JP2002226857A - Polymerable liquid crystal composition and optical element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable liquid crystal composition which exhibits good liquid crystallinity and gives a polymer having excellent retardation and transparency after polymerized. SOLUTION: This polymerizable liquid crystal composition contains a polymerizable liquid crystalline compound having a polymerizing functional group in the molecule and represented by the general formula (1): P-S1-A-S2-M P is a polymerizing functional group; A is a ring selected from the group consisting of aromatic rings, aliphatic rings, heterogeneous rings, and condensed rings; M is a mesogen portion having 2 to 16 identical or different rings selected from the group consisting of aromatic rings, aliphatic rings, heterogeneous rings, and condensed rings; S1 is a binding chain selecting from (CH2)w, (CH2)wO, (CH2)wC(=O)O, or (CH2)wOC(=O) [(v) is an integer of 1 to 20]; S2 is a binding chain of C(=O)-O-(CH2)m-O, O(CH2)m-O-C(=O), O-C(=O)-(CH2)m-O or O(CH2)m- C(=O)-O [(n) is an integer of 2 to 15]}.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a retardation plate, a polarizing plate, a polarizing prism, a waveguide, a piezoelectric element, a nonlinear optical element, various optical filters, a liquid crystal pigment utilizing selective reflection of a cholesteric liquid crystal phase, and a liquid crystal-resin. Compound display, holographic liquid crystal display, polymer stabilized liquid crystal (ferroelectric liquid crystal, antiferroelectric liquid crystal) display,
The present invention relates to a polymerizable liquid crystal composition useful as a coating agent for optical fibers and the like, and a polymer obtained by polymerizing the liquid crystal composition.

[0002]

2. Description of the Related Art A liquid crystal compound having a polymerizable functional group (hereinafter, referred to as a polymerizable liquid crystal compound) or a polymerizable liquid crystal composition containing such a compound is aligned in a liquid crystal state, and then ultraviolet rays are irradiated in that state. Irradiation with such active energy rays as above can produce a polymer in which the alignment state structure of liquid crystal molecules is fixed. The polymer obtained in this way is
Since it has anisotropy of physical properties such as refractive index, dielectric constant, magnetic susceptibility, elastic modulus, and coefficient of thermal expansion, for example, a retardation plate, a polarizing plate, a polarizing prism, a waveguide, a piezoelectric element, It can be applied as a coating material such as a nonlinear optical element, various optical filters, a pigment utilizing selective reflection of a cholesteric liquid crystal phase, and an optical fiber.

[0003] As a polymerizable liquid crystal composition used in such applications, Japanese Patent Application Laid-Open No. 8-3111 discloses a polymerizable liquid crystal composition containing a polymerizable compound having one (meth) acryl group in one molecule. Offered. Although the polymerizable liquid crystal composition disclosed in this publication has the property of exhibiting liquid crystallinity at room temperature, it has problems in that the retardation after polymerization is lowered, and the transparency and mechanical strength are insufficient.

[0004]

Accordingly, an object of the present invention is to provide a polymerizable liquid crystal composition exhibiting good liquid crystallinity and having excellent retardation and transparency after polymerization. To provide.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies on the correlation between the chemical structure and the physical properties of a polymerizable liquid crystal composition, and as a result, have found that a polymerizable functional group has a connecting chain S having a specific structure.
A composition comprising a compound represented by the following general formula (1), wherein the compound is bonded to ring A via a linking group 1 and further connected to a mesogen moiety M via a connecting chain S2 having a specific structure. It has been found that the above problems can be solved by providing a product, and the present invention has been completed. Therefore, the present invention
(A) General formula (1) P-S1-A-S2-M (1) (P represents a polymerizable functional group, and A represents a ring selected from the group consisting of an aromatic ring, an alicyclic ring, a heterocyclic ring, and a condensed ring. the stands, .S1 M is representative of the mesogen portion having an aromatic ring, alicyclic, the same or different 2 to 16 ring selected from the group consisting of heterocyclic and fused _{ring, - (CH 2) w -} , - (CH ₂ ) _w O-,-
_{(CH 2) w C (=} O) O-, and - (CH _{2) w} OC
(= O)-(v represents an integer of 1 to 20), and S2 represents -C (=
_{O) -O- (CH 2) m} -O -, - O (CH 2) m -O-C
(= O) -, - O -C (= O) - (CH 2) m -O- and _{-O (CH 2) m -C (} = O) -O- (n is an integer of 2 to 15 Represents a connecting chain represented by. A) providing a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound having one polymerizable functional group in one molecule.

Further, the present invention provides (B) an optical element using the polymerizable liquid crystal composition described in the above (A) in order to solve the above problems.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound represented by the following general formula (1).

P-S1-A-S2-M (1) (P represents a polymerizable functional group, A represents a ring selected from the group consisting of an aromatic ring, an alicyclic ring, a heterocyclic ring and a condensed ring, and M represents a ring. S1 represents a mesogen moiety having the same or different 2 to 16 rings selected from the group consisting of an aromatic ring, an alicyclic ring, a heterocyclic ring and a condensed ring, wherein S1 is at least 1 Represents a connecting chain composed of 1 to 18 kinds of atoms, and S2 represents a connecting chain whose main chain is composed of at least one kind of 5 to 18 atoms selected from carbon, oxygen, silicon and sulfur.)

In the general formula (1), the polymerizable functional group P
Is not particularly limited as long as it is a functional group having polymerizability. Specifically, for example, acryloyloxy group, methacryloyloxy group, ClCH ＝ CHC (＝ O) O—,
Acrylamide group, methacrylamide group, ClCH = C
HC (= O) NH-, a vinyl group, CH ₂ = CCl-, C
HCl = CH-, an epoxy group, an ethynyl group, a mercapto group, a vinyloxy group, a maleimide group and the like. Among them, an acryloyloxy group, a methacryloyloxy group, a vinyl group, an epoxy group, a mercapto group, a vinyloxy group and a maleimide group are preferred, and an acryloyloxy group, a methacryloyloxy group, an epoxy group, a vinyloxy group and a maleimide group are particularly preferred.

In the general formula (1), S1 represents a connecting chain whose main chain is composed of at least one atom selected from carbon, oxygen, silicon and sulfur. The number of atoms constituting the connecting chain S1 is preferably 1 to 20, and particularly preferably 1 to 18. Examples of the linking chain include an alkyl chain, an alkylene chain, an alkenylene chain, an alkynylene chain, an oxyalkylene chain, and an oxyalkylenoyl chain. Further, these connecting chains may have a bond such as an ether bond, a thioether bond, an ester bond, an amide bond, an imine bond, a double bond, a triple bond, or the like.

