JP2683223B2 - Liquid crystal composition and liquid crystal device containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] TECHNICAL FIELD The present invention relates to a liquid crystal display device and a liquid crystal-optical shutter.
Related to a liquid crystal composition used for a liquid crystal element used for
More specifically, a new type with improved response characteristics to electric fields
Liquid crystal composition. Further, to improve the alignment state of liquid crystal molecules
The liquid crystal composition with improved display and driving characteristics.
Is what you do. [0003] 2. Description of the Related Art Liquid crystal device having bistability
Is recommended by Clark and Lagerwall
Proposed (JP-A-56-107216, US)
Japanese Patent No. 4367924). Bistable liquid crystal
In general, a chiral smectic C phase (SmC
^* ) Or H phase (SmH^* A ferroelectric liquid crystal having
Can be This ferroelectric liquid crystal has a first optical
A bistable state consisting of a stable state and a second optically stable state
The optical modulator used in the TN type liquid crystal because it has
Unlike the child, for example, the first for one electric field vector
Liquid crystal is aligned in the optically stable state of
, The liquid crystal is aligned in the second optically stable state.
Also, this type of liquid crystal responds to an applied electric field to
Takes one of two stable states and does not apply an electric field.
When it is not, it has the property of maintaining that state (bistability).
You. In addition to the features having bistability as described above,
Ferroelectric liquid crystal has an excellent feature that it has high-speed response.
With. Therefore, regarding a liquid crystal material having ferroelectricity
Is widely researched, but the
Dielectric liquid crystal materials include low temperature operation characteristics, high speed response, etc.
It is difficult to say that it has sufficient characteristics for use in liquid crystal devices.
No. [0006] Further, the conventional strong induction having bistability
In the case of electronic liquid crystal elements, the uniform alignment of the liquid crystal is essential.
However, because it was not formed satisfactorily, sufficient characteristics were obtained.
The reality was that there was no such thing. Therefore, rubbing so far
Strong bistability in the presence of treated and orthographically treated surfaces
Method for attempting to align a dielectric liquid crystal in a uniform alignment state
Has been proposed. The present inventors have already rubbed the above.
By using a substrate that has been subjected to treatment or oblique deposition processing,
Bistable ferroelectric liquid crystals with uniform alignment can be obtained
That was known. However, according to the experiments by the present inventors,
The aforementioned bistable states are not necessarily Clark and Lagerwol.
The ideal pair shown in the above-mentioned literature published by
It turned out to have no steady state. That is, by Clark and Lagerwol
Non-helical chiral smectic for bistability
Tilt angle in the lock phase (angle θ shown in FIG. 3 described later)
Angle in the chiral smectic phase with
Has the same angle as the apex angle Θ) of the triangular pyramid shown in FIG.
However, the tilt angle θ in the non-helical structure is actually
Is smaller than the tilt angle Θ in the spiral structure. I
The tilt angle θ in this non-helical structure is
Is less than the tilt angle Θ of
It was found to be due to the twisted arrangement of crystal molecules. One
Mari, in a chiral smectic phase with a non-helical structure
Is a liquid crystal molecule5As shown in
Liquid adjacent to the lower substrate below the axis 82 of liquid crystal molecules adjacent to the plate
Twist continuously to axis 83 of crystal molecules (direction of twist alignment)
It is twisted and arranged at an angle δ, which means that it has a non-helical structure.
The tilt angle θ at is smaller than the tilt angle θ at the spiral structure.
Has become a cause. Reference numeral 81 in the figure is a rabin formed on the upper and lower substrates.
Uniaxial orientation axis obtained by
It represents. By the way, a liquid crystal element utilizing the birefringence of liquid crystal
For a child, the transmittance under orthogonal Nicols is [0011] [Outside 9] Is represented by Tilt angle θ in the aforementioned non-helical structure
Is the twisted alignment of the liquid crystal molecules in the first and second alignment states.
It will appear as an angle in the direction of the average molecular axis. Above
According to, the maximum when the tilt θ is 22.5 °
Is a non-helical structure that realizes bistability.
