JPH05255193A - Carboxylic acid ester compound, liquid crystal material, liquid crystal composition and liquid crystal element - Google Patents

Abstract

PURPOSE:To provide the subject compound consisting of a specific carboxylic acid ester compound having a tetrahydronaphthalene structure and useful for a liquid crystal element having broad working temperature range, high switching speed, extremely low power consumption and stable contrast. CONSTITUTION:The objective carboxylic acid ester compound expressed by formula I (R is 3-20C alkyl, etc.; X and Y are COO, OCO, etc.; A is phenylene, group of formula II, etc.; R* is 4-20C optically active group; B is phenylene, group of formula II etc.; (m) is 1 or 2; (n) is 0-2) and highly useful as a liquid crystal material can be produced by reacting 6-hydroxynaphthalene-2-carboxylic acid in tetrahydrofuran in the presence of palladium/carbon in an autoclave under hydrogen pressure at 105 deg.C for 3hr, reacting the resultant 5,6,7,8 tetrahydro-6-hydroxynaphthalene-2-carboxylic ac id with 4-hydroxybenzoic acid R-1'-trifluoromethylheptyl ester in the presence of a condensation agent and reacting the reaction product with 4-decyloxybenzoic acid.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel carboxylic acid ester compound, a liquid crystal material comprising this compound, a liquid crystal composition containing this compound and a liquid crystal device filled with a liquid crystal substance containing this compound.

[0002]

BACKGROUND OF THE INVENTION A display device using a liquid crystal compound which is widely used at present is usually driven by a TN (twist nematic) mode. However, in this method, it is necessary to change the position of the molecules of the liquid crystal compound in the device in order to change the displayed image, which requires a long driving time and is necessary for changing the molecular position of the liquid crystal compound. There is a problem that the voltage to be applied, that is, the power consumption also increases.

Unlike a switching element using a TN mode or STN mode, a switching element using a ferroelectric liquid crystal compound can function as a switching element simply by changing the orientation direction of the molecules of the liquid crystal compound. The switching time is greatly reduced. Furthermore, the spontaneous polarization (P
Since the value of Ps × E given by s) and the electric field strength (E) is the effective energy strength for changing the orientation direction of the molecules of the liquid crystal compound, the power consumption is also very small.
Since such a ferroelectric liquid crystal compound has two stable states depending on the direction of the applied electric field, that is, bistability, the switching threshold characteristic is very good, and it is used as a display device for moving images. It is particularly suitable for use.

[0004]

2. Description of the Related Art When such a ferroelectric liquid crystal compound or antiferroelectric liquid crystal compound is used in an optical switching device, the ferroelectric liquid crystal compound or antiferroelectric liquid crystal compound has an operating temperature range of Is required to be around room temperature or lower, the operating temperature range is wide, the switching speed is high (fast), and the switching threshold voltage is within an appropriate range. Of these, the operating temperature range is a particularly important characteristic when the ferroelectric liquid crystal compound or the antiferroelectric liquid crystal compound is put into practical use.

However, in the known ferroelectric liquid crystal compounds, for example, RB Meyer, et.al.,
"J.de.Phys., Vol. 36, l6
9, 1975 ”or Masaaki Taguchi, Takamasa Harada's paper“ Proceedings of the 11th Liquid Crystal Conference, 168 pages, 1985 ”, which generally have a narrow operating temperature range and a wide operating temperature range. Even liquid crystalline liquid crystal compounds have not been practically satisfied as ferroelectric liquid crystal compounds, such as in a high temperature range not including room temperature.

Further, the same tendency also applies to antiferroelectric liquid crystal compounds, and no antiferroelectric liquid crystal has been practically satisfactory.

[0007]

OBJECT OF THE INVENTION It is an object of the present invention to provide a novel carboxylic acid ester compound and a liquid crystal material comprising this compound. Another object of the present invention is to provide a liquid crystal composition containing this carboxylic acid ester compound and a liquid crystal device using this compound. More specifically, the present invention provides a novel carboxylic acid ester compound capable of forming a liquid crystal element having a wide operating temperature, a high switching speed, an extremely low power consumption, and a stable contrast, and a use thereof. The purpose is to

[0008]

SUMMARY OF THE INVENTION The carboxylic acid ester compound of the present invention is
It can be expressed by the following formula [I].

[0009]

[Chemical 13]

However, in the formula [I], R is selected from the group consisting of an alkyl group having 3 to 20 carbon atoms, an alkoxy group having 3 to 20 carbon atoms and a halogenated alkyl group having 3 to 20 carbon atoms. X and Y are each independently -COO-, -OCO-, -CH ₂ CH _2- , -CH _{2
O -, - OCH 2 -,} - SS -, - CO-CH 2 - and -CH ₂ -CO- represents a group or a single bond selected from the group consisting of, A is

[0011]

[Chemical 14]

B represents a group selected from the group consisting of

[0013]

[Chemical 15]

R represents a group selected from the group consisting of
^* Is an optically active group having at least one asymmetric carbon (asymmetric carbon) and having 4 to 20 carbon atoms (a hydrogen atom bonded to a carbon atom constituting the optically active group may be substituted with a halogen atom). ), M represents 1 or 2, n
Represents an integer of 0 to 2.

The liquid crystal material of the present invention has the above formula [I].
It is characterized by comprising a carboxylic acid ester compound represented by. Furthermore, the liquid crystal composition of the present invention is characterized by containing the carboxylic acid ester compound represented by the above formula [I]. Furthermore, the liquid crystal element of the present invention is a liquid crystal element including a cell composed of two substrates facing each other and a gap formed by the substrate, and a liquid crystal substance filled in the gap of the cell. The liquid crystal substance contains a carboxylic acid ester compound represented by the above formula [I].

The present invention provides a novel carboxylic acid ester compound. This carboxylic acid ester compound is highly useful as a liquid crystal material. Accordingly, the liquid crystal composition containing the compound and the liquid crystal element in which the liquid crystal material composed of the carboxylic acid ester compound is filled between the two substrates have excellent liquid crystal properties. By using such a carboxylic acid ester compound of the present invention as a liquid crystal material, various kinds of excellent characteristics such as wide operating temperature range, high switching speed, extremely low power consumption, and stable contrast can be obtained. You can get the device.

[0017]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be specifically described below. First, the carboxylic acid ester compound and the liquid crystal material of the present invention will be described. The carboxylic acid ester compound of the present invention can be represented by the following formula [I].

[0018]

[Chemical 16]

However, in the above formula [I], R is a group consisting of an alkyl group having 3 to 20 carbon atoms, an alkoxy group having 3 to 20 carbon atoms and a halogenated alkyl group having 3 to 20 carbon atoms. It is one kind of group selected. In the above formula [I], when R is an alkyl group having 3 to 20 carbon atoms, it may be in any form of straight chain, branched chain and alicyclic, but especially R is straight chain. The carboxylic acid ester compound, which is a linear alkyl group, exhibits an excellent liquid crystallinity because it has a rigid structure in which the molecule extends straight. Specific examples of such a linear alkyl group include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group and octadecyl group. it can.

When R is an alkoxy group having 3 to 20 carbon atoms, there can be mentioned the alkoxy groups having an alkyl group as described above. Specific examples of such an alkoxy group include hexoxy group, heptoxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, tetradecyloxy group, heptadecyloxy group, hexadecyl group. An oxy group and an octadecyloxy group can be mentioned.

Further, when R is a halogenated alkyl group having 3 to 20 carbon atoms, at least a part of hydrogen atoms of the above alkyl group is F, Cl, Br and I.
And a group substituted with a halogen atom such as. Among the compounds having R as described above, the compound having an alkoxy group exhibits particularly excellent liquid crystallinity.

Further, in the formula [I], X and Y
Are each independently -COO-, -OCO-, -CH ₂ CH _2- , -CH ₂ O
_{-, - OCH 2 -, -} SS -, - CO-CH 2 - and represents a group or a single bond selected from -CH ₂ -CO- the group consisting of. Of these, when the carboxylic acid ester compound of the present invention is used as a liquid crystal material, X and Y are independently -COO-, -OCO
It is preferably a group or a single bond selected from the group consisting of —, —CH ₂ CH ₂ —, —CH ₂ O—, and —OCH ₂ —. Furthermore, among these, X and Y are independently -COO.
It is preferably either-, -OCO- or a single bond. Considering the linearity of the molecule, among X and Y,
It is preferable that at least either one, preferably both, is —COO—.

In the formula [I], A is

[0024]

[Chemical 17]

Represents a group selected from the group consisting of: Further, in the formula [I], B is

[0026]

[Chemical 18]

Represents a group selected from the group consisting of: Also,
In the formula [I], R ^* represents an optically active group having at least one asymmetric carbon atom and having 4 to 20 carbon atoms. further,
The hydrogen atom bonded to the carbon atom constituting the optically active group may be substituted with a halogen atom such as F, Cl, Br or I.