Specifically,-(CH ₂ ) _w -,-(C
_{H 2) w O -, -} (CH 2) w C (= O) O-, and - (C
A linking chain selected from the group consisting of H ₂ ) _w OC (ＯO) — (v represents an integer of 1 to 20);
(CH ₂ ) _w O— is particularly preferred.

In the general formula (1), S2 represents a connecting chain whose main chain is composed of at least one atom selected from carbon, oxygen, silicon and sulfur. The connecting chain is preferably a linear or branched one having flexibility.
The number of atoms constituting 2 is preferably 5 to 20, and 5 to 18
Is particularly preferred. Examples of the connecting chain include an alkylene chain, an alkenylene chain, an alkynylene chain, an oxyalkylene chain, and an oxyalkylenoyl chain. Among them, a chain having an alkylene chain is preferable. In these connecting chains, an ether bond, a thioether bond, an ester bond,
It may have a bond such as an amide bond, an imine bond, a double bond, and a triple bond.

Specifically, S2 is represented by -C (= O) -O-
_{(CH 2) m -O -,} - O (CH 2) m -O-C (= O)
-, - O-C (= O) - (CH 2) m -O-, or -O
_{(CH 2) m -C (=} O) -O- (n represents. An integer of 2 to 15) connecting chain is preferably represented by, -C (=
_{O) -O- (CH 2) m} -O- or -O (CH _{2) m} -O-
C (= O)-is particularly preferred.

In the general formula (1), A represents a ring selected from the group consisting of an aromatic ring, an alicyclic ring, a heterocyclic ring and a condensed ring. For example, cyclopentane ring, furan ring, pyrrole ring, thiophene ring, thiazole ring, thiadiazole ring,
Benzene ring, cyclohexane ring (one CH ₂ group constituting the cyclohexane ring, or two or more _non-adjacent CH ₂ groups to constitute the ring may be replaced by -O- or -S- ), Cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, naphthalene ring, tetralin ring, decalin ring, and the like. Among them, a benzene ring and a cyclohexane ring are preferred.

Specifically, for example, a 1,4-phenylene ring, a 1,4-cyclohexylene ring (one CH ₂ group constituting a cyclohexylene ring or two or more non-adjacent groups constituting this ring) the CH ₂ groups may be replaced by -O- or -S-) 1,3-dioxane -
2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, pyrazine-2,5-diyl, piperidine-2,5-diyl, piperidine-1,4-diyl, piperazine-2, 5-diyl, 1,4-cyclohexylene, 1,4-cyclohexenylene, naphthalene-
2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6
A ring selected from -diyl and 1,4-bicyclo [2.2.2] octylene is more preferred.

The ring A may be further substituted with at least one substituent selected from the group consisting of a halogen group, a cyano group, a hydroxyl group, an alkyl group, an alkoxy group and an alkanoyl group. Specifically, as the halogen group, a fluorine atom, a bromine atom and a chlorine atom are preferable, and a fluorine atom and a chlorine atom are particularly preferable. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an n-
A butyl group is preferred, and a methyl group and an ethyl group are particularly preferred. As the alkoxy group, a methoxy group, an ethoxy group,
Propoxy and butoxy groups are preferred. The alkanoyl group is preferably an acetyl group, a propionyl group, or a butyryl group.

In the general formula (1), M represents a mesogen moiety having at least two or more identical or different rings selected from the group consisting of an aromatic ring, an alicyclic ring, a heterocyclic ring and a condensed ring. There is no particular limitation on the structure of the mesogen moiety,
Those having 6 rings are preferred, those having 2 to 8 rings are more preferred, and those having 2 to 4 rings are most preferred. The number of atoms constituting the ring is not particularly limited, and may be 3 or more as long as it can constitute the ring.
Is more preferable.

Examples of the ring having 3 to 5 atoms include cyclopropane, oxirane, cyclobutane, cyclopentane, cyclopentanone, tetrahydrofuran,
Dioxolan-2-one, furan, pyrrole, pyrroline, pyrrolidine, oxazole, isoxazole, thiophene, thiazole, isothiazole, thiadiazole, imidazole, imidazoline, imidazolidine, pyrazole, pyrazoline, pyrazolidine, 1,2,3-triazole, 1, , 2,4-triazole, tetrazole and the like.

Examples of the ring having 6 atoms include benzene, pyridine, pyrazine, pyridazine, pyrimidine,
1,2,4-triazine, 1,3,5-triazine, tetrazine, dihydrooxazine, cyclohexane, cyclohexene, cyclohexadiene, cyclohexanone,
Examples thereof include piperidine, piperazine, tetrahydropyran, dioxane, tetrahydrothiopyran, dithiane, oxathiane, and dioxaborinane.

Examples of the ring having 7 or more atoms include naphthalene, dioxanaphthalene, tetralin, quinoline, coumarin, quinoxaline, decalin, indane, benzoxazole, benzothiazole, phenanthrene, dihydrophenanthrene, and perhydrophenanth. Len, dioxaperhydrophenanthrene, fluorene,
Fluorenone, cycloheptane, cycloheptatrienone, cholesten and the like.

As the ring constituting the mesogen moiety M, in addition to these, as a bridged ring, bicyclo (2,2,2)
2) Octane and bicyclo (2,2,2) octene. Examples of the ring having a spiro bond include 1,5-dioxaspiro (5,5) undecane and 1,5-dithiaspiro (5,5) undecane.

Specifically, the mesogen moiety M of the general formula (1)
Preferably has one or more structural units represented by the following general formula (2).

E- (Y1-F) n-Y2-G (2)

In the above general formula (2), E, F and G
Is independently 1,4-phenylene, 1,4-
Cyclohexylene, 1,4-cyclohexenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,
6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, 1,4-bicyclo [2.2.2] octylene, 1,3-dioxane-2,5-diyl, pyridine-2 , 5-diyl, pyrazine-2,5-diyl, pyridazine-3,6-diyl and pyrimidine-2,5-diyl. The site E bonds to the ring A via the connecting chain S2 in the formula represented by the general formula (1).

Any of E, F and G may be substituted with at least one substituent selected from the group consisting of a halogen group, a cyano group, a hydroxyl group, an alkyl group, an alkoxy group and an alkanoyl group. Is also preferable.

