JPH09110794A - Naphthalene compound, liquid crystal composition and liquid crystal element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new naphthalene compound having high spontaneous polarization and low viscosity, excellent in high speed response, and useful as a component for liquid crystal compositions used for ferroelectric liquid crystal elements. SOLUTION: A compound of formula I [R1 is a halogen-substituted linear 1-24C alkyl; R2 is a (branched) 1-24C alkyl; A is (substituted) (non)aromatic carbon homocyclic group or heterocyclic group; X is -OCH2 -,-OC(=O)-; Y is a single bond, an ether bond, an ester bond; C* is an asymmetric carbon]. For example, 2-(6- [4-(dodecyloxy)phenyl]carbonyloxy}naphthalen-2-yl)propionic acid 3-(perfluorooctyl)propyl ester. The compound of formula I is obtain by reacting a compound of formula II with a compound of the formula: R2 -Y-A-CH2 Br or R2 -Y-A-COCl.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel naphthalene compound. More specifically, the present invention relates to a novel naphthalene compound useful as a component of a liquid crystal composition used for a liquid crystal display device, a liquid crystal composition containing the compound, and a liquid crystal device using the liquid crystal composition.

[0002]

2. Description of the Related Art At present, a TN (twisted nematic) type display system is most widely used as a liquid crystal display device. This TN type display system is inferior in terms of response speed to light emitting type devices (cathode tube, electroluminescence, plasma display, etc.). An STN (Super Twisted Nematic) type display device having a twist angle of 180 to 270 ° has also been developed.
The response speed is still poor. Although various efforts have been made to improve the TN type display element having a high response speed, it has not been realized yet. However, in a new display method using a ferroelectric liquid crystal, which has been actively researched in recent years, there is a possibility that the response speed is remarkably improved [Applied Phys.lett., 36,899 (1980)].

This method utilizes a chiral smectic phase such as a chiral smectic C phase exhibiting ferroelectricity. It is known that not only the chiral smectic C phase but also the chiral smectic F, G, H, I phases exhibit ferroelectricity. These smectic liquid crystal phases belong to a tilt-based chiral smectic phase, and among them, a chiral smectic C phase having low viscosity is preferable. A large number of liquid crystal compounds exhibiting a chiral smectic C phase have already been synthesized and studied, but the conditions for use as a ferroelectric liquid crystal device are: (a) a chiral smectic C phase in a wide temperature range including room temperature. (B) In order to obtain a good orientation, the chiral smectic C phase has an appropriate phase series on the high temperature side and has a large helical pitch, and (c) has an appropriate tilt angle. D) The viscosity is small, and (e) the spontaneous polarization is large to some extent. However, there is no known thing which satisfies these alone.

Therefore, a liquid crystal compound exhibiting a chiral smectic C phase is used as a liquid crystal composition exhibiting a chiral smectic C phase by being mixed with another chiral smectic C phase or some liquid crystal compounds exhibiting a smectic C phase. In any case, the liquid crystal compound exhibiting the chiral smectic C phase is required to have a low viscosity and have a spontaneous polarization larger than a certain level in order to realize a high-speed response. Further, a compound that does not exhibit a chiral smectic C phase by itself can be used as a liquid crystal compound exhibiting a smectic C phase or a liquid crystal composition exhibiting a chiral smectic C phase by mixing it with a liquid crystal composition as a chiral dopant. Also in this case, a compound having the same properties as the above (a) to (e) is required. As described above, the conventional compound exhibiting a chiral smectic C phase is insufficient in its viscosity and spontaneous polarization, and there is a problem in providing a liquid crystal material having a fast response, and its improvement is desired.

[0005]

An object of the present invention is to provide a compound having a large spontaneous polarization and a small viscosity as a component of a liquid crystal composition used for a liquid crystal display device, etc. It is to enable the provision of liquid crystal display materials.

[0006]

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted extensive studies on a novel naphthalene compound, and as a result, found a certain kind of naphthalene compound, and completed the present invention. It was. That is, the present invention
The present invention relates to a naphthalene compound represented by the general formula (1) (chemical formula 4).

[0007]

Embedded image [Wherein, R ₁ is a halogen atom-substituted C 1-2
4 represents a straight-chain alkyl group, R ₂ represents a straight-chain or branched-chain alkyl group having 1 to 24 carbon atoms, and A represents an aromatic or non-aromatic carbon group which may have a substituent. Represents a prime ring or a heterocycle, and X represents a -OCH ₂ -group or -OC
Represents a (= O)-group, Y represents a bonding group selected from a single bond, an ether bond and an ester bond, and C * represents an asymmetric carbon.]

Further, in the general formula (1), an aromatic or non-aromatic carbon allocyclic ring or heterocyclic ring which may have a substituent represented by A is selected from the following group (Formula 5). The present invention relates to the above-mentioned naphthalene compound, which relates to the above-mentioned naphthalene compound in which an asymmetric carbon is optically active in the (S) configuration or the (R) configuration, and a liquid crystal containing at least one of these naphthalene compounds. The present invention relates to a composition and a liquid crystal display device using the liquid crystal composition.

[0009]

Embedded image [Wherein, L ₁ and L ₂ represent a hydrogen atom, a halogen atom or a hydroxyl group, and the 1,4-cyclohexylene ring has a trans configuration] The present invention is further represented by the general formula (2) The present invention relates to a hydroxynaphthalene compound represented.