Particularly, in the above formula [I], R ^* is preferably a group represented by the following formula [II]. ^{-Q 1 -C * H (Q 2} ) -Q 3 ··· [II] However, in the formula [II], Q ¹ is, - (CH _{2) q} - represents a.
Here, q is an integer of 0 to 6. Also, Q ² and Q
³ is each independently an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group or a halogen atom, and Q ² and Q ³ are different from each other. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. it can. In addition, examples of the fluoroalkyl group having 1 to 10 carbon atoms include groups in which at least a part of hydrogen atoms bonded to carbon atoms of the above-described alkyl group are substituted with fluorine atoms. Further, examples of the halogen atom include F, Cl, Br or I. However, Q ² and Q ³ are always different groups or atoms from each other, and they are not the same. Further, when one of Q ² and Q ³ is a halogen atom, the other is usually either an alkyl group or a fluoroalkyl group.

Q ¹ , Q ² and Q ³ in the above formula [II]
Has a CH ₂ group (-CH ₂ -structure) or a CF ₂ group (-CF
_At least some of these are -O
-, -S-, -CO-, -CHX-; (X is a halogen atom), -CHCN-, -O-
It may be substituted with at least one group selected from the group consisting of CO-, -O-COO-, -CO-O- and -CH = CH-.
However, in this case, these groups are introduced so that the heteroatoms (N, O, etc.) forming these groups are not directly bonded. Therefore, by substituting these groups,
No new bond such as -OO- or -NO- can be formed.

Further, among these, R ^* is -C ^* H (CF
₃ ) -C ₆ H ₁₃ , -C ^* H (CH ₃ ) -C ₆ H ₁₃ , -C ^* H (CH ₃ ) -C ₅ H ₁₁ , -C ^* H (C
₂ H ₅ ) -C ₅ H ₁₁ , -C ^* H (C ₂ H ₅ ) -C ₆ H ₁₃ , -CH ₂ -C ^* H (CH ₃ ) -C ₂ H ₅ ,
^{_{- (CH 2) 3 -C *}} H (CH 3) -C 2 H 5 and _{^{-C * H (CF 3) -CH}} 2 -COO-C 2 H 5
It is preferably a group selected from the group consisting of That is, R ^* is an optically active group having at least one asymmetric carbon. The carbon atom bonded to the carbon atom constituting the optically active group may have a halogen atom such as a fluorine atom as described above.

Of these groups, any one of the following groups is preferable in consideration of the characteristics when the carboxylic acid ester compound of the present invention is used as a liquid crystal material. _{^{-C * H (CF 3) -C}} 6 H 13 -C * H (CH 3) -C 6 H 13 Further, in the equation [I], m represents 1 or 2, n
Represents an integer of 0 to 2. In particular, when this carboxylic acid ester compound is used as a liquid crystal material, n is 0
Alternatively, it is preferably 1.

Further, in the above formula [I], the 5,6,7,8-tetrahydronaphthyl group constituting the main skeleton has 5,6,7,
8-tetrahydro-1,5-naphthyl group, 5,6,7,8-tetrahydro-1,6-naphthyl group, 5,6,7,8-tetrahydro-2,6-naphthyl group and 5,6,7 There is a 8,8-tetrahydro-1,7-naphthyl group. In particular, when the carboxylic acid ester compound of the present invention is used as a liquid crystal material, it is preferable that the whole molecule be linear, and therefore, as the 5,6,7,8-tetrahydronaphthyl group, 5,6,7 The 8,8-tetrahydro-2,6-naphthyl group is particularly preferred.

Therefore, specific examples of the carboxylic acid ester compound represented by the above formula [I] include the compounds shown in the following Table 1-1 to Table 1-7. In addition,
In the table below, R, R ^* , X, Y, m, n
The bonding states of the tetrahydronaphthyl group represent the respective states in the following formula [I].

[0034]

[Chemical 19]

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

[Table 4]

[0039]

[Table 5]

[0040]

[Table 6]

[0041]

[Table 7]

The carboxylic acid ester compound as described above can be produced by combining known synthetic techniques. For example, the above carboxylic acid ester compound can be synthesized according to the synthetic route shown below.

[0043]

[Chemical 20]

That is, by adding 6-hydroxynaphthalene-2-carboxylic acid to a solvent such as tetrohydrofuran and reducing it with hydrogen gas under high pressure in the presence of a reducing catalyst such as palladium / carbon, 6,7,8-Tetrahydro-6-hydroxynaphthalene-2-carboxylic acid is obtained. Then 4
-N, N-dimethylaminopyridine, using methylene chloride as a solvent, while adding N, N'-dicyclohexylcarbodiimide solution dropwise, an ester compound obtained from hydroxybenzoic acid and an alcohol having an asymmetric carbon, and obtained in the above step 4-by reacting the resulting 5,6,7,8-tetrahydro-6-hydroxynaphthalene-2-carboxylic acid
(5 ', 6', 7 ', 8'-Tetrahydro-6'-hydroxy-2'-naphthoyloxy) benzoic acid ester is obtained.

Furthermore, using 4-N, N-dimethylaminopyridine and methylene chloride as a solvent, 4-N-N-dicyclohexylcarbodiimide solution was added dropwise while separately synthesizing 4-alkoxybenzoic acid and the above-mentioned step. 4- (5 ', 6', 7 ', 8'-tetrahydro-6'-hydroxy-2'-obtained in
The carboxylic acid ester of the present invention can be obtained by reacting a naphthoyloxy) benzoic acid ester.

The above method is an example of the method for producing the carboxylic acid ester compound of the present invention, and the carboxylic acid ester compound of the present invention is not limited by this production method. For example, among the carboxylic acid ester compounds of the present invention produced by the above method, 4- [6 ′-(4 ″ -decyloxybenzoyloxy) -5 ′, represented by the following formula,
6 ', 7', 8'-Tetrahydro-2'-naphthoyloxy] benzoic acid
FIG. 1 shows the ¹ H-NMR chart of R-1 ″ ′-trifluoromethylheptyl ester [Exemplified compound (4)].

In the following equation, "(e)" is equatorial,
"(A)" indicates the axial conformation.

[0048]

[Chemical 21]

In the above formula, the numbers 1 to 14 represent hydrogen atoms, and these numbers correspond to the numbers given to the peaks in FIG. Furthermore, 6- [6 '-(4 "
-Decyloxybenzoyloxy) -5 ', 6', 7 ', 8'-tetrahydro-2'-naphthoyloxy] -1,2,3,4-tetrahydronaphthalene-2-carboxylic acid R-1 "'- FIG. 2 shows a ¹ H-NMR chart of trifluoromethylheptyl ester [Exemplified Compound (21)].

[0050]

[Chemical formula 22]

In the above formula, the numbers 1 to 14 are hydrogen.
Indicates an atom, which is the number assigned to the peak in Figure 2.
It corresponds to the issue. In addition, 6- [6 '-(4 "-
Decyloxybenzoyloxy) -5 ', 6', 7 ', 8'-tetrahi
Doro-2'-naphthoyloxy] -5,6,7,8-tetrahydronaphth
Thallen-2-carboxylic acid R-1 "'-trifluoromethylhepti
Of luster [Exemplified Compound (22)] ¹H-NMR
The chart is shown in FIG.

[0052]

[Chemical formula 23]

In the above formula, the numbers 1 to 12 represent hydrogen atoms, and these numbers correspond to the numbers given to the peaks in FIG. Furthermore, 6- [4 "-represented by the following equation
(5'-decyl-2'-pyrimidinyl) benzoyloxy] -5,6,
7,8-Tetrahydronaphthalene-2-carboxylic acid R-1 "'-trifluoromethylheptyl ester [Exemplified compound (13
The ¹ H-NMR chart of 0)] shown in FIG.

[0054]

[Chemical formula 24]

In the above formula, the numbers 1 to 16 represent hydrogen atoms, and these numbers correspond to the numbers given to the peaks in FIG. Formula [I] obtained as described above
The carboxylic acid ester compound represented by can be suitably used as a liquid crystal material. In particular, the carboxylic acid ester compound of the present invention having optical activity can be used as a ferroelectric liquid crystal compound or an antiferroelectric liquid crystal compound.

Among such carboxylic acid ester compounds, the following formulas [4], [21], [22] and [1]
The compound represented by [30] exhibits particularly excellent liquid crystal properties.

[0057]

[Chemical 25]

Table 2 shows the phase transition temperatures of the compounds represented by the formulas [4], [21], [22] and [130], which are particularly excellent as liquid crystal materials. In Table 2 below, Cry represents a crystalline phase and Sm
X is an unidentified smectic phase, Sm C _A ^* is an antiferroelectric phase, Sm A is a smectic A phase, and Iso
Represents an isotropic liquid.

[0059]

[Table 8]

In the liquid crystal material of the present invention, as shown in Table 2, many compounds exhibit a smectic phase in a wide temperature range. Conventionally, almost no liquid crystal material is known that exhibits a smectic phase in a wide temperature range when the liquid crystal compound is used alone. The liquid crystal material of the present invention has a wide temperature range showing a smectic phase, and the optical switching device manufactured using such a liquid crystal material is also excellent in high-speed response.