The maximum tilt angle θ is about 10 °, and
In consideration of application as a display device, the transmittance is 3 to
There is a problem that about 5% is not sufficient. [0012] OBJECTS OF THE INVENTION Therefore, the object of the present invention is to achieve the above-mentioned drawbacks or
Ferroelectric liquid crystal composition having eliminated disadvantages and the liquid crystal composition
It is to provide a liquid crystal device using the. More specifically, a specific liquid crystal compound is mixed.
The characteristics of low-temperature operation characteristics, high-speed response, etc.
Display characteristics that are not obtained with a single liquid crystalline compound.
Liquid crystal composition having liquid crystallinity and liquid crystal using the composition
It is to provide an element. [0014] [0015] [Means and Actions for Achieving the Purpose]
Optics with a structure in which a fluorine atom is directly bonded to an asymmetric carbon
An active liquid crystalline compound (hereinafter referred to as F-based liquid crystalline compound),
Preferably the following general formula (3) [0016] [Outside 10] R_Three And R_Four Is a straight chain having 1 to 16 carbon atoms
Is a branched alkyl group, alkoxyalkyl group or halo
It is an alkyl genide and may have an asymmetric carbon. a,
b, c and d are 0 or 1 or 2 and e is 0 or
Or 1. C^* Represents an asymmetric carbon atom. )
Liquid crystal compound of optically active fluoroalkane derivative
And at least one of the following general formula (1) [0018] [Outside 11] (Where R₁ Is a straight-chain or branched C 1-18 carbon atom.
Is a rualkyl group, x is 0 or 1, and y is an integer of 0-8.
is there. Also C^* Represents an asymmetric carbon atom. ) More preferable
Is a liquid having an optically active group represented by the following general formula (2)
Crystalline compound [0019] [Outside 12]A₁ And A_Two Is a divalent hexavalent ring which may have a substituent
Indicates a membered ring group. (As a substituent, an alkyl group, an alcohol
Xyl group, halogen atom (chlorine, bromine, or fluorine) or
A cyano group, and as a divalent 6-membered ring group, [0020] [Outside 13] Is raised. ) (R_Two And R₁ Each has 4 carbon atoms
~ 16 and 1-18 linear or branched alkyl groups
Yes, y is an integer of 0 to 8 and x is 0 or 1. C^*
Represents an asymmetric carbon atom. ) Optically active liquid crystal represented by
Contain at least one type of active compound as a compounding ingredient
And a pair of liquid crystal compositions characterized by
To provide a liquid crystal element arranged between the electrode substrates of
is there. As a result, low temperature operation characteristics and high speed responsiveness are obtained.
Which properties are improved and cannot be obtained with a single liquid crystalline compound.
It has been found that good display characteristics can be obtained. The present inventionLiquid crystal compositionIs an asymmetric carbon atom
Has an optically active group in which a fluorine atom is directly bonded to
A liquid crystal compound having a stell bond, which has an optical activity
Group containing a group as the carboxylic acid component of the ester bond
At least one compound and an optically active group
Of liquid crystalline compounds contained as alcohol components of
At least one kindfurtherContainedMay be. The optically active group is an ester-bonded carvone.
The liquid crystal compound contained as an acid component is preferably the following general
Formula (4) [0024] [Outside 14] And the optically active group is an ester-bonded alcohol.
The liquid crystal compound contained as a component is preferably the following general
Formula (5) [0025] [Outside 15]Is represented by In the above general formulas (4) and (5), R
_Five , R₆ , R₇ And R₈ Is a straight or branched chain having 1 to 16 carbon atoms
A branched alkyl group, C^* Represents an asymmetric carbon atom.