[0010]

Embedded image [Wherein, R ₁ is a halogen atom-substituted C 1-2
4 represents a straight-chain alkyl group]

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the naphthalene compound of the present invention, R ₁ represents a linear alkyl group having 1 to 24 carbon atoms substituted with a halogen atom, and preferably a linear alkyl group having 4 to 16 carbon atoms substituted with a halogen atom. Represents Further, R ₁ is preferably a group represented by the general formula (3) (formula 7).

[0012]

Embedded image In the general formula (3), X _{1 to} X ₁₁ represent a hydrogen atom or a halogen atom, preferably a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, more preferably a hydrogen atom or a fluorine atom. Or a chlorine atom. However, all of X _{1 to} X ₁₁ do not become hydrogen atoms at the same time, and at least one of X _{1 to} X ₁₁ is a halogen atom. s, t, u and v represent an integer of 0 to 15, but in the general formula (3), the total sum of s, t, u and v is 0 to 23.

Specific examples of R ₁ include, for example, fluoromethyl group, difluoromethyl group, 2-fluoroethyl group, 1,2-difluoroethyl group and 2-fluoro-n-
Propyl group, 3-fluoro-n-propyl group, 1,3-
Difluoro-n-propyl group, 2,3-difluoro-n
-Propyl group, 2-fluoro-n-butyl group, 3-fluoro-n-butyl group, 4-fluoro-n-butyl group, 3
-Fluoro-2-methylpropyl group, 2,3-difluoro-n-butyl group, 2,4-difluoro-n-butyl group, 3,4-difluoro-n-butyl group, 2-fluoro-n-pentyl group , 3-fluoro-n-pentyl group, 5
-Fluoro-n-pentyl group, 2,4-difluoro-n
-Pentyl group, 2,5-difluoro-n-pentyl group,
2-fluoro-3-methylbutyl group, 2-fluoro-n
-Hexyl group, 3-fluoro-n-hexyl group, 4-fluoro-n-hexyl group, 5-fluoro-n-hexyl group, 6-fluoro-n-hexyl group, 2-fluoro-n
-Heptyl group, 4-fluoro-n-heptyl group, 5-fluoro-n-heptyl group, 2-fluoro-n-octyl group, 3-fluoro-n-octyl group, 6-fluoro-n
-Octyl group, 4-fluoro-n-nonyl group, 7-fluoro-n-nonyl group, 3-fluoro-n-decyl group, 6
-Fluoro-n-decyl group, 4-fluoro-n-dodecyl group, 8-fluoro-n-dodecyl group, 5-fluoro-
n-tetradecyl group, 9-fluoro-n-tetradecyl group,

2-chloroethyl group, 3-chloro-n-propyl group, 2-chloro-n-butyl group, 4-chloro-n
-Butyl group, 2-chloro-n-pentyl group, 5-chloro-n-pentyl group, 5-chloro-n-hexyl group, 4-
Chloro-n-heptyl, 6-chloro-n-octyl, 7-chloro-n-nonyl, 3-chloro-n-decyl, 8-chloro-n-dodecyl, trifluoromethyl, perfluoro Ethyl group, perfluoro-n-propyl group, perfluoro-n-butyl group, perfluoro-
n-pentyl group, perfluoro-n-hexyl group, perfluoro-n-heptyl group, perfluoro-n-octyl group, perfluoro-n-nonyl group, perfluoro-n
-Decyl group, perfluoro-n-undecyl group, perfluoro-n-dodecyl group, perfluoro-n-tetradecyl group, 1-hydroperfluoroethyl group, 1-hydroperfluoro-n-propyl group, 1-hydro Perfluoro-n-butyl group, 1-hydroperfluoro-n-pentyl group, 1-hydroperfluoro-n-hexyl group, 1
-Hydroperfluoro-n-heptyl group, 1-hydroperfluoro-n-octyl group, 1-hydroperfluoro-n-nonyl group, 1-hydroperfluoro-n-decyl group, 1-hydroperfluoro-n -Undecyl group, 1-
Hydroperfluoro-n-dodecyl group, 1-hydroperfluoro-n-tetradecyl group,

1,1-dihydroperfluoroethyl group,
1,1-dihydroperfluoro-n-propyl group, 1,
1-dihydroperfluoro-n-butyl group, 1,1-dihydroperfluoro-n-pentyl group, 1,1-dihydroperfluoro-n-hexyl group, 1,1-dihydroperfluoro-n-heptyl group, 1,1-dihydroperfluoro-n-octyl group, 1,1-dihydroperfluoro-n-nonyl group, 1,1-dihydroperfluoro-n
-Decyl group, 1,1-dihydroperfluoro-n-undecyl group, 1,1-dihydroperfluoro-n-dodecyl group, 1,1-dihydroperfluoro-n-tetradecyl group, 1,1-dihydroperfluoro -N-pentadecyl group, 1,1-dihydroperfluoro-n-hexadecyl group, 1,1,2-trihydroperfluoroethyl group,
1,1,3-trihydroperfluoro-n-propyl group, 1,1,3-trihydroperfluoro-n-butyl group, 1,1,4-trihydroperfluoro-n-butyl group, 1,4-trihydroperfluoro-n-pentyl group, 1,1,5-trihydroperfluoro-n-pentyl group, 1,1,3-trihydroperfluoro-n-hexyl group, 1,1, 6-trihydroperfluoro-n-
Hexyl group, 1,1,5-trihydroperfluoro-n
-Heptyl group, 1,1,7-trihydroperfluoro-
n-heptyl group, 1,1,8-trihydroperfluoro-n-octyl group, 1,1,9-trihydroperfluoro-n-nonyl group, 1,1,11-trihydroperfluoro-n- Undecyl group,