As the halogen group, a fluorine atom, a bromine atom and a chlorine atom are preferred, and a fluorine atom and a chlorine atom are particularly preferred. Examples of the alkyl group include a methyl group, an ethyl group,
An n-propyl group and an n-butyl group are preferred, and a methyl group and an ethyl group are particularly preferred. As the alkoxy group, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group are preferable. As the alkanoyl group, an acetyl group, a propionyl group and a butyryl group are preferred.

These substituents may have at least one atom selected from carbon, oxygen, silicon and sulfur.
And may be linked to any one of E, F, and G in the mesogen portion. As these linking chains, specifically, alkyl chains, alkylene chains, alkenylene chains, alkynylene chains,
An oxyalkylene chain, an oxyalkylenoyl chain and the like can be mentioned. In these connecting chains, an ether bond,
It may have a bond such as a thioether bond, an ester bond, an amide bond, an imine bond, a double bond, and a triple bond.

In the above general formula (2), Y1 and Y2
They are each independently a single _{bond, -CH 2 CH 2 -, -} C
_{H 2 O-, -OCH 2 -,} -C (= O) O -, - OC
(= O)-, -C≡C-, -CH = CH-, -CF = C
_{F -, - (CH 2)} 4 -, - CH 2 CH 2 CH 2 O-, -
_{OCH 2 CH 2 CH 2 -,} - CH = CH-CH 2 CH 2 -,
_{-CH 2 CH 2 -CH = CH -} , - CH = CH-C (=
O) O- or -OC (= O) -CH = CH-,
n represents an integer of 0 to 3. When there are a plurality of Y1 and F, each of Y1 and F may be the same or different.

Among them, E, F and G are 1,4-phenylene, Y1 or Y2 is -C≡C-, and the other Y1 or Y2 is a single bond, -C (= O) O-, Or -O
Structural units that are C (= O)-are preferred.

The structural unit represented by the general formula (2) includes, for example, a structural unit represented by the following formula.

[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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(The aromatic ring, alicyclic ring, heterocyclic ring and condensed ring in the formulas (1) to (446) consist of a cyano group, a halogen atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group and an alkanoyl group. It may be substituted with one or more substituents selected from the group.)

Specifically, as the polymerizable liquid crystal compound used in the present invention, among the polymerizable liquid crystal compounds represented by the general formula (1), the following general formulas (4) and (5):

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[0066]

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(Wherein X represents a hydrogen atom or a methyl group, Y3 is a single bond, -OC (= O)-, -C (=
O) O -, - C≡C- and represents -CH ₂ CH ₂ - linking group selected from the group consisting of, R represents a hydroxyl group, a cyano group,
Represents a halogen group, an alkyl group having 1 to 7 carbon atoms, an alkoxy group or an alkanoyl group, q represents an integer of 1 to 20, m represents an integer of 2 to 15, and p represents 0
Or an integer of 1. The 1,4-cyclohexylene group and the 1,4-phenylene group each independently represent a cyano group, a halogen atom, an alkyl group having 1 to 7 carbon atoms,
It may be substituted with one or more substituents selected from the group consisting of an alkoxy group and an alkanoyl group. A) a polymerizable liquid crystal compound represented by the formula:

The following general formulas (6), (7) and (8):

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[0069]

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[0070]

Embedded image (Wherein, X represents a hydrogen atom or a methyl group, Y3 and Y4 each independently represent a single bond, -OC (= O)
—, —C (＝ O) O—, —C≡C— and —CH ₂ CH ₂ —
Wherein R represents a hydroxyl group, a cyano group, a halogen group, an alkyl group having 1 to 7 carbon atoms, an alkoxy group or an alkanoyl group;
Represents an integer of 1 to 20, m represents an integer of 3 to 16, and p represents an integer of 0 or 1. Also, 1,4
The -phenylene group may be independently substituted with one or more alkyl groups having 1 to 7 carbon atoms, alkoxy groups, alkanoyl groups, or cyano groups, or halogen atoms. )
A polymerizable liquid crystal compound represented by the following general formulas (9) and (10):

[0071]

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[0072]

Embedded image (Wherein, X represents a hydrogen atom or a methyl group, and R is
A hydroxyl group, a cyano group, a halogen group, an alkyl group having 1 to 7 carbon atoms, an alkoxy group or an alkanoyl group,
q represents an integer of 1 to 20, and m represents an integer of 2 to 15. Further, a 1,4-cyclohexylene group and 1,1,
The 4-phenylene group may be each independently substituted with one or more substituents selected from the group consisting of a cyano group, a halogen atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group and an alkanoyl group. good. A) a polymerizable liquid crystal compound represented by the following general formulas (11), (12), (13),
(14) and (15),

[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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(Wherein, X represents a hydrogen atom or a methyl group, and Y3, Y4 and Y5 each independently represent a single bond, -OC (= O)-, -C (= O) O-, -C≡C-
And -CH2CH2- represents a linking group selected from the group consisting of: q represents an integer of 1 to 20, m represents 3 to 1
6 represents an integer, ring J represents a 1,4-cyclohexylene group, 1,4-phenylene group, R is a hydroxyl group, a cyano group, a halogen group, an alkyl group having 1 to 7 carbon atoms,
Represents an alkoxy group or an alkanoyl group, p and s
Represents 0 or 1 each independently. Also, 1,
The 4-cyclohexylene group and the 1,4-phenylene group each independently represent a cyano group, a halogen atom,
7 may be substituted with one or more substituents selected from the group consisting of an alkyl group, an alkoxy group and an alkanoyl group. )) Are particularly preferred.

Although the (meth) acrylate compound has been mentioned as a preferred example of the compound of the present invention, a compound having an epoxy group as a reactive group is also preferred. As such compounds, for example, the following general formulas (16) and (1)
The compound represented by 7) can be mentioned.

