited to these.

[0129]

Embedded image

[0130]

Embedded image

[0131]

Embedded image

(In the above, the cyclohexane ring has a trans configuration, C represents a crystal phase, N represents a nematic phase, S represents a smectic phase, I represents an isotropic liquid phase, and a number represents a phase transition temperature.)

Among these compounds, monofunctional acrylate compounds and methacrylate compounds each having a cyano group have a large birefringence, and therefore have the general formula (1-
A liquid crystal composition having a large birefringence can be prepared by combination with the compound represented by a).
Therefore, the compound represented by the above formula (xciii) can be suitably added to the liquid crystal composition of the present invention. In addition, since a monofunctional acrylate compound or a methacrylate compound having a tran skeleton also has a large birefringence, a liquid crystal composition having a large birefringence in combination with the compound represented by the general formula (1-a) of the present invention. Can be prepared. Therefore, the compounds represented by the above formulas (xc), (xcviii) and (xcix) can be suitably added to the liquid crystal composition of the present invention. Further, it is preferable to simultaneously use a monofunctional acrylate compound and a methacrylate compound having a cyano group and a monofunctional acrylate compound and a methacrylate compound having a tolan skeleton, from the viewpoint of obtaining a large birefringence.

Further, a liquid crystal compound having no polymerizable functional group can be added to the liquid crystal composition of the present invention according to the intended use. When the polymer of the liquid crystal composition of the present invention is used with a display element such as a polymer stabilized liquid crystal,
Or if you want to change the refractive index with temperature,
The total amount of the liquid crystal compound having no polymerizable functional group in the liquid crystal composition of the present invention is preferably set in a range of 10 to 97% by weight. Further, when it is not preferable that the refractive index changes with temperature, or when importance is attached to heat resistance and mechanical properties, the total amount of the liquid crystal compound having no polymerizable functional group in the liquid crystal composition of the present invention. Is preferably set in the range of 0 to 10% by weight.

Further, a compound having a polymerizable functional group and exhibiting no liquid crystallinity can be added to the liquid crystal composition of the present invention. Such compounds typically include
As long as it is recognized as a polymer-forming monomer or a polymer-forming oligomer in this technical field, it can be used without any particular limitation, and acrylate, methacrylate and vinyl ether are particularly preferable.

The liquid crystal compound having a polymerizable functional group, the liquid crystal compound having no polymerizable functional group, and the polymerizable compound having no liquid crystallinity may be added in an appropriate combination. It is necessary to adjust the addition amount of each component so that the liquid crystallinity of the composition is not lost.

Further, to the liquid crystal composition of the present invention, a polymerization initiator such as a thermal polymerization initiator and a photopolymerization initiator can be added for the purpose of improving the polymerization reactivity. Examples of the thermal polymerization initiator include, for example, benzoyl peroxide, azobisisobutyronitrile, and the like, and examples of the photopolymerization initiator include, for example, benzoin ethers, benzophenones, acetophenones, and benzylacetals. No. The addition amount of the polymerization initiator is preferably 10% by weight or less based on the liquid crystal composition, and 5% by weight.
The content is more preferably not more than 0.5, and particularly preferably in the range of 0.5 to 1.5% by weight.

Further, a stabilizer can be added to the liquid crystal composition of the present invention in order to improve the storage stability. Stabilizers that can be used for such purposes include, for example, hydroquinone, hydroquinone monoalkyl ethers, tert-butyl catechol, and the like. The addition amount is preferably 1% by weight or less, more preferably 0.5% by weight or less based on the liquid crystal composition.

Further, a chiral (optically active) compound may be added to the liquid crystal composition of the present invention for the purpose of obtaining a polymer having a helical structure of a liquid crystal skeleton therein. A chiral compound that can be used for such a purpose need not itself exhibit liquid crystallinity, and may or may not have a polymerizable functional group. Also,
The direction of the helix can be appropriately selected depending on the intended use of the polymer. As such chiral compounds, cholesteryl pelargonic acid having a cholesteryl group as an optically active group, cholesterol stearate, "CB-15" having a 2-methylbutyl group as an optically active group,
"C-15" (all manufactured by BDH), "S-1082"
(Merck), "CM-19", "CM-20",
“CM” (manufactured by Chisso), “S-811” having a 1-methylheptyl group as an optically active group (manufactured by Merck), “CM-21”, “CM-22” (manufactured by Chisso), And the like. The preferable addition amount of the chiral compound depends on the use of the liquid crystal composition, but the value (d / P) obtained by dividing the thickness (d) of the polymer obtained by polymerization by the helical pitch (P) in the polymer is 0.1. It is preferable to adjust so as to be in the range of 1 to 20.

When the liquid crystal composition of the present invention is used as a raw material of a polarizing film or alignment film, a printing ink, a paint, or the like, a metal, a metal complex, a dye,
Pigments, dyes, surfactants, gelling agents, ultraviolet absorbers, antioxidants, ion exchange resins, metal oxides of titanium oxide, and the like can also be added.

