JP2002302674A - Liquid crystal composition, liquid crystal device using the same, and azo compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal composition exhibiting a high order parameter. SOLUTION: This liquid crystal composition contains a compound which has a plurality of chromophores of which at least two chromophores are mutually connected so that their conjugated planes are alignable in parallel to each other. The composition also contains a compound represented by formula (1a) or (1a)' (wherein D<a1> , D<a2> , D<a1> ', and D<a2> ' are each a substituent containing a chromophore; R<a1> to R<a6> and R<a1> ' to R<a6> ' are each hydrogen atom or a substituent; and X and Y are each oxygen atom or an optionally substituted carbon atom).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel liquid crystal device, particularly to a guest-host type liquid crystal device, and more particularly to a liquid crystal composition and a novel azo compound which can be used for a guest-host type liquid crystal device.

[0002]

2. Description of the Related Art Many types of liquid crystal elements have been proposed (for example, edited by the 142nd Committee of the Japan Society for the Promotion of Science, Liquid Crystal Device Handbook, Nikkan Kogyo Shimbun, 1989).
Year). For example, in a guest-host type liquid crystal element, a liquid crystal composition in which a dichroic dye is dissolved in a liquid crystal is sealed in a cell, an electric field is applied to the cell, and the dichroic dye is adjusted according to the movement of the liquid crystal by the electric field. In this method, the display is performed by changing the orientation of the cell and changing the light absorption state of the cell. This guest-host method is expected as a reflection type liquid crystal element in that bright display is possible. Here, as for the guest host method, for example, “Handbook of Liquid Crystal
s "(B. Bahadur, D. Demus, J. Goodby, GW Gray,
HW Spiess, V. Vill, Vol. 2A, Wiley-VCH, 1998
), Chapter 3.4, pages 257-302. For dichroic dyes used in liquid crystal devices, see “Dichroic Dyes for Liquid Crystal Display”.
(By AVIvashchenko, CRC, 1994) has a detailed description.

A dichroic dye used in a liquid crystal element is required to have appropriate absorption characteristics, high order parameters, and high performance such as high solubility and durability in a host liquid crystal. Here, the order parameter S is given by S = (3) when the molecular long axis of a molecule which is thermally fluctuated is inclined with respect to the director by a time average deviation angle θ.
cos ² θ-1) / 2. When S = 0.0, it indicates that the molecule is in a completely disordered state.
A value of 1.0 indicates that the molecules are aligned with the molecular long axis aligned with the direction of the director. Conventional 2
The chromatic dye does not give a sufficiently high order parameter, and as a result, the display contrast in the guest-host type liquid crystal display device has been reduced. Therefore, development of a dichroic dye giving higher order parameters is desired.

On the other hand, various dyes having a plurality of chromophores have been developed. For example, EP 98,522, E
P 80,153 discloses a dye compound in which two azo chromophores are linked by a covalent bond. However, the disclosed dye compounds are compounds in which a plurality of chromophores are linked by an ester bond, an amide bond or an ether bond, and are intended to immobilize two azo chromophores in a specific orientation. Thus, the order parameter of the dye has not been improved. On the other hand, Bull. Chem. Soc. Jpn., T. Katoh et al., No. 70
Vol. 2, p. 2287, 1997, discloses a dye having two chromophores bonded to the 1,8-position of naphthalene, but does not mention application to liquid crystal compositions and order parameters.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and a liquid crystal composition exhibiting a high two-color ratio and capable of improving display contrast when used in a display device. It is an object to provide a liquid crystal element. Another object of the present invention is to provide a novel azo compound useful as a dichroic dye, particularly, a novel azo compound giving a high order parameter.

[0006]

In order to solve the above-mentioned problems, a liquid crystal composition of the present invention has a plurality of chromophores, and at least two of the plurality of chromophores are the chromophores of the chromophores. It is characterized in that the conjugate planes contain compounds which are connected to each other in a parallel orientation. The two chromophores are preferably azo dye chromophores.

In order to solve the above problems, a liquid crystal composition of the present invention is characterized by containing a compound represented by any of the following general formulas (1a) and (1a) ′.

[0008]

Embedded image

In the formula, D ^a1 and D ^a2 each independently represent a substituent containing a chromophore, R ^{a1 to} R ^a6 each independently represent a hydrogen atom or a substituent, and among R ^{a1 to} R ^a6 Two bonded to adjacent carbon atoms may be bonded to each other to form a ring.

[0010]

Embedded image

[0011] In the formula, D ^a1 'and D ^a2' are each independently represents a substituent containing a chromophore, R ^a1 '~R ^a6' represents a hydrogen atom or a substituent each independently, R ^a1 ' ~ R ^a6 '
Two of which may be bonded to adjacent carbon atoms to form a ring. X and Y each independently represent an oxygen atom, a sulfur atom,> NR ¹ , a substituted or unsubstituted carbon atom, and R ¹ represents an alkyl group or a hydrogen atom.

In order to solve the above problems, the liquid crystal composition of the present invention contains a compound in which three or more chromophores are linked by a dendrimer residue having a dendrimer-like structure. It is characterized by doing. The compound is preferably a compound represented by the following general formula (1b).

[0013]

Embedded image

Where X^bIs a dendritic polymer (dendrimer)
A dendrimer residue having the same structure^bIs colored
Represents a group, L^bRepresents a linking group, and n^b1Represents 0 or 1
You. n ^bRepresents an integer of 3 to 256;
Three or more D^b, L^bAnd n^b1Are identical to each other
May be different.

[0015] In order to solve the above-mentioned problems, the liquid crystal composition of the present invention comprises three or more chromophores by a cyclic group containing three or more atoms directly or via a linking group. Is characterized by containing a compound linked. The compound is preferably a compound represented by the following general formula (1c).

[0016]

Embedded image

In the formula, X ^c represents a cyclic group capable of binding to n ^c1- (L ^c ) _nc -D ^c , D ^c represents a chromophore, L ^c represents a linking group, and n ^c Represents 0 or 1. n ^c1 is 3-2
Represents an integer of 56, and three or more D ^c and L ^c are present in the molecule.
And n ^c may be the same or different. )

In order to solve the above problems, a liquid crystal device according to the present invention is characterized by including a layer containing the liquid crystal composition according to the present invention.

To solve the above problems, the azo compound of the present invention is characterized by being represented by the following general formula (3a).

[0020]

Embedded image

Where R^a1~ R^a16Is independently hydrogen
Represents an atom or a substituent;^a1~ R^{a 16}Adjacent to
Two bonded to a carbon bond are bonded to each other to form a ring
May be formed. L^a1’And L^a2’Each independently
Represents a substituted or unsubstituted alkynylene group. Where R^a7
~ R^a11At least one selected from the group consisting of^a12~ R
^a16At least one selected from the following is each independently
Represents a substituent represented by the formula:

[0022]

Embedded image

[0023] In the formula, R ^a17 to R ^a21 represents a hydrogen atom or a substituent each independently, form a ring, but two bonded to adjacent carbon atoms bonded to each other among the R ^a17 to R ^{a 21} It may be.

In order to solve the above-mentioned problem, the azo compound of the present invention is represented by the following general formula (2c) ″.

[0025]

Embedded image

[0026] In the formula, n ^c2 represents an integer of 3 to 8, the unit in brackets is repeated ^c2 or n to form a ring.
R ^c1 , R ^c3 and R ^c4 each independently represent a substituent;
^c1 represents a linking group, n ^c represents 0 or 1. Ar ^c1 and Ar ^c2 are each independently substituted or unsubstituted,
Represents an aryl group or a heteroaryl group. 3 in the molecule
L ^c1 , n ^c , R ^c1 , R ^c3 , R ^c4 , and Ar ^c1
And Ar ^c2 may be the same or different.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In this specification, “to” indicates a range including numerical values described before and after it as a minimum value and a maximum value, respectively.

The liquid crystal composition of the present invention has a liquid crystal and a plurality of chromophores, and at least two chromophores of the plurality of chromophores are connected so that conjugate planes of the chromophores can be aligned in parallel with each other. And a compound obtained by the above method. The compound has a function as a dichroic dye (hereinafter, referred to as a dichroic dye)
"Dichroic dye"). A compound having such a structure gives a high order parameter and contributes to an improvement in the two-color ratio of the liquid crystal composition.

Here, "the conjugate planes of two chromophores are parallel to each other" means that when the compound is subjected to Newman projection along the normal vector of the conjugate plane of one chromophore, the conjugate planes of the two chromophores are formed. When the angle is α, α is 0 ° to 30
° refers to an arrangement. "Orientably linked" means
In addition to compounds having a structure in which the chromophores are completely fixed in an arrangement in which the conjugate planes are parallel to each other, when the chromophores are aligned with the liquid crystal, the chromophores can be aligned so that the conjugate planes of the chromophores are parallel to each other. It is meant to include linked compounds as well.

As an example of the dichroic dye, there can be mentioned the compounds shown in FIG. In FIG. 1, A and B each represent a conjugate plane of a chromophore, and L represents a linking group. However,
Figure 1 is a schematic representation of the compound,
The structures of the compounds are not shown exactly and should not be construed as limiting the invention.

The angle α formed by the conjugate planes A and B of the chromophore is preferably from 0 ° to 30 °, and from 0 ° to 2 °.
It is preferably 0 °, more preferably 0 ° to 15 °. The angle α can be directly measured by X-ray crystal structure analysis of the compound. In addition, the angle α can be estimated. As a method of calculating the angle α, the optimized structure of the compound is calculated by molecular orbital calculation (for example, MOPAC, PMC).
3 methods) and measuring the angle formed by the conjugate planes of the chromophores. According to this method, in a compound having a plurality of chromophores, it can be determined whether or not the chromophores are in parallel.

L may be any structure as long as the chromophores can connect the chromophores so that the conjugate planes of the chromophores can be oriented in parallel with each other, but preferably, as shown in FIG. It is preferable that the planes A and B and the linking group L are linking groups that link two chromophores so as to form a U-shape. That is, it is preferable that the covalent bonds involved in the linking in the linking group are parallel to each other. Examples of such a linking group include ring structures such as naphthalene ring 1,8, anthracene ring 1,8, anthracene ring 1,9, anthraquinone ring 1,8, and xanthene ring 1,8. And a form in which both chromophores are linked at the cyclophane 2 and 2 ′ positions. Preferred are a 1,8-position of a naphthalene ring and a 1,8-position of an anthracene ring, and particularly preferred is a 1,8-position of a naphthalene ring.
Rank. In addition, L is preferably a dendrimer residue having a dendritic polymer (dendrimer) -like structure, or a cyclic group contained in calixarene, kempic acid, or the like.

The dichroic dye has a plurality of chromophores.
The chromophore may be any, for example,
Chromophores such as azo dyes, anthraquinone dyes, perylene dyes, merocyanine dyes, azomethine dyes, phthaloperylene dyes, indigo dyes, azulene dyes, dioxazine dyes, polythiophene dyes, and the like.
chroic Dyes for Liquid Crystal Display ”(AV Iv
ashchenko, CRC, 1994).

Preferred are chromophores of azo dyes, anthraquinone dyes and perylene dyes, and particularly preferred are chromophores of azo dyes and anthraquinone dyes. Further, the chromophores whose conjugate planes are connected in parallel to each other are preferably chromophores of the same kind of dye, and more preferably both are chromophores of azo dyes.