[0080]

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[0081]

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(Wherein Y 3, Y 4 and Y 5 are each independently a single bond, —OC (＝ O) —, —C (＝ O) O
Represents a linking group selected from the group consisting of-, -C≡C- and -CH2CH2-, q represents an integer of 1 to 20, m represents an integer of 2 to 15, and n represents 3 to 16 And ring J is a 1,4-cyclohexylene group,
Represents a 1,4-phenylene group, R represents a hydroxyl group, a cyano group, a halogen group, an alkyl group having 1 to 7 carbon atoms, an alkoxy group or an alkanoyl group, and p and s each independently represent 0 or 1 Represents In addition, the 1,4-cyclohexylene group and the 1,4-phenylene group each independently represent a cyano group, a halogen atom, and a C1 to C1 group.
7 may be substituted with one or more substituents selected from the group consisting of an alkyl group, an alkoxy group and an alkanoyl group. )

As a preferred example of the compound of the present invention, a compound having a vinyloxy group as a reactive group is also preferred.
As such a compound, for example, the following general formula (1)
Compounds represented by 8) and (19) can be mentioned.

[0084]

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[0085]

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(Wherein Y3, Y4 and Y5 each independently represent a single bond, -OC (= O)-, -C (= O) O
Represents a linking group selected from the group consisting of-, -C≡C- and -CH2CH2-, q represents an integer of 1 to 20, m represents an integer of 2 to 15, and ring J represents 1, 4-
Represents a cyclohexylene group, a 1,4-phenylene group,
R is a hydroxyl group, a cyano group, a halogen group, a group having 1 to 1 carbon atoms.
7 represents an alkyl group, an alkoxy group or an alkanoyl group, and p and s each independently represent 0 or 1. The 1,4-cyclohexylene group and the 1,4-phenylene group are each independently selected from the group consisting of a cyano group, a halogen atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group and an alkanoyl group. It may be substituted with one or more substituents. )

As a preferable example of the compound of the present invention, a compound having a maleimide group as a reactive group is also preferable. As such a compound, for example, the following general formula (2)
Compounds represented by 0) and (21) can be mentioned.

[0088]

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[0089]

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(Wherein Y 3, Y 4 and Y 5 are each independently a single bond, —OC (＝ O) —, —C (＝ O) O
Represents a linking group selected from the group consisting of-, -C≡C- and -CH2CH2-, q represents an integer of 1 to 20, m represents an integer of 2 to 15, and ring J represents 1, 4-
Represents a cyclohexylene group, a 1,4-phenylene group,
R is a hydroxyl group, a cyano group, a halogen group, a group having 1 to 1 carbon atoms.
7 represents an alkyl group, an alkoxy group or an alkanoyl group, and p and s each independently represent 0 or 1. The 1,4-cyclohexylene group and the 1,4-phenylene group are each independently selected from the group consisting of a cyano group, a halogen atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group and an alkanoyl group. It may be substituted with one or more substituents. )

When applied to the production of an optical element, the liquid crystal composition of the present invention preferably exhibits a liquid crystal phase at room temperature, typically at 25 ° C.

The liquid crystal composition of the present invention may be any composition that exhibits a phase generally recognized as a liquid crystal phase in this technical field. Among such compositions, as a liquid crystal phase, a nematic phase, a smectic A phase, a (chiral) smectic C phase,
Those expressing a cholesteric phase are preferred. Among them, the nematic phase is particularly preferable because it has good orientation. In the case of showing a (chiral) smectic C phase, a smectic A phase in a temperature range higher than the temperature range of the (chiral) smectic C phase, a nematic phase in a temperature range higher than the temperature range of the smectic A phase, The liquid crystal compositions that express each other are preferable because good alignment properties tend to be obtained.

The liquid crystal composition of the present invention can be used in combination with a known and commonly used liquid crystal compound. Among them, one (meth) acryloyloxy group and (meth)
Liquid crystalline compounds having a polymerizable functional group selected from the group consisting of acrylamide, vinyl, epoxy, ethynyl, mercapto, vinyloxy and maleimide groups are preferred. As such a polymerizable liquid crystal compound,
For example, the general formula (3)

[0094]

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(Wherein X represents a hydrogen atom or a methyl group, and M represents a mesogen moiety having 2 to 16 identical or different rings selected from the group consisting of aromatic rings, alicyclic rings, heterocyclic rings and condensed rings) Wherein Y ₃ is a single bond, -O-, -OC (=
O)-, -C (= O) O- and -CH = CH-C (=
O) represents a linking group selected from the group consisting of O-, Z ₁
Represents a hydrogen atom, a halogen atom, a cyano group, or a hydrocarbon group having 1 to 20 carbon atoms. )), And are preferably used.

In the general formula (2), the mesogen moiety M
Represents a structure similar to that of the mesogen moiety M in the general formula (1).

Specifically, for example, the following general formula (22)

Embedded image (Wherein, X represents a hydrogen atom or a methyl group, and r is
And the 6-membered rings K, L and M each independently represent a 1,4-phenylene group, pyridine-2,5
-Diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,4-cyclohexylene group, 1
One or two non-adjacent CH ₂ groups represent a 1,4-cyclohexylene group or a 1,4-cyclohexenyl group substituted with an oxygen or sulfur atom, and these 6-membered rings K, L and M
Further comprises a cyano group, a halogen atom,
7 may be substituted with one or more substituents selected from the group consisting of an alkyl group, an alkoxy group and an alkanoyl group, and Y ₁ and Y ₂ are each independently a single bond,-
CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —C (=
O) O-, -OC (= O)-, -C≡C-, -CH = C
H -, - CF = CF - , - (CH 2) 4 -, - CH 2 CH 2
_{CH 2 O -, - OCH 2} CH 2 CH 2 -, - CH = CH-C
_{H 2 CH 2 -, - CH} 2 CH 2 -CH = CH -, - CH = C
HC (= O) O- and -OC (= O) -CH = CH-
And Y ₃ represents a single bond, —O—, —OC (＝ O) —, —C (＝ O) O— and —CH ＝ CH—C (＝ O) O And Z ₁ represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. )) Are preferred.

The liquid crystalline (meth) acrylate compound represented by the general formula (22) which can be contained in the liquid crystal composition of the present invention includes a compound represented by the general formula (23):

[0099]

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(Wherein X represents a hydrogen atom or a methyl group, and R ₁ represents an alkyl group having 1 to 10 carbon atoms), or a compound represented by the general formula (24):

[0101]

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(Wherein X represents a hydrogen atom or a methyl group, and R ₂ represents an alkyl group having 1 to 10 carbon atoms). These compounds represented by the general formula (23) and the compounds represented by the general formula (24) may be used alone or in combination. When used in combination, the general formula (23)
And the concentration of the compound represented by the general formula (24) is preferably equalized. The amount used is 90
% By weight or less, more preferably 80% by weight or less. However, compounds that can be used in the liquid crystal composition of the present invention are not limited to these compounds.

