JPS63308090A - Liquid crystal composition and liquid crystal element containing said composition - Google Patents

Abstract

PURPOSE:To provide a liquid crystal composition containing an optically active liquid crystal compound having fluorine atom. directly bonded to asymmetric carbon and a specific liquid crystal compound having optically active group, free from radical change in response speed with temperature and suitable for liquid crystal element, etc. CONSTITUTION:The objective liquid crystal composition can be produced by compounding (A) one or more optically active liquid crystal compounds having fluorine atom. directly bonded to asymmetric carbon and (B) one or more optically active liquid crystal compounds expressed by formula (R1 is 1-18C alkyl; x is 0 or 1; y is integer of 0-8; C* is asymmetric carbon atom.) A liquid crystal element is produced by using a pair of glass substrates 2 each having a transparent electrode 3 and an insulating orientation-controlling layer 4 at the inside and a polarizing plate 8 at the outside and sandwiching the liquid crystal composition 1 between the glass substrates 2 interposing a spacer 5 therebetween, connecting both transparent electrodes 3 with a lead wire 6 and imposing electric potential to the electrodes with a power source 7.

Description

[Detailed Description of the Invention] [Technical Field] The present invention relates to a liquid crystal composition used for liquid crystal elements used in liquid crystal display elements, liquid crystal light shutters, etc. This invention relates to a liquid crystal composition.

The present invention also relates to a liquid crystal composition that has improved display and driving characteristics by improving the alignment state of liquid crystal molecules.

[Conventional technology and its problems]

The use of a liquid crystal element with bistable properties makes C1ark and L
proposed by Agerwall (Japanese Unexamined Patent Application Publication No. 1983-1999)
107216, US Pat. No. 4,367,924, etc.). Bistable liquid crystals are generally chiral smectic C phase (S m C”) or H phase (S m H
A ferroelectric liquid crystal with a medium) is used. This ferroelectric liquid crystal has a bistable state consisting of a first optically stable state and a second optically stable state with respect to an electric field, so TN
Unlike the optical modulation elements used in type liquid crystals, for example, the liquid crystal is oriented in a first optically stable state for one electric field vector and in a second optically stable state for the other electric field vector. The liquid crystal is aligned. In addition, this type of liquid crystal
It has a property (bistability) of taking one of the above two stable states in response to an applied electric field and maintaining that state when no electric field is applied.

In addition to the above-mentioned feature of bistability, ferroelectric liquid crystals have the excellent feature of high-speed response.

For this reason, extensive research has been conducted on liquid crystal materials with ferroelectric properties, but the ferroelectric liquid crystal materials developed to date have sufficient characteristics such as low temperature operation characteristics and high speed response to be used in liquid crystal devices. It is hard to say that it has these characteristics.

Further, in the conventional ferroelectric liquid crystal elements having bistability, the actual situation is that sufficient characteristics cannot be obtained because a uniform alignment state of the liquid crystal is not necessarily formed satisfactorily. For this reason, methods have been proposed for aligning ferroelectric liquid crystals exhibiting bistability into a uniform alignment state in the presence of surfaces subjected to rubbing treatment or oblique evaporation treatment. The present inventors have already found that a bistable ferroelectric liquid crystal having a uniform alignment state can be obtained by using a substrate that has been subjected to the above-mentioned rubbing treatment or oblique evaporation treatment.

However, according to experiments conducted by the present inventors, it has been found that the above-mentioned bistable state does not necessarily have the ideal bistable state shown in the above-mentioned literature published by Clark and Lagerwall.

In other words, according to Clark and Lagerwall, the tilt angle in a chiral smectic phase with a non-helical structure that achieves bistability (angle θ shown in Figure 3 below) is the same as the tilt angle in a chiral smectic phase with a helical structure (angle θ shown in Figure 3 below). It should have the same angle as the apex angle ■) of the triangular pyramid shown in Figure 2, but in reality, the tilt angle θ in the non-helical structure is smaller than the tilt angle ■ in the helical structure. . Furthermore, it has been found that the reason why the tilt angle θ in the non-helical structure is smaller than the tilt angle 2 in the helical structure is due to the twisted arrangement of the liquid crystal molecules in the non-helical structure. In other words, in the chiral smectic phase with a non-helical structure, as shown in FIG. (the direction of the twisted arrangement), they are continuously twisted at a twist angle δ, and this causes the tilt angle θ in the non-helical structure to be smaller than the tilt angle 2 in the helical structure.

In the figure, numeral 81 represents a coaxial alignment obtained by rubbing or oblique vapor deposition on the upper and lower substrates.

By the way, in the case of a liquid crystal element that utilizes the birefringence of liquid crystal, the transmittance under crossed Nicols is expressed as follows. The above l [tilt θ in the helical structure
is expressed as the angle between the average molecular axes of the twisted liquid crystal molecules in the first and second alignment states. According to the above equation, the maximum transmittance occurs when the tilt θ is 22.5°, but in a non-helical structure that achieves bistability, the tilt angle θ is large (approximately 10'). Therefore, when considering the application as a display device, there is a problem that the transmittance is about 3 to 5%, which is not sufficient.

[Purpose of the invention]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a ferroelectric liquid crystal composition that eliminates the above-mentioned drawbacks or disadvantages, and a liquid crystal element using the liquid crystal composition.

More specifically, by mixing specific liquid crystal compounds, we can improve properties such as low-temperature operating characteristics and high-speed response.
It has display characteristics that cannot be obtained with a single liquid crystal compound.
An object of the present invention is to provide a liquid crystal composition and a liquid crystal element using the composition.

A second object of the present invention is to provide a liquid crystal composition with an increased tilt angle in a non-helical chiral smectic phase that achieves a stable state, and a liquid crystal element using the liquid crystal composition.

[Means and actions to achieve the purpose]

Therefore, the present invention provides an optically active liquid crystal compound having a structure in which a fluorine atom is directly bonded to an asymmetric carbon (hereinafter referred to as an F-based liquid crystal compound), preferably the following general formula (3) or -Q
C-CH=CH-, X3 is a single bond! Orshow. =
(ya-, -(lead-9-g)- are respectively -(+R3 and R4 are linear or branched alkyl groups having 1 to 16 carbon atoms, alkoxyalkyl groups or halogenated alkyl groups, and represent asymmetric carbon atoms. You may have one.

a, b, c and d i′! O or 1 or 2, and e is O or l. C* represents an asymmetric carbon atom. ) and at least one optically active fluoroalkane derivative liquid crystal compound represented by the following general formula (1)
% Formula % (1) (In the formula, R1 is a linear or branched alkyl group having 1 to 18 carbon atoms, X is 0 or lSy is an integer of 0 to 8, and C0 is an asymmetric carbon ) More preferably, a liquid crystalline compound having an optically active group represented by the following general formula (2) CH3 R2-X, -A, -Y, -A2-X2+ CH2-
)-CH-(-CH2SOR, (2) ratio (where xl and x2 are single bonds, -0-, -CO-.

Indicates a divalent water-containing ring group which may have.

(Examples of substituents include alkyl groups, alkoxy groups, halogen atoms (chlorine, bromine, or fluorine), or cyano groups, and examples of divalent water-containing ring groups include R2 and R1, each having a carbon number 4-16 and 1-1
8 linear or branched alkyl group, y is an integer of 0 to 8, and X is 0 or 1. C0 represents an asymmetric carbon atom. ) A liquid crystal composition characterized by containing at least one optically active liquid crystal compound represented by the following as a compounded component, and a liquid crystal element formed by disposing the liquid crystal composition between a pair of electrode substrates. It is.