Further, the present invention provides an optically anisotropic substance comprising a polymer of the liquid crystal composition of the present invention. The optically anisotropic body of the present invention can be produced by polymerizing the liquid crystal composition of the present invention in an oriented state. For example, after the substrate surface is rubbed with a cloth or the like, or the substrate surface on which an organic thin film is formed is rubbed with a cloth or the like, or is carried on a substrate having an alignment film in which SiO ₂ is obliquely deposited, or after being sandwiched between substrates. It can be produced by a method of polymerizing the liquid crystal composition of the present invention. Examples of other alignment treatment methods include the use of flow alignment of the liquid crystal composition and the use of an electric or magnetic field. These alignment means may be used alone or in combination. Among them, a method using a substrate whose surface is rubbed with a cloth or the like is particularly preferable because of its simplicity.

At this time, the substrate that can be used may be an organic material or an inorganic material. As a material constituting the substrate, for example, polyethylene terephthalate, polycarbonate, polyimide, polyamide,
Organic materials such as polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone, triacetylcellulose, cellulose, polyetheretherketone; silicon, glass, quartz, quartz, Inorganic materials such as calcite. In addition, when used as a retardation film of a liquid crystal display device, a film is formed using the above organic material as a substrate, and then affixed to the liquid crystal display device, or by directly forming a film on a panel substrate by coating. May be applied. The form of the substrate may be a film or a plate, or a block like a prism.

If it is not possible to obtain an appropriate orientation by rubbing these substrates with a cloth or the like, an organic thin film such as a polyimide thin film or a polyvinyl alcohol thin film is formed on the substrate surface according to a known method, and this is coated with a cloth. Rubbing may be carried out. Further, the use of a polyimide thin film that gives a pretilt angle as used in a normal twisted nematic (TN) element or a super twisted nematic (STN) element makes it possible to further refine the molecular orientation structure inside the optically anisotropic body. It is particularly preferable because it can be controlled to

When the alignment state is controlled by an electric field, a substrate having an electrode layer can be used. In this case, it is preferable to form an organic thin film such as the above-mentioned polyimide thin film on the electrode.

One or more substrates may be used. When two substrates are used, an optically anisotropic body can be produced by injecting and holding a polymerizable liquid crystal (composition) between the two substrates and then polymerizing the liquid crystal. After using one substrate and applying a polymerizable liquid crystal (composition), polymerization may be performed. As an application method, for example, spin coating, die coating, extrusion coating, roll coating, wire bar coating,
Gravure coating, spray coating, dipping, printing, and the like.

A photo-alignment method can be used as an alignment treatment method instead of rubbing. This is a method of applying polarized light, preferably polarized ultraviolet light, to an organic thin film having a functional group that undergoes photodimerization reaction in a molecule such as polyvinyl cinnamate or an organic thin film having a functional group that isomerized by light or an organic thin film such as polyimide. Irradiation forms an alignment film. By applying a photomask to this photoalignment method, patterning of the alignment can be easily achieved, so that the molecular orientation inside the optically anisotropic body can be precisely controlled.

Although there is no particular limitation on the orientation of the liquid crystal,
For example, homeotropic alignment, homogeneous alignment, hybrid alignment, tilted homogeneous alignment, twisted nematic alignment, super twisted nematic alignment, and the like can be used. The orientation may be patterned.

The polymerization method is not particularly limited, and heat, light, radiation, electron beam and the like can be used as an energy source. Since rapid progress of polymerization is desirable, a method of performing photopolymerization by irradiating energy such as ultraviolet rays or electron beams is preferable. As the light source for the photopolymerization, a polarized light source or a non-polarized light source may be used. When photopolymerization is performed in a state where the liquid crystal composition is sandwiched between two substrates, at least the substrate on the irradiation surface side must have appropriate transparency.
Further, the temperature at the time of irradiation is preferably within a temperature range where the liquid crystal state of the liquid crystal composition of the present invention is maintained. In particular,
When an optically anisotropic body is to be produced by photopolymerization, it is preferable to carry out polymerization at a temperature as close to room temperature as possible, that is, at a temperature of 20 to 30 ° C., from the viewpoint of avoiding unintended thermal polymerization. The optically anisotropic body of the present invention obtained by polymerization may be subjected to a heat treatment for the purpose of reducing the initial property change and stably exhibiting the property. The heat treatment temperature is preferably in the range of 50 to 250 ° C, and the heat treatment time is preferably in the range of 30 seconds to 12 hours.

The optically anisotropic body of the present invention produced by such a method may be used after peeling from the substrate, or may be used without peeling. Further, it may be used by being laminated with another optical element. When applied to a liquid crystal display element, a retardation film may be produced as the optically anisotropic body of the present invention and laminated on the liquid crystal display element. A retardation film may be produced as the optically anisotropic body of the present invention and laminated with a polarizing film. When used as an optical low-pass filter, for example, it may be laminated with an optical filter for correcting visibility. The optical anisotropic body of the present invention may be laminated with another optical anisotropic body, for example, to adjust the wavelength dispersion of retardation.

[0150]

The present invention will be described in more detail with reference to the following examples. However, the invention is not limited to the scope of these examples.