When the chromophore is an azo dye chromophore, the type thereof is not particularly limited, and may be any chromophore such as a monoazo dye, a bisazo dye, a trisazo dye, a tetrakisazo dye or a pentakisazo dye. . Preferred are chromophores of monoazo dyes, bisazo dyes and trisazo dyes. A chromophore of an azo dye having a ring structure is preferable, for example, an aromatic group (benzene ring, naphthalene ring, etc.) and / or a heterocyclic ring (quinoline ring, pyridine ring, thiazole ring, benzothiazole ring, oxazole ring, benzoxazole ring) , An imidazole ring, a benzimidazole ring, a pyrimidine ring, etc.).

When the chromophore is a chromophore of an anthraquinone dye, a chromophore of an anthraquinone dye having a substituent containing at least one of an oxygen atom, a sulfur atom and a nitrogen atom is preferable, for example, alkoxy, aryloxy, alkylthio, An anthraquinone dye chromophore having an arylthio, alkylamino, or arylamino group as a substituent is preferable. The number of substituents on the anthraquinone ring of the substituent is not particularly limited, but is preferably di-, tri-, or tetrakis-substitution, and particularly preferably di- or tri-substitution. The position of the substituent on the anthraquinone ring is not particularly limited, but is preferably 1,4.
Di-substitution, 1,5-di substitution, 1,4,5-tri substitution,
1,2,4-position tri-substitution, 1,2,5-position tri-substitution, 1,
It is a tetra-substituted structure at the 4,5,8-position or a tetra-substituted 1,2,5,6-position.

In the liquid crystal composition of the present invention, a compound represented by any of the following formulas (1a) and (1a) ′ can be used as the dichroic dye. The compounds represented by the following general formulas (1a) and (1a) ′ show high order parameters and are useful as dichroic dyes.

[0038]

Embedded image

In the above general formulas (1a) and (1a) ',
And R^a1~ R^a6And R^a1’-R ^a6’Each independently
Represents a hydrogen atom or a substituent. Examples of the substituent include:
Substituent group W below^aIs mentioned. Substituent group W^a: C1-40, preferably C1
12, more preferably an azo group having 1 to 8 carbon atoms (for example,
Phenylazo group, 1-naphthylazo group, 2-naphthylua
Zo group, 4-butylphenylazo group, 4-propylphenyl
Luazo group, 4-butoxy-2-methylphenylazo group,
4-trifluoromethylphenylazo group, 2-thiazoly
Luazo group, 4-quinolylazo group);
Preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms
Azoxy group (for example, phenylazoxy group, 1-naphthyl)
Luazoxy group, 2-naphthyl azoxy group, 4-butyl
Enylazoxy group, 4-propylphenylazoxy group,
4-butoxy-2-methylphenylazoxy group,
Trifluoromethylphenylazoxy group, 2-thiazolyl
Azoxy group, 4-quinolylazoxy group);
0, preferably 6 to 30, more preferably carbon number
6 to 20 arylthio groups (for example, phenylthio group, p
-Methylphenylthio group, p-chlorophenylthio group,
2-pyridylthio group, 1-naphthylthio group, 9,10-
Dioxoanthracenyl-1-thio group, 4-phenylthio
O-9,10-Dioxoanthracenyl-1-thio
Group); halogen atom (for example, chlorine, bromine, iodine,
A) mercapto group; cyano group; carboxyl group; phosphorus
Acid group; sulfo group; hydroxy group; having 1 to 10 carbon atoms, preferably
C2 to C8, more preferably C2 to C5
Rubamoyl group (for example, methylcarbamoyl group, ethylca
A rubamoyl group, a morpholinocarbonyl group);

C 0-10, preferably C 2-10
8, more preferably a sulfamoyl group having 2 to 5 carbon atoms (for example, a methylsulfamoyl group, an ethylsulfamoyl group, a piperidinosulfonyl group); a nitro group; 12, more preferably an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group,
Heptyl group, octyl group, cyclohexyl group, 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4
-Propylcyclohexyl group, 4-butylcyclohexyl group); having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms;
More preferably, an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, a 2-methoxyethoxy group,
A phenylethoxy group); an aryloxy group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms (e.g., phenoxy group, p-methylphenoxy group, p-chlorophenoxy group, naphthoxy group) An acyl group having 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (e.g., acetyl, benzoyl, trichloroacetyl);
Preferably it has 2 to 12 carbon atoms, more preferably 2 to 2 carbon atoms.
8 acyloxy groups (eg, acetyloxy group, benzoyloxy group); having 1 to 20 carbon atoms, preferably 2 carbon atoms
To 12, more preferably an acylamino group having 2 to 8 carbon atoms (e.g., an acetylamino group); a sulfonyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms (e.g., Methanesulfonyl group, ethanesulfonyl group, benzenesulfonyl group);

C 1-20, preferably C 1-1
0, more preferably a sulfinyl group having 1 to 8 carbon atoms (for example, methanesulfinyl group, ethanesulfinyl group,
A benzenesulfinyl group); a sulfonylamino group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms (for example, methanesulfonylamino group,
Ethanesulfonylamino group, benzenesulfonylamino group); amino group; having 1 to 20 carbon atoms, preferably 1 carbon atom
To 12, more preferably a substituted amino group having 1 to 8 carbon atoms (e.g., a methylamino group, a dimethylamino group, a benzylamino group, an anilino group, a diphenylamino group); 10, more preferably an ammonium group having 3 to 6 carbon atoms (eg, trimethylammonium group, triethylammonium group); a hydrazino group having 0 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. (For example, a trimethylhydrazino group), having 1 to 15 carbon atoms, preferably having 1 to 1 carbon atoms.
0, more preferably a ureido group having 1 to 6 carbon atoms (e.g., ureido group, N, N-dimethylureido group);
To 15, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atom imide group (for example, succinimide group);
An alkylthio group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms (for example, a methylthio group, an ethylthio group, or a propylthio group); 12, more preferably an alkoxycarbonyl group having 2 to 8 carbon atoms (e.g., methoxycarbonyl group, ethoxycarbonyl group, 2-benzyloxycarbonyl group); 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, more preferably An aryloxycarbonyl group having 6 to 10 carbon atoms (for example, a phenoxycarbonyl group);

C 1 -C 18, preferably C 1 -C 1
0, more preferably an alkyl group having 1 to 5 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group); 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 1 carbon atoms. 5 substituted alkyl groups (eg, hydroxymethyl group, trifluoromethyl group, benzyl group, carboxyethyl group, ethoxycarbonylmethyl group, acetylaminomethyl group); having 2 to 18 carbon atoms, preferably 3 to 10 carbon atoms, Preferably a substituted or unsubstituted alkenyl group having 3 to 5 carbon atoms (eg, vinyl group, phenylethenyl group); 2 to 18 carbon atoms, preferably 3 to 1 carbon atoms
0, more preferably a substituted or unsubstituted alkynyl group having 3 to 5 carbon atoms (eg, ethynyl group, phenylethenyl group); 2 to 18 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 carbon atoms. To 5 substituted or unsubstituted cyclic aliphatic hydrocarbon groups (e.g., 1-cyclohexenyl group, cyclohexyl group, cyclopentyl group);
0, preferably a substituted or unsubstituted aryl group having 6 to 25 carbon atoms, more preferably 6 to 15 carbon atoms (for example, a phenyl group, a naphthyl group, a p-carboxyphenyl group,
-Nitrophenyl group, 3,5-dichlorophenyl group, p
-Cyanophenyl group, m-fluorophenyl group, p-tolyl group, perylenyl group); a substituted or unsubstituted heterocyclic ring having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 to 6 carbon atoms. Groups (for example, a pyridyl group, a 5-methylpyridyl group, a thienyl group, a furyl group, a morpholino group, and a tetrahydrofurfuryl group). These substituents may be further substituted by one or more of these substituents.

Two of R ^{a1 to} R ^a6 and R ^a1 ′ to R ^a6 ′ bonded to adjacent carbon atoms may be bonded to each other to form a ring. Examples of the ring formed include a benzene ring and a naphthalene ring.

R ^{a1 to} R ^a6 and R ^a1 ′ to R ^a6 ′ are each preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an alkoxy group, and are preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group. , A trifluoromethyl group, a phenyl group or a trifluoromethoxy group.

In the general formulas (1a) and (1a) ',
And D^a1, D^a2, D^a1’And D ^a2’Each independently
Represents a substituent containing a chromophore. D^a1, D^a2, D^a1'and
D^a2′ Represent the types of chromophores contained in the respective substituents.
Is not particularly limited, azo dyes, anthraquinone dyes,
Perylene dye, merocyanine dye, azomethine dye,
Taloperylene dye, indigo dye, azulene dye, geo
Selected from xazine dyes and polythiophene dyes
Chromophores of any dyes. Each dye
For a specific example, see “Dichroic Dyes for Liquid Cry
stal Display "(by A. V. Ivashchenko, CRC, 1994)
Described in (1). D^a1, D^a2, D^a1'and
D^a2′ Include azo dyes, anthraquinone dyes,
Preferably, the substituent is a substituent containing a chromophore of a len dye.
Substituents containing chromophores of azo dyes or anthraquinone dyes
Is preferably a substituent containing a chromophore of an azo dye.
It is particularly preferred.

In the above formula (1a) ′, X and Y each independently represent an oxygen atom, a sulfur atom,> NR ¹ or a substituted or unsubstituted carbon atom. Substituted or unsubstituted carbon atoms represented by X and Y respectively include> CR ² R ³ and> CＯO. Here, R ¹ , R ² and R ³ each independently represent an alkyl group (eg, a methyl group or an ethyl group) or a hydrogen atom. It is preferred that X is an oxygen atom and Y is a substituted or unsubstituted carbon atom.

Among the compounds represented by the general formula (1a), a compound represented by the following general formula (2a) is preferable.

[0048]

Embedded image

In the general formula (2a), R ^{a1 to} R ^a6
Has the same meaning as in the general formula (1a), and the same applies to specific examples. The general formula (2a)
In the ^formula , R ^{a7 to} R ^a16 each independently represent a hydrogen atom or a substituent. Specific examples of substituents R ^a7 to R ^a16 represents respectively are the same as those exemplified as the substituent group W ^a, and preferred examples are also the same. Where R
at least one selected from ^a7 to R ^a11, and R ^a12 ~
At least one selected from R ^a16 independently represents a substituent containing an azo group. As the substituent containing an azo group, an azo group having 1 to 40 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms (for example, phenylazo group, 1-naphthylazo group, 2-naphthylazo group, 4
-Butylphenylazo group, 4-propylphenylazo group, 4-butoxy-2-methylphenylazo group, 4-trifluoromethylphenylazo group, 2-thiazolylazo group, 4-quinolylazo group). Among them, ^Ra9
And R ^a14 are each preferably a substituent containing an azo group.

At least one selected from R ^{a7 to} R ^a11
And at least one selected from R ^{a12 to} R ^a16 each preferably independently represents a substituent represented by the following formula. In particular, it is preferable that R ^a9 and R ^a14 are substituents represented by the following formulas. A substituent represented by the following general formula (D) represented by at least one selected from R ^{a7 to} R ^a11 and at least one selected from R ^{a12 to} R ^a16 is
They may be the same or different. Among them, the same is preferable.