The present invention also relates to a liquid crystal compound having an optically active group in which a fluorine atom is directly bonded to an asymmetric carbon atom and also having an ester bond, the liquid crystal compound containing the optically active group as a carboxylic acid component of the ester bond. a liquid crystal composition containing at least one type of liquid crystalline compound and at least one type of liquid crystalline compound containing the optically active group as an alcohol component of the ester bond; and the liquid crystal composition is disposed between a pair of electrode substrates. The present invention provides a liquid crystal element made of

The liquid crystal compound containing the optically active group as a carboxylic acid component of an ester bond is preferably represented by the following general formula (4) % formula (4), and is a liquid crystal compound containing the optically active group as an alcohol component of an ester bond. The compound preferably has the following general formula (5)% formula% In the general formulas (4) and (5), RII+ R
6+R7 and R8 are linear or branched alkyl groups having 1 to 16 carbon atoms, and C1 represents an asymmetric carbon atom. X5 and x6 represent a single bond, -0- or -COO-, and x7 represents 10- or 100-.

A3. A4. A and A6 are water-containing ring groups that may have a substituent, A3 and A4 are ◎), Y3- (Y3 is a single bond, -CH=CH- or -CH2CH2-,
indicates 1 or 2. ), A, and 80 are ÷◎
:), Y4- (Y4 represents a single bond, -CH=CH- or -CH2CH2-, n represents 1 or 2), and m represents O or 1.

However, the carboxylic acid component represented by the above formula represents the part (A) below.

R, -C” H-CH2+A 3-CO-A 4-X
5-R6(A) Furthermore, the alcohol component refers to the portion (B) below.

That is, the present invention is a liquid crystal composition containing a liquid crystal compound having an optically active group in which a fluorine atom is directly bonded to an asymmetric carbon atom and an ester bond, and in which the optically active group is bonded to the carbon of the ester bond. By mixing at least one type of liquid crystalline compound containing as an acid component and at least one type of liquid crystalline compound containing the optically active group as an alcohol component of the ester bond, it is possible to improve low-temperature operation characteristics, high-speed response, etc. It was discovered that the display characteristics could be improved and display characteristics that could not be obtained with a single liquid crystal compound could be obtained.

Furthermore, in another liquid crystal composition of the present invention, the direction of Ps is positive and 1PS1≧8nc/crtr (l Tc-T I
= 15), preferably at least one type of chiral smectic liquid crystal compound of 20 nc/crrf or more, and P
The direction of s is negative and IPS1≧8nc/c rd (l T
c-T I =15), preferably 20nc/cr+f
An object of the present invention is to provide a liquid crystal composition containing at least one of the above chiral smectic liquid crystal compounds.

The chiral smectic phase mentioned above is Sm*C, Sm*H
, Sm*F.

Sm*I and Sm*G phases are shown. Furthermore, the above-mentioned 1T
c-TI means a value at a temperature 15° C. lower than the upper limit temperature exhibiting the chiral smectic liquid crystal phase. For example, in the case of a material having a chiral smectic C phase, the temperature is 15° C. lower than the upper limit temperature exhibiting the chiral smectic C phase.

The twist angle and twist direction due to the above-mentioned twisted arrangement are determined by the surface condition of the liquid crystal and the substrate and the interaction between liquid crystal molecules, but the twisted arrangement can be resolved by using a liquid crystal element made of the above liquid crystal composition. . The ferroelectric liquid crystal device that eliminates the twisted alignment can obtain the maximum transmittance/shading rate contrast under non-orthogonal Nicols, and the liquid crystal device with the bistable state of twisted alignment has the maximum contrast under non-orthogonal Nicols. However, at this time, the contrast has a viewing angle dependence that differs depending on the viewing direction.However, in addition to eliminating such a twisted arrangement, the above-mentioned viewing angle dependence can also be eliminated.

This will be described in detail below.

Through this research, the present inventors found that by mixing an F (fluorine)-based liquid crystal compound and the liquid crystal compound of formula (1) above, the smectic C1 phase was improved compared to when each liquid crystal compound was used alone. It has been found that it is possible to provide a liquid crystal element that has a wider temperature range, an improved response speed, and improved display characteristics. The present invention will be explained in more detail below. "%" and "parts" indicating quantitative ratio in the following descriptions
All are based on weight.

The liquid crystalline compounds include general F-type liquid crystalline compounds (preferably those represented by general formula (3)) and liquid crystalline compounds having an optically active group represented by general formula (1) (preferably general formula (2)). It is what is expressed.

The structural formulas and liquid crystal phase transition temperatures of specific examples of liquid crystalline compounds represented by general formulas (2) and (3) are shown in Tables 1 and 2 below.
Shown below. However, the present invention is not limited to only those listed here.

In the table, the symbols in the phase transition temperature column indicate the following phases, respectively.

Crystal: Crystal phase, S m A: Smectic A phase, S m C”
: Chiral smectic C phase, N: Nematic phase, Ch: Cholesteric phase, Iso: Tokichi phase, Sml, Sm2. Sm3: SmA, SmC”
Other optically active liquid crystalline compounds represented by general formula (2) can be synthesized by the following method.

As a starting material, use the general formula (6) % formula % (6) (where R6 is a lower alkyl group, C1 is an asymmetric carbon atom, x and z are O or l. When X is O, 2 is O or 1, and when X is 1, 2 is O.) From the compound represented by the following reaction process formulas (1) and (2)
An optically active alcohol or an optically active alponic acid can be synthesized according to the method or by repeating the process formula (2).

OH3 ■ D+CH2+-CH-+CH2-OR, (7) Y * (Here, R1 is a straight chain or branched alkyl group having 1 to 18 carbon atoms, y is an integer of O to 8, and X is O or 1. D is -OH or COH.) Step (1) OH3 JinR, -0-+CH2qcH+cH,-)-; CH20M
(7)-1 step (2) The optically active alcohol or optically active carboxylic acid synthesized in this way and the corresponding alcohol,
By reacting with derivatives such as thiol or carboxylic acid derivatives by a conventional method, the following general formulas (8) and (9) are shown. Further, A2 represents a divalent water-containing ring group which may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom (chlorine, bromine, fluorine), a cyano group,
Examples of divalent water-containing ring groups include Baku) (CH, -(■-◇G), HqΣ and ヅ←.

R1 is a linear or branched alkyl group having 1 to 18 carbon atoms, y is an integer of 0 to 8, and X is O or 1.

Y is -0- or -S-, Y6 is a single bond, -
CH=CH- or -CH2CH2. C0 represents an asymmetric carbon atom. ) An optically active alcohol and an optically active carboxylic acid having an ether or ester bond can be obtained.

(7), (8), and (9) are further expressed by the following general formula (10),
(11) % Formula % (10) (Here, R2 represents a branched or straight-chain alkyl group having 4 to 16 carbon atoms. A1 represents a divalent water-containing ring group which may have a substituent, and , is a single bond, -O-, -CO-.

Y7 and Y9 are single bonds, -CH2CH2- or -C
H=CH-, and Y8 is 10- or -8-. ) by reacting with an alcohol, thiol derivative, or carboxylic acid derivative by a conventional method,
An optically active liquid crystal compound represented by the general formula (2) can be synthesized.