<Example 1> (Production of compound represented by formula (cviii))

[0152]

Embedded image

(First Step) (Production of Compound Represented by Formula (cix))

[0154]

Embedded image

300 ml capacity equipped with thermometer and dropping funnel
Was charged with 29.0 g of 4-iodophenol, 9 mg of paratoluenesulfonic acid and 50 ml of dichloromethane, and the mixture was stirred and suspended in an ice bath. To this, a solution of 22.2 g of 3,4-dihydro-2H-pyran in 220 ml of dichloromethane was added dropwise over about 1 hour while maintaining the temperature at 10 ° C. or lower.
Further, stirring was continued at room temperature for about 4 hours under a nitrogen atmosphere. When a brownish homogeneous solution was obtained, the disappearance of the raw materials was confirmed by thin layer chromatography and gas chromatography, and then the reaction was terminated.

The reaction solution was treated with a saturated aqueous solution of sodium hydrogen carbonate,
After washing in order with a saturated saline solution, the organic layer was dried with anhydrous potassium carbonate. After filtering off potassium carbonate, the solvent was removed to obtain a crude product (47.2 g). The resulting crude product is subjected to silica gel chromatography (silica gel 250
g, hexane / dichloromethane = 2/1) to obtain 37.1 g of the desired product (93% yield).

¹³ C-NMR (75 MHz, DMSO-d ₆ ): δ (p
pm) = 18.391, 24.527, 29.618, 6
1.432, 84.182, 95.655, 119.0
39, 137.824, 156.338

(Second step) (Production of compound represented by formula (cx))

[0159]

Embedded image

In a 1 L four-necked flask equipped with a thermometer and a nitrogen inlet tube, 60 g of the compound represented by the formula (cix) obtained in the first step and trimethylsilylacetylene.
26 g were added, and 240 g of dimethylformamide and 70 g of triethylamine were further added and dissolved.

While maintaining the temperature of the reaction system at 25 ° C., under a nitrogen atmosphere, 2.74 g of triphenylphosphine palladium (0) and 0.75 g of copper (I) iodide were added and reacted. The reaction was stopped after confirming that the raw materials had disappeared by gas chromatography.

[0162] 1 L of ethyl acetate was added to the reaction mixture, and the mixture was washed three times with 500 ml of saturated saline, and the organic layer was separated.
The organic layer was dried over potassium carbonate, and the potassium carbonate was removed by filtration. The solvent was removed to obtain 61 g of a crude product.

¹³ C-NMR (75 MHz, DMSO-d ₆ ): δ (p
pm) = 0.004, 18.461, 24.555, 2,
9.671, 61.567, 92.361, 95.62
7, 115.037, 116.419, 132.99
2,156.902

(Third step) (Production of compound represented by formula (cxi))

[0165]

Embedded image

In a 300-ml three-necked flask equipped with a nitrogen inlet tube, a thermometer, and a dropping funnel, 46 g of tetrabutylammonium fluoride and 65 g of dichloromethane were sufficiently dissolved. While maintaining the temperature at 10 ° C. or lower in an ice bath under a nitrogen atmosphere, a solution of 39 g of the compound represented by the formula (cx) obtained in the second step in 100 ml of dichloromethane was added dropwise over 30 minutes. After completion of the dropwise addition, stirring was continued at room temperature for about 3 hours, and after confirming disappearance of the raw materials by gas chromatography, the reaction was terminated.

The reaction mixture was washed twice with a saturated saline solution, dried over anhydrous potassium carbonate, and the potassium carbonate was filtered off. The solvent was removed to obtain 70 g of a crude product. The crude product thus obtained was purified using column chromatography (silica gel / dichloromethane) to obtain 25 g of the desired product
I got

¹³ C-NMR (75 MHz, DMSO-d ₆ ): δ (p
pm) = 18.448, 24.551, 29.651, 6
1.555, 79.197, 83.367, 95.61
4, 114.531, 116.489, 133.02
1,156.832

(Fourth Step) (Production of Compound Represented by Formula (cxii))

[0170]

Embedded image

Aluminum chloride 32 was placed in a 1-L four-necked flask equipped with a dropping funnel, a thermometer, and a hydrogen chloride exhaust pipe.
g and 120 ml of dichloromethane were added and suspended by stirring. Acetyl chloride (21 g) was added dropwise thereto over 2 hours. Further, 4-bromo-2-fluorobiphenyl 5
200 ml of 0 g dichloromethane solution was added dropwise. After about 4 hours, 4 g of acetyl chloride and 5 g of aluminum chloride were added. After 3 hours, the disappearance of the raw materials was confirmed by gas chromatography, and then the reaction was terminated.

In a 1 L beaker, crushed ice
0 g, and the reaction solution was slowly added thereto. After about 30 minutes of stirring with a mechanical stirrer to completely inactivate the aluminum chloride, the organic layer was separated. The organic layer was washed twice with a saturated saline solution, dried over anhydrous magnesium sulfate, and then the solvent was removed to obtain 57 g of a product.

¹³ C-NMR (75 MHz, DMSO-d ₆ ): δ (p
pm) = 26.706, 119.368, 119.71
3, 121.860, 126.622, 128.19
3, 128.456, 128.933, 132.19
8, 136.138, 138.474, 157.20
2,160.533,197.413

(Fifth step) (Production of compound represented by formula (cxiii))

[0175]

Embedded image

A reactor equipped with a thermometer and a Dimroth condenser was charged with 750 ml of formic acid and 50 g of the compound represented by the formula (cxii) obtained in the fourth step, and 50 ml of a 34.5% aqueous hydrogen peroxide solution was added with stirring. The mixture was heated with a mantle heater and refluxed for 12 hours, and then the reaction was terminated.