[0051]

Embedded image

In the general formula (D), Ar ¹ represents a substituted or unsubstituted aryl group or heteroaryl group. The aryl group includes both those having a single ring structure and those having a condensed ring structure. An aryl group having 2 to 20 carbon atoms is preferable, and specifically, an aryl group including a benzene ring, a naphthalene ring, and an anthracene ring is preferable. The heteroaryl group includes both a single ring structure and a condensed ring structure. As the heteroaryl group, a heteroaryl group having 2 to 20 carbon atoms is preferable, and a pyridine ring, a quinoline ring, an isoquinoline ring, a pyrimidine ring, a pyrazine ring, a thiophene ring, a furan ring, an oxazole ring, a thiazole ring, an imidazole ring, and a pyrazole ring ring,
A group containing an oxadiazole ring, a thiadiazole ring, or a triazole ring, or a condensate formed by condensing two or more of these heteroaromatic rings or one or more of these heteroaromatic rings with the aromatic ring of the aforementioned aryl group; Examples include a group containing a ring.

Ar¹May be substituted, and the substituent
Is the substituent group W described above.^aIs mentioned. The substituent and
A halogen atom, an alkyl group, an aryl group,
Coxy group is preferred, fluorine atom, chlorine atom, methyl
Group, trifluoromethyl group, phenyl group, trifluoro group
A methoxy group is more preferred. Also, Ar¹Is -N = N-
Ar 'group, -N = N-Ar "-N = N-Ar' group, etc.
It is also preferable to take the structure of a polyazo dye by substitution with
No. Here, for Ar ′ and Ar ″, Ar ¹
And the specific examples and examples of the substituents are the same as those of Ar.
You.

In the general formula (D), Ar ¹ is preferably a substituted or unsubstituted aryl group, that is, the general formula (D) is preferably a group represented by the following formula.

[0055]

Embedded image

In the formula, R ^{a17 to} R ^a21 each independently represent a hydrogen atom or a substituent. Specific examples of substituents R ^a17 to R ^{a 21} represents respectively are the same as those exemplified as the substituent group W ^a, and preferred examples are also the same. As described above, -N = N-Ar 'group, -N = N-Ar "-
It may be substituted with an N = N-Ar 'group or the like. R ^{a1 7}
And two of R ^a21 bonded to adjacent carbon atoms may be bonded to each other to form a ring, and the formed ring includes a benzene ring and a naphthalene ring.

In the formula (2a), L ^a1 and L ^a2 each represent a linking group. n ^a1 and n ^a2 each represent 0 or 1, and when n ^a1 = 0 and n ^a2 = 0,
The benzene ring substituted with an azo group is bonded to the naphthalene ring by a single bond. The linking groups represented by L ^a1 and L ^a2 each consist of at least one atom selected from a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom, or an atomic group containing at least one atom. The linking group is preferably linked so that the conjugated planes of the chromophore can be oriented in parallel. From such a viewpoint, a linear and rigid group is preferable, but it may have a certain degree of freedom. As a rigid linking group, a carbon number of 6 to
30 arylene groups (for example, p-phenylene group, o-
Phenylene group, m-phenylene group, 1,4-naphthylene group, 1,3-naphthylene group, 4,4′-biphenylene group, 4,4′-2,2′-dimethylbiphenylene group,
4,4′-2,2′-dimethoxybiphenylene group, 4,
4'-2,2'-dichlorobiphenylene group), carbon number 2
To 20 alkenylene groups (for example, ethenylene group), alkynylene groups having 2 to 20 carbon atoms (for example, ethynylene group, butanediynylene group, phenylethynylene group, 2-
Pyridylethynylene group, 1,4-bisethynylenephenyl group, etc.) and a heterocyclic divalent group (for example, 2,6-pyridinylene group). As a linking group having a certain degree of freedom, an alkylene group having 1 to 20 carbon atoms (for example,
Methylene group, ethylene group, propylene group, butylene group,
Pentylene group, 1,4-cyclohexylene group), amide group, ester group, sulfonamide group, sulfonic ester group, ureido group, sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, -NR- , R represents a hydrogen atom, an alkyl group or an aryl group), and a linking group having 1 to 60 carbon atoms formed by combining two or more thereof.

[0058] Incidentally, L ^a1 and L ^a2 may be further substituted with a substituent, examples of the substituent include substituents exemplified as the substituent group W ^a and the like.

The compound represented by the general formula (2a) is
n ^a1 and n ^a2 are 0, or n ^a1 and n ^a2 are 1
In it and is preferably L ^a1 and L ^a2 is an arylene group or an alkynylene group, n ^a1 and n ^a2 is 0, or n ^a1 and n ^a2 is 1 and L ^a1 and L ^a2 is alkynylene group It is more preferable that n ^a1 and n ^a2 are 1 and L ^a1 and L ^a2 are alkynylene groups, and a compound represented by the following formula (3a) is most preferable.

[0060]

Embedded image

In the general formula (3a), R ^{a1 to} R a
^a16 each independently represents a hydrogen atom or a substituent;
^Two of ^{a1 to Ra16} , which are bonded to adjacent carbon bonds, may be bonded to each other to form a ring. Where R
at least one selected from ^a7 to R ^a11, and R ^a12 ~
At least one selected from ^Ra16 independently represents a substituent represented by the following formula.

[0062]

Embedded image

[0063] In the formula, R ^a17 to R ^a21 represents a hydrogen atom or a substituent each independently, form a ring, but two bonded to adjacent carbon atoms bonded to each other among the R ^a17 to R ^{a 21} It may be.

In formula (3a), R ^{a1 to} R ^a21 have the same ^meanings as those in formulas (1a) and (2a), and preferred examples are also the same. The general formula (3a)
In the ^formula , L ^a1 ′ and L ^a2 ′ each independently represent an alkynylene group. The alkynylene group includes a substituted or unsubstituted alkynylene group. Examples of the substituent groups include exemplified substituent group as a substituent group W ^a of the foregoing, specifically a phenylene group, a pyridyl group, a naphthylene group, 1,
4-cyclohexyl group and the like. L ^a1 'and L
^a2 ′ is preferably a substituted or unsubstituted alkynylene group having 2 to 20 carbon atoms, specifically, an ethynylene group, a butanediynylene group, a phenylethynylene group,
Examples include a pyridylethynylene group and a 1,4-bisethynylenephenyl group.

Hereinafter, specific examples of the compound represented by the general formula (1a) are shown, but the present invention is not limited by the following specific examples.

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

[0071]

Embedded image

[0072]

Embedded image

The compounds represented by the general formulas (1a) to (3a) can be synthesized according to the methods described in various documents. For example, for the synthesis of azo dyes and anthraquinone dyes, see “Dichroic Dyes for Liquid
Crystal Display "(by AVIvashchenko, CRC, 19
1994) and "Review Synthetic Dyes" (Hirokuchi Hiroshi, Sankyo Publishing,
(1968).
As a method of linking these dyes with a linking group, for example, when naphthalene 1,8 is used as the linking group, J. Org. Chem. Vol. 37, HO House et al., 1003, 197
It can be performed according to the method described in 2 years. In particular, when an aromatic group or a heterocyclic group is introduced at the 1,8-position of naphthalene, a coupling reaction using a general organometallic complex is suitable.

In the liquid crystal composition of the present invention, a compound in which three or more chromophores are linked by a dendrimer residue having a dendrimer-like structure is used as the dichroic dye. Can be. The compound having the dendrimer residue exhibits a high order parameter and is useful as a dichroic dye. Dendritic macromolecules are macromolecules having highly branched side chains, and are described in, for example, “Polymer”, edited by The Society of Polymer Science, Japan (1998, 803-829).
Page), "Science and Function of Dendrimers" (Kunhiko Okada, Inc.)
(IPC, published in 2000). It is preferable that the compound has a chromophore bound to a terminal portion of the dendrimer residue. It is more preferable that a chromophore is bonded to all dendritic side chain terminals of the dendrimer residue, but due to synthetic reasons, physical properties or other reasons, it is not necessary to color at all side chain terminals. Even if the groups are not bound, they are useful in the present invention. It is preferable that a chromophore is bonded to 10% or more of the dendritic side chain terminal of the dendrimer residue, and it is more preferable that a chromophore is bonded to 50% or more.

The compound having the dendrimer residue is
Has three or more chromophores. The chromophore may be any, for example, chromophores such as azo dyes, anthraquinone dyes, perylene dyes, merocyanine dyes, azomethine dyes, phthaloperylene dyes, indigo dyes, azulene dyes, dioxazine dyes, polythiophene dyes, etc. Specifically, "Dichroic Dyes for Liquid
Crystal Display ”(AV Ivashchenko, CRC, 199
4 years). Preferred are chromophores of azo dyes, anthraquinone dyes and perylene dyes, and particularly preferred are chromophores of azo dyes and anthraquinone dyes.

When the chromophore is an azo dye chromophore, the kind thereof is not particularly limited, and may be any chromophore such as a monoazo dye, a bisazo dye, a trisazo dye, a tetrakisazo dye or a pentakisazo dye. . Preferred are chromophores of monoazo dyes, bisazo dyes and trisazo dyes. A chromophore of an azo dye having a ring structure is preferable, for example, an aromatic group (benzene ring, naphthalene ring, etc.) and / or a heterocyclic ring (quinoline ring, pyridine ring, thiazole ring, benzothiazole ring, oxazole ring, benzoxazole ring) , An imidazole ring, a benzimidazole ring, a pyrimidine ring, etc.).

When the chromophore is a chromophore of an anthraquinone dye, a chromophore of an anthraquinone dye having a substituent containing at least one of an oxygen atom, a sulfur atom and a nitrogen atom is preferable, for example, alkoxy, aryloxy, alkylthio, An anthraquinone dye chromophore having an arylthio, alkylamino, or arylamino group as a substituent is preferable. The number of substituents on the anthraquinone ring of the substituent is not particularly limited, but is preferably di-, tri-, or tetrakis-substitution, and particularly preferably di- or tri-substitution. The position of the substituent on the anthraquinone ring is not particularly limited, but is preferably 1,4.
Di-substitution, 1,5-di substitution, 1,4,5-tri substitution,
1,2,4-position tri-substitution, 1,2,5-position tri-substitution, 1,
It is a tetra-substituted structure at the 4,5,8-position or a tetra-substituted 1,2,5,6-position.

The compound having a dendrimer residue is
It can be represented by the following general formula (1b).

[0079]

Embedded image

In the general formula (1b), X ^b represents a dendrimer residue having a dendritic polymer (dendrimer) -like structure, n ^b represents an integer of 3 to 256, and D ^b represents color development. L ^b represents a linking group, and n ^b1 represents 0
Or represents 1. n ^b is preferably 3 to 100, and 3 to 5
0 is preferred. Note that D ^b , which is present in three or more molecules in the molecule,
L ^b and n ^b1 may be the same or different from each other.

The dendrimer residue represented by X ^b is 3 to
256 chromophore directly or via the L ^b is a dendrimer residues with possible dendritic side chain end coupling. X
^b is preferably a dendrimer residue having a side chain branched by a partial structure containing any of the following groups.

[0082]

Embedded image

In the formula (1b), L ^b represents a linking group. n ^b1 represents 0 or 1, and when n ^b1 = 0,
Chromophore D ^b is attached to the dendrimer residue by a single bond. The linking group represented by L ^b is at least one atom selected from a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom,
Or, it consists of an atomic group containing at least one kind of atom. Specifically, an alkylene group having 1 to 20 carbon atoms (for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a 1,4-cyclohexylene group),
To 30 arylene groups (for example, p-phenylene group, o-
Phenylene group, m-phenylene group, 1,4-naphthylene group, 1,3-naphthylene group, 4,4′-biphenylene group, 4,4′-2,2′-dimethylbiphenylene group,
4,4′-2,2′-dimethoxybiphenylene group, 4,
4'-2,2'-dichlorobiphenylene group), carbon number 2
-20 alkenylene groups (for example, ethenylene group), alkynylene groups having 2 to 20 carbon atoms (for example, ethynylene group), amide groups, ester groups, sulfamide groups, sulfonate groups, ureido groups, sulfonyl groups, sulfinyl groups, Thioether group, ether group, carbonyl group,
—NR— (where R is a hydrogen atom or an alkyl group or an aryl group) and one or more heterocyclic divalent groups (eg, a 2,6-pyridinylene group) having 1 to 60 carbon atoms. The following linking groups are mentioned.