Specific examples of the compound represented by formula (22) include compounds represented by formulas (a-1) to (a-25). The phase transition temperatures are shown below the structural formulas of the compounds represented by the exemplified formulas (a-1) to (a-25). (In the formula, the cyclohexane ring represents a transcyclohexane ring. The numbers represent phase transition temperatures, C represents a crystal phase, N represents a nematic phase, S represents a smectic phase, and I represents an isotropic liquid phase.)

[0104]

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[0105]

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[0106]

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[0107]

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The liquid crystal composition of the present invention may contain other monofunctional (meth) acrylate compounds in addition to the (meth) acrylate compound represented by the general formula (22). Examples of such compounds include compounds represented by the following formulas (a-26) to (a-35). However, compounds that can be used in the liquid crystal composition of the present invention are not limited to these. In addition, the expression (a-26) to the expression (a-35)
The phase transition temperature is shown below the structural formula of the compound represented by. (In the formula, the cyclohexane ring represents a transcyclohexane ring. The numbers represent phase transition temperatures, C represents a crystal phase, N represents a nematic phase, S represents a smectic phase, and I represents an isotropic liquid phase.)

[0109]

[Of 60]

[0110]

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Further, in addition to the compounds listed above, the liquid crystal composition of the present invention has (meth) a liquid crystal skeleton in the side chain.
An acrylate compound may be contained. Examples of such a compound include compounds represented by the following formulas (a-36) to (a-45).
(Wherein the cyclohexane ring represents a transcyclohexane ring. The numbers represent phase transition temperatures, C represents a crystal phase,
N represents a nematic phase, S represents a smectic phase, and I represents an isotropic liquid phase. )

[0112]

Embedded image

[0113]

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Further, in addition to the compounds described above, the liquid crystal composition of the present invention may contain another liquid crystal (meth) acrylate compound in the liquid crystal composition of the present invention. Examples of such a compound include compounds represented by the following formulas (a-46) to (a-61).

[0115]

Embedded image

[0116]

Embedded image (Wherein X ⁶ and X ⁷ each independently represent a hydrogen atom or a methyl group, and s and t each independently represent
Represents an integer of 2 to 18).

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. However, from the viewpoint of ensuring the heat resistance of the polymer produced using the liquid crystal composition, the amount of addition is preferably 80% by weight or less, more preferably 30% by weight or less, and particularly preferably 10% by weight or less.

The liquid crystal composition of the present invention may contain a compound having a polymerizable functional group and exhibiting no liquid crystallinity. Such compounds include:
In general, any substance recognized as a polymer-forming monomer or a polymer-forming oligomer in this technical field can be used without any particular limitation.

The purpose of the liquid crystal composition of the present invention is to irradiate active energy rays in a temperature range of a liquid crystal phase to polymerize a polymerizable compound in the composition. Therefore, in order to avoid undesirable thermal polymerization during the active energy ray irradiation step and to produce a polymer with excellent uniformity, the liquid crystal composition of the present invention is used at room temperature (typically 25 ° C.) or room temperature. Those exhibiting liquid crystal properties in the vicinity are preferred. For example, when the liquid crystal composition of the present invention is irradiated with an active energy ray in the (chiral) smectic C phase to polymerize the polymerizable compound in the composition, the (chiral) smectic C phase develops at or near room temperature. Are preferred.

Further, a chiral (optically active) compound can 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. The chiral compound used for such a purpose need not itself exhibit liquid crystallinity, and may or may not have a polymerizable functional group. The direction of the helix of the chiral compound can be appropriately selected depending on the intended use of the polymer.

Examples of such a chiral compound include cholesteryl pelargonic acid having a cholesteryl group as a chiral group, cholesterol stearate, and DH Co., Ltd. having a 2-methylbutyl group as a chiral group (BDH; UK). "CB-15", "C
-15 ", Merck (Germany)" S-1082 ",
"CM-19", "CM-20", "CM" manufactured by Chisso;
"S-811" manufactured by Merck having a 1-methylheptyl group as a chiral group, "CM-21" manufactured by Chisso, "C
M-22 ".

The preferable amount of the chiral compound to be added depends on the use of the liquid crystal composition, but the value obtained by dividing the thickness (d) of the polymer obtained by polymerization by the helical pitch (P) in the polymer. An amount in which (d / P) is in the range of 0.1 to 100 is preferable, and an amount in which the (d / P) is in the range of 0.1 to 20 is more preferable.

Further, a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator may be added to the liquid crystal composition of the present invention for the purpose of improving the polymerization reactivity. Examples of the thermal polymerization initiator include benzoyl peroxide, bisazobutyronitrile and the like. Examples of the photopolymerization initiator include benzoin ethers, benzophenones, acetophenones, and benzyl ketals. When a thermal polymerization initiator or a photopolymerization initiator is added, the amount added is 10% by weight based on the liquid crystal composition.
Or less, preferably 5% by weight or less, more preferably 0.5% by weight or less.
More preferably, the range is from 1.5 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. Examples of usable stabilizers include hydroquinone, hydroquinone monoalkyl ethers, tertiary butyl catechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols and the like. When using a stabilizer,
1% by weight or less based on the liquid crystal composition, preferably 0.5% by weight or less.
% By weight or less is particularly preferred.

As described above, the liquid crystal composition of the present invention comprises:
In addition to the liquid crystalline (meth) acrylate represented by the general formula (1) or (2), a liquid crystal compound having a polymerizable functional group, a liquid crystal compound having no polymerizable functional group, and a polymerizable compound having no liquid crystal property The compound, the polymerization initiator, and the stabilizer may be appropriately combined and added, but it is necessary to adjust the amount of each component added so that at least the liquid crystal composition of the obtained liquid crystal composition is not lost.

When the liquid crystal composition of the present invention is used as a raw material for a polarizing film or an alignment film, or as a printing ink, a paint, or a protective film, a metal, a metal complex, a dye, or the like may be used according to the purpose. , Pigments, dyes, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, metal oxides such as titanium oxide , Etc. can also be added.