The reaction mixture was ice-cooled in a fume hood, and a 10% aqueous sodium bisulfite solution was added thereto until the peroxide was completely decomposed. The reaction product was extracted twice from the reaction mixture with 500 ml of ethyl acetate.
The water washing was repeated until H = 4. The organic layer was further neutralized by washing with a saturated aqueous solution of sodium hydrogen carbonate, and finally washed twice with a saturated saline solution. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed to obtain 50 g of a crude product. This was subjected to column chromatography (Alumina 50
Purification was performed using 0 g / toluene → ethyl acetate) to obtain 30 g (yield: 70%) of the desired product.

(Sixth step) (Preparation of compound represented by formula (cxiv))

[0179]

Embedded image

In a 200 ml two-necked flask equipped with a thermometer, a dropping funnel and a nitrogen inlet tube, 4- (4-bromo-2) was added.
-Fluorophenyl) phenol 30 g, dichloromethane 50 ml, p-toluenesulfonic acid 10 mg were added, cooled on an ice water bath, and kept at 10 ° C or lower.
20 ml of a dichloromethane solution of 18.9 g of 3,4-dihydro-2H-pyran was added dropwise over 30 minutes. After completion of the dropwise addition, stirring was continued at room temperature until disappearance of the raw materials was confirmed by gas chromatography.

The reaction mixture was washed with a saturated aqueous solution of sodium hydrogen carbonate and saturated saline in this order, dried over anhydrous potassium carbonate, and then the solvent was removed to obtain a crude product. The crude product thus obtained is subjected to column chromatography (silica gel / hexane: toluene: dichloromethane = 1: 1:
Purification was performed using 1) to obtain 30.5 g of the desired product.

(Seventh step) (Production of compound represented by formula (cviii))

[0183]

Embedded image

In a 1-L four-necked flask equipped with a nitrogen inlet tube, a Dimroth condenser and a thermometer, 20.7 g of the compound represented by the formula (cxi) obtained in the third step and the compound obtained in the sixth step ( 30 g of the compound represented by cxiv), 300 ml of dimethylformamide and 60 ml of triethylamine were added, and 2.4 g of triphenylphosphine palladium (0) and 0.98 g of copper (I) iodide were added thereto as catalysts.
After replacing with nitrogen, the mixture was heated to 90 ° C. and reacted for about 4 hours. After confirming the disappearance of the raw materials by thin-layer chromatography, 500 ml of toluene was added to the reaction solution, and the organic layer was separated. The organic layer was washed three times with a saturated saline solution, dried over potassium carbonate, and then the solvent was removed to obtain a crude product. The crude product thus obtained was purified using column chromatography (silica gel / toluene) to obtain 31 g of the desired product.

¹³ C-NMR (75 MHZ, DMSO-d ₆ ): δ (p
pm) = 18.662, 25.143, 30.194, 6
2.040, 87.077, 90.572, 96.27
2, 115.823, 116.472, 118.71
0, 119.039, 123.747, 127.58
4, 128.440, 130.11, 130.24
1, 130.298, 133.037, 156.94
7, 157.350, 157.613, 160.887

FT-IR (cm ^-1 ): 2940, 2880, 2
850, 2210, 1600, 1540, 1510, 1
400, 1350, 1280, 1200, 1180, 1
110, 1040, 1020, 960, 920, 77
0, 830

<Example 2> (Production of compound represented by formula (cxv))

[0188]

Embedded image

In a 500-ml four-necked flask equipped with a Dimroth condenser and a thermometer, 10 g of the compound represented by the formula (cviii) obtained in the seventh step of Example 1 and 100 ml of tetrahydrofuran were added, and the mixture was heated with a drier. Dissolved.

To this, 100 ml of 10% hydrochloric acid was added to add about 30
Stirring was continued for minutes. After confirming the disappearance of the starting materials by thin layer chromatography, 500 ml of ethyl acetate was added to the reaction mixture. After separating the organic layer, it was washed twice with a saturated saline solution.
After the organic layer was dried over magnesium sulfate, the solvent was removed to quantitatively obtain the desired product.

¹³ C-NMR (75 MHz, DMSO-d ₆ ): δ (p
pm) = 86.221, 91.140, 111.957,
115.510, 115.782, 115.921, 1
18.109, 118.438, 122.649, 12
2.781, 124.821, 124.845, 12
7.576, 129.838, 130.398, 15
7.556, 158.362, 160.188

FT-IR (cm ^-1 ): 3400, 2360, 2
200, 1900, 1650, 1610, 1550, 1
510, 1490, 1440, 1410, 1370, 1
320, 1250, 1180, 1100, 1010, 9
50, 870, 830, 820, 620, 590, 54
0

<Example 3> (Production of compound represented by formula (cxvi))

[0194]

Embedded image

To a 300 ml four-necked reactor were added 7.0 g (23 mmol) of the compound of the formula (cxv) obtained in Example 2 and 60 ml of dimethylformamide. To this were added 7.0 g (50.6 mmol) of well ground potassium carbonate and 0.84 g (5.1 mmol) of potassium iodide and heated to 80 ° C. with vigorous stirring. 2
After stirring for an hour, 10 ml of a solution of 9.2 g (50.6 mmol) of 6-bromo-1-hexanol in dimethylformamide was added dropwise to the reaction mixture over 5 minutes. Subsequently, stirring was continued for 6 hours, and after confirming disappearance of the raw materials by thin layer chromatography, the reaction was terminated.