L ^b may be further substituted with a substituent. Examples of the substituent include a substituent group W described below.
^The substituents exemplified as ^b can be mentioned.

In the general formula (1b), n^b1Is 0
Yes or n^b1Is 1 and L ^b1Is an alkylene group,
Arylene group, -NR-, ether group (-O-) and
Containing at least one carbonyl group (—C (＝ O) —)
It is preferably a linking group. More preferably, n^b1Is
0 or n^b1Is 1 and L^b1Is alkylene
Group or alkylene group and -NR-, ether group
(-O-) and / or a carbonyl group (-C (=
More preferably, the linking group contains O)-).

In the general formula (1b), the chromophore D ^b
Is as described above, and particularly preferably a chromophore of an azo dye. Examples of the compound containing a chromophore of an azo dye include a compound represented by the following general formula (2b).

[0087]

Embedded image

In the general formula (2b), X ^b represents a dendrimer residue having a dendrimer-like repeating structure, and Ar ^b1 and Ar ^b2 each independently represent an optionally substituted aryl group. Or L represents a heteroaryl group, L ^b represents a linking group, and n ^b1 represents 0 or 1. n ^b ′ represents an integer of 3 to 128, and represents three or more Ar ^b1 , Ar ^b2 , L ^b and n ^b1 present in the molecule.
May be the same or different. X ^b , L ^b ,
n ^b1 has the same meaning as each group in the formula (1b), and the preferred range is also the same. n ^b ′ is 3 to 100
Is preferably, and more preferably 3 to 50.

In the general formula (2b), Ar^b1And
And Ar^b2The aryl group represented by each has a monocyclic structure
And those having a condensed ring structure. Ally
The aryl group is preferably an aryl group having 2 to 20 carbon atoms.
Specifically, benzene ring, naphthalene ring, anthra
Aryl groups containing a sen ring are preferred. Ar^b1And Ar
^b2Each of the heteroaryl groups represented by
And those having a condensed ring structure. Said hetero
As the aryl group, a heteroaryl having 2 to 20 carbon atoms
Group is preferred, pyridine ring, quinoline ring, isoquinoline
Ring, pyrimidine ring, pyrazine ring, thiophene ring, furan
Ring, oxazole ring, thiazole ring, imidazole ring,
Pyrazole ring, oxadiazole ring, thiadiazole
Ring, a group containing a triazole ring, or a heterocyclic group thereof.
Two or more aromatic rings or one or more of these heteroaromatic rings
Condensed with the aromatic ring of the aryl group described above.
Examples include a group containing a ring.

[0090] Ar ^b1 and Ar ^b2 may be substituted, examples of the substituent include the following substituent group W ^b. Substituent group ^Wb : halogen atom (for example, chlorine, bromine, iodine, fluorine); mercapto group; cyano group; carboxyl group; phosphoric acid group; sulfo group; hydroxy group;
0, preferably a carbamoyl group having 2 to 8 carbon atoms, more preferably 2 to 5 carbon atoms (e.g., methylcarbamoyl group, ethylcarbamoyl group, morpholinocarbonyl group); 0 to 10 carbon atoms, preferably 2 to 8 carbon atoms More preferably a sulfamoyl group having 2 to 5 carbon atoms (for example, a methylsulfamoyl group, an ethylsulfamoyl group, a piperidinosulfonyl group); a nitro group;
Preferably it has 1 to 12 carbon atoms, more preferably 1 carbon atom
To 8 alkyl groups (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group); having 2 to 18 carbon atoms, preferably 3 to 10 carbon atoms, more preferably carbon atom A substituted or unsubstituted alkenyl group having 3 to 5 carbon atoms (for example, a vinyl group or a phenylethenyl group); having 2 to 18 carbon atoms, preferably having 3 to 1 carbon atoms
0, more preferably a substituted or unsubstituted alkynyl group having 3 to 5 carbon atoms (eg, ethynyl group, phenylethenyl group); 2 to 18 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 carbon atoms. To 5 substituted or unsubstituted cyclic aliphatic hydrocarbon groups (for example, 1-cyclohexenyl group, cyclohexyl group, cyclopentyl group, 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, 4-butyl Cyclohexyl group);
C1-C20, preferably C1-C10, more preferably C1-C8 alkoxy group (for example, methoxy group, ethoxy group, 2-methoxyethoxy group, 2-phenylethoxy group); 20, preferably 6 carbon atoms
To 12, more preferably an aryloxy group having 6 to 10 carbon atoms (for example, phenoxy group, p-methylphenoxy group, p-chlorophenoxy group, naphthoxy group); 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms. More preferably, an acyl group having 2 to 8 carbon atoms (eg, an acetyl group, a benzoyl group, a trichloroacetyl group);

C1-20, preferably C2-1
2, more preferably an acyloxy group having 2 to 8 carbon atoms (eg, acetyloxy group, benzoyloxy group); an acylamino group having 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms ( For example, an acetylamino group); having 1 to 20 carbon atoms, preferably 1 to 1 carbon atoms
0, more preferably a sulfonyl group having 1 to 8 carbon atoms (e.g., methanesulfonyl group, ethanesulfonyl group, benzenesulfonyl group); 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms (For example, methanesulfinyl group, ethanesulfinyl group, benzenesulfinyl group); having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 1 carbon atoms.
8 sulfonylamino group (for example, methanesulfonylamino group, ethanesulfonylamino group, benzenesulfonylamino group); amino group; substitution having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms. Amino group (for example, methylamino group, dimethylamino group, benzylamino group, anilino group, diphenylamino group);
An ammonium group having 0 to 15 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms (for example, trimethylammonium group, triethylammonium group); 0 to 15 carbon atoms, preferably 1 to 10 carbon atoms; More preferably, a hydrazino group having 1 to 6 carbon atoms (eg, a trimethylhydrazino group); 1 to 15 carbon atoms, preferably 1 carbon atom
-10, more preferably a ureido group having 1 to 6 carbon atoms (e.g., a ureido group, an N, N-dimethylureido group);
An imide group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms (for example, succinimide group); 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms;
More preferably, an alkylthio group having 1 to 8 carbon atoms (e.g., a methylthio group, an ethylthio group, a propylthio group); an arylthio group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms (e.g., Phenylthio, p-methylphenylthio, p-chlorophenylthio, 2-pyridylthio, naphthylthio);

C2-20, preferably C2-1
2, more preferably an alkoxycarbonyl group having 2 to 8 carbon atoms (e.g., methoxycarbonyl group, ethoxycarbonyl group, 2-benzyloxycarbonyl group);
-20, preferably 6-12, more preferably 6-10, aryloxycarbonyl group (for example, phenoxycarbonyl group); C1-18, preferably 1-10, more preferably carbon number 1-5 unsubstituted alkyl groups (for example, methyl group, ethyl group, propyl group, butyl group); having 1-18 carbon atoms, preferably 1 carbon atom
10 to 10, more preferably a substituted alkyl group having 1 to 5 carbon atoms (for example, hydroxymethyl group, trifluoromethyl group, benzyl group, carboxyethyl group, ethoxycarbonylmethyl group, acetylaminomethyl group);
20, preferably a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (for example, phenyl group, naphthyl group, p-carboxyphenyl group,
p-nitrophenyl group, 3,5-dichlorophenyl group,
p-cyanophenyl group, m-fluorophenyl group, p-
Tolyl group); having 1 to 20 carbon atoms, preferably 2 to 1 carbon atoms
0, more preferably a substituted or unsubstituted heterocyclic group having 4 to 6 carbon atoms (for example, pyridyl group, 5-methylpyridyl group, thienyl group, furyl group, morpholino group, tetrahydrofurfuryl group); An azo group having preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms (for example, phenylazo group, 1-naphthylazo group, 2-naphthylazo group, 4-butylphenylazo group, 4-propylphenylazo group, 4-butoxy-2-methylphenylazo group, 4-trifluoromethylphenylazo group, 2-thiazolylazo group, 4-quinolylazo group).
These substituents may be further substituted by one or more of these substituents.

As the substituent, a halogen atom, an alkyl group, an aryl group and an alkoxy group are preferred, and a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, a phenyl group and a trifluoromethoxy group are more preferred. Ar ^b1 and Ar ^b2 each represent -N = N-Ar ^b3
It is also preferable to take the structure of the polyazo dye by being substituted with a group, -N = N-Ar ^b4 -N = N-Ar ^b5 group or the like. Here, Ar ^b3 , Ar ^b4 and Ar ^b5 are Ar ^b1 and Ar ^b
b2 has the same meaning as that of ^b2, and specific examples and examples of the substituent are Ar
^{Same as b1} and Ar ^b2 .

The specific examples of the compounds represented by formula (1b) are shown below, but the present invention is not limited by the following specific examples.

[0095]

Embedded image

[0096]

Embedded image

[0097]

Embedded image

The compounds represented by the general formulas (1b) and (2b) can be synthesized according to the methods described in various documents. For example, for the synthesis of azo dyes and anthraquinone dyes, see “Dichroic Dyes for Li
quid Crystal Display ”(AV Ivashchenko, CRC
, 1994), "Review Synthetic Dyes" (Hiroshi Horiguchi, Sankyo Shuppan, 1968) and various references cited therein. Regarding the synthesis of the dendrimer residue and the introduction of a chromophore to the dendrimer residue, “Polymer” (edited by the Society of Polymer Science, 1998,
803-829), "Science and Function of Dendrimers"
(Author: Okada Kunhiko, IPC, 2000)
And the references cited therein.

In the liquid crystal composition of the present invention, as the dichroic dye, three or more chromophores are formed by a cyclic group containing three or more atoms directly or via a linking group. A linked compound (hereinafter, also referred to as a “compound having a cyclic group”) may be used. The compounds exhibit high order parameters and are useful as dichroic dyes. Examples of the cyclic group include a cyclic group having a ring structure of calixarene, cycloalkane, cycloalkene, cycloalkyne, cyclophane, cyclic ether, cyclic thioether, lactone, lactam and lactide. In the present specification, “cyclophane” and “calixarene” include any of a benzene ring, a condensed aromatic ring, a heteroaromatic ring, and a condensed heteroaromatic ring in addition to a cyclic compound in which a benzene ring is connected by a carbon chain. One or two or more of them are linked by a carbon chain. Regarding these cyclic compounds, see the Chemical Society of Japan, `` Chemical Review No.
31 Chemistry for Supramolecules "(published in 1997 by the Institute of Gakkai Publishing, 1997). For calixarenes, see "Calixarenes" by David C. Gutsche (Roya
l Society of Chemistry, published in 1989).