The optically active fluoroalkane derivative represented by the above general formula (3) is preferably a 2-fluoro-1-alkanol shown in the specification of Japanese Patent Application No. 60-232886, etc.
p-hydroxybenzoic acid (2-fluoroalkyl) ester, p-hydroxybiphenylcarboxylic acid (2-
It is synthesized from optically active intermediates such as fluoroalkyl) ester, hydroquinone (2-fluoroalkyl)ether, and 4-(4'-(2-fluoroalkyl)oxyphenyl)phenol.

For example, in the case of the following combination of these optically active intermediates.

) A liquid crystal compound is obtained.

The liquid crystal composition of the present invention contains 1 to 99% of at least one liquid crystal compound having an optically active group represented by general formula (1), preferably at least one liquid crystal compound represented by general formula (2), and an F-based liquid crystal. It is preferable to form the liquid crystal compound by mixing 99 to 1% of at least one type of liquid crystalline compound, preferably a liquid crystalline compound represented by the general formula (3).

Further, another liquid crystal composition of the present invention showing good results is a liquid crystal compound having an optically active group in which a fluorine atom is directly bonded to an asymmetric carbon atom and having an ester bond,
A liquid crystal containing at least one type of liquid crystal compound containing the optically active group as the carboxylic acid component of the ester bond and at least one type of liquid crystal compound containing the optically active group as the alcohol component of the ester bond. It is a composition.

The liquid crystal compound containing the optically active group as a carboxylic acid component of an ester bond is preferably represented by the following general formula (4) % formula (4), and is a liquid crystal compound containing the optically active group as an alcohol component of an ester bond. The liquid crystalline compound preferably has the following general formula (5).Representative examples of the liquid crystalline compound are shown below. A liquid crystal compound containing the optically active group as a carboxylic acid component of an ester bond, preferably represented by the general formula (4) 4-7
F No 1111 No
l111LJ U * II
IIOO Not II
IIOO The optically active liquid crystal compound represented by the above general formula (4) is preferably p-2-fluoroalkoxybenzoic acid, p-2-fluoroalkoxybenzoic acid,
It is synthesized from optically active intermediates such as '-2-fluoroalkoxybiphenyl-p-carboxylic acid.

For example, a liquid crystalline compound represented by general formula (4) can be obtained from these optically active intermediates by the following synthetic route.

■ R, -CHCH20-A 3-(:OH rate (1 *, 11 (However, the signs in the above formula match the above-mentioned signs.)
Further, specific examples of liquid crystal compounds containing the optically active group as an alcohol component of an ester bond, preferably liquid crystal compounds represented by general formula (5), are shown below in II.
II *O0 5-7F "No-10F Cl0H210+CO-◎-0CH2CHC5HI+1
1* Il* 5-18
FI C9H190-◎-Co-10-OCH2CHC8HI
OII* The optically active liquid crystal compound represented by the above general formula (5) is preferably 2-fluoro-1-alkanol, p-hydroxybenzoic acid (2-fluoroalkyl ) ester, p-hydroxybiphenylcarboxylic acid (2-fluoroalkyl)
It is synthesized from optically active intermediates such as ester, hydroquinone (2-fluoroalkyl) ether, and 4-(4'-(2-fluoroalkyl)oxyphenyl]phenol).

For example, from these optically active intermediates, a liquid crystal compound represented by general formula (5) (however, the symbols in the above formula are the same as those described above) is produced by the following synthetic route.The liquid crystal composition of the present invention The substance is a liquid crystal compound containing the above-mentioned optically active group as a carboxylic acid component of an ester bond, preferably a liquid crystal compound having the above-mentioned general formula (
4) A small amount of the liquid crystalline compound shown in (1 to 9)
9% and the above-mentioned optically active group as an alcohol component of the ester bond, preferably a liquid crystal compound containing the above-mentioned general formula (5).
) at least one liquid crystalline compound represented by 99-1
It is desirable to create the mixture by mixing at a ratio of %.

FIG. 1 is a schematic cross-sectional view of an example of a liquid crystal display element having a ferroelectric liquid crystal layer, for explaining the structure of the ferroelectric liquid crystal element.

In FIG. 1, 1 is a ferroelectric liquid crystal layer, 2 is a glass substrate, 3 is a transparent electrode, 4 is an insulating alignment control layer, 5 is a spacer, 6 is a lead wire, 7 is a power source, 8 is a polarizing plate, 9 indicates a light source.

The two glass substrates 2 are each made of In2O3゜SnO.
2 or ITO (Indium-Tin Oxid
A transparent electrode made of a thin film such as e) is coated. On top of this, a thin film of a polymer such as polyimide is rubbed with gauze or acetate flocked cloth to form an insulating alignment control layer that aligns the liquid crystals in the rubbing direction. The insulating layer may be made of silicon nitride, hydrogen-containing silicon carbide, silicon oxide, boron nitride, hydrogen-containing boron nitride, cerium oxide, aluminum oxide, zirconium oxide, titanium oxide, or fluoride. An inorganic insulating layer such as magnesium is formed, and then polyvinyl alcohol, polyimide, polyamideimide, polyesterimide, polyvaraxylene, polyester, polycarbonate, polyvinyl acetal, polyvinyl chloride, polyvinyl acetate, polyamide, polystyrene, cellulose resin , an organic insulating material such as melamine resin, Yulia resin, acrylic resin or photoresist resin as an orientation control layer, 2
The layer may form an insulating orientation control layer, and
It may be a single layer of an insulating orientation control layer made of an inorganic material or an insulating orientation control layer of an organic material. If this insulating alignment control film is inorganic, it can be formed by a vapor deposition method, or if it is organic, it can be formed in a solution containing an organic insulating material or its precursor solution (0.1 to 20% by weight in a solvent, preferably 0.1 to 20% by weight, preferably 0.1 to 20% by weight in a solvent). 2 to 1.0% by weight) by a spinner coating method, dip coating method, screen printing method, spray coating method, roll coating method, etc., and is cured and formed under predetermined curing conditions (e.g., heating). be able to. The thickness of the insulating orientation control layer is usually 5
Suitable numbers are 0 to 1μ, preferably 100 to 5000 people, and more preferably 500 to 3000 people.

These two glass substrates 2 are kept at an arbitrary distance by a spacer 5. For example, there is a method in which silica beads or alumina beads having a predetermined diameter are used as spacers and sandwiched between two glass substrates, and the periphery is sealed using a sealing material such as an epochino adhesive. In addition, a polymer film, glass fiber, or the like may be used as a spacer. A ferroelectric liquid crystal is sealed between these two glass substrates.

A ferroelectric liquid crystal layer containing a ferroelectric liquid crystal is generally 0
．． It is 5μ to 20μ, preferably 1μ to 5μ.

The transparent electrode 3 is connected to an external power source 7 by a lead wire. Further, a polarizing plate 8 is bonded to the outside of the glass substrate 2.

Since the device shown in FIG. 1 is of a transmission type, it is equipped with a light source 9.