The reaction mixture was added dropwise to 10% hydrochloric acid with stirring, and the deposited precipitate was collected by filtration. The precipitate was washed with methanol, recrystallized in the order of tetrahydrofuran and toluene and purified, and the obtained crystals were washed with diisopropyl ether. This is dried under vacuum to obtain the desired product 5.
6 g (48% yield) were obtained.

¹³ C-NMR (75 MHz, DMSO-d ₆ ): δ (p
pm) = 25.246, 25.353, 25.394,2
8.610, 28.684, 32.435, 32.46
0, 60.621, 67.489, 67.613, 8
6.760, 90.774, 113.598, 114.
634, 114.864, 118.286, 118.6
07, 122.793, 122.925, 126.31
4, 127.754, 127.794, 127.98
3, 129.156, 133.041, 156.98
4, 158.670, 159.205, 160.241

FT-IR (cm ^-1 ): 3320, 2940, 2
860, 2360, 2340, 1610, 1520, 1
510, 1480, 1400, 1280, 1250, 1
080, 1010, 840, 820

<Example 4> (Production of compound represented by formula (cxvii))

[0200]

Embedded image

A 100 ml three-necked reactor was charged with 3.0 g (6.0 mmol) of the compound represented by the formula (cxvi) obtained in Example 3 and 30 ml of tetrahydrofuran. A Dimroth condenser was attached, and the mixture was heated and stirred at 60 ° C. under a nitrogen atmosphere to make the solution substantially uniform. After adding 1.3 g (14 mmol) of acrylic acid chloride thereto, 15 ml of a solution of 1.5 g (12 mmol) of dimethylaminopyridine in tetrahydrofuran was added dropwise over 30 minutes. After completion of the dropwise addition, stirring was further continued for 4 hours. After confirming disappearance of the raw materials by thin layer chromatography, the reaction was terminated. Methylene chloride was added to the reaction mixture, and diluted hydrochloric acid was added to make the mixture acidic, and the precipitated solid was separated by filtration. The residue was washed with methylene chloride, and the washings were combined with the organic layer and washed twice with saturated saline and once with saturated aqueous sodium hydrogen carbonate. The organic layer was dried over magnesium sulfate and the solvent was removed to obtain about 3 g of a crude product. The crude product was purified by silica gel column chromatography using methylene chloride as a mobile phase, and further recrystallized from ethanol to obtain 0.8 g of the desired product (yield: 22%).

¹³ C-NMR (75 MHz, CDCl ₃ ): δ (pp
m) = 25.701, 28.523, 29.016, 2
9,090,29.658,64.432,64.45
7, 67.805, 86.919, 90.555, 11
4.497, 114.530, 114.760, 11
8.618, 118.947, 123.545, 12
3.668, 127.386, 127.501, 12
8.397, 128.545, 129.960, 13
0.001, 130.116, 130.174, 13
0.453, 133.077, 157.546, 15
8.895, 159.306, 160.820, 16
6.248

¹ H-NMR (300 MHz, CDCl ₃ ): δ (pp
m) = 1.260 (2H), 1.493 (8H), 1.7
15-1.813 (8H), 3.995 (4H), 4.1
75 (4H), 5.79-5.829 (2H), 6.0
79-6.166 (2H), 6.373-6.430
(2H), 6.878-6.972 (4H), 7.253
~ 7.474 (7H)

Example 5 (Preparation of Liquid Crystal Composition) A liquid crystal composition (A) comprising 50 parts by weight of a compound represented by the following formula (lxxxviii) and 50 parts by weight of a compound represented by the following formula (xc) was prepared. .

[0205]

Embedded image

The liquid crystal composition (A) exhibited a nematic liquid crystal phase at room temperature, and the nematic-isotropic liquid phase had a phase transition temperature of 46 ° C. Also, the refractive index of ordinary light n ₀ = 1.51
0, the refractive index of extraordinary light n _e = 1.662, birefringence 0.
152.

A liquid crystal composition (B) comprising 90 parts by weight of the liquid crystal composition (A) and 10 parts by weight of the liquid crystal acrylate compound represented by the formula (cxvii) obtained in Example 4 was obtained.
This liquid crystal composition (B) showed a liquid crystal phase at room temperature. Also,
The refractive index of ordinary light n ₀ = 1.509, the refractive index of extraordinary light n _e =
1.681 and the birefringence was 0.172.

It can be seen that the birefringence of the liquid crystal composition can be increased by about 13% by adding 10% of the compound of the present invention.