Specific examples of the cyclic compound include calixarene, crown ether, cyclodextrin, kemp's acid, cyclophan, calixresorcarene, etc., which constitute the ring of these compounds. The compound having the cyclic group can be synthesized by bonding three or more chromophores to the atom directly or via a linking group. Among them, calixarene, kempic acid, cyclophan, calixresorcarene are preferably used, and calixarene and kempic acid are particularly preferable. The ring structure includes atoms bonded directly or via a linking group to the chromophore,
It is preferably composed of a repeating unit consisting of an atom not bonded to a chromophore. When the ring structure is composed of such a repeating unit, it is preferable that the chromophore is bonded to all the repeating units, but even if the chromophore is not necessarily bonded to all the ring constituent atoms,
Useful for the present invention. It is preferable that a chromophore is bonded to 10% or more of the repeating units directly or via a linking group, and it is more preferable that 50% or more of the repeating units is directly or via a linking group. .

The substituent containing the chromophore may be bonded to the cyclic group at any angle of equatorial (pseudo-equatorial) and axial (including pseudo-axial). Preferably, all the substituents containing the chromophore are bonded at an axial angle.

The compound having a cyclic group has three or more chromophores. The chromophore may be any, for example, chromophores such as azo dyes, anthraquinone dyes, perylene dyes, merocyanine dyes, azomethine dyes, phthaloperylene dyes, indigo dyes, azulene dyes, dioxazine dyes, polythiophene dyes, etc. Specifically, "Dichroic Dyes for Liquid Crystal
Display "(AV Ivashchenko, CRC, 1994). Preferred are chromophores of azo dyes, anthraquinone dyes and perylene dyes, and particularly preferred are chromophores of azo dyes and anthraquinone dyes.

When the chromophore is an azo dye chromophore, the type thereof is not particularly limited, and may be any chromophore such as a monoazo dye, a bisazo dye, a trisazo dye, a tetrakisazo dye or a pentakisazo dye. . Preferred are chromophores of monoazo dyes, bisazo dyes and trisazo dyes. A chromophore of an azo dye having a ring structure is preferable, for example, an aromatic group (benzene ring, naphthalene ring, etc.) and / or a heterocyclic ring (quinoline ring, pyridine ring, thiazole ring, benzothiazole ring, oxazole ring, benzoxazole ring) , An imidazole ring, a benzimidazole ring, a pyrimidine ring, etc.).

When the chromophore is a chromophore of an anthraquinone dye, a chromophore of an anthraquinone dye having a substituent containing at least one of an oxygen atom, a sulfur atom and a nitrogen atom is preferable, for example, alkoxy, aryloxy, alkylthio, An anthraquinone dye chromophore having an arylthio, alkylamino, or arylamino group as a substituent is preferable. The number of substituents on the anthraquinone ring of the substituent is not particularly limited, but is preferably di-, tri-, or tetrakis-substitution, and particularly preferably di- or tri-substitution. The position of the substituent on the anthraquinone ring is not particularly limited, but is preferably 1,4.
Di-substitution, 1,5-di substitution, 1,4,5-tri substitution,
1,2,4-position tri-substitution, 1,2,5-position tri-substitution, 1,
It is a tetra-substituted structure at the 4,5,8-position or a tetra-substituted 1,2,5,6-position.

The compound having a cyclic group can be represented by the following general formula (1c).

[0106]

Embedded image

In the general formula (1c), X ^c is n ^c1
-(L ^c ) _nc represents a cyclic group capable of binding to D ^c ,
^c represents a chromophore, L ^c represents a linking group, and n ^c represents 0 or 1. n ^c1 represents an integer of from 3 to 256, 3 in the molecule
D ^c , L ^c and n ^{c which} are present more than one may be the same or different from each other.

The cyclic group represented by X ^c is as described above, and includes calixarene, cycloalkane,
Cycloalkene, cycloalkyne, cyclophane, cyclic ether, cyclic thioether, lactone, a group having any ring structure of lactam and lactide is preferred,
A group having a ring structure of calixarene, cycloalkane or cyclophane is more preferable. The chromophore represented by D ^c, are as defined above, in particular, is preferably a chromophore of the azo dyes or anthraquinone dyes.

In the general formula (1c), L ^c represents a linking group. n ^c represents 0 or 1, when n ^c = 0, the chromophore D ^c is the single bond to bond to the cyclic group. Linking group L ^c represents a carbon atom, a nitrogen atom, consisting of atomic group containing at least one atom or at least one atom is selected from sulfur and oxygen atoms. Specifically, an alkylene group having 1 to 20 carbon atoms (for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group,
1,4-cyclohexylene group, an arylene group having 6 to 30 carbon atoms (for example, p-phenylene group, o-phenylene group, m-phenylene group, 1,4-naphthylene group, 1,3
-Naphthylene group, 4,4'-biphenylene group, 4,4 '
-2,2'-dimethylbiphenylene group, 4,4'-2,
2'-dimethoxybiphenylene group, 4,4'-2,2 '
-Dichlorobiphenylene group), an alkenylene group having 2 to 20 carbon atoms (eg, ethenylene group), an alkynylene group having 2 to 20 carbon atoms (eg, ethinylene group), an amide group,
Ester group, sulfoamide group, sulfonic acid ester group,
Ureido group, sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, -NR- (where R is a hydrogen atom or an alkyl group, an aryl group), a heterocyclic divalent group (for example, 2,6-pyridinylene Group) is 1
And a linking group having 1 or more and 60 or less carbon atoms formed by combining one or more of them. In addition, L ^c may be further substituted with a substituent.
The substituents exemplified as the above-described substituent group ^Wb are exemplified.

N ^c is 0, or n ^c is 1, and L ^c is an alkylene group, an arylene group, a substituted or unsubstituted amino group (—NR—: R represents a hydrogen atom or an alkyl group), The linking group preferably contains at least one of an ether group (—O—) and a carbonyl group (—C (＝ O) —). More preferably, n ^c is 0 or n ^c is 1 and L ^c is an alkylene group, or an alkylene group and -NR-, an ether group, (-O-) and /
Alternatively, a linking group containing a carbonyl group (—C (＝ O) —) is more preferable.

The compound represented by the general formula (1c) is preferably a compound represented by the following general formula (2c).

[0112]

Embedded image

In the general formula (2c), n ^c2 is 3 to
Represents any integer of 8, and the unit in parentheses is repeated ^nc2 times to form a ring. ^nc2 is preferably 3-6. R ^{c1 to} R ^c4 each independently represent a hydrogen atom or a substituent, and at least one of R ^{c1 to} R ^c4 is a chromophore D ^c
And a substituent containing Three or more R ^c1-
R ^c4 and D ^c may be the same or different from each other.

Examples of the substituent represented by R ^{c1 to} R ^c4 include a halogen atom (eg, chlorine, bromine, iodine, fluorine); a mercapto group; a cyano group; a carboxyl group; a phosphate group; a sulfo group; A carbamoyl group having 1 to 10, preferably 2 to 8 carbon atoms, more preferably 2 to 5 carbon atoms (eg, a methylcarbamoyl group, an ethylcarbamoyl group, a morpholinocarbonyl group);
-10, preferably 2 to 8 carbon atoms, more preferably 2 to 5 carbon atoms (for example, methylsulfamoyl group, ethylsulfamoyl group, piperidinosulfonyl group); nitro group; 40, preferably an alkyl group having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group,
Pentyl group, hexyl group, heptyl group, octyl group);
A substituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (for example, hydroxymethyl group, trifluoromethyl group, benzyl group, carboxyethyl group, ethoxycarbonylmethyl group, acetyl An aminomethyl group); a substituted or unsubstituted alkenyl group having 2 to 18 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms (eg, vinyl group, phenylethenyl group); ~ 18, preferably 3 ~ carbon atoms
10, more preferably a substituted or unsubstituted alkynyl group having 3 to 5 carbon atoms (eg, ethynyl group, phenylethenyl group); 2 to 18 carbon atoms, preferably 3 to 10 carbon atoms,
More preferably, a substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 5 carbon atoms (for example, a 1-cyclohexenyl group,
Cyclohexyl group, cyclopentyl group, 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, 4-butylcyclohexyl group): 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms 1 to 8 alkoxy groups (e.g., methoxy, ethoxy, 2-methoxyethoxy, 2-
A phenylethoxy group); an aryloxy group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms (for example, phenoxy group, p-methylphenoxy group, p-chlorophenoxy group, naphthoxy group) An acyl group having 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (eg, acetyl, benzoyl, trichloroacetyl);
0, preferably an acyloxy group having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (for example, an acetyloxy group,
A benzoyloxy group); an acylamino group having 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (eg, acetylamino group);

C1-20, preferably C1-1
0, more preferably a sulfonyl group having 1 to 8 carbon atoms (e.g., methanesulfonyl group, ethanesulfonyl group, benzenesulfonyl group); 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms (For example, methanesulfinyl group, ethanesulfinyl group, benzenesulfinyl group); having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 1 carbon atoms.
8 sulfonylamino group (for example, methanesulfonylamino group, ethanesulfonylamino group, benzenesulfonylamino group); amino group; substitution having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms. Amino group (for example, methylamino group, dimethylamino group, benzylamino group, anilino group, diphenylamino group);
An ammonium group having 0 to 15 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms (for example, trimethylammonium group, triethylammonium group); 0 to 15 carbon atoms, preferably 1 to 10 carbon atoms; More preferably, a hydrazino group having 1 to 6 carbon atoms (eg, a trimethylhydrazino group); 1 to 15 carbon atoms, preferably 1 carbon atom
-10, more preferably a ureido group having 1 to 6 carbon atoms (e.g., a ureido group, an N, N-dimethylureido group);
An imide group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms (for example, succinimide group); 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms;
More preferably, an alkylthio group having 1 to 8 carbon atoms (e.g., a methylthio group, an ethylthio group, a propylthio group); an arylthio group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms (e.g., Phenylthio, p-methylphenylthio, p-chlorophenylthio, 2-pyridylthio, naphthylthio);
An alkoxycarbonyl group having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (for example, methoxycarbonyl group, ethoxycarbonyl group,
A benzyloxycarbonyl group); having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, and more preferably 6 to 1 carbon atoms.
0 aryloxycarbonyl group (for example, phenoxycarbonyl group); having 6 to 20 carbon atoms, preferably having 6 to 1 carbon atoms
5, more preferably a substituted or unsubstituted aryl group having 6 to 10 carbon atoms (e.g., phenyl, naphthyl, p-
Carboxyphenyl group, p-nitrophenyl group, 3,5
-Dichlorophenyl group, p-cyanophenyl group, m-fluorophenyl group, p-tolyl group);
Preferably it has 2 to 10 carbon atoms, more preferably 4 carbon atoms.
To 6 substituted or unsubstituted heterocyclic groups (eg, pyridyl group, 5-methylpyridyl group, thienyl group, furyl group, morpholino group, tetrahydrofurfuryl group);
40, preferably an azo group having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms (for example, phenylazo group, 1-naphthylazo group, 2-naphthylazo group, 4-butylphenylazo group, 4-propylphenylazo group , 4-butoxy-2-methylphenylazo group, 4-trifluoromethylphenylazo group, 2-thiazolylazo group, 4-quinolylazo group). These substituents may be further substituted by one or more of these substituents.
Further, a structure in which a benzene ring or a naphthalene ring is condensed can be used.

R ^{c1 to} R ^{c4 each} represent a hydrogen atom, a halogen atom,
It is preferably an alkyl group, an aryl group, or an alkoxy group, and more preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, a phenyl group, or a trifluoromethoxy group.