FIG. 2 schematically depicts an example of a cell for explaining the operation of a ferroelectric liquid crystal element. 21a and 21b are
In2O3, 5n02 or ITO (Ind
It is a substrate (glass plate) coated with a transparent electrode made of a thin film such as Sm-Tin Oxide), between which a liquid crystal molecular layer 22 is oriented perpendicular to the glass surface.
A C"phase or S m H" phase liquid crystal is sealed. A thick line 23 represents a liquid crystal molecule, and this liquid crystal molecule 23 has a dipole moment (P±) 24 in a direction perpendicular to the molecule. When a voltage higher than a certain threshold is applied between the electrodes on the substrates 21a and 21b, the liquid crystal molecules 2
The helical structure of 3 unravels and the dipole moment (P±)2
4 are all oriented in the direction of the electric field (so that the liquid crystal molecules 23 can change the alignment direction. The liquid crystal molecules 23 have an elongated shape and exhibit refractive index anisotropy in the long axis direction and the short axis direction. Therefore, it is easily understood that, for example, if crossed Nicol polarizers are placed above and below a glass surface, a liquid crystal optical modulation element whose optical characteristics change depending on the polarity of applied voltage can be obtained.

The liquid crystal cell preferably used in the optical modulation element of the present invention can have a sufficiently thin thickness (for example, 10 μm or less). As the liquid crystal layer becomes thinner, the helical structure of the liquid crystal molecules unravels even when no electric field is applied, as shown in Figure 3, and the dipole moment Pa or pb is directed upward (34a) or downward (34a). 34b).When an electric field Ea or Eb of different polarity above a certain dark value is applied to such a cell by the voltage applying means 31a and 31b as shown in FIG. 3, the dipole moment becomes , the direction changes upward 34a or downward 34b in response to the electric field vector of the electric field Ea or Eb, and accordingly the liquid crystal molecules are oriented in either the first stable state 33a or the second stable state 33b. .

As mentioned earlier, there are two advantages to using such ferroelectricity as an optical modulation element.

The first is that the response speed is extremely fast, and the second is that the alignment of liquid crystal molecules has bistability.

To further explain the second point, for example, with reference to FIG. 3, when the electric field Ea is applied, the liquid crystal molecules are oriented in a first stable state 33a, and this state remains stable even when the electric field is turned off. When an electric field Eb in the opposite direction is applied, the liquid crystal molecules are oriented to a second stable state 33b and change their orientation, but they remain in this state even after the electric field is turned off. Further, as long as the applied electric field Ea or Eb does not exceed a certain darkness value, the previous orientation state is maintained.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, in the following examples, spontaneous polarization will be described in detail in Miyasato et al., "Direct measurement method of spontaneous polarization of ferroelectric liquid crystals using triangular waves", Journal of the Japan Society of Applied Physics ■, No. 10, L (661) 1983,
("Direct Method with T
rangularW a v e s f o r
M e a s u r i n g S p
o n t a n e o u 5Polariza
tt*n in Ferroelectric
LiquidCrysta+”, as descr
ibed by K, Miyasat.

et al, (Jap, J, Appl, Phys, 2
2. No, 10. L661 (1983))).

In addition, regarding the polarity of Ps, the definition of Clark et al. (N
.

A, CIark and S, T, Lagerwe.
ll, Fe'rroelectrics.

It was measured according to Heel P, 25 (1984)).

Note that a liquid crystal compound that does not exhibit a chiral smectic phase when used alone exhibits a smectic C phase, and after being mixed with a liquid crystal compound that does not have Ps at a ratio of 10:90 to have a chiral smectic C phase, Ps was measured, and using this value as 10% of the original value, liquid crystal compound 15 and liquid crystal compound 41 described in Tables 1 and 2 of Example 1 were mixed at a ratio of 84:16 to obtain a liquid crystal composition. Ta. This liquid crystal composition exhibited the following phase transition.

That is, in this liquid crystal composition, the temperature range of the chiral smectic C phase is expanded to both the high temperature side and the low temperature side compared to the liquid crystal compound 15 alone, and SmC'' is kept relatively stable even at supercooled temperatures.

The results of spontaneous polarization and response speed of the above liquid crystal composition are shown in Table 3 below.
Shown below.

Table 3 The above response speed was determined by sandwiching the above liquid crystal composition between a pair of electrode substrates with a polyimide coating covering the electrodes subjected to a rubbing treatment, setting the liquid crystal layer thickness to 2 μm, and applying a voltage of 20 V as a peak-to-peak voltage. The response speed was measured by detecting the optical response under crossed Nicols (from the time of voltage application until the amount of transmitted light changes by 90%).

As can be seen from the above, the mixed liquid crystal composition according to the present invention has a wider temperature range of the S m C'' phase than a single liquid crystal compound, and the large spontaneous polarization of the F-based liquid crystal compound The response speed has been improved due to this.

Example 2 Liquid crystalline compound 5 listed in Table 1 above. 6. 10 to 1:
The liquid crystal composition Δ mixed at a ratio of 1:2 exhibits the following phase transition.

4.9 89.4 92.7 Also shown are the spontaneous polarization values and helical windings of each liquid crystal compound 5°6.10 of the liquid crystal composition Δ.

Spontaneous polarization wound liquid crystal compound 5 (Tc-T=10℃) +21
nc/cm” Left 6 (Tc-T=10℃) +1
5nc/cm2 left 10 (Tc-T=10℃) +20
nc/cm" left and liquid crystalline compound 4 listed in Table 2 above
A liquid crystal composition obtained by mixing 4 and 48 in a ratio of 1:3 exhibits the following phase transition.

In addition, each of the liquid crystal compounds 44,
48 results are also shown.

Spontaneous polarization wound liquid crystal compound 44 (Tc-T=lO℃) -4
1nc/am' left 48 (Tc-T=10℃) -
61 nc/cm" left Figure 7 shows the change in phase transition temperature (heating process) of the liquid crystal composition obtained by mixing these two liquid crystal compositions Δ and Δ as a phase diagram. It is clear from Figure 7. As can be seen, the temperature range of chiral smectic C especially expands to the low temperature side near the mixing ratio of A:B=80+20.

Moreover, among this composition 1, Aao-B20 (A:
B-80/20 mixture), a device was prepared in the same manner as in Example 1, and the response speed was measured under exactly the same conditions.
The response characteristics were improved compared to when 0% was used.

(The response speed of liquid crystal composition A at 25°C is 61
0 Al5ec. ) In this liquid crystal element (the measurement conditions are the same as those in Example 11 below), the tilt angle was 15° and the maximum transmittance was 13%.

Example 3 Liquid crystalline compound 1.4 listed in Table 1 above. 10. 15
and 16, and liquid crystal compound 41 listed in Table 2 above were further mixed in the proportions shown in Table 4 below to obtain a liquid crystal composition.

Table 4 This liquid crystal composition exhibited the following phase transition.

-20,256,266,4 Using the above composition, an element was prepared in the same manner as in Example 1, and the optical response speed measured under the same conditions was 25°C.
It was 22011 sec.

That is, in this liquid crystal composition, the temperature range of the chiral smectic C phase is expanded particularly to the low temperature side, and the liquid crystal composition maintains a stable state at room temperature, and the response speed is improved.

Example 4 Liquid crystal compound 10 listed in Table 1 above. 15. 16 and liquid crystalline compounds 33, 44, and 46 listed in Table 2 above, respectively. 20. 5. 5. 10. Using liquid crystal compositions mixed at 25% each, the phase transition was investigated and the optical response speed was confirmed in the same manner as in Example 3. It was found that the smectic A phase spread to the lower temperature side compared to the single liquid crystal compound, which was an improvement in the response speed. We were able to obtain a liquid crystal device.