Example 6 (Preparation of Liquid Crystal Composition) To 80 parts by weight of the liquid crystal composition (A) prepared in Example 5,
Liquid crystalline acryle represented by the formula (cxvii) obtained in Example 4
Liquid crystal composition (C) comprising 20 parts by weight of a salt compound
Was. This liquid crystal composition (C) showed a liquid crystal phase at room temperature. Ma
The refractive index n of ordinary light ₀= 1.508, refractive index n of extraordinary light_e
= 1.697 and the birefringence was 0.189.

It can be seen that the birefringence of the liquid crystal composition could be increased by about 25% by adding 20% of the compound of the present invention.

<Example 7> (Preparation of liquid crystal composition) The liquid crystal acrylate compound 30 represented by the formula (cxvii) obtained in Example 4 was added to 70 parts by weight of the liquid crystal composition (A) prepared in Example 5. A liquid crystal composition (D) consisting of parts by weight was obtained. This liquid crystal composition (D) showed a liquid crystal phase at room temperature. The refractive index of the ordinary n ₀ = 1.508, the refractive index of extraordinary light n _e
= 1.711, and the birefringence was 0.203.

It can be seen that the birefringence of the liquid crystal composition could be increased by about 34% by adding 30% of the compound of the present invention.

As can be seen from the above examples, the compound of the present invention significantly increases the birefringence of the liquid crystal composition by adding a small amount to the base liquid crystal. Further, since the compound of the present invention is also excellent in compatibility, it does not increase the melting point in exchange for the effect of increasing the birefringence, so that it is very advantageous for producing an optically anisotropic material. it is obvious.

<Example 8> (Production of optically anisotropic substance) One part by weight of photopolymerization initiator "C-101" (manufactured by Toagosei Co., Ltd.) was added to 99 parts by weight of the liquid crystal composition (B) prepared in Example 5. Parts were dissolved. When this was injected into a transparent glass homogeneous alignment liquid crystal cell having a cell gap of 50 μm, it was confirmed by observation with a polarizing microscope that good uniaxial alignment was obtained. The cell was irradiated with ultraviolet light at 25 ° C. for 1 minute to photopolymerize the liquid crystal composition. When this cell was observed using a polarizing microscope, it was confirmed that an optically anisotropic body in which uniaxial orientation was uniformly fixed was obtained. When the haze of this cell was measured, it was 11.9%.

<Example 9> (Production of optically anisotropic substance) 1 part by weight of a photopolymerization initiator "C-101" (manufactured by Toagosei Co., Ltd.) was added to 99 parts by weight of the liquid crystal composition (C) prepared in Example 6. Parts were dissolved. When this was injected into a transparent glass homogeneous alignment liquid crystal cell having a cell gap of 50 μm, it was confirmed by observation with a polarizing microscope that good uniaxial alignment was obtained. The cell was irradiated with ultraviolet light at 25 ° C. for 1 minute to photopolymerize the liquid crystal composition. When the cell was observed using a polarizing microscope, it was confirmed that an optically anisotropic body in which uniaxial orientation was uniformly fixed was obtained. When the haze of this cell was measured, it was 11.9%.

<Example 10> (Production of optically anisotropic substance) One part by weight of a photopolymerization initiator "C-101" (manufactured by Toagosei Co., Ltd.) was added to 99 parts by weight of the liquid crystal composition (D) prepared in Example 7. Parts were dissolved. When this was injected into a transparent glass homogeneous alignment liquid crystal cell having a cell gap of 50 μm, it was confirmed by observation with a polarizing microscope that good uniaxial alignment was obtained. The cell was irradiated with ultraviolet light at 25 ° C. for 1 minute to photopolymerize the liquid crystal composition. When the cell was observed using a polarizing microscope, it was confirmed that an optically anisotropic body in which uniaxial orientation was uniformly fixed was obtained. The haze of this cell was measured and found to be 11.1%.

<Comparative Example 1> (Production of Optically Anisotropic Body) A photopolymerization initiator "C-101" (manufactured by Toagosei Co., Ltd.) was added to 99 parts by weight of the liquid crystal composition (A) prepared in Example 5 in an amount of 1 part by weight. Parts were dissolved. When this was injected into a transparent glass homogeneous alignment liquid crystal cell having a cell gap of 50 μm, it was confirmed by observation with a polarizing microscope that good uniaxial alignment was obtained. The cell was irradiated with ultraviolet light at 25 ° C. for 1 minute to photopolymerize the liquid crystal composition. When the cell was observed using a polarizing microscope, it was confirmed that an optically anisotropic body in which uniaxial orientation was uniformly fixed was obtained. When the haze of this cell was measured, it was 14.7%.

As can be seen from the above examples, the compound of the present invention can significantly increase the birefringence of a liquid crystal composition by adding a small amount to a base liquid crystal. It can be understood that the optically anisotropic body created by polymerization has high transparency. Furthermore, although retardation is represented by the product of the birefringence and the cell thickness, the compounds of the present invention cause a significant increase in the birefringence,
It can be understood that a large retardation can be obtained.