The liquid crystal composition containing the liquid crystal compound of the present invention is polymerized into a polymer, whereby a retardation plate,
Polarizers, polarizing prisms, waveguides, piezoelectric elements, nonlinear optical elements, various optical filters, liquid crystal pigments utilizing selective reflection of cholesteric liquid crystal phases, liquid crystal-resin composite displays, holographic liquid crystal displays, polymer stabilized liquid crystals (strong Dielectric liquid crystal, anti-ferroelectric liquid crystal) display,
It can be applied to various uses such as a coating agent for optical fibers and the like. Above all, a polymer obtained by polymerizing the liquid crystal composition of the present invention in an oriented state has anisotropy in physical properties and is useful. Such a polymer is, for example, a substrate obtained by rubbing the surface of a polymerizable liquid crystal composition of the present invention with a cloth or the like, a substrate obtained by rubbing the surface of a substrate on which an organic thin film is formed with a cloth, or SiO ₂ . It can be produced by supporting on a substrate having an obliquely deposited alignment film or by sandwiching between substrates, and then polymerizing a polymerizable compound.

The method for supporting the polymerizable liquid crystal composition on a substrate includes, for example, spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, spray coating, dipping, printing, and the like. And the like. In coating, an organic solvent can be added to the polymerizable liquid crystal composition. Examples of the organic solvent that can be used for such purposes include, for example, ethyl acetate, tetrahydrofuran, toluene, hexane, methanol, ethanol, dimethylformamide, methylene chloride, isopropanol, acetone, methyl ethyl ketone, acetonitrile, cellosolves, and the like. Can be These organic solvents can be used alone or in combination of two or more, and may be appropriately selected in consideration of the vapor pressure and the solubility of the polymerizable liquid crystal composition. The amount of the organic solvent added is
Preferably, it is less than 90% by weight of the coating material. When the content is 90% by weight or more, the obtained film thickness tends to be thin, which is not preferable.

As a method for volatilizing the added organic solvent, natural drying, heating drying, drying under reduced pressure, and drying under reduced pressure can be used. In order to further improve the applicability of the polymerizable liquid crystal material, a method of providing an intermediate layer such as a polyimide thin film on a substrate and a method of adding a leveling agent to the polymerizable liquid crystal material are also effective. In particular, the method of providing an intermediate layer such as a polyimide thin film on a substrate is effective as a means for improving the adhesion when the adhesion between a polymer obtained by polymerizing a polymerizable liquid crystal material and the substrate is not good. .

As a method of sandwiching the polymerizable liquid crystal material between the substrates, there is an injection method utilizing a capillary phenomenon.
Means for reducing the pressure in the space formed between the substrates and then injecting the polymerizable liquid crystal material is also effective.

As a method of the alignment treatment other than the rubbing treatment or the oblique deposition of SiO ₂ , a method utilizing the flow orientation of the liquid crystal material, a method utilizing an electric field or a magnetic field, and the like can be mentioned. These alignment means can be used alone or in combination of two or more methods.

Further, as an alignment treatment method instead of rubbing, a photo alignment method can be used. This method is, for example, an organic thin film having a functional group that undergoes a photodimerization reaction in a molecule such as polyvinyl cinnamate, an organic thin film having a functional group that isomerized by light, or an organic thin film such as a polyimide. By irradiating polarized ultraviolet rays, an alignment film is formed. By applying a photomask to this photoalignment method, patterning of the alignment can be easily achieved, so that the molecular orientation inside the polymer can be precisely controlled.

The shape of the substrate may be a flat plate or a substrate having a curved surface. The material constituting the substrate can be used regardless of an organic material or an inorganic material. Examples of the organic material serving as the substrate material include, for example, polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone,
Triacetyl cellulose, cellulose, polyether ether ketone and the like, and, as the inorganic material,
For example, silicon, glass, calcite and the like can be mentioned.

When the proper orientation cannot be obtained 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 surface of the substrate according to a known method, and this is coated with a cloth or the like. You may rub. In addition, the usual twisted nematic (T
N) element or super twisted nematic (S
The polyimide thin film giving a pretilt angle used in the TN) element is particularly preferable because the molecular orientation structure inside the polymer can be more precisely controlled.

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

The alignment state of the liquid crystal composition may be any of various alignment states generally known in the technical field of liquid crystal.
For example, a homogeneous (horizontal) orientation, a tilted homogeneous orientation, a homeotropic (vertical) orientation, a tilted homeotropic orientation, a hybrid orientation, a twisted nematic orientation, and a super twisted nematic orientation can be exemplified. Patterning may be performed by changing the combination of these orientations or the orientation state for each location.

In the case of the tilted homogeneous alignment and the tilted homeotropic alignment, both cases mean that the angle between the substrate surface and the long axis of the liquid crystal molecule is other than 0 ° or 90 °. The angle between the substrate surface and the long axis of the liquid crystal molecules may be selected depending on the use and function of the obtained polymer. When the angle between the substrate surface and the long axis of the liquid crystal molecules is set in the range of 10 to 80 degrees, more preferably 20 to 70 degrees, the obtained polymer is an optical member for broadly improving the viewing angle of the liquid crystal display. Can be used as

Also, when the alignment state of the liquid crystal composition is set to hybrid alignment, the obtained polymer can be used as an optical member for widening the viewing angle of a liquid crystal display. When the angle between the substrate surface and the long axis of the liquid crystal molecule is set to 30 to 60 degrees, more preferably 40 to 50 degrees, and particularly preferably 45 degrees, the obtained polymer has
The polarization separation ability can be efficiently provided. Such a polymer is useful as a polarization separation element or an optical low-pass filter.

When the alignment state of the liquid crystal composition is set to hybrid alignment, the obtained polymer is useful as a polarizing optical element or an optical low-pass filter. on the other hand,
An alignment structure having a helical structure typified by a twisted nematic alignment, a super twisted nematic alignment, and a cholesteric alignment is also useful. When the twist angle is set to 60 to 270 degrees, the obtained polymer is useful for optical compensation of a liquid crystal display device. When the helical pitch is adjusted so as to selectively reflect a specific wavelength region, the obtained polymer is useful as a notch filter or a reflective color filter.

When the wavelength region for selectively reflecting light is set in the infrared region, the obtained polymer is useful as a heat ray cut filter. In addition, in the case of a homogeneous alignment and a homeotropic alignment state, the obtained polymer is compared with a stretched plastic,
Since the anisotropy of the refractive index is large, there is an advantage that a material having the same anisotropy of the refractive index can be designed to be thin. There is also a possibility that an optical compensator can be formed inside the liquid crystal cell. This characteristic is important when used for optical compensation of a reflection type liquid crystal display element, and is particularly useful as a 波長 wavelength plate.