Example 5 Liquid crystal compound 22 listed in Table 1 above. 30 and liquid crystal compounds 33, 44, and 46.47 listed in Table 2 above at 15%, respectively. 5. 10. 15.35. It was confirmed that the same results as in Example 4 could be obtained even if liquid crystal compositions were mixed in a proportion of 20%.

Example 6 Liquid crystal composition (5-a) mixed with liquid crystal compound 5-12 and liquid crystal compound 5-26 in a ratio of 3:1 and liquid crystal compound 4-3
mixed with. FIG. 4 shows the relationship between the orientation ratio and phase transition temperature of this mixed system.

Here, the phase transition temperature of the liquid crystal compound 4-3 is as shown below.
.

Although it is a monotropic liquid crystal, the blending ratio of 4-3 is 30wt.
%, the Sc” phase expands at both low and high temperatures, ranging from 46 to 72°C. (Here, Crystal is the crystalline phase,
(c" indicates chiral smectic C phase, SA indicates smectic A phase, and Iso indicates isotropic liquid.) Example 7 Two 0.7 m thick glass plates were prepared, and an ITO film was placed on each glass plate. was formed to create a voltage application electrode, and 5i02 was further vapor-deposited on this to form an insulating layer.A silane coupling agent [KBM-60 manufactured by Shin-Etsu Chemical Co., Ltd.] was placed on a glass plate.
2) Surface treatment was performed by applying a 0.2% isopropyl alcohol solution for 15 seconds at a rotation speed of 200 Or, p, m. Thereafter, a heat drying treatment was performed at 120° C. for 20 minutes.

Further surface treatment was performed. Polyimide resin and precursor [Toshi ■5P-510] 2% dimethylacetamide solution were placed on a glass plate with an ITO film at a rotational speed of 2000 rpm.

It was applied for 15 seconds using a spinner. 60 minutes after film formation,
A heating condensation firing treatment was performed at 300°C. The thickness of the coating film at this time was about 700. This fired coating was rubbed with acetate flocked cloth, then washed with isopropyl alcohol solution, and alumina beads with an average particle size of 1.5 μm were sprinkled on one glass plate, and each rubbed axis The glass plates were glued together so that they were parallel to each other using an adhesive sealant [Rixon Bond (Chisso@)], and dried by heating at 100° C. for 60 minutes to create a cell. The cell thickness of this cell was measured using a Bereck phase plate and was found to be approximately 1.6 μm.

Next, the liquid crystal composition of Example 6 (blending ratio of 4-3 was 30 wt%)
) was heated to form an isotropic liquid, which was vacuum injected into the cell prepared above. The material was slowly cooled from the Toyoshi phase to 65°C at a rate of 0.5°C/h, and a pair of polarizers were placed in a crossed nicol state at the same temperature. When observed under a microscope, a monodomain non-helical Sc" state was formed. It was confirmed that

Next, by applying a voltage of 1OV as a peak-to-peak voltage, the optical response under crossed Nicols was detected (from the time the voltage was applied until the amount of transmitted light changed by 90%) and the response speed was measured. . For comparison, the response speeds of the mixed components of liquid crystal composition (5-a) and liquid crystal compound 4-3 were also measured in the same manner. The response speed results are shown in FIG. As can be seen from the figure, the mixed liquid crystal composition of the present invention has improved temperature characteristics of response speed.

Example 8 A liquid crystal composition (4
-a) was obtained. A liquid crystal composition (5-b) was also obtained by mixing liquid crystal compounds having the optically active group as an alcohol component of an ester bond in the proportions shown below.

Liquid crystal composition (4-a) 4-3/4-6/4-8=8/1/1 (weight ratio) Liquid crystal composition (5-b) 5-515-1275-1315-27=2/4 /1/
2 (weight ratio) This liquid crystal composition (4-a), (5
Liquid crystal composition q obtained by mixing -b) at a ratio of 1:3
A device was prepared using the same method as in Example 7, and the response speed was measured under exactly the same conditions. The results are shown below. The response speeds of liquid crystal composition (4-a) and liquid crystal composition (5-b) measured in the same manner are also shown.

Liquid crystal composition (4-a) 60°C 75°C -20μ formula % formula % (5) 35μsec 20μsec 18μ formula liquid crystal composition q 55°C65℃ 70℃ 30μsec 234sec 20
μsec The above results are shown in FIG.

Next, when the device using liquid crystal composition q was driven at 60° C. with a driving voltage ±IOV and a pulse width of 50 μsec, a good switching state with a contrast of 17 was obtained.

As can be seen from the above, the mixed liquid crystal composition according to the present invention had improved response characteristics in a low temperature range and had good display characteristics.

Example 9 When the response speed and switching state were checked under exactly the same conditions as in Example 8 using liquid crystal composition p mixed in the following proportions in the same device as in Example 7, it was found that the mixed liquid crystal composition according to the present invention It was found that the response characteristics and display characteristics in the low temperature range were improved.

[Liquid crystal composition]

Liquid crystal composition 4-b [4-3/4-5=3/1 (weight ratio)] and liquid crystal composition 5-c [5-515-10=2
/1 (weight ratio)] in a ratio of 2=3.

Example 10 The response speed and switching state of a liquid crystal composition mixed in the same device as in Example 7 in the following proportions were checked under exactly the same conditions as in Example 6, and it was found that the mixed liquid crystal composition according to the present invention It was found that the response characteristics and display characteristics in the low temperature range were improved.

[Liquid crystal composition E]

Liquid crystal composition 4-C [4-4/4-8=1/2 (weight ratio)] and liquid crystal composition 5-D [5-415-28=1/
4 (weight ratio)] and were mixed at a ratio of 1:4.

Example 11 The following liquid crystal compounds were mixed in the following composition ratio to obtain a liquid crystal composition.

Next, using Composition F, a liquid crystal element having a liquid crystal film thickness of approximately 3 μm was prepared. (Liquid crystal element 1) The structure of the substrate of the 3 μm cell is two 0.7 mm thick glass plates each made of 1000 ITO (Induim Tin).
0xide) and 200 PI (polyimide) coatings.The PI coating is uniaxially oriented by rubbing, and the two substrates are placed in a cell with their respective rubbing axes parallel to each other. I assembled it.

The cell thickness (distance between the upper and lower substrates) was maintained with a 3 μm bead-like spacer.

The above-mentioned mixed liquid crystal was vacuum injected into this liquid crystal cell under the Tokichi phase and then slowly cooled from the Tokichi phase to 30°C at a rate of 0.5°C/h, thereby making it possible to align the liquid crystal.

Subsequent experiments were conducted at 30'C.

When this cell was observed under crossed nicol conditions, uniform, defect-free monodomains were obtained.

Next, by rotating the cell of the liquid crystal element 1 under crossed nicol conditions, a position with the least amount of transmitted light was searched for. Its darkest state turned black. This revealed that the liquid crystal molecules are aligned in one direction, creating a bistable state of domains with extremely high contrast between black and yellow. When the tilt angle was measured, it was 22°.

Next, a 3 μm cell was created in exactly the same manner as the method used to create the 3 μm cell described above, except that the following liquid crystal composition q was used. (Liquid crystal element 2) (Ps = 1.1 nc/crrr for composition q) This liquid crystal has a very low contrast in the SmC* state, and it was found that a bistable state of blue and yellow domains exists. .