The liquid crystal material of the present invention can be used alone, or can be mixed with other liquid crystal materials and used as a liquid crystal composition. For example, the liquid crystal material of the present invention can be used as a base material of an antiferroelectric liquid crystal composition or an auxiliary agent of a liquid crystal composition containing a compound exhibiting a smectic phase as a base material. That is, among the carboxylic acid ester compounds of the present invention, the compound exhibiting a smectic phase is
It can be used as a main component of a liquid crystal composition or as an auxiliary agent of a liquid crystal composition containing another liquid crystal material as a main component, and a compound that does not exhibit a smectic phase is a liquid crystal composition containing another liquid crystal material as a main component. It can be used as an auxiliary agent.

Examples of the liquid crystal compound which can be used in the present invention together with the compound represented by the formula [I] are:
(+)-4 '-(2 "-Methylbutyloxy) phenyl-6-octyloxynaphthalene-2-carboxylic acid ester, 4'-decyloxyphenyl-6-((+)-2" -methylbutyloxy) Naphthalene-2-carboxylic acid ester,

[0063]

[Chemical formula 26]

In addition to liquid crystal compounds such as

[0065]

[Chemical 27]

Or

[0067]

[Chemical 28]

Examples thereof include compounds having a cyclic structure as described above and having optical activity. further,

[0069]

[Chemical 29]

A Schiff base type liquid crystal compound such as

[0071]

[Chemical 30]

An azoxy liquid crystal compound such as

[0073]

[Chemical 31]

A benzoic acid ester liquid crystal compound such as

[0075]

[Chemical 32]

A cyclohexylcarboxylic acid ester liquid crystal compound such as

[0077]

[Chemical 33]

A phenyl-based liquid crystal compound such as

[0079]

[Chemical 34]

Terphenolic liquid crystal compounds such as

[0081]

[Chemical 35]

A cyclohexyl liquid crystal compound such as

[0083]

[Chemical 36]

Pyrimidine type liquid crystal compounds such as the above can be mentioned. The liquid crystal composition of the present invention contains the carboxylic acid ester compound represented by the above formula [I] and other compounds including the compounds exemplified above. The blending ratio of the carboxylic acid ester compound represented by the formula [I] in this liquid crystal composition can be arbitrarily set in consideration of the characteristics of the obtained liquid crystal composition. The composition of the present invention contains 1 to 99 parts by weight, preferably 5 to 75 parts by weight of the carboxylic acid ester compound represented by the formula [I] in 100 parts by weight of the liquid crystal material in the composition. It is contained in an amount within the range of. In this liquid crystal composition,
In addition to the above-mentioned liquid crystal material, additives such as a conductivity-imparting agent and a life-improving agent which are usually added to liquid crystal compositions may be added.

The liquid crystal composition used in the present invention can be produced by mixing the above-mentioned carboxylic acid ester compound and, if desired, other liquid crystal compounds and additives. A liquid crystal composition (liquid crystal substance) containing the above-mentioned liquid crystal material causes an optical switching phenomenon when a voltage is applied, and thus it is possible to manufacture a display device having good responsiveness by utilizing this phenomenon. In the present invention, as for the element or the method of driving the element utilizing such a phenomenon, for example, JP-A-56-107216 and 59-
Reference can be made to 118744.

Liquid crystal substances used in such a display device include smectic C phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase,
A compound exhibiting any one of the smectic J phase and the smectic K phase can be used. However, except for the smectic C phase, the response speed of the display device using such a liquid crystal substance is generally slow (low). Therefore, it has been conventionally considered effective to drive the smectic C phase having a high response speed in practical use.

However, the inventor of the present invention disclosed in Japanese Patent Application Laid-Open No. 64-3632
In the present invention, not only the smectic C phase but also the smectic A phase can be used by utilizing the driving method of the display device in the smectic A phase as already proposed in the publication. That is, by utilizing this driving method, the liquid crystal element of the present invention can be driven in a wide range, and the electro-optical response speed can be increased.

The liquid crystal device of the present invention comprises a cell filled with a liquid crystal substance and a polarizing plate. That is, for example, as shown in FIG. 5, the liquid crystal device of the present invention includes two transparent substrates 11 arranged so as to form a gap 14 filled with a liquid crystal substance.
A cell 1 including a and 11b and transparent electrodes 15a and 15b formed on the surfaces of the two transparent substrates 11a and 11b facing the liquid crystal substance 12.
3, a liquid crystal substance 12 filled in a gap 14 of the cell 13, and one polarizing plate (not shown) arranged on both outer sides of the cell 13.

In the present invention, as the transparent substrate, for example, glass or transparent polymer plate can be used. When a glass substrate is used, an undercoat layer (unnecessary component permeation preventive layer) containing silicon oxide or the like as a main component is formed on the glass substrate surface in order to prevent deterioration of the liquid crystal substance due to elution of the alkaline component. It can be provided. The thickness of the transparent substrate is usually in the range of 0.01 to 1.0 mm in the case of a glass substrate, for example.

Further, in the present invention, a flexible transparent substrate can be used as the transparent substrate. in this case,
A flexible transparent substrate can be used as at least one of the transparent substrates, and both may be flexible substrates. A polymer film or the like can be used as such a flexible transparent substrate. When a flexible transparent substrate is used as the transparent substrate, the thickness t (m
It is preferable that m), the elastic modulus E (Kgf / m ² ) and the width a (mm) of the gap formed in the cell have the relationship represented by the following equation.

[0091]

[Equation 1]

A transparent electrode is provided on the surface of such a transparent substrate. The transparent electrode is, for example, iridium oxide,
It is formed by coating the transparent substrate surface with tin oxide or the like. The transparent electrode can be formed by a known method. The thickness of the transparent electrode is usually 100-200.
It is in the range of 0 angstrom. The transparent substrate provided with such a transparent electrode may further be provided with an alignment layer or a ferroelectric layer on the transparent electrode. Examples of the alignment layer include an organic thin film and an inorganic thin film formed by chemically adsorbing an organic silane coupling agent or a carboxylic acid polynuclear complex. Examples of organic thin films include polyethylene, polypropylene,
Mention may be made of polymeric thin films such as polyesters, polyamides, polyvinyl alcohol (poval) and polyimides. Such organic thin films can be applied, adhered, vapor deposited, or polymerized on the substrate (eg plasma polymerization).
And the like.

Further, as an example of the inorganic thin film, silicon oxide,
Mention may be made of oxide thin films such as germanium oxide and alumina, nitride thin films such as silicon nitride and other semiconductor thin films. Such an inorganic thin film can be formed by a method such as vapor deposition (for example, oblique vapor deposition) and sputtering. Further, as a method of imparting orientation to the thin film as described above, there are a method of imparting anisotropy or shape specificity to the thin film itself during film formation, and a method of imparting orientation from the outside after forming the thin film. Specifically, after forming a thin film by coating a polymer material such as a polyimide resin on the transparent electrode, a method of rubbing the thin film in a certain direction, a method of imparting orientation by stretching the polymer film, A method of obliquely vapor-depositing an oxide can be used.

Such a thin film (eg, orientation layer) may be formed so as to also serve as a spacer described later. Two transparent substrates as described above are arranged so that the respective transparent electrodes face each other and a gap for filling the liquid crystal substance is formed by the transparent substrates. The width of the gap formed as described above is usually 1 to 10 μm, preferably 1 to 5 μm. Such a gap can be formed, for example, by disposing two substrates so as to sandwich the spacer. As such a spacer, for example, a polyimide-based polymer substance obtained by patterning a photosensitive polyimide precursor can be used. By using the spacer, a monodomain is formed due to the interface effect between the spacer and the liquid crystal substance.

Further, as shown in FIG. 6 (a) and FIG. 6 (b) which is a sectional view taken along the line AA, for example, a concentric spacer 26 acting as an alignment film is used to separate the alignment film from the spacer. It can also be integrated. In FIGS. 6A and 6B, the transparent substrate is 27, the transparent electrode is 25, and the liquid crystal substance is 23.
Indicated by. In addition, as shown in FIG. 7 (a) and this AA cross-sectional view (b), for example, a comb-shaped spacer 36 acting as an alignment film is used to integrate the alignment film and the spacer. You can also In FIGS. 7 (a) and 7 (b), the transparent substrate is 37, the transparent electrode is 35, and the liquid crystal material is 33.

Further, as shown in FIG. 8, in addition to the spacers as described above, a fiber 46 is mixed in the liquid crystal substance 43 so that the transparent substrate 47 to which the transparent electrode 45 is attached is fixed. Can also be held so as to form a gap. As the fiber used here, it is preferable to use a fiber whose average diameter and average length are represented by the following formula.

[0097]

[Equation 2]

However, in the above formula, d represents the average diameter of the fiber, and q represents the average length of the fiber.
Although various fibers can be used as the fiber used here, a fiber formed by spinning alkali glass is particularly preferable. Furthermore, instead of the above-mentioned fibers, or together with the above-mentioned fibers, a granular material can be blended.