The method of polymerizing the liquid crystal composition of the present invention is preferably a method of polymerizing by irradiating an active energy ray such as an ultraviolet ray or an electron beam from the viewpoint of rapid polymerization. When using ultraviolet light, a polarized light source may be used, or a non-polarized light source may be used. In addition, when performing polymerization in a state where the liquid crystal composition is sandwiched between two substrates, at least the substrate on the irradiation surface side must be given appropriate transparency to active energy rays.
Further, at the time of light irradiation, only a specific portion is polymerized using a mask, and then, by changing conditions such as an electric field, a magnetic field, or temperature, the orientation state of the unpolymerized portion is changed, and the active energy ray is further irradiated. Alternatively, a method of performing polymerization after polymerization may be used. 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 a polymer is to be produced by photopolymerization, the temperature should be as close to room temperature as possible, ie, typically at 25 ° C., in order to avoid unintentional thermal polymerization. It is preferable to carry out polymerization. The intensity of the active energy ray is preferably in the range of 0.1 mW / cm ^{2 to 2} W / cm ² . When the strength is less than 0.1 mW / cm ² , a large amount of time is required to complete photopolymerization, and the productivity tends to deteriorate. When the strength exceeds ² W / cm ² , the polymerizable liquid crystal composition Is undesirably deteriorated.

After irradiating the polymerizable liquid crystal composition of the present invention with actinic rays, heat treatment can be performed for the purpose of reducing the change in the initial properties of the obtained polymer and stably exhibiting the properties. . 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 polymer comprising the polymerizable liquid crystal composition of the present invention produced by such a method can be used alone by peeling from the substrate, or can be used without peeling from the substrate. Further, the polymer comprising the polymerizable liquid crystal composition of the present invention can be used by laminating two or more, or can be used by being bonded to another substrate.

[0145]

The present invention will be described in more detail with reference to the following examples. However, the invention is not limited to these examples. The measurement of haze in the following examples was performed by the compensation method (JIS, K7361).

(Example 1) [Preparation of liquid crystal composition (1)] Formula (a-1)

[0147]

Embedded image 45 parts by weight of a liquid crystalline acrylate compound represented by the formula: (a-4)

[0148]

Embedded image 45 parts by weight of a liquid crystalline acrylate represented by the formula:
-62)

[0149]

Embedded image A composition (A) comprising 10 parts by weight of a liquid crystalline acrylate represented by the formula was prepared. The composition (A) is prepared at room temperature (25
° C) to give a nematic liquid crystal phase. Further, n _e (refractive index of extraordinary light) measured at 589nm in 1.6702, n _o
(Refractive index of ordinary light) is 1.511, and birefringence is 0.159.
It was 2.

(Example 2) [Preparation of liquid crystal composition (2)] 35 parts by weight of the liquid crystal acrylate compound represented by the formula (a-1) in Example 1 and the liquid crystal represented by the formula (a-4) (B) comprising 35 parts by weight of a liquid crystalline acrylate and 30 parts by weight of a liquid crystalline acrylate represented by the formula (a-62). The composition (B) exhibited a nematic liquid crystal phase at room temperature (25 ° C.). Further, in the 1.6813 (refractive index of extraordinary light) n _e measured at 589 nm, (refractive index of ordinary light) n _o is 1.512, the birefringence index was 0.1693.

(Comparative Example 1) [Preparation of Liquid Crystal Composition (3)] 50 parts by weight of the liquid crystalline acrylate compound represented by the formula (a-1) in Example 1 and the liquid crystal represented by the formula (a-4) A composition (C) comprising 50 parts by weight of a water-soluble acrylate was prepared. Composition (C) exhibited a nematic liquid crystal phase at room temperature (25 ° C.). The nematic phase-isotropic liquid phase transition temperature was 46 ° C. Also, n measured at 589 nm
_e (refractive index of extraordinary light) in 1.662, (refractive index of ordinary light) n _o is 1.510, the birefringence was 0.152.

(Example 3) [Preparation of optically anisotropic substance (1)] 99 parts by weight of the composition (A) prepared in Example 1,
Initiator "Irgacure 651" (Ciba-Geigy) 1
A composition (D) consisting of parts by weight was prepared. Cell gap
5 and 50 micron anti-parallel alignment liquid crystal glass
(A glass cell that has been subjected to an alignment treatment to
), The composition (D) was injected at room temperature. After injection,
It can be confirmed that uniform uniaxial orientation is obtained
Was. Next, at room temperature (25 ° C.), USHIO's UIS-
30mW / cm using 25102 ^TwoUV radiation
Is 90, 180 and 360 mJ / cm^TwoIrradiate until it becomes
Thus, the composition (D) was polymerized to obtain a polymer. Obtained
Polymer has a different refractive index depending on the direction,
It could be confirmed that it functions as an anisotropic body. Moth
The transparency (haze value) of the polymer as it is
The retardation is shown in Table 1.

[0153]

TABLE 1 Haze and retardation of polymer of composition (D)

(Example 4) [Preparation of optically anisotropic body (2)] 99 parts by weight of the composition (B) prepared in Example 2, a photopolymerization initiator "Irgacure 651" (manufactured by Ciba Geigy) 1
A composition (E) consisting of parts by weight was prepared. The composition (E) was injected at room temperature into an anti-parallel alignment liquid crystal glass cell having a cell gap of 5 and 50 μm (a glass cell subjected to an alignment treatment so as to uniaxially align the liquid crystal). After the injection, it was possible to quickly confirm that a uniform uniaxial orientation was obtained. Next, at room temperature (25 ° C.), USHIO U
UV light of 30 mW / cm ² using IS-25102,
The composition (E) was polymerized by irradiation until the irradiation amount became 90, 180 and 360 mJ / cm ² , thereby obtaining a polymer. The resulting polymer has a different refractive index depending on the direction,
It was confirmed that it functions as an optically anisotropic body. The haze and retardation of the polymer as it was in the glass cell are shown in Table 2.