[0219]

Industrial Applicability The polymerizable compound of the present invention and the liquid crystal composition containing the same can achieve both a large birefringence and a decrease in melting point. Can be improved. Therefore, the polymerizable liquid crystal compound of the present invention and a liquid crystal composition containing the same are used as materials for forming optically anisotropic films such as retardation films and polarizing beam splitters, optical low-pass filters, and optical elements such as polarizing prisms. Useful.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 19/38 C09K 19/38 (72) Inventor Sadao Takehara 2-23-16 F, Haruji, Sakura-shi, Chiba Term (reference) 4C062 AA22 4H006 AA01 AA03 AB64 AC24 AC42 AC43 AC44 AC48 AC53 AC63 BM30 BM71 BP30 BT12 BT26 BT34 BT36 4H027 BA01 BA13 BB03 BB04 BB06 BD02 BD24 CB02 CE02 CM02 4J100 AE09PALPP BC08 BC02P02P02B BC65P BC73P CA01 CA04 DA66 JA39

Claims (24)

[Claims] 1. A compound of the general formula (1-a) (Wherein X ^a , X ^b and X ^c each independently represent a fluorine atom, a chlorine atom or a methyl group, and l, m and n
Represents an integer of 0 to 4, and at least one of l, m and n represents an integer of 1 or more. q and t each independently represent an integer of 1 to 20; R ¹ and R ² each independently represent a linear or branched divalent hydrocarbon group having 1 to 18 carbon atoms; Wherein Y ¹ and Y ² each independently represent a single bond, a linking group selected from the group consisting of —O— and —S—, and Q ¹ and Q ² each independently represent acryloyloxy. Group, methacryloyloxy group, ClCH = CHCOO-, acrylamide group, methacrylamide group, ClCH = CHCONH-, vinyl group, CH
₂ = CCl-, CHCl = CH-, it represents an epoxy group, an ethynyl group, a reactive functional group selected from mercapto and CH ₂ = CHO- group consisting. A polymerizable compound represented by the formula: 2. The polymerizable polymer according to claim 1, wherein 1 is 0, m and n are 0 or 1, at least one of m and n is 1, and X ^b and X ^c are fluorine atoms. Compound. 3. General formula (1-b) (Wherein X ¹ , X ² and X ³ each independently represent a fluorine atom or a hydrogen atom, and at least one group among X ¹ , X ² and X ³ represents a fluorine atom; And t each independently represent an integer of 1 to 10,
¹ and R ² each independently represent an alkylene group having 1 to 18 carbon atoms or an alkenylene group having 2 to 18 carbon atoms, and Y ¹ and Y ² each independently represent a single bond or -O- And Q ¹ and Q ² each independently represent an acryloyloxy group or a methacryloyloxy group. A) a polymerizable compound represented by the formula: 4. A compound represented by the general formula (1-c): (In the formula, q and t each independently represent an integer of 1 to 3, and R ¹ and R ² each independently represent an alkylene group having 1 to 18 carbon atoms or 2 to 18 carbon atoms. Wherein Y ¹ and Y ² both represent —O—, and Q ¹ and Q ² each independently represent an acryloyloxy group or a methacryloyloxy group.) 5. Q and t are both 1, R ¹ and R
5. The polymerizable compound according to claim 4, wherein each ² is independently an alkylene group having 1 to 12 carbon atoms. 6. The liquid crystal display device according to claim 1, which exhibits liquid crystallinity.
The polymerizable compound according to the item. 7. A compound of the general formula (2-a) (Wherein, X ^d , X ^e and X ^f each independently represent a fluorine atom, a chlorine atom or a methyl group, and l, m and n
Each independently represents an integer of 0 to 4;
And n represents an integer of 1 or more; q and t each independently represent an integer of 0 to 20;
(1) When q is 1 or more, R ³ represents a linear or branched divalent hydrocarbon group having 1 to 18 carbon atoms;
³ is a single bond, -COO-, -O-, -OCO-, -C
Represents a linking group selected from the group consisting of O- and -S-, (2) when t is 1 or more, R ⁴ is -C 1-1
8 represents a linear or branched divalent hydrocarbon group;
⁴ is a single bond, -COO-, -O-, -OCO-, -CO
- and it represents a linking group selected from the group selected from -S-, Q ³ and Q ⁴ are, each independently, selected hydroxyl, an iodine atom, a bromine atom, a chlorine atom, from the group consisting of amino groups and carboxyl groups Represents a reactive functional group or a protected amino group, a protected hydroxyl group or a protected carboxyl group. A compound represented by the formula: 8. L is 0, m and n are each independently an integer of 0 to 2, but at least one of m and n is an integer of 1 or more, and X ^e and X ^f are Both are fluorine atoms, (1) when q is 1 or more, R ³ is a linear or branched divalent hydrocarbon group having 1 to 18 carbon atoms, and Y ³ is a single bond,- COO -, - a linking group selected from the group consisting of O- and -S-, (2) when t is 1 or more, R ⁴ is shaped straight having 1 to 18 carbon atoms or a branched divalent Wherein Y ⁴ is a single bond, -O-,-
The compound according to claim 7, which is a linking group selected from the group consisting of OCO- and -S-. 9. A compound of the general formula (2-b) (In the formula, q and t each independently represent an integer of 0 to ^3. (1) When q is 1 or more, R ³ represents an alkylene group having 1 to 18 carbon atoms or 2 -18 represents an alkenylene group, and Y ³ represents -COO- or -O-