2- (perfluoroethyl) ethyl group, 2
-(Perfluoro-n-propyl) ethyl group, 2- (perfluoro-n-butyl) ethyl group, 2- (perfluoro-n-pentyl) ethyl group, 2- (perfluoro-n
-Hexyl) ethyl group, 2- (perfluoro-n-heptyl) ethyl group, 2- (perfluoro-n-octyl)
Ethyl group, 2- (perfluoro-n-decyl) ethyl group, 2- (perfluoro-n-nonyl) ethyl group, 2-
(Perfluoro-n-dodecyl) ethyl group, 2-trifluoromethylpropyl group, 3- (perfluoro-n-propyl) propyl group, 3- (perfluoro-n-butyl) propyl group, 3- (perfluoro -N-hexyl)
Propyl group, 3- (perfluoro-n-heptyl) propyl group, 3- (perfluoro-n-octyl) propyl group, 3- (perfluoro-n-decyl) propyl group, 3
-(Perfluoro-n-dodecyl) propyl group, 4-
(Perfluoroethyl) butyl group, 4- (perfluoro-n-propyl) butyl group, 4- (perfluoro-n-
Butyl) butyl group, 4- (perfluoro-n-pentyl) butyl group, 4- (perfluoro-n-hexyl) butyl group, 4- (perfluoro-n-heptyl) butyl group, 4- (perfluoro-) n-octyl) butyl group, 4
-(Perfluoro-n-decyl) butyl group,

5- (perfluoro-n-propyl) pentyl group, 5- (perfluoro-n-butyl) pentyl group, 5- (perfluoro-n-pentyl) pentyl group,
5- (perfluoro-n-hexyl) pentyl group, 5-
(Perfluoro-n-heptyl) pentyl group, 5- (perfluoro-n-octyl) pentyl group, 6- (perfluoroethyl) hexyl group, 6- (perfluoro-n-
Propyl) hexyl group, 6- (perfluoro-n-butyl) hexyl group, 6- (perfluoro-n-hexyl)
Hexyl group, 6- (perfluoro-n-heptyl) hexyl group, 6- (perfluoro-n-octyl) hexyl group, 7- (perfluoroethyl) heptyl group, 7- (perfluoro-n-propyl) heptyl Group, 7- (perfluoro-n-butyl) heptyl group, 7- (perfluoro-n-pentyl) heptyl group and the like.
In the naphthalene compound represented by the general formula (1), A
Represents an aromatic or non-aromatic carbon allocyclic ring or heterocyclic ring which may have a substituent, and is preferably 6 kinds of aromatic or non-aromatic carbon Represents a prime or heterocycle.

[0018]

Embedded image In the formula, L ₁ and L ₂ represent a hydrogen atom, a halogen atom or a hydroxyl group, and the 1,4-cyclohexylene ring has a trans configuration. The naphthalene compound represented by the general formula (1) of the present invention has the following formulas (1-1) to (1) depending on the kind of A.
-6) It is roughly classified into six types of structures represented by (Chemical Formula 9).

[0019]

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R ₂ represents a linear or branched alkyl group having 1 to 24 carbon atoms, and preferably a linear or branched alkyl group having 4 to 18 carbon atoms. Specific examples of R ₂ include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group,
n-heptyl group, n-octyl group, n-nonyl group, n-
Decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n- Eicosyl group,
n-heneicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, 1-methylethyl group, 1,1
-Dimethylethyl group, 1-methylpropyl group, 1-methylbutyl group, 1-methylpentyl group, 1-methylhexyl group, 1-methylheptyl group, 1-methyloctyl group,
1-methylnonyl group, 1-methyldecyl group, 2-methylpropyl group, 2-methylbutyl group, 2-ethylbutyl group, 2-methylpentyl group, 2-methylhexyl group, 2
-Methylheptyl group, 2-ethylhexyl group, 2-methyloctyl group, 2-methylnonyl group, 2-methyldecyl group, 2,3-dimethylbutyl group, 2,3,3-trimethylbutyl group, 3-methylbutyl group, 3 -Methylpentyl group, 3-ethylpentyl group, 4-methylpentyl group, 4
-Ethylhexyl group, 2,3-dimethylpentyl group,
2,4-dimethylpentyl group, 2,4,4-trimethylpentyl group, 2,3,3,4-tetramethylpentyl group, 3-methylhexyl group, 2,5-dimethylhexyl group, 3-ethylhexyl group, Examples thereof include a 3,5,5-trimethylhexyl group, a 4-methylhexyl group, a 6-methylheptyl group, a 3,7-dimethyloctyl group and a 6-methyloctyl group. When R ₂ is an alkyl group having a branched chain, the alkyl group may have an asymmetric carbon, and the asymmetric carbon may be optically active,
It may be non-optically active.