However, at least one of R ^{c1 to} R ^c4 is a substituent containing the chromophore D ^c . Preferably, at least one of R ^c1 and R ^c2 is a substituent containing a chromophore D ^c , and R ^c3 and R ^c4 are each a substituent other than a hydrogen atom or a substituent containing a chromophore D ^{c. one of c1} and R ^c2 is a substituent containing the chromophore D ^c , the other is a substituent other than the substituent containing the chromophore D ^c , and R 1
^It is preferred that both ^c3 and ^Rc4 are hydrogen atoms. As the substituent containing a chromophore D ^c, azo dyes, substituents containing chromophore anthraquinone dyes preferred. Chromophore D ^c
Is preferably a chromophore containing an azo group represented by the following general formula (D), and more preferably a chromophore containing an azo group represented by the following general formula (D) ′.

[0118]

Embedded image

[0119]

Embedded image

In the general formulas (D) and (D) ′, Ar
¹ and Ar ² each independently represent an optionally substituted aryl or heteroaryl group. The aryl group includes both those having a single ring structure and those having a condensed ring structure. An aryl group having 2 to 20 carbon atoms is preferable, and specifically, an aryl group including a benzene ring, a naphthalene ring, and an anthracene ring is preferable. The heteroaryl group includes both a single ring structure and a condensed ring structure. The heteroaryl group may have 2 to 20 carbon atoms.
Heteroaryl group is preferred, pyridine ring, quinoline ring, isoquinoline ring, pyrimidine ring, pyrazine ring, thiophene ring, furan ring, oxazole ring, thiazole ring,
Imidazole ring, pyrazole ring, oxadiazole ring,
A group containing a thiadiazole ring, a triazole ring, or a group containing a condensed ring formed by condensing two or more of these heteroaromatic rings or one or more of these heteroaromatic rings with the aromatic ring of the aryl group described above; No.

[0121] Ar ¹ and Ar ² may be each substituted, examples of the substituent include the aforementioned substituent group W ^b. As the substituent, a halogen atom, an alkyl group, an aryl group, and an alkoxy group are preferable, and a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, a phenyl group, and a trifluoromethoxy group are more preferable. Ar ¹ and Ar ² each represent a —N ＝ N—Ar ′ group;
It is also preferable to take the structure of a polyazo dye by being substituted with a group such as -N = N-Ar "-N = N-Ar '. here,
Ar ′ and Ar ″ have the same meanings as Ar ¹ and Ar ² , and specific examples and examples of the substituents are the same as Ar ¹ and Ar ² .

Each of R ^{c1 to} R ^c4 may be a chromophore itself or a substituent comprising a chromophore and a linking group. Examples of the substituent groups include linking groups represented by L ^c in the general formula (1c), which also applies to the specific examples and preferred ranges.

Among the compounds represented by the general formula (2c), the compound represented by the following general formula (2c) ′ is preferable because it can be easily synthesized by using kempic acid.

[0124]

Embedded image

In the general formula (2c) ′, n ^c2 is 3
Represents an integer of any one of to 8, and the unit in parentheses is repeated ^nc2 times to form a ring. L ^c1 represents a linking group, and n ^c represents 0 or 1. R ^c1 , R ^c3 and R ^c4 each independently represent a hydrogen atom or a substituent, and D ^c represents a chromophore.
L ^c1 , R ^c1 , R ^c3 , R ^c4 and D ^c present in three or more molecules in the molecule may be the same or different.

In the general formula (2c) ′, n ^c2 , R
^{For c1} , ^Rc3 and ^Rc4 , the aforementioned general formula (2c)
Has the same meanings as the respective groups in and above, and the same applies to specific examples and preferred ranges.

In the general formula (2c) ', L^c1Wa
Represents a linking group, n^cRepresents 0 or 1. n^c= 0,
Chromophore D^cIs directly linked to the carbonyl group by a single bond
You. L ^c1Represents a carbon atom, a nitrogen atom,
At least one atom selected from a yellow atom and an oxygen atom
Or an atomic group containing at least one atom
You. Specifically, an alkylene group having 1 to 20 carbon atoms (eg,
For example, methylene group, ethylene group, propylene group, butylene
Group, pentylene group, 1,4-cyclohexylene group), charcoal
Arylene group having a prime number of 6 to 30 (for example, p-phenylene
Group, o-phenylene group, m-phenylene group, 1,4-na
Butylene group, 1,3-naphthylene group, 4,4'-biphe
Nylene group, 4,4'-2,2'-dimethylbiphenylene
A 4,4'-2,2'-dimethoxybiphenylene group,
4,4'-2,2'-dichlorobiphenylene group), carbon
Alkenylene groups of 2 to 20 (for example, ethenylene
Alkynylene group having 2 to 20 carbon atoms (for example,
Nylene group), amide group, ester group, sulfamide group,
Sulfonic acid ester group, ureido group, sulfonyl group,
Rufinyl group, thioether group, ether group, carbonyl
Group, -NR- (where R is a hydrogen atom or an alkyl
Group, aryl group), heterocyclic divalent group (for example, 2,6-
Pyridinylene group) in combination with one or more
And a linking group having 1 to 60 carbon atoms to be formed.
Note that L^c1May be further substituted by a substituent.
The substituents include the substituent group W described above.^bAs example
The substituents indicated, and the positions in which hydrogen atoms have been removed from the substituents.
And substituents.

It is preferred that n ^c1 is 0, that is, the chromophore D ^c is directly bonded to the carbonyl group. Also, ^nc1 is 1
In the ^formula , L ^c1 represents an alkylene group, an arylene group,-
It is preferably a linking group containing at least one of NR- and an ether group (-O-). More preferably, n ^c1
Is more preferably 0, or n ^c1 is 1 and L ^c1 is an alkylene group or a linking group containing an alkylene group and an ether group (—O—) and / or —NR—.

In the formula (2c) ′, the chromophore represented by D ^c is as defined above. A chromophore of an azo dye or an anthraquinone dye is preferred, and a chromophore of an azo dye is more preferred. In particular, the chromophore D ^c is preferably a chromophore containing an azo group represented by the aforementioned general formula (D), and is preferably a chromophore containing an azo group represented by the aforementioned general formula (D) ′. More preferably, there is.

That is, among the compounds represented by the general formula (2c) ′, a compound represented by the following general formula (2c) ″ is particularly preferable.

[0131]

Embedded image

In the general formula (2c) ″, n ^c2 is 3 to 8
^Wherein n ^c2 units in parentheses are repeated to form a ring. R ^c1 , R ^c3 and R ^c4 each independently represent a substituent, L ^c1 represents a linking group, and n ^c represents 0 or 1. Ar ^c1 and Ar ^c2 each independently represent a substituted or unsubstituted aryl group or heteroaryl group. Three or more R ^c1 , R ^c3 ,
R ^c4 , L ^c1 , n ^c , Ar ^c1 and Ar ^c2 may be the same or different from each other. The general formula (2c) ''
In the formula, n ^c , R ^c1 , R ^c3 , R ^c4 , L ^c1 , A ^c1 and A ^c2 are respectively as defined for each group in the aforementioned general formula (2c), and specific examples and preferred ranges are as follows. The same is true for

As the compound represented by the general formula (1c), a compound represented by the following general formula (3c) is also preferable.

[0134]

Embedded image

In the general formula (3c), n ^c3 represents an integer of 3 to 10, and the number of units in parentheses is repeated n ^c3 to form a ring. ^nc3 is preferably 3 to 8,
More preferably, it is 3 to 6. R ^{c5 to} R ^c10 each independently represent a hydrogen atom or a substituent, and at least one of R ^{c5 to} R ^c10 represents a substituent containing a chromophore D ^c .
R ^{c5 to} R ^c10 and D ^c present in three or more molecules in the molecule may be the same or different.

R ^{c5 to} R ^c10 each independently represent a hydrogen atom or a substituent, and at least one of R ^{c5 to} R ^c10 represents a substituent containing a chromophore D ^c . Among them, R ^c5 and / or R ^c7 is preferably a substituent containing the chromophore D ^c . The substituents represented by R ^{c5 to} R ^c10 have the same ^meanings as the substituents represented by R ^{c1 to} R ^c4 in formula (2c), and the same applies to specific examples and preferred ranges. The substituent containing a chromophore represented by each of R ^{c1 to} R ^c4 is preferably a substituent containing an azo group represented by the aforementioned general formula (D), and is preferably represented by the aforementioned general formula (D) ′. More preferably, the substituent is an azo group-containing substituent. R ^{c5 to} R ^c10 may be a chromophore itself or a substituent comprising a chromophore and a linking group. Examples of the substituent groups include linking groups represented by L ^c in the general formula (1c), which also applies to the specific examples and preferred ranges.

Among the compounds represented by the general formula (3c), the compound represented by the following general formula (3c) ′ is preferable because it can be easily synthesized by using calixarene.

[0138]

Embedded image

In the general formula (3c) ', n^c3Is 3-10
Represents an integer, and the unit in parentheses is n^c3Repeated
To form a ring. n^c3Is preferably 3 to 8,
More preferably, it is 3 to 6. R^c5’And R^c6~ R
^c9Each independently represents a hydrogen atom or a substituent,
R^c5’And R^c6~ R^c8At least one of the chromophores
D ^cRepresents a substituent containing R that is present more than 3 times in the molecule
^c5’, R^c6~ R^c9And D^cAre the same but different
It may be.

In the formula (3c) ′, the substituents represented by R ^c5 ′ and R ^{c6 to} R ^c9 are exemplified as the substituents represented by R ^{c5 to} R ^c10 in the formula (3c). The same ones are mentioned, and the preferable range is also the same. 'At least one of and R ^c6 to R ^c8 represents a substituent containing a chromophore D ^c, R ^c5' R ^c5 of or R ^c7 represents a substituent containing a chromophore D ^c is preferred. As the chromophore D ^c, is preferred chromophore of the azo dyes or anthraquinone dyes, chromophores of the azo dyes are more preferred. In particular, the chromophore D ^c is represented by the aforementioned general formula (D)
Alternatively, a substituent containing an azo group represented by the general formula (D) ′ is preferable. R ^c5 ′ and R ^{c6 to} R ^c8 are chromophores D
^c itself (preferably, a group itself represented by the general formula (D) or the general formula (D) ′);
It may be a substituent composed of a chromophore D ^c (preferably, the group represented by the general formula (D) or the general formula (D) ′) and a linking group. As the linking group, the general formula (1c) in the same ones as exemplified for the linking group L ^c can be mentioned the preferred range is also the same.

Hereinafter, specific examples of the compounds represented by formulas (1c), (2c) and (3c) are shown, but the present invention is not limited by the following specific examples.

[0142]

Embedded image

[0143]

Embedded image

[0144]

Embedded image

The formulas (1c), (2c) and (3)
The compound represented by c) can be synthesized according to the methods described in various documents. For example, for the synthesis of azo dyes and anthraquinone dyes, see “Dichroic D
yes for Liquid Crystal Display ”(AV Ivashchenk
o, CRC Co., 1994), "Review Synthetic Dyes" (Hiroguchi Hiroshi, Sankyo Shuppan, 1968) and various references can be made with reference thereto. Regarding the synthesis of a cyclic compound and introduction of a chromophore into the cyclic compound, see "Chemical Review No.31 Chemistry for Supramolecules" (edited by The Chemical Society of Japan, published by Gakkai Shuppan, 1997),
xarenes '' (David C. Gutsche, Royal Society of Chem
istry, 1989) and references cited therein.