Examples of such particles include particles made of melamine resin, urea resin, benzoguanamine resin or the like and having a particle size of 1 to 10 μm.
The two transparent substrates arranged with a gap as described above are usually bonded by sealing the periphery with a sealing material. An epoxy resin, a silicone resin, or the like can be used as the sealing material. further,
The epoxy resin or the like may be modified with an acrylic material or a silicone rubber.

The liquid crystal cell having the above-mentioned structure is filled with the liquid crystal substance containing the carboxylic acid ester compound represented by the formula [I] as described above. Such a liquid crystal substance filled in the gap of the liquid crystal cell can be aligned by using a uniaxial alignment control method such as a temperature gradient method using a spacer edge or a surface treatment method using an alignment film. Further, in the present invention, for example, the initial alignment of the liquid crystal substance can be performed by applying an electric field using a DC bias voltage while heating the liquid crystal substance.

The liquid crystal cell thus filled with the liquid crystal substance and initially aligned is arranged between two polarizing plates. Further, as shown in FIG. 9, the two transparent substrates 57, the transparent electrodes 55 and the liquid crystal substance 53 prepared as described above are used.
It is also possible to dispose two or more cells 58 composed of 2 between the two polarizing plates 56. In the liquid crystal element of the present invention, it is possible to arrange the polarizing plates such that the polarization planes of the respective polarizing plates form an angle of 70 to 110 degrees. The polarizing plates are preferably arranged so that the polarization directions of the two polarizing plates are orthogonal to each other, that is, the angle is 90 degrees.

As such a polarizing plate, for example, a resin film such as a polyvinyl alcohol resin film or a polyvinyl butyral resin film is stretched in the presence of iodine or the like to absorb iodine in the film to impart a polarizing property. A film can be used. Such a polarizing film may have a multi-layer structure by coating the surface with another resin or the like.

In the present invention, the liquid crystal cell as described above is ± 10 from the state where the amount of light transmitted between the polarizing plates arranged as described above is the smallest (that is, the darkest state).
It can be arranged between two polarizing plates so as to form an angle (rotation angle) within a range of degrees, preferably in the darkest state. Further, it is preferable to form an angle (rotation angle) within a range of ± 10 degrees from the state in which the amount of transmitted light is the largest (that is, the brightest state) between the polarizing plates arranged as above. It can be placed between the two polarizing plates so as to be in a state.

As shown in FIG. 9, the liquid crystal device of the present invention can be manufactured by filling the gap 14 of the cell 13 with the liquid crystal substance 15 as described above and initially aligning the liquid crystal substance 15. it can. The liquid crystal substance 15 is usually heated until it becomes a molten state, and in this state, it is filled (injected) into the gap 14 of the cell whose inside is depressurized. After filling the liquid crystal material in this manner, the liquid crystal material injection port provided in the cell 13 is sealed.

Then, the cell 13 with the injection port thus sealed is heated to a temperature above the temperature at which the liquid crystal substance 15 filled in the cell exhibits an isotropic phase, and thereafter, the liquid crystal substance 15 exhibits liquid crystal. Cool to temperature. Further, in the present invention, it is preferable that the cooling rate at the time of this cooling is 2 ° C./minute or less. In particular, the rate of temperature decrease is preferably in the range of 0.1 to 2.0 ° C./minute, and more preferably in the range of 0.1 to 0.5 ° C./minute. By cooling the cell 13 at such a cooling rate, the initial compounding state of the liquid crystal substance 15 is improved, and a liquid crystal element having a liquid crystal phase composed of a monodomain with few alignment defects can be easily formed. Here, the initial orientation refers to the alignment state of the liquid crystal substance before the voltage is applied to the liquid crystal element to change the orientation vector of the liquid crystal substance.

The liquid crystal element of the present invention thus formed has remarkably excellent characteristics such as contrast as compared with the conventional liquid crystal element. For example, a surface-stabilized ferroelectric liquid crystal element,
It can be suitably used as a helical modulation element, a transient scattering type element, a guest-host type element, a vertical alignment liquid crystal element and the like. For example, when the liquid crystal element of the present invention is driven by applying an electric field, the frequency is usually 1 Hz to 100 KHz, preferably 10 Hz to
10KHz, electric field is usually 0.01-60Vp-p / μm
^t (voltage per 1 μm thickness), preferably 0.05 to 30 V
It can be driven by applying a controlled electric field to pp / μm ^t .

By using an optically active liquid crystal substance containing the carboxylic acid ester compound represented by the above formula [I], the liquid crystal element of the present invention is applied with an electric field when driven. By changing the width of the waveform (driving wave) of the electric field to be generated, the amount of light transmitted through this liquid crystal element is reduced to 2
It comes to draw different kinds of hysteresis curves. One of them is a driving method utilizing a so-called bistable type, and the other is a driving method utilizing a so-called tristable type.

A liquid crystal cell filled with a liquid crystal substance having optical activity as described above is placed between two polarizing plates arranged so that their polarization planes are orthogonal to each other so as to be in the darkest state without applying an electric field. In the liquid crystal device of the present invention arranged in, for example, a frequency of 50 Hz to 100 KHz,
This liquid crystal element can be driven by applying an electric field having any one of a 10 KHz rectangular wave (or pulse wave), a triangular wave, a sine wave, and a waveform obtained by combining these. For example, when a rectangular wave (or a pulse or a combination wave of both) is applied, the width of the electric field is set to 10 milliseconds or less, preferably 0.01 to 10 milliseconds to drive the liquid crystal element. The speed can be increased, and in this region, the liquid crystal device of the present invention can be used as a bistable liquid crystal device. Further, by making the width of this electric field larger than 10 milliseconds, preferably in the range of 33 to 1000 milliseconds, in a region where it is not necessary to drive at such a high speed,
The liquid crystal device of the present invention can be used as a tristable liquid crystal device. Here, the width of the electric field means, for example, in the case of a rectangular wave, the length (that is, time) of the electric field maintained at a predetermined voltage.

Various liquid crystal display devices and electro-optical display devices can be manufactured using the liquid crystal element of the present invention.
Further, among the liquid crystal elements of the present invention, a liquid crystal element filled with a liquid crystal substance exhibiting a smectic phase is a liquid crystal display device such as a memory type liquid crystal display device such as a heat writing type liquid crystal display element or a laser writing type liquid crystal display element. Alternatively, an electro-optical display device can be manufactured. Furthermore, by using a liquid crystal material containing a carboxylic acid ester compound exhibiting ferroelectricity, in addition to the above-mentioned applications, liquid crystal such as optical switching elements such as optical shutters or liquid crystal printers, piezoelectric elements and pyroelectric elements. A display device or an electro-optical display device can be manufactured.

That is, since the liquid crystal substance used in the present invention exhibits tristable or bistable properties, the liquid crystal device of the present invention is provided with an optical switching function or an optical switching function by reversing the electric field so as to achieve the bistable state. It can have a display function. Further, the liquid crystal substance used in the present invention is
In the case of exhibiting bistability, it has spontaneous polarization, so that once a voltage is applied, it has a memory effect even after the electric field is erased. Further, it is not necessary to continuously apply an electric field to the liquid crystal element in order to maintain this memory, and it is possible to reduce power consumption in the display device using the liquid crystal element of the present invention. Moreover, since this display device has a stable contrast, it is very clear.

Further, in the switching element of the present invention using the liquid crystal material represented by the above formula [I], the switching operation can be performed only by changing the orientation direction of the molecules. In this case, the primary term of the electric field strength is Since it acts to drive this switching element, the switching element of the present invention can be driven at a low voltage. By using this switching element, a high-speed response of several tens of microseconds or less can be realized, so that the operation time of the element is significantly shortened. Therefore, by using the liquid crystal element of the present invention, a large-screen display (liquid crystal display device) having many scanning lines can be easily manufactured. In addition, the memory property can be maintained even when tristable is exhibited. Moreover, since this display can be driven at room temperature or lower, the display can be driven without using auxiliary means for controlling the driving temperature.

Further, the liquid crystal substance used in the present invention is
Even in the smectic A phase, which is generally not shown to have bistability, the molecules are inductively tilted when an electric field is applied, and this property can be used to perform optical switching. That is, since a practical response speed cannot be achieved when a conventional ferroelectric liquid crystal compound is used, the present inventor has already proposed in Japanese Patent Application No. 62-157808 even in the smectic A phase which is not usually used. The display device of the present invention can be driven by utilizing the driving method and device described above. Further, the liquid crystal substance used in the present invention exhibits two or more stable states even in the smectic F phase having a higher order than the smectic C phase. Therefore, a plurality of stable states in these phases are used. Optical switching can be performed in the same manner as described above.

The display device using the liquid crystal element of the present invention can be driven by various methods. Specific examples of this driving method include the methods described below. In the first method, the liquid crystal element of the present invention is interposed between two polarizing plates, and an external voltage is applied to the liquid crystal element,
This is a method of displaying by utilizing the two polarizing plates and the birefringence of the liquid crystal substance by changing the orientation vector of the liquid crystal substance.