In the naphthalene compound represented by the general formula (1), C * represents an asymmetric carbon, and the asymmetric carbon may be optically active or non-optically active. When C * is optically active, its absolute configuration may be the (S) configuration or the (R) configuration. C * is
Preferably, it is an optically active carbon in the (S) configuration or the (R) configuration. In the naphthalene compound represented by the general formula (1), X is —OCH ₂ — group or —OC (═O) —.
Represents a group. Y represents a bonding group selected from a single bond, an ether bond and an ester bond, and the ester bond is -O.
It means a C (= O)-group and a -C (= O) O- group.
Specific examples of the naphthalene compound of the present invention include, for example,
The compounds (chemical formula 10 to chemical formula 31) shown below can be mentioned. Incidentally, in the embodiment _{(-C m H 2m + 1 -n} ) represents a straight-chain alkyl group, m represents an integer of 1 to 24.

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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The naphthalene compound represented by the general formula (1) of the present invention can be produced, for example, from the hydroxynaphthalene compound represented by the general formula (2). The naphthalene compound represented by the general formula (1) and the hydroxynaphthalene compound represented by the general formula (2) of the present invention can be produced, for example, through the following steps. -Process for producing hydroxynaphthalene compound represented by the general formula (2) (Chemical Formula 32)

[0045]

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2- (6'-methoxy-represented by the formula (4)
2- (6'-hydroxy-2'-naphthyl) propion represented by the formula (5) by reacting 2'-naphthyl) propionic acid with hydrogen bromide, boron tribromide or the like to demethylate Produces an acid. Next, 2- (6'-hydroxy-2 '
-Naphthyl) propionic acid and an alcohol having a halogen atom represented by the general formula (6) in the presence of an acid catalyst (eg, p-toluenesulfonic acid, sulfuric acid, etc.) in a solvent such as toluene, xylene, etc. Can be azeotropically dehydrated to produce a hydroxynaphthalene compound represented by the general formula (2). In addition, 2- (6'-hydroxy-2'-
Protecting groups such as acetyl group, benzyl group, tetrahydropyranyl group are introduced into naphthyl) propionic acid in advance, and then carboxylic acid is converted to carboxylic acid chloride by chlorinating agents such as thionyl chloride and oxalyl chloride. Then, an alcohol having a halogen atom represented by the general formula (6) is allowed to act in the presence of a base (eg, pyridine, triethylamine, etc.), and then the protecting group is removed to give a compound represented by the general formula (2). The represented hydroxynaphthalene compounds can be prepared. -Process for producing naphthalene compound represented by the general formula (1) (Chemical Formula 33)

[0047]

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In the general formula (1), X is --OCH _2-.
The compound represented by the group includes a hydroxynaphthalene compound represented by the general formula (2) and a bromomethane derivative represented by the general formula (7) as a base (sodium hydride, potassium hydride, potassium carbonate, carbonic acid). It can be produced by reacting in the presence of sodium, potassium hydroxide, sodium hydroxide, etc.). In addition, the general formula (2)
And a hydroxymethane derivative represented by the general formula (8) with triphenylphosphine and diethylazodicarboxylic acid (DE
It can also be produced by reacting in the presence of AD).

In the general formula (1), X is -OC (=
The compound represented by the O)-group is obtained by combining the hydroxynaphthalene compound represented by the general formula (2) and the carboxylic acid halide represented by the general formula (9) with a base (organic base such as triethylamine or pyridine or , An inorganic base such as sodium carbonate or sodium hydroxide). In addition, the general formula (2)
A hydroxynaphthalene compound represented by
It can be produced by reacting the carboxylic acid derivative represented by 0) in the presence of dicyclohexylcarbodiimide (DCC) and a base catalyst (4-pyrrolidinopyridine, 4-dimethylaminopyridine, etc.).

The naphthalene compound of the present invention includes a naphthalene compound which exhibits liquid crystallinity by itself and a naphthalene compound which does not exhibit liquid crystallinity by itself. The naphthalene compound exhibiting liquid crystallinity includes a liquid crystal compound exhibiting a smectic C phase (hereinafter abbreviated as Sc phase), a naphthalene compound exhibiting a chiral smectic C phase (hereinafter abbreviated as Sc * phase), and a liquid crystal. There are naphthalene compounds that exhibit properties but not the Sc phase and Sc * phase. Each of these compounds can be effectively used as a component of a liquid crystal composition.

Next, the liquid crystal composition of the present invention will be described. The liquid crystal composition generally comprises two or more components,
The liquid crystal composition of the present invention contains at least one kind of the naphthalene compound of the present invention as an essential component. Examples of the naphthalene compound of the present invention used in the liquid crystal composition of the present invention include a naphthalene compound that does not exhibit liquid crystallinity, a naphthalene compound that exhibits an Sc phase, a naphthalene compound that exhibits an Sc * phase, and a Sc phase and Sc that exhibit liquid crystallinity. * A naphthalene compound showing no phase, preferably a naphthalene compound showing a Sc phase or a naphthalene compound showing a Sc * phase.

The liquid crystal composition of the present invention is preferably a liquid crystal composition showing a phase of chiral smectic C, F, G, H, I or the like, and more preferably a liquid crystal composition showing a Sc * phase. is there. The liquid crystal composition exhibiting an Sc * phase of the present invention includes a naphthalene compound of the present invention, a liquid crystal compound exhibiting an Sc * phase other than the naphthalene compound of the present invention, a liquid crystal compound exhibiting an Sc phase other than the naphthalene compound of the present invention, and optical activity It is a composition prepared by combining a plurality of compounds selected from the compounds, and contains at least one naphthalene compound of the present invention.