In the liquid crystal composition of the present invention, one kind of the compound of the present invention (the aforementioned compound used as the dichroic dye in the present invention is referred to as “the compound of the present invention”) may be used alone. However, a plurality of types may be mixed and used.
When a plurality of dyes are mixed, the compound of the present invention is
The compounds of the present invention may be used as a mixture, or the compounds of the present invention and known dichroic dyes may be used as a mixture. 2 that can be used together
Examples of the coloring pigment include, for example, "Dichroic Dyes for Liqu
id Crystal Display "(by AV Ivashchenko, CRC,
1994) can be used. For example,
When the liquid crystal composition of the present invention is used for displaying black, it is necessary to absorb light in the entire visible region, and it is preferable to use a mixture of a plurality of dichroic dyes.

The host liquid crystal usable in the liquid crystal composition of the present invention is not particularly limited as long as it can coexist with the compound of the present invention. For example, a liquid crystal compound exhibiting a nematic phase or a smectic phase can be used. Specific examples thereof include an azomethine compound, a cyanobiphenyl compound, a cyanophenyl ester, a fluorine-substituted phenyl ester, a cyclohexanecarboxylic acid phenyl ester, a fluorine-substituted cyclohexanecarboxylic acid phenyl ester, a cyanophenylcyclohexane, a fluorine-substituted phenylcyclohexane, a cyano-substituted phenylpyrimidine, Fluorine-substituted phenylpyrimidine, alkoxy-substituted phenylpyrimidine,
Fluorine-substituted alkoxy-substituted phenylpyrimidine, phenyldioxane, tolan compounds, fluorinated tolan compounds, alkenylcyclohexylbenzonitrile and the like. "Liquid Crystal Device Handbook" (edited by the 142nd Committee of the Japan Society for the Promotion of Science, Nikkan Kogyo Shimbun, 1989)
Pp. 154 to 192 and 715 to 722 can be used. A fluorine-substituted host liquid crystal suitable for driving a TFT can also be used.

The liquid crystal composition of the present invention has the purpose of adjusting the physical properties of the host liquid crystal to a desired range (for example, to adjust the temperature range of the liquid crystal phase to a desired range).
A compound having no liquid crystallinity may be added. Further, compounds such as a chiral compound, an ultraviolet absorber, and an antioxidant may be contained. Such additives are described in, for example, "Liquid Crystal Device Handbook" (edited by the 142nd Committee of the Japan Society for the Promotion of Science, Nikkan Kogyo Shimbun, 1989), 199-20.
TN and STN chiral agents described on page 2.

In the liquid crystal composition of the present invention, the content of the host liquid crystal and the compound of the present invention is not particularly limited, but the content of the compound of the present invention is 0.1 to 15 with respect to the content of the host liquid crystal. % By mass, preferably 0.5% by mass.
It is particularly preferred that the amount is 6% by mass.

The liquid crystal composition of the present invention can be prepared by dissolving the compound of the present invention in a host liquid crystal. The dissolution can be performed using mechanical stirring, heating, ultrasonic waves or a combination thereof.

The liquid crystal device of the present invention is a liquid crystal device having a liquid crystal layer containing the liquid crystal composition of the present invention. The liquid crystal element of the present invention can be composed of, for example, a pair of electrode substrates and a liquid crystal layer containing the liquid crystal composition of the present invention sandwiched between the pair of electrode substrates. As the electrode substrate, one obtained by forming an electrode layer on a substrate usually made of glass or plastic can be used. Examples of the plastic substrate include an acrylic resin, a polycarbonate resin, and an epoxy resin. For the substrate, see, for example, 218-23 of “Liquid Crystal Device Handbook” (edited by the 142nd Committee of the Japan Society for the Promotion of Science, Nikkan Kogyo Shimbun, 1989).
Those described on page 1 can be used. The electrode layer formed on the substrate is preferably a transparent electrode layer. For example, indium oxide, indium tin oxide (ITO),
It can be formed from tin oxide or the like. For the transparent electrode, see, for example, “Liquid Crystal Device Handbook” (edited by the 142nd Committee of the Japan Society for the Promotion of Science, Nikkan Kogyo Shimbun, 1989).
Year)), pages 232 to 239.

It is preferable that an alignment-treated layer (alignment film) is formed on the surface of the substrate in contact with the liquid crystal layer. As the alignment treatment, for example, a method of applying and aligning a quaternary ammonium salt, a method of applying polyimide and aligning by rubbing treatment, a method of aligning by depositing SiO _x in an oblique direction, and further, photoisomerization An alignment method by light irradiation used is exemplified. For the alignment film, for example, see “Liquid Crystal Device Handbook” (edited by the 142nd Committee of the Japan Society for the Promotion of Science, Nikkan Kogyo Shimbun, 1989).
Years), pp. 240-256.

In the liquid crystal device of the present invention, for example, a pair of substrates are opposed to each other at a distance of 1 to 50 μm via a spacer or the like, and the liquid crystal composition of the present invention is injected into a space formed between the substrates. Can be produced. About the spacer, for example, "Liquid crystal device handbook"
(The 142nd Committee of the Japan Society for the Promotion of Science, Nikkan Kogyo Shimbun,
1989), pp. 257-262.

The liquid crystal element of the present invention can be driven by a simple matrix driving method or an active matrix driving method using a thin film transistor (TFT) or the like. For the driving method, for example, see “Liquid Crystal Device Handbook” (edited by the 142nd Committee of the Japan Society for the Promotion of Science,
The details are described on pages 387 to 460 of Nikkan Kogyo Shimbun, 1989) and can be used as a driving method of the liquid crystal element of the present invention.

The liquid crystal device of the present invention can be used for a liquid crystal display. Although there is no particular limitation on the method, for example, “Liquid Crystal Device Handbook” (edited by the 142nd Committee of the Japan Society for the Promotion of Science, Nikkan Kogyo Shimbun, 19
89), page 309, guest-host system, homogeneous alignment, homeotropic alignment, W
focal-conic orientation and homeotropic orientation as a hite-Taylor type (phase transition), Su
combination with per Twisted Nematic (STN), combination with ferroelectric liquid crystal (FLC), and "reflective color LCD comprehensive technology" (supervised by Tatsuo Uchida,
Helmier type GH mode, １ ／ wavelength plate type GH mode, and two-layer type described in Chapter 2-1 (GH mode reflection type color LCD), pages 15 to 16 of CMC Corporation, 1999). GH mode, phase transition type G
H mode, polymer dispersed liquid crystal (PDLC) type GH mode, and the like.

Further, the liquid crystal device of the present invention is disclosed in
67990, 10-239702, 10-13
No. 3223, No. 10-339881, No. 11-524
No. 11, 11-64880, JP-A-2000-221
It can be used for a laminated GH mode described in various publications such as 538, and a GH mode liquid crystal display using microcapsules described in Japanese Patent Application Laid-Open No. 11-24090. Further, Japanese Patent Application Laid-Open No. 6-235
No. 931, No. 6-235940, No. 6-265859
Nos. 7-56174, 9-146124, 9
No. 197388, No. 10-20346, No. 10-3
No. 1207, No. 10-31216, No. 10-3123
No. 1, No. 10-31232, No. 10-31233,
No. 10-31234, No. 10-82986, No. 10
-90674, 10-11113, 10-1
No. 11523, No. 10-123509, No. 10-12
No. 3510, No. 10-206581, No. 10-253
No. 993, No. 10-268300, No. 11-1492
No. 52, JP-A-2000-2874, etc., can be used for the reflection type liquid crystal display.
Also, JP-A-5-61025 and JP-A-5-265053
Nos. 6-3691 and 6-23061 and 5-2
Nos. 03940, 6-242423, 6-2893
No. 76, No. 8-278490, No. 9-81174, etc. can be used for a polymer dispersed liquid crystal type GH mode liquid crystal display.

In addition, the liquid crystal device of the present invention can be applied to a spatial light modulator, a light or heat writing type liquid crystal display, and the like.

[0158]

The present invention will be described more specifically with reference to the following examples. Materials, reagents, ratios, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. <Example 1: Synthesis of exemplary compound a-5>

[0159]

Embedded image

Under nitrogen atmosphere, raw material (M-1) 0.18
g, raw material (M-2) 0.30 g, palladium (II) acetate
20 mg, 50 mg of triphenylphosphine and 50 mg of copper iodide were reacted in 10 ml of triethylamine with stirring in an oil bath set to an external temperature of 80 ° C. for 6 hours. After cooling the reaction solution, water was added, and organic matter was extracted with chloroform and dried. After evaporating the organic solvent under reduced pressure, the residue was purified by silica gel chromatography (eluent: a mixed solvent of chloroform and methanol) to obtain 0.12 g of the desired compound (exemplified compound a-5) as pale yellow crystals. The properties of the obtained compound are shown below. Melting point = 226-236 ° C. (decomposition) Absorption maximum 380 nm (solvent: dimethylformamide) Absorption coefficient 6.5 × 10 ⁴

Example 2 Synthesis of Exemplified Compound c-1

[0162]

Embedded image

Under a nitrogen atmosphere, 0.50 g of the raw material (1)
And 78 mg of kempic acid in dimethylformamide 1
It was dissolved in 2 mL, and at room temperature, 0.23 g of hydroxybenzotriazole (HOBt) and 0.15 g of triethylamine were added, and the mixture was stirred for 10 minutes. afterwards,
At room temperature, 0.35 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC) was added, and the mixture was stirred at room temperature for 1 day. After adding water to the reaction solution, the organic matter was extracted with ethyl acetate and dried,
The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel chromatography (eluent: chloroform / methanol 10: 1).
Purified with a mixed solvent) to obtain the target compound (exemplified compound c-
0.18 g of 1) was obtained as a yellow powder. The properties of the obtained compound are shown below. Absorption maximum 353 nm (solvent: dimethylformamide) extinction coefficient 8.22 × 10 ⁴ proton NMR (CDCl ₃ ): δ 0.95 (t, 9)
H), 1.1 (d, 3H), 1.2 (s, 9H), 1..
3-1.35 (m, 6H), 1.5-1.7 (m, 12
H) 1.8-1.9 (m, 6H), 2.6 (t, 6
H), 2.9 (d, 3H), 3.1 (m, 6H), 3.
9 (t, 6H), 6.9 (d, 6H), 7.2 (d, 6
H), 7.45 (m, 3H), 7.8 (d, 6H),
7.9 (d, 6H)

Example 3 1.0 of the compounds shown in Table 1
mg of liquid crystal (trade name: ZLI-1132;
E. FIG. (Merck) to prepare a liquid crystal composition. This liquid crystal composition was injected into a commercially available substrate for a liquid crystal cell, to produce a guest-host liquid crystal element 1 and a liquid crystal element 1 for comparison. The liquid crystal cell substrate used was E.I. H.
C. A glass plate (thickness 0.7 mm) on which an ITO transparent electrode layer and a polyimide alignment film (with parallel arrangement by rubbing treatment) are formed, with a cell gap of 8 μm and an epoxy resin seal. there were.

The manufactured liquid crystal element 1 and the comparative liquid crystal element 1 were irradiated with polarized light parallel to and perpendicular to the rubbing direction, respectively, to obtain respective absorption spectra (A‖).
And A⊥) were measured on a Shimadzu UV3100. The order parameter S was determined from A 大 and A⊥ at the maximum absorption wavelength according to the following equation 1. The determined order parameter S is used as the maximum absorption wavelength (λ
max) are shown in Table 1. Formula 1 S = (A‖−A⊥) / (A‖ + 2 × A⊥)

[0166]

[Table 1]

[0167]

Embedded image

From the results shown in Table 1, it can be seen that, compared with the conventionally known mono-type azo dye (Comparative Dye M-2), Exemplified Compound a-5, which is the compound of the present invention, gives higher order parameters. Was.