A pulsed electric field was applied to this liquid crystal element 2 to align the direction of the liquid crystal molecules to one stable state, and the cell was rotated under crossed Nicol conditions to find a position where the amount of transmitted light was the smallest. However, the darkest state was not black but blue. If the liquid crystal molecules are parallel to the substrate and aligned in one direction, black color should be obtained.

The present inventors believed that this coloring was caused by the twisted arrangement of liquid crystal molecules with respect to the vertical direction (normal line) of the substrate, and conducted further experiments.

By shifting the angles of the polarization axes of the polarizer on the light source side and the analyzer on the observer side, the twisted array state can be detected by determining whether a darker state can be obtained.

From the perspective of the observer, clockwise rotation is positive and counterclockwise rotation is negative. Move the analyzer from crossed nicols to lO°~1 in the negative direction.
It was possible to rotate 3 degrees and then rotate the liquid crystal cell to look for the dark state. Also, move the polarizer from crossed nicols to l in the positive direction.
A similar dark state was obtained even when rotated by 0° to 13°. Therefore, it can be seen that the liquid crystal molecules in this device form a twisted arrangement in the positive direction, and the long axes of the liquid crystal molecules on the adjacent surfaces of the upper and lower substrates are twisted with a twist angle δ of 10° to 13°. . Further, when the tilt angle θ was measured, it was found to be 6° around the rubbing axis.

As mentioned above, the direction of Ps is negative and Ps<-10nc/cd
A liquid crystal element l using a liquid crystal composition y consisting of a liquid crystal compound with a left spiral winding direction and a liquid crystal compound with a positive Ps direction of Ps > 10 nc/cm'' and a right spiral winding direction is as follows. It was found that the twisted alignment was eliminated and the contrast was significantly improved compared to liquid crystal element 2 which had a twisted alignment.

Example 12 A cell with the same configuration as Example 11 was created except for the cell thickness (5 p m, 10 p m, 20 μm).
Then, liquid crystal composition F was injected to obtain liquid crystal elements (liquid crystal elements 3 to 5).

Using the above element, microscopic observation was performed while applying an electric field in the same manner as in Example 11.

The observation results of the tilt angle θ, the color of the darkest state, and the color of the brightest state are shown below.

Tilt angle θ Darkest state Brightest state Liquid crystal element 3 22° Black Blue liquid crystal element 4
22° Black White liquid crystal element 5 20°
It was found that the twisted alignment of liquid crystal elements 3 to 5 using the liquid crystal compositions as described above was eliminated and the contrast was good. When the cell thickness becomes 108 or more,
The brightest state became white, and the improvement in contrast was particularly noticeable.

Example 13 The following liquid crystal compounds were mixed in the following composition ratio to obtain a liquid crystal composition.

! A cell having the same structure as Example 11 except for the cell thickness (1.2 μm) was prepared, and a liquid crystal element 6 was obtained using the above liquid crystal composition.

Observation of this cell under crossed Nicol conditions revealed uniform, defect-free monodomains and the presence of a bistable state of high-contrast black and white domains.

Using this liquid crystal element 6, microscopic observation was performed while applying an electric field as in Example 11, and the tilt angle was 18°.
Met.

Furthermore, when the transmittance was measured, a very high transmittance of 16% was obtained.

Next, when the threshold characteristics using a pulsed electric field were measured, it was found that the threshold characteristics were very excellent, 6 V at 500 μs and 1.3 V at 100 m5t'.

Example 14 Liquid crystal Example 1 was prepared by mixing the following liquid crystal compounds in the following composition ratio.
A cell having the same structure as Example 1 was prepared except for the cell thickness (1.2 μm) and the PI coating was changed to a PVA (polyvinyl alcohol) coating, and a liquid crystal element 7 was obtained using the liquid crystal composition ①.

When this cell was observed under crossed nicol conditions, uniform, defect-free monodomains were obtained.

By rotating the cell under crossed Nicol conditions, almost the entire surface became the darkest state when the cell was set to the darkest position.

Using this liquid crystal element 7, the tilt angle was measured in the same manner as in Example 11 and was found to be 15'. Furthermore, when the transmittance was measured, a very high transmittance of 13% was obtained.

Example 15 The following liquid crystal compounds were mixed in the following composition ratio to prepare a liquid crystal composition l.
I got it.

Racemic Form F Racemic Form A cell exactly the same as in Example 14 was prepared, and the above liquid crystal composition I was prepared.
A liquid crystal element 8 was obtained using the following method.

When this cell was observed under crossed nicol conditions at 35° C., uniform, defect-free monodomains were obtained.

When the liquid crystal was set to the darkest position in the "S m C" state, almost the entire surface was in the darkest state.

When the tilt angle of this liquid crystal element 8 was measured in the same manner as in Example 11, it was 20°. Further, when the contrast ratio was measured, an extremely excellent contrast ratio of 50:1 was obtained.

〔Effect of the invention〕

As explained above, according to the present invention, a liquid crystal composition with a wide temperature range can be obtained, and at the same time, a liquid crystal element with excellent response in a low temperature range and excellent display characteristics without sudden changes in response speed due to temperature can be obtained. I was able to get it.

Furthermore, according to the present invention, Ps≧8nc/c rd (l
at least one chiral smectic liquid crystal compound with a temperature of Tc-T1=15°C), and Ps≦-8n c/c
(preferably IPs1≧10 n c / c i) , more preferably 1Ps1≧20nc/crds, where ITc−TI=
15°C), the tilt angle of the bistable state can be expanded, and a display element or shutter element can be realized that is endowed with the amount of transmitted light and contrast, and has high-speed response, pixel density, and large area.

[Brief explanation of the drawing]

FIG. 1 is a schematic cross-sectional view of an example of a ferroelectric liquid crystal element of the present invention; FIGS. 2 and 3 are perspective views schematically showing an example of an element cell for explaining the operation of a ferroelectric liquid crystal element; FIG. 4 is a phase diagram showing a change in phase transition temperature depending on the composition when liquid crystal composition 5-a and liquid crystal compound 4-3 were mixed according to Example 6. FIG. 5 shows liquid crystal composition 5-a of Example 7 and liquid crystal compound 4.
FIG. 3 is a diagram showing the results of the response speeds of a mixture of Liquid Crystal Compound 5-3, Liquid Crystal Composition 5-a, and Liquid Crystal Compound 4-3, respectively. FIG. 6 is a diagram showing the results of Example 8. FIG. 7 shows a phase diagram showing changes in phase transition temperature due to mixing of liquid crystal composition N and liquid crystal composition D according to Example 2. FIG. 8 is a plan view schematically showing liquid crystal molecules arranged in a twisted manner along the normal line of the substrate. In Figure 1, l・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・Ferroelectric liquid crystal layer, 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, I.・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
Incident light, ■・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
Transmitted light. In Figure 2, 21a ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・ Board, 2
1b ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・ Board, 22
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
...Ferroelectric liquid crystal layer, 23 ......
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・Liquid crystal molecules, 24 ・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・Layer polar moment (P
±). In Figure 3, 31a ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
...Voltage application means, 31b ......
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・Voltage application means,
33a ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・First stable state, 33b ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
......Second stable state, 34a...
・・・・・・・・・・・・・・・・・・・・・Upward dipole moment, 34b ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・Downward dipole moment, Ea・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・Upward electric field, Eb...
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
...Downward electric field. In FIG. 8, 81 . . . axial alignment axes formed on the upper and lower substrates, 82 . . .
・・・・・・・・・Axes of liquid crystal molecules adjacent to the upper substrate, 83・・・・・・・・・・・・・・・・・・Axes of liquid crystal molecules adjacent to the lower substrate shaft. ■-: 3 紫■IC ℃