The liquid crystal compound showing the Sc * phase other than the naphthalene compound of the present invention is not particularly limited, but for example, an optically active phenylbenzoate liquid crystal compound, an optically active biphenylbenzoate liquid crystal compound,
Optically active naphthalene-based liquid crystal compound, optically active phenylnaphthalene-based liquid crystal compound, optically active tolan-based liquid crystal compound,
Examples thereof include optically active phenylpyrimidine liquid crystal compounds and optically active naphthylpyrimidine liquid crystal compounds.
The liquid crystal compound exhibiting the Sc phase other than the naphthalene compound of the present invention is not particularly limited, but, for example,
Examples thereof include a phenylbenzoate liquid crystal compound, a biphenylbenzoate liquid crystal compound, a naphthalene liquid crystal compound, a phenylnaphthalene liquid crystal compound, a tolan liquid crystal compound, a phenylpyrimidine liquid crystal compound, and a naphthylpyrimidine liquid crystal compound. The optically active compound refers to a compound which does not exhibit liquid crystallinity by itself but has the ability to develop the Sc * phase when mixed with a liquid crystal compound exhibiting the Sc phase or a liquid crystal composition exhibiting the Sc phase. Although the optically active compound is not particularly limited, for example, an optically active phenylbenzoate-based non-liquid crystal compound, an optically active biphenylbenzoate-based non-liquid crystal compound, an optically active naphthalene-based non-liquid crystal compound, an optically active phenylnaphthalene-based non-liquid crystal compound. Examples thereof include liquid crystal compounds, optically active phenylpyrimidine-based non-liquid crystal compounds, and optically active tolan-based non-liquid crystal compounds.

In the liquid crystal composition of the present invention, in addition to the above-mentioned components, smectic and nematic liquid crystal compounds which do not show an Sc phase as an optional component, compounds which do not show liquid crystallinity other than the naphthalene compound of the present invention (for example, , Anthraquinone dye, azo dye, and other dichroic dyes, and conductivity-imparting agents, life-improving agents, and the like). The content of the naphthalene compound of the present invention in the liquid crystal composition of the present invention is not particularly limited, but is usually 5 to 99% by weight.

In the liquid crystal composition of the present invention, the liquid crystal composition exhibiting chiral smectic C, F, G, H and I phases is a liquid crystal composition exhibiting ferroelectricity. A liquid crystal composition exhibiting ferroelectricity causes a switching phenomenon when a voltage is applied, and a liquid crystal display element having a high response speed can be manufactured by utilizing this phenomenon [see, for example, JP-A-56-107216 and JP-A-SHO-216216]. 59-118744, Applied Phys. Lett., 36, 899.
(1980)} etc.].

Next, the liquid crystal element of the present invention will be described. The liquid crystal element of the present invention comprises the liquid crystal composition of the present invention arranged between a pair of electrode substrates. FIG. 1 is a schematic cross-sectional view showing an example of a liquid crystal element having a chiral smectic phase for explaining the configuration of a liquid crystal element utilizing ferroelectricity. In the liquid crystal element, a liquid crystal layer 1 exhibiting a chiral smectic phase is arranged between a pair of glass substrates 2 each provided with a transparent electrode 3 and an insulating alignment control layer 4, and the layer thickness is set by a spacer 5. In addition, the pair of transparent electrodes 3 is connected via a lead wire 6 so that a voltage can be applied from a power source 7. Further, the pair of glass substrates 2 is sandwiched by the pair of polarizing plates 8 arranged in the crossed Nicols state, and the light source 9 is arranged on the outer side of one side thereof. As the transparent electrode 3 provided on the two glass substrates 2, for example,
Examples of the transparent electrode include a thin film of In ₂ O ₃ , SnO ₂ or ITO (Indium Tin Oxide).

The insulating orientation control layer 4 is for rubbing a thin film of a polymer such as polyimide with gauze or acetate flocking cloth to orient the liquid crystal. Examples of the material of the insulating orientation control layer 4 include silicon nitride, silicon nitride containing hydrogen, silicon carbide, silicon carbide containing hydrogen, silicon oxide, boron nitride, boron nitride containing hydrogen. Insulating layer of inorganic material such as cerium oxide, aluminum oxide, zirconium oxide, titanium oxide and magnesium fluoride, polyvinyl alcohol, polyimide, polyamideimide, polyesterimide, polyparaxylene, polyester, polycarbonate, polyvinyl acetal, poly Examples of the organic insulating layer include vinyl chloride, polyvinyl acetate, polyamide, polystyrene, cellulose resin, melamine resin, urea resin and acrylic resin.

The insulating orientation control layer 4 may be an insulating orientation control layer having a two-layer structure in which an organic insulating layer is formed on an inorganic insulating layer, and the insulating orientation controlling layer 4 is composed of only an inorganic insulating layer or an organic insulating layer. It may be an orientation control layer. When the insulating orientation control layer is an inorganic insulating layer, it can be formed by an evaporation method or the like. In the case of an organic insulating layer, its precursor solution is applied by a spinner coating method, a permeation coating method, a screen printing method, a spray coating method, a roll coating method, or the like under predetermined curing conditions (for example, under heating). ) And can be formed by curing. The layer thickness of the insulating orientation control layer 4 is usually 1
0 angstrom to 1 μm, preferably 10 to 30
00 angstrom, more preferably 10 to 10
00 angstroms.