[0155]

TABLE 2 Haze and retardation of polymer of composition (E)

(Comparative Example 2) [Preparation of Optically Anisotropic Body (3)] 99 parts by weight of the composition (C) prepared in Comparative Example 1 and polymerization
Initiator "Irgacure 651" (Ciba-Geigy) 1
A composition (F) consisting of parts by weight was prepared. Cell gap
5 and 50 micron anti-parallel alignment liquid crystal glass
(A glass cell that has been subjected to an alignment treatment to
), The composition (F) was injected at room temperature. After injection,
It can be confirmed that uniform uniaxial orientation is obtained
Was. Next, at room temperature (25 ° C.), USHIO's UIS-
30mW / cm using 25102 ^TwoUV radiation
Is 90, 180 and 360 mJ / cm^TwoIrradiate until it becomes
Thus, the composition (F) was polymerized to obtain a polymer. Obtained
Polymer has a different refractive index depending on the direction,
It could be confirmed that it functions as an anisotropic body. Moth
Haze and retardation of polymer as it is in Lassell
The options are shown in Table 3.

[0157]

TABLE 3 Haze and retardation of polymer of composition (F) The results of Examples 3, 4 and Comparative Example 2 are shown in Tables 1, 2 and 3, and the use of the liquid crystal composition containing the compound of the present invention reduced the haze of the polymer produced by polymerization. It can also be seen that the retardation has been improved.

[0158]

The polymerizable liquid crystal composition of the present invention exhibits good liquid crystal properties and can improve the haze and retardation of a polymer obtained by polymerization. Therefore, the compound of the present invention is, for example, a phase difference plate, a polarizing plate, a polarizing prism, a waveguide, a piezoelectric element, a nonlinear optical element, various optical filters, a pigment utilizing selective reflection of a cholesteric liquid crystal phase and the like, and a coating agent such as an optical fiber. It is extremely useful for application to

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) G02B 5/30 G02B 5/30 G02F 1/13 500 G02F 1/13 500 F term (reference) 2H048 FA04 FA12 2H049 BA02 BA05 BA06 BA42 4H027 BA01 BA13 BD07 4J005 AA09 4J100 AL08P AL08Q AL65R AM47S BA02P BA02R BA02S BA03P BA03S BA04P BA04R BA04S BA15P BA15R BA15S BA40P BA40Q BA40S BB07P BB07Q BC04P BC04QCA43 BC43 BC04 BC43 BC04 BC43 BC04

Claims (8)

[Claims] 1. General formula (1) P-S1-A-S2-M (1) (P represents a polymerizable functional group, and A is selected from the group consisting of an aromatic ring, an alicyclic ring, a heterocyclic ring and a condensed ring. represents a ring, .S1 M is representative of the mesogen portion having an aromatic ring, alicyclic, the same or different 2 to 16 ring selected from the group consisting of heterocyclic and fused ring, - (CH _{2) w} - ,-(CH ₂ ) _w O-,-
_{(CH 2) w C (=} O) O-, and - (CH _{2) w} OC
(= O)-(v represents an integer of 1 to 20), and S2 represents -C (=
_{O) -O- (CH 2) m} -O -, - O (CH 2) m -O-C
(= O) -, - O -C (= O) - (CH 2) m -O-, and _{-O (CH 2) m -C (} = O) -O- (n is 2 to 15
Represents an integer. ) Represents a connecting chain selected from the group consisting of: A) a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound having one polymerizable functional group in one molecule. 2. The compound represented by the general formula (1) wherein ring A is 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 1,3
-Dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, pyrazine-2,5
-Diyl, piperidine-2,5-diyl, piperidine-
1,4-diyl, piperazine-2,5-diyl, 1,4
-Cyclohexylene, 1,4-cyclohexenylene, naphthalene-2,6-diyl, decahydronaphthalene-
2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl and 1,4-bicyclo [2.2.
2) The polymerizable liquid crystal composition according to claim 1, wherein a compound having a ring structure selected from the group consisting of octylene is used. 3. The compound represented by the general formula (1) wherein the mesogen moiety M is represented by the following general formula (2) E- (Y1-F) n-Y2-G (2) (wherein E, F and G is independently 1,4-
Phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6- Diyl, 1,4-bicyclo [2.2.2] octylene, 1,3-dioxane-
Represents 2,5-diyl, pyridine-2,5-diyl, pyrazine-2,5-diyl, pyridazine-3,6-diyl or pyrimidine-2,5-diyl; Y1 and Y2
They are each independently a single _{bond, -CH 2 CH 2 -, -} C
_{H 2 O-, -OCH 2 -,} -C (= O) O -, - OC
(= O)-, -C≡C-, -CH = CH-, -CF = C
_{F -, - (CH 2)} 4 -, - CH 2 CH 2 CH 2 O-, -
_{OCH 2 CH 2 CH 2 -,} - CH = CH-CH 2 CH 2 -,
_{-CH 2 CH 2 -CH = CH -} , - CH = CH-C (=
O) O- or -OC (= O) -CH = CH-,
n represents an integer of 0 to 3. When there are a plurality of Y1 and F, each of Y1 and F may be the same or different. The polymerizable liquid crystal composition according to claim 1 or 2, wherein the compound is 4. A mesogen moiety M represented by the general formula (2), wherein E, F and G are 1,4-phenylene, Y1 or Y2 is -C≡C-, and the other Y1 or The polymerizable liquid crystal composition according to claim 3, wherein Y2 is a single bond, -C (= O) O-, or -OC (= O)-. 5. The compound represented by the general formula (1), wherein the polymerizable group P is an acryloyloxy group, a methacryloyloxy group, an epoxy group, a vinyloxy group or a maleimide group. 13. The polymerizable liquid crystal composition according to any one of the above. 6. A compound selected from the group consisting of one (meth) acryloyloxy group, (meth) acrylamide group, vinyl group, epoxy group, ethynyl group, mercapto group, vinyloxy group and maleimide group in one molecule. The polymerizable liquid crystal composition according to any one of claims 1 to 5, further comprising a liquid crystal compound having a polymerizable functional group. 7. A liquid crystalline compound having one polymerizable functional group in one molecule is represented by the following general formula (3): (Wherein, X represents a hydrogen atom or a methyl group, M represents a mesogen moiety having the same or different 2 to 16 rings selected from the group consisting of an aromatic ring, an alicyclic ring, a heterocyclic ring, and a condensed ring; Y ₃ is a single bond, -O-, -OC (= O)-, -C
Represents a linking group selected from the group consisting of (ＣO) O— and —CH ＝ CH—C (＝ O) O—, wherein Z ₁ is a hydrogen atom, a halogen atom, a cyano group, or a carbon atom having 1 to 20 carbon atoms. Or an alkenyl group having 2 to 20 carbon atoms. The polymerizable liquid crystal composition according to claim 6, which is a compound represented by the formula: 8. An optical element using the polymerizable liquid crystal composition according to claim 1.