The second method is a method of utilizing the dichroism of a dye by using a liquid crystal substance containing a dichroic dye. This method is a method of changing the absorption direction of light by the dye by changing the alignment direction of the liquid crystal compound to perform display. The dye used in this case is usually a dichroic dye,
Examples of such dichroic dyes include azo dyes, naphthoquinone dyes, cyanine dyes and anthraquinone dyes.

A display device manufactured by using the liquid crystal element of the present invention can be manufactured by an electrical address display system such as static drive, simple matrix drive or composite matrix drive, an optical address display system, a thermal address display system and a light beam display system. It can be driven. Also,
When the display device of the present invention is driven by an electric field, a non-linear element or an active element can be used as an element for driving each picture element. More specifically, as the non-linear element of the two-terminal element, for example, as shown in FIG.
Metal), a diode, etc. may be arranged to utilize an element utilizing these non-linearities. Further, as the active element of the three-terminal element, for example, as shown in FIG. 10 (b), a TFT (thin film transistor), a Si-MOS (Si-me
tal oxide semi conductor field-effect transisto
r), SOS (Sillicon on Sapphire), and the like are included in the picture element.

[0116]

The present invention provides a novel carboxylic acid ester compound. This carboxylic acid ester compound is highly useful as a liquid crystal material. Therefore, the liquid crystal element in which the liquid crystal composition containing this compound and the liquid crystal material composed of this carboxylic acid ester compound are filled between the two substrates has excellent liquid crystal characteristics.

By blending a liquid crystal substance of the same kind and / or another kind with such a compound of the present invention, a liquid crystal can be used without impairing the ferroelectricity or antiferroelectricity of the compound of the present invention. The temperature range can be widened. Therefore, by using such a compound, it is possible to obtain a liquid crystal element or the like having high-speed response, high contrast, and stable contrast in a wide temperature range.

Furthermore, in a liquid crystal display manufactured using such an element, the operation time can be shortened significantly. In such a display, power consumption can be reduced, and high contrast and stable contrast can be obtained. Further, low voltage driving is also possible. Further, when the carboxylic acid ester compound of the present invention is used as an antiferroelectric liquid crystal compound, it becomes easy to realize a memory property and it is possible to impart characteristics such as improving the orientation.

By using such a carboxylic acid ester compound of the present invention as a liquid crystal material, excellent characteristics such as wide operating temperature range, high switching speed, extremely low power consumption, and stable contrast can be obtained. It is possible to obtain various devices having

[0120]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to these examples. In addition, R and S represent the R and S forms of the optically active substance.

[0121]

Example 1 4- [6 '-(4 "-decyloxybenzoyloxy) -5', 6 ', 7',
8'-Tetrahydro-2'-naphthoyloxy] benzoic acid R-1 "'-
Synthesis of trifluoromethylheptyl ester [exemplary compound (4)]

[0122]

[Chemical 37]

First stage 6-hydroxynaphthalene-2-carboxylic acid 30 g (160
(5 mmol), 5% palladium / carbon (5 g) and tetrahydrofuran (500 ml) were placed in an autoclave having a volume of 1 liter and mixed, and heated to 105 ° C. under a nitrogen atmosphere. While maintaining the temperature at 105 ° C., the autoclave was maintained at a hydrogen pressure of 20 Kg / cm ² G and the reaction was carried out for 3 hours under stirring.

After the lapse of 3 hours, the mixture was allowed to cool to room temperature, the hydrogen gas was depressurized, the obtained reaction mixture was filtered using Celite as a filter aid, and the obtained filtrate was concentrated. By recrystallizing the obtained mixture using toluene, 16.1 g of white crystals were obtained. The value of M / e measured by FD-mass spectrum of this compound was 192.

From the results of this analysis, this compound was identified as 5,6,7,
It was identified as 8-tetrahydro-6-hydroxynaphthalene-2-carboxylic acid. Second step 0.96 g (5 mmol) of 5,6,7,8-tetrahydro-6-hydroxynaphthalene-2-carboxylic acid obtained in the first step,
4-Hydroxybenzoic acid R-1′-trifluoromethylheptyl ester separately synthesized by a conventional method 1.52 g (5 mmol), 4-N, N-dimethylaminopyridine 0.061 g (0.5
Mmol) and methylene chloride (30 ml) in a mixture of N, N '
10 ml of a methylene chloride solution containing 1.13 g (5.5 mmol) of dicyclohexylcarbodiimide was added dropwise at room temperature with stirring over 5 hours.

Further, the reaction was carried out at room temperature for 14 hours. The reaction mixture was filtered, and the obtained filtrate was concentrated. By separating the concentrate using column chromatography,
4- (5 ', 6', 7 ', 8'-tetrahydro- which is a colorless transparent viscous liquid
2.18 g (4.56 mmol) of 6'-hydroxy-2'-naphthoyloxy) benzoic acid R-1 "-trifluoromethylheptyl ester was obtained.

Third step 4- (5 ', 6', 7 ', 8'-Tetrahydro-6'- obtained in the second step
Hydroxy-2'-naphthoyloxy) benzoic acid R-1 "-trifluoromethylheptyl ester 0.48 g (1 mmol), 4-decyloxybenzoic acid 0.278 g (1 mmol), which was separately synthesized by a conventional method, 4- 0.012 g (0.1 mmol) of N, N-dimethylaminopyridine and methylene chloride 1
Methylene chloride solution containing 0.25 g (1.2 mmol) of N, N'-dicyclohexylcarbodiimide in 0 ml of mixture 5
ml was added dropwise at room temperature with stirring over 3 hours.

Further, the reaction was carried out at room temperature for 3 hours. The reaction mixture was filtered, and the obtained filtrate was concentrated. The concentrate was separated using column chromatography to obtain 0.45 g of a white solid. The M / e value obtained using the FD-mass spectrum of this white solid was 738.

FIG. 1 shows the ¹ H-NMR spectrum chart of this compound. From the results of these analyses, this compound was identified as 4- [6 '-(4 "-decyloxybenzoyloxy) -5', 6 ', 7', 8'-tetrahydro-2'-naphthoyloxy. ] Benzoic acid R-1 "'-trifluoromethylheptyl ester [identified as Exemplified Compound (4).

[0130]

Example 2 6- [6 '-(4 "-decyloxybenzoyloxy) -5', 6 ', 7',
Synthesis of 8'-tetrahydro-2'-naphthoyloxy] -1,2,3,4-tetrahydronaphthalene-2-carboxylic acid R-1 "'-trifluoromethylheptyl ester [exemplary compound (21)]

[0131]

[Chemical 38]

First stage 6-n-decyloxy-naphthalene-2-carboxylic acid 3.86 g
(11.8 mmol) and 1,2-diethoxyethane 130 ml
To the above mixture was added 3.0 g (130 mg atom) of sodium metal under stirring at 120 ° C. under nitrogen atmosphere, and the mixture was further heated to reflux temperature.

Iso-amyl alcohol 10 was added to this mixture.
g (114 mmol) was added dropwise over 1 hour, and then 11
The reaction was carried out under reflux for an hour. After cooling to room temperature, the remaining metallic sodium was added with ethanol to solubilize it as sodium alcoholate, and then the reaction mixture was acidified with 20% hydrochloric acid. After adding 100 ml of water to the reaction mixture, the organic phase was separated and the organic phase was washed with water.

The organic phase was concentrated under reduced pressure to give 4.25 g of a solid.
Got By recrystallizing this solid using toluene, 2.95 g (8.89 mmol) of 1,2,3,4-tetrahydro-6-n-decyloxynaphthalene-2-carboxylic acid was obtained. Second step 6-decyloxynaphthalene-2 obtained by the first step method
-16.6 g (50 mmol) of carboxylic acid and 250 cc of acetic acid,
86.5 g (0.5 mol) of 47% hydrobromic acid was added at 130 ° C for 7 hours.
Heated to reflux for hours. After adding distilled water and concentrating under reduced pressure, 10.60 g (50 mmol) of 1,2,3,4-tetrahydro-6-hydroxynaphthalene-2-carboxylic acid was obtained.

Third step 10.60 g (50 mmol) of 1,2,3,4-tetrahydro-6-hydroxynaphthalene-2-carboxylic acid obtained in the second step, 12.85 g (75 mmol) of benzyl bromide. , 85
% Potassium hydroxide 6.6 g (100 mmol), sodium iodide 0.525 g (3.5 mmol), ethanol 20
A mixture of 0 ml and 25 ml of distilled water was heated to reflux at 100 ° C. for 12 hours. Further, 50 ml of 10% potassium hydroxide was added to the reaction solution, and the mixture was heated under reflux for 2 hours. After cooling to room temperature, the mixture was added to cold water, and the reaction mixture was acidified with 36% hydrochloric acid. The precipitate was separated by filtration and recrystallized from toluene to give 1,2,3,4-tetrahydro-6
-Benzyloxynaphthalene-2-carboxylic acid 13.08 g
(46.4 mmol) was obtained.