The two glass substrates 2 are held by the spacer 5 at arbitrary intervals. For example, silica beads or alumina beads having a predetermined diameter are sandwiched between the glass substrates 2 as spacers, and the periphery of the two glass substrates 2 is sealed with a sealing material (for example, an epoxy adhesive). Can be kept at intervals. Further, a polymer film or glass fiber may be used as the spacer. Liquid crystal exhibiting a chiral smectic phase is sealed between the two glass substrates. The thickness of the liquid crystal layer 1 is generally set to 0.5 to 20 μm, preferably 1 to 5 μm. The transparent electrode 3 is connected to an external power source 7 by a lead wire. Further, on the outside of the glass substrate 2, a pair of polarizing plates 8 whose polarization axes are, for example, in a crossed Nicol state are arranged. The example of FIG. 1 is a transmissive type, and includes a light source 9.

The display system of the liquid crystal device using the liquid crystal composition of the present invention is not particularly limited,
For example, (a) helical distortion type, (b) SSFLC (Surface Stabilized Ferroelectric Liquid Crystal) type, (c) TSM (Transient Scattering Mode) type, (d) GH ( A guest-host type display scheme can be used.
Further, the naphthalene compound of the present invention and a liquid crystal composition containing the compound can be used in fields other than display liquid crystal devices (for example, nonlinear optical functional devices, electronic materials such as capacitor materials, limiters, memories, amplifiers, modulators). It can be applied to electronic devices such as, heat, light, pressure, mechanical deformation and the like and voltage and voltage conversion devices and sensors, and power generation devices such as thermoelectric power generation devices.

[0061]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples. The symbols I, Ch, SA, Sc in the examples are
*, Sx and C have the following meanings. I: isotropic liquid Ch: cholesteric phase SA: smectic A phase Sc *: chiral smectic C phase Sx: unidentified smectic phase C: crystalline phase

Production Example 1: [Production of (S) -2- (6'-hydroxy-2'-naphthyl) propionic acid] (S) -2- (6'-methoxy-2'-naphthyl) propionic acid 20 g Was dissolved in 250 ml of acetic acid, 100 ml of 48 wt% hydrobromic acid was added to this solution, and the mixture was heated under reflux for 20 hours. Then, it was cooled to room temperature, discharged into 450 ml of water, and 150 g of sodium chloride was further added. The precipitate is filtered off, washed with water and dried to give (S) -2- (6'-hydroxy-2 '
17 g of naphthyl) propionic acid were obtained.

Production Example 2: [(S)-(2-Perfluoro-n-octylethyl) -2 '-(6 "-hydroxy-2"-
Production of Naphthyl) propionate] 2.0 g of (S) -2- (6′-hydroxy-2′-naphthyl) propionic acid obtained in Production Example 1 and 2-perfluoro-n
-Octylethanol 5.58 g, p-toluenesulfonic acid 30 mg and toluene 30 ml were charged into a flask equipped with a water separator, while removing water produced as a by-product, 1
The mixture was refluxed for 9 hours. Toluene was distilled off, and (S)-(2
4.7 g of -perfluoro-n-octylethyl) -2 '-(6 "-hydroxy-2" -naphthyl) propionate were obtained (melting point: 116-119 ° C).

Production Example 3: Production of ((S)-[3- (perfluoro-n-octyl) propyl] -2 '-(6 "-hydroxy-2" -naphthyl) propionate] In Production Example 2, 2 Instead of using perfluoro-n-octylethanol, 3-perfluoro-n-
(S)-[3- (Perfluoro-n-octyl) propyl] -2 '-(6 "-hydroxy-2"-was prepared according to the method described in Preparation Example 2 except that 5.75 g of octyl propanol was used. 5.7 g of naphthyl) propionate were obtained (melting point: 120-121 ° C).

Example 1: [In Example Compound 47, m
Of the compound in which is 12] (S)-[3- (perfluoro-n-octyl) propyl] -2 '-(6 "-hydroxy-2" -naphthyl) propionate 677 mg, 4-n-dodecyloxybenzoic acid Acid 3
06 mg, dicyclohexylcarbodiimide 206 mg
And 4-pyrrolidinopyridine (20 mg) were dissolved in 6 ml of chloroform, and the mixture was stirred at room temperature for 12 hours. Next, chloroform was distilled off to obtain a colorless solid. The obtained solid was separated and purified by silica gel column chromatography (eluent: toluene), and recrystallized twice from methanol to obtain 634 mg of a compound of Exemplified Compound 47 in which m was 12 as colorless crystals. _{^{· 1 H-NMR (CDCl 3}} ; ppm) δ = 0.8~2.4 (m, 30H), 3.90 (q, 1
H), 4.10 (t, 2H), 4.21 (t, 2H),
7.1-8.4 (m, 10H) The phase transition temperature of this compound became an isotropic liquid (I) at 83 ° C. during the temperature raising process, and showed an SA phase at 83 ° C. during the temperature lowering process.

Example 2: [Preparation of Compound in which m is 14 in Exemplified Compound 47] Instead of using 4-n-dodecyloxybenzoic acid in Example 1, 320 mg of 4-n-tetradecyloxybenzoic acid was used. By following the procedure described in Example 1 except that was used, 692 mg of compound 47 in which m was 14 was obtained. _{^{· 1 H-NMR (CDCl 3}} ; ppm) δ = 0.8~2.4 (m, 34H), 3.92 (q, 1
H), 4.11 (t, 2H), 4.21 (t, 2H),
7.1 to 8.4 (m, 10H) The phase transition temperature of this compound became an isotropic liquid (I) at 90 ° C during the temperature raising process, and showed an SA phase at 80 ° C during the temperature lowering process.