Claims (1)

[Claims] 1) At least one optically active liquid crystal compound having a structure in which a fluorine atom is directly bonded to an asymmetric carbon and the following general formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1 ) (In the formula, R_1 is a linear or branched alkyl group having 1 to 18 carbon atoms, x is 0 or 1, and y is an integer of 0 to 8. C^* represents an asymmetric carbon atom. 1. A liquid crystal composition comprising at least one liquid crystal compound having an optically active group represented by: 2) The liquid crystal composition according to claim 1, wherein the liquid crystal compound having an optically active group represented by the general formula (1) is a liquid crystal compound represented by the following general formula (2). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) (In the formula, X_1 and X_2 are single bonds, -O-, ▲Mathematical formulas,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, Y_1 is a single bond, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CH_2CH_
2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, A_1 and A_
2 represents a divalent six-membered ring-containing group which may have a substituent. R_2 and R_1 have 4 to 16 carbon atoms and 1 carbon number, respectively.
-18 linear or branched alkyl group, y is 0
An integer of ~8, x is 0 or 1. C^* indicates an asymmetric carbon atom. 3) Claims 1 and 2, wherein the optically active liquid crystal compound having a structure in which a fluorine atom is directly bonded to the asymmetric carbon is a liquid crystal compound represented by the following general formula (3). liquid crystal composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(3) (In the formula, Y_2 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, X_3 is a single bond, -O-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ , X_4 indicates -O- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
are ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. R_3 and R_4 are a linear or branched alkyl group, an alkoxyalkyl group, or a halogenated alkyl group having 1 to 16 carbon atoms, and may have an asymmetric carbon. a, b, c and d are 0, 1 or 2; e is 0 or 1; C^* represents an asymmetric carbon atom. ) 4) The substituents of A_1 and A_2 in the general formula (2) are an alkyl group, an alkoxy group, a halogen atom (chlorine, bromine or fluorine), or a cyano group, and the divalent six-membered ring-containing group has the formula ▲, There are chemical formulas, tables, etc.▼,▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, Liquid crystal compositions according to scopes 2 and 3. 5) At least one optically active liquid crystal compound having a structure in which a fluorine atom is directly bonded to an asymmetric carbon and the following general formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (In the formula, R_1 is a linear or branched alkyl group having 1 to 18 carbon atoms, x is 0 or 1, and y is an integer of 0 to 8. C^* represents an asymmetric carbon atom) 1. A liquid crystal element having a liquid crystal composition comprising at least one liquid crystal compound having an active group. 6) The liquid crystal element according to claim 5, wherein the liquid crystal compound having an optically active group represented by the general formula (1) is a liquid crystal compound represented by the following general formula (2). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) (In the formula, X_1 and X_2 are single bonds, -O-, ▲Mathematical formulas,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, Y_1 is a single bond, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CH_2CH_
2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, A_1 and A_
2 represents a divalent six-membered ring-containing group which may have a substituent. R_2 and R_1 have 4 to 16 carbon atoms and 1 carbon number, respectively.
~18 linear or branched alkyl group, y is 0~
An integer of 8, x is 0 or 1. C^* indicates an asymmetric carbon atom. ) 7) Claims 5 and 6, wherein the optically active liquid crystal compound having a structure in which a fluorine atom is directly bonded to the asymmetric carbon is a liquid crystal compound represented by the following general formula (3). liquid crystal element. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(3) (In the formula, Y_2 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, X_3 is a single bond, -O-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ , X_4 indicates -O- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ R_3 and R_4 are a linear or branched alkyl group, an alkoxyalkyl group, or a halogenated alkyl group having 1 to 16 carbon atoms, and may have an asymmetric carbon. a, b, c and d are 0, 1 or 2; e is 0 or 1; C^* represents an asymmetric carbon atom. ) 8) The substituents A_1 and A_2 in the general formula (2) are an alkyl group, an alkoxy group, a halogen atom (chlorine, bromine or fluorine), or a cyano group, and the divalent six-membered ring group has the formula ▲, There are chemical formulas, tables, etc.▼,▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, The liquid crystal element according to ranges 6 and 7. 9) At least one optically active liquid crystal compound having a structure in which a fluorine atom is directly bonded to an asymmetric carbon and the following general formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (In the formula, R_1 is a linear or branched alkyl group having 1 to 18 carbon atoms, x is 0 or 1, and y is an integer of 0 to 8. C^* represents an asymmetric carbon atom) A liquid crystal composition containing at least one liquid crystal compound having an optically active group, wherein the liquid crystal compound is Ps.
≧8nc/cm^2 (|Tc-T|=15) or Ps≦
8nc/cm^2 (|Tc-T|=15), and Ps≧8nc/cm^2 and Ps≦-8nc/c
There are at least 1 liquid crystal compound satisfying m^2, respectively.
The liquid crystal composition according to claim 1, characterized in that it contains each species. 10) At least one liquid crystalline compound having an optically active group represented by the general formula (2) above, and ▲a mathematical formula, a chemical formula, a table, etc.▼(2) (wherein X_1 and X_2 are single bonds, - O-, ▲ formula,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, Y_1 is a single bond, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CH_2CH_
2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, A_1 and A_
2 represents a divalent six-membered ring-containing group which may have a substituent. However, the substituents of A_1 and A_2 are an alkyl group, an alkoxy group, a halogen atom (chlorine, bromine, or fluorine), or a cyano group, and the divalent six-membered ring group is ▲ mathematical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. R_2 and R_1 have 4 to 16 carbon atoms and 1 carbon number, respectively.
-18 linear or branched alkyl group, y is 0
An integer of ~8, x is 0 or 1. C^* indicates an asymmetric carbon atom. ) A liquid crystal composition containing at least one liquid crystal compound represented by the following general formula (3), which has a ▲ mathematical formula, a chemical formula, a table, etc. ▼ (3) (wherein Y_2 is ▲ a mathematical formula, There are chemical formulas, tables, etc.
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, X_3 is a single bond, -O-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ , X_4 indicates -O- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
There are ▼mathematical formulas, chemical formulas, tables, etc.▼▲mathematical formulas,
There are chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. R_3 and R_4 have 1 or more carbon atoms
16 linear or branched alkyl group, alkoxyalkyl group, or halogenated alkyl group, and may have an asymmetric carbon. a, b, c and d are 0, 1 or 2; e is 0 or 1; C^* represents an asymmetric carbon atom. ) The liquid crystal compound has Ps≧8nc/cm^2 (|
Tc-T|=15) or Ps≦-8nc/cm^2(|
Tc-T|=15), and Ps≧8nc/cm^