Fourth stage 1,2,3,4-tetrahydro-6-benzyloxynaphthalene-2-carboxylic acid obtained in the third stage 5.64 g (20 mmol), R-1-trifluoromethylheptanol 3.68g
(20 mmol), 4-N, N-dimethylaminopyridine 0.2
To a mixture of 44 g (0.2 mmol) and 70 ml of methylene chloride was added N, N'-dicyclohexylcarbodiimide 4.53.
25 ml of a methylene chloride solution containing g (22 mmol) was added dropwise at room temperature with stirring over 2 hours.

Further, the reaction was carried out at room temperature for 2 hours. The reaction mixture was filtered, and the obtained filtrate was concentrated. The colorless liquid 1,2,3,4-tetrahydro-6-benzyloxynaphthalene-2-carboxylic acid R-1'-trifluoromethylheptyl ester was isolated by separating the concentrate using column chromatography. 19 g (18.3 mmol) were obtained.

Fifth step 1,2,3,4-tetrahydro-6-benzyloxynaphthalene-2-carboxylic acid R-1'-trifluoromethylheptyl ester obtained in the fourth step 8.19 g (18.3 mmol) 5%
Palladium / carbon 3.6g and tetrahydrofuran 5
Hydrogen was bubbled into 0 ml of the mixture at room temperature under atmospheric pressure for 24 hours. The reaction mixture was filtered using Celite as a filter aid, and the obtained filtrate was concentrated to give 1,2,3,4-tetrahydro-6-hydroxynaphthalene-2-carboxylic acid R-1 as a brown liquid. '-Trifluoromethylheptyl ester 6.
78 g (18.3 mmol) were obtained.

Sixth Step 1.02 g (3 mmol) of 1,2,3,4-tetrahydro-6-hydroxynaphthalene-2-carboxylic acid R-1′-trifluoromethylheptyl ester obtained in the fifth step, 5,76,5,7,8-Tetrahydro-6-hydroxynaphthalene-2-carboxylic acid obtained in the first step of Example 1 0.576 g (3 mmol), 4
In a mixture of 0.037 g (0.3 mmol) of -N, N-dimethylaminopyridine and 20 ml of methylene chloride, 0.68 g (3.3 mmol) of N, N'-dicyclohexylcarbodiimide was added.
10 ml of a methylene chloride solution containing was added dropwise with stirring at room temperature over 2 hours.

Further, the reaction was carried out at room temperature for 18 hours. The reaction mixture was filtered, and the obtained filtrate was concentrated. By separating the concentrate using column chromatography,
Colorless liquid 5 ', 6', 7 ', 8'-Tetrahydro-6'-hydroxy-2'-naphthoyloxy] -5,6,7,8-tetrahydronaphthalene-2-carboxylic acid R-1 " -0.55 g (1.03 mmol) of trifluoromethylheptyl ester was obtained.

Step 7 5 ', 6', 7 ', 8'-Tetrahydro-6'-hydroxy-2'-naphthoyloxy] -5,6,7,8-tetrahydronaphthalene obtained in Step 6 2-carboxylic acid R-1 "-trifluoromethylheptyl ester 0.55 g (1.03 mmol), 0.286 g (1.03 g) of 4-decyloxybenzoic acid separately synthesized by a conventional method
Mmol), 4-N, N-dimethylaminopyridine 0.013
To a mixture of g (0.103 mmol) and 10 ml of methylene chloride, 0.255 of N, N'-dicyclohexylcarbodiimide was added.
5 ml of a methylene chloride solution containing g (1.2 mmol) was added dropwise at room temperature over 4 hours with stirring.

Further, the reaction was carried out at room temperature for 4 hours. The reaction mixture was filtered, and the obtained filtrate was concentrated. The concentrate was separated using column chromatography to obtain 0.46 g of a white solid. The M / e value of this white solid measured by the FD-mass spectrum was 792.

FIG. 2 shows the ¹ H-NMR spectrum chart of this compound. From the results of these analyses, this compound was identified as 6- [6 '-(4 "-decyloxybenzoyloxy) -5', 6 ', 7', 8'-tetrahydro-2'-naphthoyloxy]. -1,2,3,4-Tetrahydronaphthalene-2-carboxylic acid R-
It was identified as 1 "'-trifluoromethylheptyl ester [Exemplified Compound (21)]

[0144]

Example 3 6- [6 '-(4 "-decyloxybenzoyloxy) -5', 6 ', 7',
Synthesis of 8'-tetrahydro-2'-naphthoyloxy] -5,6,7,8-tetrahydronaphthalene-2-carboxylic acid R-1 "'-trifluoromethylheptyl ester [exemplified compound (22)]

[0145]

[Chemical Formula 39]

First stage 5,6,7,8-tetrahydro-6 obtained in the first stage of Example 1
-Hydroxynaphthalene-2-carboxylic acid 0.38 g (2 mmol), benzyl alcohol 0.22 g (2 mmol),
To a mixture of 0.024 g (0.2 mmol) of 4-N, N-dimethylaminopyridine and 15 ml of methylene chloride, 0.45 g (2.2 mmol) of N, N'-dicyclohexylcarbodiimide was added.
10 ml of a methylene chloride solution containing 1 at room temperature with stirring.
It dripped over 5 hours.

Further, the reaction was carried out at room temperature for 14 hours. The reaction mixture was filtered, and the obtained filtrate was concentrated. By separating the concentrate using column chromatography,
White solid 5,6,7,8-tetrahydro-6-hydroxynaphthalene-2-carboxylic acid benzyl ester 0.40 g (1.
4 mmol) was obtained.

Second stage 0.40 g of 5,6,7,8-tetrahydro-6-hydroxynaphthalene-2-carboxylic acid benzyl ester obtained in the first stage
(1.42 mmol), 0.395 g (1.42 mmol) of 4-decyloxybenzoic acid separately synthesized by a conventional method, 0.017 g (0.14 mmol) of 4-N, N-dimethylaminopyridine and 10 ml of methylene chloride were added to N, 5 ml of a methylene chloride solution containing 0.35 g (1.42 mmol) of N'-dicyclohexylcarbodiimide was added dropwise at room temperature with stirring over 4 hours.

Further, the reaction was carried out at room temperature for 116 hours. The reaction mixture was filtered, and the obtained filtrate was concentrated. The concentrate was separated by column chromatography to give 0.53 g of 6- (4'-decyloxybenzoyloxy) -5,6,7,8-tetrahydronaphthalene-2-carboxylic acid benzyl ester as a white solid. (1.0 mmol) was obtained.

Third step 0.53 g (1.0 mmol) of 6- (4'-decyloxybenzoyloxy) -5,6,7,8-tetrahydronaphthalene-2-carboxylic acid benzyl ester obtained in the second step, 5% palladium / carbon 0.11 g and tetrahydrofuran 10 ml
Hydrogen was blown into the mixture for 15 hours at room temperature under normal pressure with stirring. The reaction mixture was filtered using Celite as a filter aid, and the obtained filtrate was concentrated to give a white solid 6-
0.42 g (0.93 mmol) of (4'-decyloxybenzoyloxy) -5,6,7,8-tetrahydronaphthalene-2-carboxylic acid was obtained.

Fourth stage 5,6,7,8-tetrahydro-6 obtained in the first stage of Example 1
-Hydroxynaphthalene-2-carboxylic acid 2.88 g (15 mmol), 1-trifluoromethylheptyl alcohol 2.76 g (15 mmol), 4-N, N-dimethylaminopyridine 0.183 g (1.5 mmol) and methylene chloride. 5
To 0 ml of the mixture, 20 ml of a methylene chloride solution containing 3.40 g (16.5 mmol) of N, N'-dicyclohexylcarbodiimide was added dropwise at room temperature over 24 hours with stirring.

Further, 2 ml of a methylene chloride solution containing 0.41 g (2.0 mmol) of N, N'-dicyclohexylcarbodiimide was added, and the mixture was reacted at room temperature for 72 hours. The reaction mixture was filtered, and the obtained filtrate was concentrated. By separating the concentrate using column chromatography, 3.11 g (8.69 mmol) of white solid 5,6,7,8-tetrahydro-6-hydroxynaphthalene-2-carboxylic acid 1'-trifluoromethylheptyl ester was obtained. ) Got.

Fifth Step 6- (4'-decyloxybenzoyloxy) -5,6,7,8-tetrahydronaphthalene-2-carboxylic acid obtained in the third step.
42 g (0.93 mmol), 5,6,7,8-obtained in the fourth stage
Tetrahydro-6-hydroxynaphthalene-2-carboxylic acid 1 '
-Trifluoromethylheptyl ester 0.44 g (0.93
Mmol), 4-N, N-dimethylaminopyridine 0.011
0.23 g of N, N'-dicyclohexylcarbodiimide to a mixture of g (0.092 mmol) and 10 ml of methylene chloride.
5 ml of a methylene chloride solution containing (1.1 mmol) was added dropwise at room temperature with stirring over 3 hours.