And (2) when t is 1 or more, R ⁴ represents an alkylene group having 1 to 18 carbon atoms or an alkenylene group having 2 to 18 carbon atoms, and Y ⁴ represents —O— or —OCO—.
And Q ³ and Q ⁴ are each independently. Hydroxyl group,
A reactive functional group selected from the group consisting of an iodine atom, a bromine atom, a chlorine atom, an amino group and a carboxyl group or a protected amino group, a protected hydroxyl group, and a protected carboxyl group. A compound represented by the formula: 10. When q and t are both 1, R ³ and R ⁴
Are each independently an alkylene group having 1 to 12 carbon atoms, Y ³ and Y ⁴ are both —O—, and Q ³ and Q ⁴ are each independently a hydroxyl group or a protected hydroxyl group The compound according to claim 9, which is 11. When q and t are both 0, Q ³ and Q ⁴
10. The compound according to claim 9, wherein each is independently a hydroxyl group or a protected hydroxyl group. A polymerizable liquid crystal composition comprising the polymerizable compound according to any one of claims 1 to 6. 13. The polymerizable liquid crystal composition according to claim 12, which exhibits a liquid crystal phase at least at 25 ° C. 14. An acrylic or methacrylic acid ester of a cyclic alcohol, phenol or aromatic hydroxy compound having as a partial structure a liquid crystal skeleton having at least two 6-membered rings in one molecule, wherein one molecule in one molecule is used. 14. The polymerizable liquid crystal composition according to claim 12, comprising a polymerizable compound having an acrylate group or a methacrylate group. 15. A compound of the general formula (3) (Wherein X ⁴ represents a hydrogen atom, a chlorine atom or a methyl group, u represents an integer of 0 or 1, and 6-membered rings A, B and C
Are each independently: And p represents an integer of 1 to 4, and Y ⁷ and Y ⁸ are
Each independently, a single _{bond, -CH 2 CH 2 -, -} CH 2
_{C (CH 3) H -,} - C (CH 3) HCH 2 -, - CH 2 O
_{-, - OCH 2 -, -} CF 2 O -, - OCF 2 -, - CO
O-, -OCO-, -C≡C-, -CH = CH-, -C
F = CF -, - (CH 2) 4 -, - CH 2 CH 2 CH 2 O
_{-, - OCH 2 CH 2 CH} 2 -, - CH = CH-CH 2 CH
₂ -, and -CH ₂ CH ₂ represents a linking chain selected from the group consisting of CH = CH-, Y ⁹ represents a single bond, -O -, - CO
Represents O- or -OCO-, Z ⁷ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an alkenyl group having 2 to 20 carbon atoms of 1 to 20 carbon atoms. The polymerizable liquid crystal composition according to any one of claims 12 to 14, comprising a polymerizable liquid crystal compound represented by the formula: 16. A compound represented by the general formula (1-a) according to claim 1, wherein the compound is represented by the general formula (4): (Wherein L ¹ represents a hydrogen atom, a chlorine atom or a methyl group, and R ⁵ represents an alkyl group having 1 to 18 carbon atoms) and a compound represented by the general formula (5): (Wherein L ² represents a hydrogen atom, a chlorine atom or a methyl group, and R ⁶ represents an alkyl group having 1 to 18 carbon atoms). Composition. 17. A compound represented by the general formula (1-b) according to claim 3, a compound represented by the general formula (4) according to claim 16, and a compound represented by the general formula (5) according to claim 16. A polymerizable liquid crystal composition comprising a compound. 18. A compound represented by the general formula (1-c) according to claim 4, a compound represented by the general formula (4) according to claim 16, and a compound represented by the general formula (5) according to claim 16. A polymerizable liquid crystal composition comprising a compound. 19. The compound represented by the general formula (1-c) according to claim 4, wherein q and t are both 1 and R ¹
And R ² are each independently an alkylene group having 3 to 11 carbon atoms, Y ¹ and Y ² are both —O—,
19. The polymerizable liquid crystal composition according to claim 18, wherein a compound in which Q ¹ and Q ² are both acryloyloxy groups is used. 20. A compound represented by the general formula (4) according to claim 16, wherein L ¹ is a hydrogen atom, and a compound represented by the general formula (5) according to claim 16 is L ² 2. A compound in which is a hydrogen atom.
20. The polymerizable liquid crystal composition according to any one of 6 to 19. 21. The compound represented by the general formula (4) according to claim 16, wherein L ¹ is a hydrogen atom and R ⁵ is an alkyl group having 2 to 7 carbon atoms. As a compound represented by the general formula (5) described above, L
² is a hydrogen atom, a polymerizable liquid crystal composition according to claim 20, wherein a compound R ⁶ is an alkyl group having 2 to 7 carbon atoms. 22. The composition according to claim 12, which contains a photopolymerization initiator.
22. The polymerizable liquid crystal composition according to any one of 21. 23. A method for producing an optically anisotropic body, comprising polymerizing the polymerizable liquid crystal composition according to claim 12 by light, an electron beam, or radiation. 24. An optically anisotropic body comprising a polymer of the polymerizable liquid crystal composition according to claim 12.