2. The liquid crystal composition according to claim 9, wherein the liquid crystal composition contains at least one liquid crystal compound satisfying the following conditions: 2 and Ps≦−8 nc/cm^2. 11) A liquid crystalline compound having an optically active group in which a fluorine atom is directly bonded to an asymmetric carbon atom and an ester bond, the liquid crystalline compound containing the optically active group as a carboxylic acid component of the ester bond. A liquid crystal composition comprising at least one kind and at least one kind of liquid crystal compound containing the optically active group as an alcohol component of the ester bond. 12) A liquid crystal compound containing the optically active group as a carboxylic acid component of an ester bond has the general formula (4) ▲ Numerical formula, chemical formula, table, etc. ▼ (4) (In the formula, R_5 and R_6 have 1 to 16 carbon atoms. is a straight-chain or branched alkyl group, and C^* represents an asymmetric carbon atom. 12. The liquid crystal composition according to claim 11, which is a compound represented by: 13) A_3 and A_4 in the above general formula (4) are general formula (4a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (4a) (In the formula, Y_3 is a single bond, -CH=CH- or -CH
_2-CH_2-, l represents 1 or 2. ) The liquid crystal composition according to claim 12, which is a group represented by: 14) A liquid crystal compound containing the optically active group as an alcohol component of an ester bond has the general formula (5) ▲ Numerical formula, chemical formula, table, etc. ▼ (5) (In the formula, R_7 and R_8 have 1 to 16 carbon atoms. is a linear or branched alkyl group, and C^* represents an asymmetric carbon atom. - or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. A_5 and A_6 represent a six-membered ring group that may have a substituent, and m represents 0 or 1.) A liquid crystal composition according to claim 11. 15) A_5 and A_6 in the above general formula (5) are general formula (5a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (5a) (In the formula, Y_4 is a single bond -CH=CH- or -CH_2
CH_2-, and n represents 1 or 2. ) The liquid crystal composition according to claim 14, which is a group represented by: 16) A liquid crystalline compound having an optically active group in which a fluorine atom is directly bonded to an asymmetric carbon atom and an ester bond, the liquid crystalline compound containing the optically active group as a carboxylic acid component of the ester bond. A liquid crystal element comprising a liquid crystal composition containing at least one kind and at least one kind of liquid crystal compound containing the optically active group as an alcohol component of the ester bond. 17) A liquid crystal compound containing the optically active group as a carboxylic acid component of an ester bond has the general formula (4) ▲ Numerical formula, chemical formula, table, etc. ▼ (4) (In the formula, R_5 and R_6 have 1 to 16 carbon atoms. is a linear or branched alkyl group, and represents a C^* asymmetric carbon atom.X_5 is a single bond, -O-, or ▲ mathematical formula, chemical formula,
There are tables, etc. ▼ indicates, and A_3 and A_4 indicate a six-membered ring-containing group which may have a substituent. ) The liquid crystal element according to claim 16, which is a compound represented by: 18) A_3 and A_4 in the above general formula (4) are general formula (4a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (4a) (In the formula, Y_3 is a single bond, -CH=CH- or -CH_
2CH_2-, l represents 1 or 2. ) The liquid crystal element according to claim 17, which is a group represented by: 19) A liquid crystal compound containing the optically active group as an alcohol component of an ester bond has the general formula (5) ▲ Numerical formula, chemical formula, table, etc. ▼ (5) (wherein R_5 and R_6 have 1 to 16 carbon atoms is a linear or branched alkyl group, and C^* represents an asymmetric carbon atom. - or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. A_5 and A_6 represent a six-membered ring group that may have a substituent, and m represents 0 or 1.) A liquid crystal element according to claim 16. 20) A_5 and A_6 in the above general formula (5) are general formula (5a) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (5a) (In the formula, Y_4 is a single bond, -CH=CH- or -CH_
2CH_2-, and n represents 1 or 2. ) The liquid crystal element according to claim 19, which is a group represented by: 21) A liquid crystalline compound having an optically active group in which a fluorine atom is directly bonded to an asymmetric carbon atom and also having an ester bond, the liquid crystalline compound containing the optically active group as a carboxylic acid component of the ester bond. A liquid crystal composition containing at least one type and at least one type of liquid crystal compound containing the optically active group as an alcohol component of the ester bond, wherein the liquid crystal compound has Ps≧8 nc/cm^2
(|Tc-T=15|) or Ps≦-8nc/cm^2
(|Tc-T=15|), and Ps≧8n
12. The liquid crystal composition according to claim 11, wherein the liquid crystal composition contains at least one liquid crystal compound satisfying c/cm^2 and Ps≦-8nc/cm^2. 22) At least one type of liquid crystalline compound represented by the general formula (4) below, and ▲Mathematical formula, chemical formula, table, etc.▼(4) (In the formula, R_5 and R_6 are linear chains having 1 to 16 carbon atoms. or a branched alkyl group, where C^* represents an asymmetric carbon atom. However, A_3 and A_4 are general formula (4a) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (4a) (In the formula, Y_3 is a single bond, -CH=CH- or -CH
_2CH_2-, l indicates 1 or 2. ) is a group represented by ) A liquid crystal composition having at least one type of liquid crystal compound represented by the following general formula (5), ▲There are mathematical formulas, chemical formulas, tables, etc.▼(5) (In the formula, R_7 and R_8 are carbon numbers It is a linear or branched alkyl group of 1 to 16, and C^* represents an asymmetric carbon atom. indicates -O- or ▲There is a numerical formula, chemical formula, table, etc.▼. A_5 and A_6 indicate a six-membered ring-containing group that may have a substituent (however, A_5 and A_6 are general formula (5a)) ▲ There are mathematical formulas, chemical formulas, tables, etc.▼(5a) (In the formula, Y_4 is a single bond, -CH=CH- or -CH_
2CH_2-, and n represents 1 or 2. ), m is 0
Or indicates 1. ) The liquid crystal compound has Ps≧8nc/cm^2 (|Tc-
T=15|) or Ps≦-8nc/cm^3(|Tc-
T=15｜), and Ps≧8nc/cm＾
22. The liquid crystal composition according to claim 21, wherein the liquid crystal composition contains at least one liquid crystal compound satisfying the following conditions: 2 and Ps≦−8 nc/cm^2. 23) Contains at least one type of chiral smectic liquid crystal compound with a positive Ps direction and at least one type of chiral smectic liquid crystal compound with a negative Ps direction,
And the Ps value of each chiral smectic liquid crystal compound is |Ps|≧8nc/cm^2 (|Tc-T|=15
) A ferroelectric liquid crystal composition. 24) The twist direction of the helical axis of the chiral smectic liquid crystal compound having a negative Ps direction is opposite to that of the chiral smectic liquid crystal compound having a positive Ps direction. A ferroelectric liquid crystal composition according to Item 23. 25) The chiral smectic liquid crystal phase is C phase, H phase,
24. The ferroelectric liquid crystal composition according to claim 23, which has an F phase, an I phase, or a G phase. 26) In a ferroelectric liquid crystal element having a ferroelectric liquid crystal composition, at least one chiral smectic liquid crystal compound having a positive Ps direction and at least one chiral smectic liquid crystal compound having a negative Ps direction. and Ps of each chiral smectic liquid crystal compound
The value is |Ps|≧8nc/cm^2 (|Tc-T|=1
5) A ferroelectric liquid crystal element comprising a ferroelectric liquid crystal composition. 27) The twist direction of the helical axis of the chiral smectic liquid crystal compound having a negative Ps direction is opposite to that of the chiral smectic liquid crystal compound having a positive Ps direction. A ferroelectric liquid device according to item 26. 28) The chiral smectic liquid crystal has C phase, H phase, F phase
27. The ferroelectric liquid crystal element according to claim 26, wherein the ferroelectric liquid crystal element is of a phase, an I phase, or a G phase.