Example 3: [Preparation of Compound in which m is 12 in Exemplified Compound 54] In Example 1, (S)-[3- (perfluoro-n
-Octyl) propyl] -2 '-(6 "-hydroxy-2"-
Instead of using naphthyl) propionate (S)
-(2-Perfluoro-n-octylethyl) -2'-
(6 "-hydroxy-2" -naphthyl) propionate 66
A compound 62 in which m is 12 in the exemplified compound 54 according to the procedure described in Example 1 except that 3 mg is used.
2 mg were obtained. _{^{· 1 H-NMR (CDCl 3}} ; ppm) δ = 0.8~2.4 (m, 28H), 3.90 (q, 1
H), 4.08 (bt, 2H), 4.20 (t, 2)
H), 7.1-8.4 (m, 10H) The phase transition temperature of this compound is shown below.

Example 4 [Production of Compound in which m is 12 in Exemplified Compound 71] (S)-[3- (Perfluoro-n-octyl) propyl] -2 '-(6 "-hydroxy-2" -Naphthyl) propionate 677 mg, 3-fluoro-4-n-dodecyloxybenzoic acid 323 mg, dicyclohexylcarbodiimide 206 mg and 4-pyrrolidinopyridine 20 mg.
Was dissolved in 6 ml of chloroform and stirred at room temperature for 12 hours. Next, chloroform was distilled off to obtain a colorless solid. The obtained solid was separated and purified by silica gel column chromatography (eluent: toluene), and recrystallized twice from methanol.
609 mg of a compound in which m was 12 was obtained as colorless crystals. _{^{· 1 H-NMR (CDCl 3}} ; ppm) δ = 0.8~2.4 (m, 30H), 3.90 (q, 1
H), 4.10 (t, 2H), 4.20 (t, 2H),
7.1 to 8.4 (m, 9H) The phase transition temperatures of this compound are shown below.

Example 5: [Preparation of Compound in which m is 12 in Exemplified Compound 76] In Example 4, (S)-[3- (perfluoro-n
-Octyl) propyl] -2 '-(6 "-hydroxy-2"-
Instead of using naphthyl) propionate (S)
-(2-Perfluoro-n-octylethyl) -2'-
(6 "-hydroxy-2" -naphthyl) propionate 66
Compound 58 in which m is 12 in Exemplified Compound 76 according to the procedure described in Example 4 except that 3 mg is used.
7 mg were obtained. _{^{· 1 H-NMR (CDCl 3}} ; ppm) δ = 0.8~2.4 (m, 28H), 3.90 (q, 1
H), 4.10 (t, 2H), 4.20 (t, 2H),
7.1 to 8.4 (m, 9H) The phase transition temperature of this compound became an isotropic liquid (I) at 90 ° C during the temperature raising process, and showed an SA phase at 80 ° C during the temperature lowering process.

Example 6: [m in Exemplified Compound 109]
Production of a compound wherein 9 is 9] Example 1 is repeated except that 324 mg of 4- (4′-n-nonyl) biphenylcarboxylic acid is used instead of using 4-n-dodecyloxybenzoic acid. According to the operation described in (3), 663 mg of the compound in which m is 9 in the exemplified compound 109 was obtained. _{^{· 1 H-NMR (CDCl 3}} ; ppm) δ = 0.8~2.1 (m, 24H), 2.72 (t, 2
H), 3.90 (q, 1H), 4.20 (t, 2H),
7.2-8.5 (m, 14H) The phase transition temperature (° C) of this compound is shown below. The numbers in parentheses indicate the phase transition temperature during the temperature decreasing process.

Example 7: [m in Exemplified Compound 110]
Of the compound wherein 8 is 8] In Example 1, except that 326 mg of 4- (4′-n-octyloxy) biphenylcarboxylic acid was used instead of using 4-n-dodecyloxybenzoic acid. In the exemplary compound 110, m
663 mg of the compound having a _{^{· 1 H-NMR (CDCl 3}} ; ppm) δ = 0.8~2.4 (m, 22H), 3.8~4.3
(M, 5H), 6.9 to 8.5 (m, 14H) The phase transition temperature (° C) of this compound is shown below.

Example 8: [m in Exemplified Compound 111]
Production of Compound in which is 8] In Example 1, (S)-[3- (perfluoro-n
-Octyl) propyl] -2 '-(6 "-hydroxy-2"-
Instead of using naphthyl) propionate and 4-n-dodecyloxybenzoic acid, (S)-(2-perfluoro-n-octylethyl) -2 '-(6 "-hydroxy-2" -naphthyl) propionate 663 mg And 4-
(4'-n-octyloxy) biphenylcarboxylic acid 3
A compound 62 in which m is 8 in the exemplified compound 111 according to the procedure described in Example 1 except that 26 mg is used.
5 mg were obtained. _{^{· 1 H-NMR (CDCl 3}} ; ppm) δ = 0.8~2.4 (m, 20H), 3.8~4.3
(M, 5H), 6.9 to 8.5 (m, 14H) The phase transition temperature (° C) of this compound is shown below.