<Example 4> Using Exemplified Compound a-11,
A commercially available fluorine-based liquid crystal (trade name: ZLI-4792; EM
and the order parameter S was measured by the same operation as in Example 1.
It was 0. From this result, it was found that Exemplified Compound a-11 of the compound represented by the general formula (1a) gives high order parameters even when a fluorine-based host liquid crystal is used.

Example 5 0.2% of the compound shown in Table 2
mg of liquid crystal (trade name: ZLI-1132;
E. FIG. (Merck) to prepare a liquid crystal composition. This liquid crystal composition was injected into a commercially available liquid crystal cell substrate to prepare guest-host liquid crystal elements 2 to 10 and a liquid crystal element 2 for comparison. The liquid crystal cell substrate used was
E. FIG. H. C. A glass plate (thickness 0.7 mm) on which an ITO transparent electrode layer and a polyimide alignment film (with a parallel arrangement by rubbing treatment) were formed.
It had a cell gap of 8 μm and an epoxy resin seal.

The manufactured liquid crystal elements 2 to 10 and the comparative liquid crystal element 2 were irradiated with polarized light parallel to and perpendicular to the rubbing direction, respectively, and their absorption spectra (A‖ and A⊥) were measured by Shimadzu UV3100.
Was measured. The order parameter S was determined from A 大 and A⊥ at the maximum absorption wavelength according to the following equation 1. Table 2 shows the maximum absorption wavelength (λmax) of the compound using the determined order parameter S. Formula 1 S = (A‖−A⊥) / (A‖ + 2 × A⊥)

[0172]

[Table 2]

[0173]

Embedded image

From the results shown in Table 2, it was found that the compound of the present invention gave higher order parameters than the conventionally known mono-type azo dye (Comparative Dye 1).

[0175]

According to the present invention, a high dichroic ratio is exhibited,
When used for a display element, a liquid crystal composition and a liquid crystal element capable of improving display contrast can be provided. Further, according to the present invention, a novel dye useful as a dichroic dye, in particular, a novel dye giving a high order parameter can be provided.

[Procedure amendment]

[Submission date] April 19, 2001 (2001.4.1
9)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Brief description of drawings

[Correction method] Added

[Correction contents]

[Brief description of the drawings]

FIG. 1 is a conceptual diagram schematically showing the structure of a dichroic dye used in the present invention.

[Description of Signs] A Conjugate plane of chromophore B Conjugate plane of chromophore L Linking group

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02F 1/13 500 G02F 1/13 500

Claims (24)

[Claims] 1. A chromophore having a plurality of chromophores, wherein at least two chromophores of the plurality of chromophores contain a compound in which conjugate planes of the chromophores are connected so that they can be oriented in parallel with each other. Liquid crystal composition. 2. The liquid crystal composition according to claim 1, wherein the two chromophores are azo dye chromophores. 3. A liquid crystal composition comprising a compound represented by any of the following general formulas (1a) and (1a) ′. Embedded image (Wherein, D ^a1 and D ^a2 each independently represent a substituent containing a chromophore, R ^{a1 to} R ^a6 each independently represent a hydrogen atom or a substituent, and R ^{a1 to} R ^a6 are adjacent to each other. Two of the carbon atoms may be bonded to each other to form a ring.) (Wherein, D ^a1 'and D ^a2' are each independently represents a substituent containing a chromophore, R ^a1 '~R ^a6' represents a hydrogen atom or a substituent each independently, R ^a1 'to R ^{two of a6} ′, which are bonded to adjacent carbon atoms, may be bonded to each other to form a ring, and X and Y are each independently an oxygen atom, a sulfur atom,> NR ¹ , substituted or unsubstituted; Represents a substituted carbon atom, and R ¹ represents an alkyl group or a hydrogen atom.) 4. D ^a1 and D ^a2 in the general formula (1a), and D ^a1 ′ and D a in the general formula (1a) ′
The liquid crystal composition according to claim 3, wherein ^a2 'is a substituent containing a chromophore of an azo dye. 5. The liquid crystal composition according to claim 3, wherein the compound represented by the general formula (1a) is represented by the following general formula (2a). Embedded image (Wherein, R ^a1 to R ^a16 are each independently a hydrogen atom or a substituent, and that two bonded to carbon bonds adjacent of R ^a1 to R ^{a 16} bond to each other to form a ring L ^a1 and L ^a2 each independently represent a linking group,
n ^a1 and n ^a2 each represent 0 or 1. However, ^Ra7 ~
At least one selected from R ^a11 , and R ^{a12 to} R
^At least one selected from ^a16 independently represents a substituent containing an azo group. ) 6. In the general formula (2a), R ^{a7 to} R a
at least one selected from ^a11 , and R ^{a12 to} R ^a16
The liquid crystal composition according to claim 5, wherein at least one selected from the group consisting of azo groups represented by the following general formula (D): Embedded image (In the formula, Ar ¹ represents a substituted or unsubstituted aryl group or heteroaryl group.) 7. A liquid crystal composition comprising a compound in which three or more chromophores are linked by a dendrimer residue having a dendritic polymer (dendrimer) -like structure. 8. The compound represented by the following general formula (1b)
The liquid according to claim 7, which is a compound to be prepared.
Crystal composition. Embedded image(Where X^bHas a dendritic polymer-like structure
Represents a dendrimer residue having^bRepresents a chromophore,
L^bRepresents a linking group, and n^b1Represents 0 or 1. n ^bIs 3
Represents an integer of ~ 256, and 3 or more
D that exists^b, L^bAnd n^b1Are the same but different
It may be. ) 9. The liquid crystal composition according to claim 7, wherein the chromophore is a chromophore of an azo dye or an anthraquinone dye. 10. The liquid crystal composition according to claim 7, wherein the compound is a compound represented by the following general formula (2b). Embedded image (In the formula, X ^b represents a dendrimer residue having a dendrimer-like repeating structure, and Ar ^b1 and Ar ^b2 each independently represent a substituted or unsubstituted aryl group or heteroaryl group. , L ^b represents a linking group, n ^b1 is .n ^b 'represents 0 or 1 represents an integer of from 3 to 128, there are three or more in a molecule a
r ^b1 , Ar ^b2 , L ^b and n ^b1 may be the same or different. ) 11. The liquid crystal composition according to claim 7, wherein the dendrimer residue has a branched structure containing any of the following groups. Embedded image 12. A liquid crystal comprising a compound in which three or more chromophores are linked by a cyclic group containing three or more atoms bonded to the chromophore directly or via a linking group. Composition. 13. The liquid crystal composition according to claim 12, wherein the compound is a compound represented by the following general formula (1c). Embedded image ( ^Wherein , X ^c represents a cyclic group capable of binding to n ^c1- (L ^c ) _nc -D ^c , D ^c represents a chromophore, L ^c represents a linking group, and n ^c represents 0 Or represents 1. n ^c1 represents an integer of 3 to 256, and three or more D ^c , L ^c and n ^c present in the molecule.
May be the same or different from each other. ) 14. The chromophore according to claim 12, wherein said chromophore is a chromophore of an azo dye or an anthraquinone dye.
Or a liquid crystal composition according to item 13. 15. The method according to claim 15, wherein the cyclic group is calixarene, cycloalkane, cycloalkene, cycloalkyne, cyclophane, cyclic ether, cyclic thioether,
15. It has any ring structure selected from lactone, lactam and lactide.
A liquid crystal composition according to any one of the above. 16. The liquid crystal composition according to claim 12, wherein the cyclic group has a ring structure of calixarene, cycloalkane, or cyclophane. 17. The liquid crystal composition according to claim 13, wherein the compound represented by the general formula (1c) is represented by the following general formula (2c). Embedded image (Wherein, n ^c2 represents an integer of 3 to 8, the unit in brackets is n ^c2 or repeated to form a ring .R ^c1 to R ^c4
Each independently represents a hydrogen atom or a substituent, R ^c1 ~
At least one of R ^c4 is a substituent containing chromophore D ^c . R ^{c1 to} R ^c4 and D ^{c which} are present in the molecule at least three ^times
May be the same or different from each other. ) 18. The liquid crystal composition according to claim 13, wherein the compound represented by the general formula (1c) is represented by the following general formula (2c) ′. Embedded image (Wherein, n ^c2 represents an integer of 3-8, the .L ^c1 to form a unit n ^c2 or repeated ring in parentheses represents a linking group, the n ^c represents 0 or 1 .R ^c1, R ^c3 and R ^c4 each represents a hydrogen atom or a substituent each independently, D ^c
Represents a chromophore. L ^c1 that is present in the molecule three or more ^times ,
n ^c , R ^c1 , R ^c3 , R ^c4 and D ^c may be the same or different. ) 19. The liquid crystal composition according to claim 13, wherein the compound represented by the general formula (1c) is a compound represented by the following general formula (3c). Embedded image (Wherein, n ^c3 represents an integer of 3 to 10, the unit in brackets is repeated ^c3 or n to form a ring .R ^c5 to R
^c10 each independently represents a hydrogen atom or a substituent;
at least one of ^c5 to R ^c10 represents a substituent containing a chromophore D ^c. R ^{c5 to} R ^c10 and D ^c present in three or more molecules in the molecule may be the same or different. ) 20. The liquid crystal composition according to claim 13, wherein the compound represented by the general formula (1c) is a compound represented by the following general formula (3c) ′. Embedded image (Wherein, n ^c3 is an integer of either 3 to 10 noise, .R ^c5 'and R ^c6 to R ^c9 forms unit is n ^c3 or repeated ring in parentheses are each independently hydrogen Represents an atom or a substituent, and at least one of R ^c5 ′ and R ^{c6 to} R ^c8 represents a substituent containing a chromophore D ^c . Three or more R ^c5 ′, R ^c6 to R ^c present in the molecule ^c9 and D ^c may be the being the same or different.) 21. The liquid crystal composition according to claim 13, wherein the chromophore D ^c contains a group represented by the following general formula (D). Embedded image (In the formula, Ar ¹ represents a substituted or unsubstituted aryl group or heteroaryl group.) A liquid crystal device comprising a layer containing the liquid crystal composition according to any one of claims 1 to 21. 23. An azotization represented by the following general formula (3a)
Compound. Embedded image(Where R^a1~ R^a16Is independently a hydrogen atom or
R represents a substituent^a1~ R^{a 16}Of adjacent carbon bonds
The two being bonded to each other to form a ring,
Is also good. L^a1’And L^a2’Is each independently substituted or
Represents an unsubstituted alkynylene group. Where R^a7~ R^a11Or
At least one selected from R, and R^a12~ R ^a16Choose from
At least one of each is independently represented by the following formula:
Represents a substituent. )(Where R^a17~ R^a21Are each independently a hydrogen atom or
Represents a substituent, R^a17~ R^{a twenty one}Of adjacent carbon atoms
Two of which may combine with each other to form a ring
No. ) 24. An azo compound represented by the following general formula (2c) ″. Embedded image (In the formula, ^nc2 represents an integer of any of 3 to 8, and the unit in parentheses is repeated ^nc2 times to form a ring. ^Rc1 , ^Rc3
And R ^c4 each independently represent a substituent, L ^c1 represents a linking group, and n ^c represents 0 or 1. Ar ^c1 and Ar ^c2
Each independently represents a substituted or unsubstituted aryl group or heteroaryl group. L ^c1 , n ^c , R ^c1 , R ^c3 , R ^c4 , Ar ^c1 and Ar present in the molecule at least 3 ^times
c2 may be the same or different. )