Further, the reaction was carried out at room temperature for 120 hours. The reaction mixture was filtered, and the obtained filtrate was concentrated. The concentrate was separated using column chromatography to obtain 0.43 g of a white solid. FD- of this white solid
The value of M / e determined by mass spectrum was 792.

FIG. 3 shows the ¹ H-NMR spectrum chart of this compound. From the results of these analyses, this compound was identified as 6- [6 '-(4 "-decyloxybenzoyloxy) -5', 6 ', 7', 8'-tetrahydro-2'-naphthoyloxy]. -5,6,7,8-Tetrahydronaphthalene-2-carboxylic acid R-
It was identified as 1 "'-trifluoromethylheptyl ester [Exemplified Compound (22)].

[0156]

Example 4 6- [4 "-(5'-decyl-2'-pyrimidinyl) benzoyloxy]
-5,6,7,8-Tetrahydronaphthalene-2-carboxylic acid R-1 "'-
Trifluoromethylheptyl ester [Exemplified compound (1
30)]

[0157]

[Chemical 40]

First step 5,6,7,8-tetrahydro-6 obtained in the fourth step of Example 3
-Hydroxynaphthalene-2-carboxylic acid 1'-trifluoromethylheptyl ester 0.44 g (0.93 mmol),
Kojima Chemical Co., Ltd. 4- (5'-decyl-2'-pyrimidinyl) benzoic acid 0.264 g (0.8 mmol), 4-N, N-dimethylaminopyridine 0.01 g (0.08 mmol) and a mixture of 20 ml of methylene chloride. 5 ml of a methylene chloride solution containing 0.18 g (0.88 mmol) of N, N'-dicyclohexylcarbodiimide was added dropwise thereto at room temperature over 1.5 hours with stirring.

Further, the reaction was carried out at room temperature for 4 hours. The reaction mixture was filtered, and the obtained filtrate was concentrated. The concentrate was separated using column chromatography to obtain 0.39 g of a white solid. FD-
The value of M / e measured by mass spectrum was 670.

FIG. 4 shows the ¹ H-NMR spectrum chart of this compound. From the results of these analyses, this compound was identified as 6- [4 "-(5'-decyl-2'-pyrimidinyl)
Benzoyloxy] -5,6,7,8-tetrahydronaphthalene-2
-Carboxylic acid R-1 "'-trifluoromethylheptyl ester [Exemplified Compound (130)] was identified.

[0161]

Example 5 The compound [4] represented by the following formula and the compound [A] represented by the following formula obtained in Example 1 were mixed with each other.
The liquid crystal composition of the present invention was manufactured by mixing in a weight ratio of 5:25. The phase transition temperature of this composition was measured. The results are shown in Table 3.
Shown in.

Further, the phase transition temperatures of the exemplified compound [4] and the compound represented by the following formula [A] are also described.

[0163]

[Table 9]

[0164]

[Chemical 41]

[0165]

Example 6 The exemplified compound [21] represented by the following formula and the compound [A] represented by the following formula obtained in Example 2 were mixed with each other.
A liquid crystal composition of the present invention was manufactured by mixing in a weight ratio of 0:50. The phase transition temperature of this composition was measured.

The results are shown in Table 4. Further exemplified compounds [2
1] and the phase transition temperature of the compound represented by the above formula [A] are also described.

[0167]

[Table 10]

[0168]

[Chemical 42]

[0169]

Example 7 The compound [22] represented by the following formula and the compound [A] represented by the following formula obtained in Example 3 were mixed with each other.
A liquid crystal composition of the present invention was manufactured by mixing in a weight ratio of 0:50. The phase transition temperature of this composition was measured.

The results are shown in Table 5. Further exemplified compounds [2
2] and the phase transition temperature of the compound represented by the following formula [A] are also described.

[0171]

[Table 11]

[0172]

[Chemical 43]

[Brief description of drawings]

Figure 1: 4- [6 '-(4 "-decyloxybenzoyloxy)
-5 ', 6', 7 ', 8'-Tetrahydro-2'-naphthoyloxy] benzoic acid R-1 "'-trifluoromethylheptyl ester [Exemplified compound (4)] ¹ H-NMR spectrum chart Is.

FIG. 2 6- [6 '-(4 "-decyloxybenzoyloxy)
-5 ', 6', 7 ', 8'-Tetrahydro-2'-naphthoyloxy] -1,
2,3,4-Tetrahydronaphthalene-2-carboxylic acid R-1 "'-trifluoromethylheptyl ester [Exemplified compound (2
1)]] ¹ H-NMR spectrum chart.

FIG. 3 6- [6 '-(4 "-decyloxybenzoyloxy)
-5 ', 6', 7 ', 8'-Tetrahydro-2'-naphthoyloxy] -5,
6,7,8-Tetrahydronaphthalene-2-carboxylic acid R-1 "'-trifluoromethylheptyl ester [Exemplified compound (2
2)]] ¹ H-NMR spectrum chart.

FIG. 4 6- [4 "-(5'-decyl-2'-pyrimidinyl) benzoyloxy] -5,6,7,8-tetrahydronaphthalene-2-carboxylic acid R-1" -trifluoromethylheptyl ester [ It is a chart of the ¹ H-NMR spectrum of exemplary compound (130)].

FIG. 5 is a diagram schematically showing a cross-sectional shape of the liquid crystal element of the present invention.

FIG. 6 is a cross-sectional view taken along the line AA of a liquid crystal element having a concentric spacer.

FIG. 7 is a cross-sectional view taken along line AA of a liquid crystal element having a comb spacer.

FIG. 8 is a diagram showing a cross-sectional structure of a liquid crystal element of the present invention using a fiber as a spacer.

FIG. 9 is a view showing a cross-sectional structure of a liquid crystal element of the present invention in which two polarizing plate cells are arranged.

FIG. 10 is a diagram showing an example of a non-linear element and a three-terminal element.

[Explanation of symbols]

 11a, 11b, 27a, 27b, 37,47,57 ・ ・ ・ Transparent substrate 12,23,33,43,53 ・ ・ ・ Liquid crystal material 13,58 ・ ・ ・ Cell 14 ・ ・ ・ Gap 15a, 15b, 25a, 25b, 35, 45, 55 ・ ・ ・ Transparent electrodes 26 ・ ・ ・ Concentric spacers 36 ・ ・ ・ Cushion spacers 46 ・ ・ ・ Fibers 56 ・ ・ ・ Polarizers

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C07D 239/26 8615-4C C09K 19/32 7457-4H 19/34 7457-4H 19/42 7457- 4H (72) Inventor Junichi Kawabata 580-2 32 Nagata, Takuji, Sodegaura, Chiba Prefecture Mitsui Petrochemical Industry Co., Ltd. (72) Toru Yamanaka 58032 Takuji, Nagaura, Sodegaura, Chiba Within Mitsui Petrochemical Industry Co., Ltd.

Claims (20)