Example 9: [m in Exemplified Compound 136]
Of the compound in which 12 is 12] Example 1 was repeated except that 328 mg of 2- (6-n-dodecyloxy) naphthalenecarboxylic acid was used instead of using 4-n-dodecyloxybenzoic acid. In the exemplary compound 136, m
765 mg of the compound of which 12 is obtained. _{^{· 1 H-NMR (CDCl 3}} ; ppm) δ = 0.8~2.3 (m, 23H), 3.90 (q, 1
H), 4.10 (t, 2H), 4.20 (t, 2H),
7.1-8.8 (m, 12H) The phase transition temperature (° C) of this compound is shown below.

Example 10: [Preparation of Compound in which m is 10 in Exemplified Compound 194] Instead of using 4-n-dodecyloxybenzoic acid in Example 1, 6-n-decyloxynicotinic acid 2 was used.
Compound 5 in which m is 10 in Exemplified Compound 194 according to the procedure described in Example 1 except that 63 mg was used.
69 mg were obtained. _{^{· 1 H-NMR (CDCl 3}} ; ppm) δ = 0.8~2.3 (m, 23H), 3.8~4.4
(M, 5H), 6.60 (d, 1H), 7.2 to 8.5
(M, 8H) The melting point of this compound was 89 ° C.

Example 11: [Preparation of Compound in which m is 5 in Exemplified Compound 223] In place of using 4-n-dodecyloxybenzoic acid in Example 1, 198 mg of 4-n-pentylcyclohexanecarboxylic acid was used. According to the procedure described in Example 1 except that the compound was used, 588 mg of the compound 223 in which m was 5 was obtained. _{^{· 1 H-NMR (CDCl 3}} ; ppm) δ = 0.8~2.5 (m, 29H), 3.90 (q, 1
H), 4.14 (t, 2H), 7.1 to 7.9 (m, 6)
H) The melting point of this compound was 103 ° C.

Example 12: [Preparation of Liquid Crystal Composition] The following compound group (Chemical Formula 34) was mixed in the following proportions and heated and melted at 100 ° C. to give a liquid crystal composition (ferroelectric liquid crystal composition). ) Was prepared.

[0077]

Embedded image The phase transition temperature (° C.) of this liquid crystal composition is shown below.

Example 13: [Production of liquid crystal element] Two 0.7 mm thick glass plates were provided with transparent electrodes and an insulating alignment control layer made of polyimide, and alumina beads having an average particle size of 2 μm were used for one glass. After spraying on the plate, a glass plate was attached using a sealant to fabricate the cell shown in (FIG. 1). The liquid crystal composition prepared in Example 12 was injected into this cell to prepare a liquid crystal element. When this liquid crystal element was sandwiched between two polarizing plates arranged in a crossed Nicols state and a voltage was applied, a clear switching phenomenon was observed.

[0079]

According to the present invention, it is possible to provide a naphthalene compound which is useful as a constituent component of a liquid crystal composition.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of an example of a liquid crystal element using a liquid crystal exhibiting a chiral smectic phase.

[Explanation of symbols]

 1: Liquid crystal layer having chiral smectic phase 2: Glass substrate 3: Transparent electrode 4: Insulating orientation control layer 5: Spacer 6: Lead wire 7: Power supply 8: Polarizing plate 9: Light source Io: Incident light I: Transmitted light

Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display area C07C 69/773 C07C 69/773 69/82 69/82 A 69/86 69/86 69/92 69/92 69 / 94 69/94 C07D 213/30 C07D 213/30 213/64 213/64 213/65 213/65 213/80 213/80 C09K 19/30 C09K 19/30 19/32 9279-4H 19/32 19 / 34 19/34 G02F 1/13 500 G02F 1/13 500 // C07M 7:00 (72) Inventor Tsutomu Ishida 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Hiroe Chishima 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Masakatsu Nakatsuka 1190, Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (6)

[Claims] 1. A naphthalene compound represented by the general formula (1). Embedded image [Wherein, R ₁ is a halogen atom-substituted C 1-2
4 represents a straight-chain alkyl group, R ₂ represents a straight-chain or branched-chain alkyl group having 1 to 24 carbon atoms, and A represents an aromatic or non-aromatic carbon group which may have a substituent. Represents a prime ring or a heterocycle, and X represents a -OCH ₂ -group or -OC
Represents a (= O)-group, Y represents a bonding group selected from a single bond, an ether bond and an ester bond, and C * represents an asymmetric carbon.] 2. An aromatic or non-aromatic carbocyclic or heterocyclic ring represented by A, which may have a substituent,
The naphthalene compound according to claim 1, which is selected from the following group (formula 2). Embedded image [In the formula, L ₁ and L ₂ represent a hydrogen atom, a halogen atom or a hydroxyl group, and the 1,4-cyclohexylene ring has a trans configuration] 3. The naphthalene compound according to claim 1, wherein the asymmetric carbon is optically active in the (S) configuration or the (R) configuration. 4. A hydroxynaphthalene compound represented by the general formula (2) (formula 3). Embedded image [Wherein, R ₁ is a halogen atom-substituted C 1-2
4 represents a straight-chain alkyl group] 5. A liquid crystal composition comprising at least one kind of the naphthalene compound according to any one of claims 1 to 3. 6. A liquid crystal display device comprising the liquid crystal composition according to claim 5.