[Claims] 1. A carboxylic acid ester compound represented by the following formula [I]: [However, in the formula [I], R represents 3 to 2 carbon atoms.
0 is an alkyl group, an alkoxy group having 3 to 20 carbon atoms and a halogenated alkyl group having 3 to 20 carbon atoms, and X and Y are each independently -COO. -, -OCO-, -CH ₂ CH
_2- , -CH ₂ O-, -OCH _2- , -SS-, -CO-CH ₂ -and -CH ₂ -CO-
Represents a group or a single bond selected from the group consisting of:
Is B represents a group selected from the group consisting of Represents a group selected from the group consisting of: R ^* is 4 carbon atoms having at least one asymmetric carbon atom;
To 20 optically active groups (a hydrogen atom bonded to a carbon atom constituting the optically active group may be substituted with a halogen atom), m represents 1 or 2, and n represents 0 to 2 Represents the integer of. 2. In the above formula [I], R ^* is the following formula [II]
Carboxylic acid ester compound of claim 1 wherein claims, characterized in that in a group represented ^{by; -Q 1 -C * H (Q} 2) -Q 3 ··· [II] [ However, formula [II ], Q ¹ represents — (CH ₂ ) _q —; [q represents an integer of 0 to 6], and Q ² and Q ³ each independently represent an alkyl group having 1 to 10 carbon atoms. Represent a mutually different group or atom selected from the group consisting of a fluoroalkyl group and a halogen atom, and Q ¹ , Q ²
And at least a part of the CH ₂ group or CF ₂ group present in Q ³ is —O—, —S—, —CO—, —CHX—; (X is a halogen atom),
At least one group selected from the group consisting of CHCN-, -O-CO-, -O-COO-, -CO-O- and -CH = CH- so that two heteroatoms are not directly bonded , May be substituted]. 3. In the above formula [I], X and Y are
The carboxylic acid ester compound according to claim 1, wherein each independently represents a group or a bond selected from the group consisting of -COO-, -OCO- and a single bond. 4. The carboxylic acid ester compound according to claim 1 or 3, wherein in the above formula [I], R is an alkoxy group. 5. The above formula [I], R ^{* _{is, -C * H (CF 3)}} -C 6 H 13, -C * H (CH 3) -C 6 H 13, -C * H (CH ₃ ) -C
₅ H ₁₁ , -C ^* H (C ₂ H ₅ ) -C ₅ H ₁₁ , -C ^* H (C ₂ H ₅ ) -C ₆ H ₁₃ , -CH ₂ -C ^* H
(CH ₃ ) -C ₂ H ₅ ,-(CH ₂ ) ₃ -C ^* H (CH ₃ ) -C ₂ H ₅ and -C ^* H (CF ₃ ) -C
The carboxylic acid ester compound according to claim 1 or 2, which is a group selected from the group consisting of H ₂ —COO—C ₂ H ₅ . 6. A liquid crystal material comprising a carboxylic acid ester compound represented by the following formula [I]; [However, in the formula [I], R represents 3 to 2 carbon atoms.
0 is an alkyl group, an alkoxy group having 3 to 20 carbon atoms and a halogenated alkyl group having 3 to 20 carbon atoms, and X and Y are each independently -COO. -, -OCO-, -CH ₂ CH
_2- , -CH ₂ O-, -OCH _2- , -SS-, -CO-CH ₂ -and -CH ₂ -CO-
Represents a group or a single bond selected from the group consisting of, A is B represents a group selected from the group consisting of Represents a group selected from the group consisting of: R ^* is 4 carbon atoms having at least one asymmetric carbon atom;
To 20 optically active groups (a hydrogen atom bonded to a carbon atom constituting the optically active group may be substituted with a halogen atom), m represents 1 or 2, and n represents 0 to 2 Represents the integer of. 7. In the above formula [I], R ^* is the following formula [II]
In the liquid crystal material according to claim 6 wherein wherein the possible wherein a group represented ^{by; -Q 1 -C * H (Q} 2) -Q 3 ··· [II] [ In Expression [II] , Q ¹ represents-(CH ₂ ) _q- ; [q represents an integer of 0 to 6], and Q ² and Q ³ each independently represent an alkyl group having 1 to 10 carbon atoms, fluoro. Q ¹ and Q ² represent groups or atoms different from each other selected from the group consisting of an alkyl group and a halogen atom,
And at least a part of the CH ₂ group or CF ₂ group present in Q ³ is —O—, —S—, —CO—, —CHX—; (X is a halogen atom),
At least one group selected from the group consisting of CHCN-, -O-CO-, -O-COO-, -CO-O- and -CH = CH- so that two heteroatoms are not directly bonded , May be substituted]. 8. In the above formula [I], X and Y are
The liquid crystal material according to claim 6, wherein each independently represents a group or a bond selected from the group consisting of -COO-, -OCO- and a single bond. 9. The liquid crystal material according to claim 6 or 8, wherein R in the above formula [I] is an alkoxy group. 10. A above formula [I], R ^{* _{is, -C * H (CF 3)}} -C 6 H 13, -C * H (CH 3) -C 6 H 13, -C * H (CH ₃ ) -C
₅ H ₁₁ , -C ^* H (C ₂ H ₅ ) -C ₅ H ₁₁ , -C ^* H (C ₂ H ₅ ) -C ₆ H ₁₃ , -CH ₂ -C ^* H
(CH ₃ ) -C ₂ H ₅ ,-(CH ₂ ) ₃ -C ^* H (CH ₃ ) -C ₂ H ₅ and -C ^* H (CF ₃ ) -C
The liquid crystal material according to claim 6 or 7, which is a group selected from the group consisting of H ₂ —COO—C ₂ H ₅ . 11. A liquid crystal composition containing a carboxylic acid ester compound represented by the following formula [I]: [However, in the formula [I], R represents 3 to 2 carbon atoms.
0 is an alkyl group, an alkoxy group having 3 to 20 carbon atoms and a halogenated alkyl group having 3 to 20 carbon atoms, and X and Y are each independently -COO. -, -OCO-, -CH ₂ CH
_2- , -CH ₂ O-, -OCH _2- , -SS-, -CO-CH ₂ -and -CH ₂ -CO-
Represents a group or a single bond selected from the group consisting of: B represents a group selected from the group consisting of Represents a group selected from the group consisting of: R ^* is 4 carbon atoms having at least one asymmetric carbon atom;
To 20 optically active groups (a hydrogen atom bonded to a carbon atom constituting the optically active group may be substituted with a halogen atom), m represents 1 or 2, and n represents 0 to 2 Represents the integer of. 12. In the above formula [I], R ^* is represented by the following formula [I
11. The group represented by [I].
The liquid crystal composition of claim ^{wherein; -Q 1 -C * H (Q} 2) -Q 3 ··· [II] [ In Expression [II], Q ¹ _{is, - (CH 2) q -} ; [q Represents an integer of 0 to 6], and Q ² and Q ³ are each independently selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group and a halogen atom, and are different from each other. Represents a group or atom, Q ¹ , Q ²
And at least a part of the CH ₂ group or CF ₂ group present in Q ³ is —O—, —S—, —CO—, —CHX—; (X is a halogen atom),
At least one group selected from the group consisting of CHCN-, -O-CO-, -O-COO-, -CO-O- and -CH = CH- so that two heteroatoms are not directly bonded , May be substituted]. 13. In the above formula [I], X and Y
11. The liquid crystal composition according to claim 10, wherein each independently represents a group or a bond selected from the group consisting of —COO—, —OCO— and a single bond. 14. The above-mentioned formula [I], wherein R is an alkoxy group.
Item 3. The liquid crystal composition according to item 3. 15. The above formula [I], R ^{* _{is, -C * H (CF 3)}} -C 6 H 13, -C * H (CH 3) -C 6 H 13, -C * H (CH ₃ ) -C
₅ H ₁₁ , -C ^* H (C ₂ H ₅ ) -C ₅ H ₁₁ , -C ^* H (C ₂ H ₅ ) -C ₆ H ₁₃ , -CH ₂ -C ^* H
(CH ₃ ) -C ₂ H ₅ ,-(CH ₂ ) ₃ -C ^* H (CH ₃ ) -C ₂ H ₅ and -C ^* H (CF ₃ ) -C
The liquid crystal composition according to claim 10 or 11, which is a group selected from the group consisting of H ₂ —COO—C ₂ H ₅ . 16. A liquid crystal device comprising a cell composed of two substrates facing each other and a gap formed by the substrates, and a liquid crystal element filled with a liquid crystal substance filled in the gap between the cells, wherein the liquid crystal substance is A liquid crystal device containing a carboxylic acid ester compound represented by the following formula [I]; [However, in the formula [I], R represents 3 to 2 carbon atoms.
0 is an alkyl group, an alkoxy group having 3 to 20 carbon atoms and a halogenated alkyl group having 3 to 20 carbon atoms, and X and Y are each independently -COO. -, -OCO-, -CH ₂ CH
_2- , -CH ₂ O-, -OCH _2- , -SS-, -CO-CH ₂ -and -CH ₂ -CO-
Represents a group or a single bond selected from the group consisting of: B represents a group selected from the group consisting of Represents a group selected from the group consisting of: R ^* is 4 carbon atoms having at least one asymmetric carbon atom;
To 20 optically active groups (a hydrogen atom bonded to a carbon atom constituting the optically active group may be substituted with a halogen atom), m represents 1 or 2, and n represents 0 to 2 Represents the integer of. 17. In the above formula [I], R ^* is represented by the following formula [I
[16] A group represented by [I].
The liquid crystal device of claim ^{wherein; -Q 1 -C * H (Q} 2) -Q 3 ··· [II] [ In Expression [II], Q ¹ _{is, - (CH 2) q -} ; [q is Represents an integer of 0 to 6], and Q ² and Q ³ are each independently a different group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group and a halogen atom. Or represents an atom, Q ¹ , Q ²
And at least a part of the CH ₂ group or CF ₂ group present in Q ³ is —O—, —S—, —CO—, —CHX—; (X is a halogen atom),
At least one group selected from the group consisting of CHCN-, -O-CO-, -O-COO-, -CO-O- and -CH = CH- so that two heteroatoms are not directly bonded , May be substituted]. 18. In the above formula [I], X and Y
17. The liquid crystal element according to claim 16, wherein each independently represents a group or a bond selected from the group consisting of —COO—, —OCO— and a single bond. 19. The formula 16 or 1 wherein R is an alkoxy group in the above formula [I].
Item 8. A liquid crystal device according to item 8. 20. A above formula [I], R ^{* _{is, -C * H (CF 3)}} -C 6 H 13, -C * H (CH 3) -C 6 H 13, -C * H (CH ₃ ) -C
₅ H ₁₁ , -C ^* H (C ₂ H ₅ ) -C ₅ H ₁₁ , -C ^* H (C ₂ H ₅ ) -C ₆ H ₁₃ , -CH ₂ -C ^* H
(CH ₃ ) -C ₂ H ₅ ,-(CH ₂ ) ₃ -C ^* H (CH ₃ ) -C ₂ H ₅ and -C ^* H (CF ₃ ) -C
The liquid crystal device according to claim 16 or 17, which is a group selected from the group consisting of H ₂ —COO—C ₂ H ₅ .