X_Five And X₆ Represents a single bond, -O- or -COO-,
X₇ Is -O- or [0027] [Outside 16] Is shown. A_Three , A_Four , A_Five And A₆ May have a substituent
A six-membered ring group, A_Three And A_Four Is [0028] [Outside 17] (Y_Three Is a single bond, -CH = CH- or -CH_Two CH_Two
Represents-, and 1 represents 1 or 2. ), A_Five
And A₆ Is [0029] [Outside 18] (Y_Four Is a single bond, -CH = CH- or -CH_Two CH_Two
-, N is 1 or 2), and m is 0
Or 1 is shown. However, the carboxylic acid formation represented by the above formula
Minute means the following part (A). [0031] [Outside 19] Also, the alcohol component refers to the part (B) below.
You. [0032] [Outside 20] Further, the liquid crystal composition of the present invention is Ps.
Direction is positive and | Ps | ≧ 8nc / cm^Two(| Tc-T | = 1
5), preferably 20 nc / cm^TwoMore chiral sumes
Direction of Ps with at least one kind of stic liquid crystalline compound
Is negative and | Ps | ≧ 8 nc / cm^Two(| Tc-T | = 1
5), preferably 20 nc / cm^TwoMore chiral sumes
Containing at least one kind of tactic liquid crystal compound,
Liquid crystal compositionMay be. The above chiral smectic
Ku phase is Sm^*C, Sm^*H, Sm^*F, Sm^*I, Sm^*
The G phase is shown. Further, the above-mentioned | Tc-T |
15 ° C from the upper limit temperature at which the iral smectic liquid crystal phase is exhibited
It means the value at the lowered temperature. Chiral smects
If it has a tic C phase, the chiral smectic
A temperature 15 ° C lower than the upper limit temperature indicating phase C
It is. Twist angle and how to twist according to the above twist arrangement
The orientation is the surface state of the liquid crystal and the substrate and the interaction between the liquid crystal molecules.
It depends on the liquid crystal element made of the above liquid crystal composition.
The twisted arrangement can be eliminated by using
You. In the ferroelectric liquid crystal element in which the twisted arrangement is eliminated,
Maximum transmittance / shading ratio contrast is obtained under crossed Nicols
Liquid crystal element that has a bistable state with a twisted arrangement
Offspring gives maximum contrast under non-orthogonal Nicols
However, at this time, the contrast differs depending on the viewing direction.
Although it has a viewing angle dependency,
With the elimination of rows, the above viewing angle dependence can be eliminated.
Can be. The details will be described below. According to the present research, the present inventors found that F (fluorine)
System liquid crystalline compound and the liquid crystalline compound of the above formula (1) are mixed
By using each liquid crystal compound by itself,
Compared to Smectic C^* The temperature range that gives the phase is wide
Liquid crystal with improved response speed and improved display characteristics
It has been found that a device can be provided. The present invention is further described below.
This will be described in detail. In the following description, the quantitative ratio is expressed
Both "%" and "parts" are based on weight. The liquid crystal compound is an F-type liquid crystal compound in general (preferred
Preferably represented by the general formula (3)) and the general formula
Liquid crystalline compound having an optically active group represented by (1)
(Preferably represented by the general formula (2)). Components represented by the general formulas (2) and (3)
The structural formulas of physical liquid crystalline compounds and the liquid crystal phase transition temperature
The results are shown in Tables 1 and 2. But the ones listed here
The present invention is not limited to this. In the table, the symbol in the column of phase transition temperature is
The following phases are shown respectively. [0039] Cryst. : Crystalline phase, SmA: Smectic A phase, SmC^*     : Chiral smectic C phase, N: nematic phase, Ch: cholesteric phase, Iso: isotropic phase, Sm1, Sm2, Sm3: SmA, SmC^* Other than
Cutic phase (unidentified). [0040] [Table 1][0041] [Table 2][0042] [Table 3][0043] [Table 4][0044] [Table 5][0045] [Table 6][0046] [Table 7][0047] [Table 8][0048] [Table 9][0049] [Table 10][0050] [Table 11]Optically active liquid crystallinity represented by the general formula (2)
The compound is synthesized by the following method. The general formula (6) is used as a starting material. [0053] [Outside 21] (Where R₀ Is a lower alkyl group, C^* Is an asymmetric carbon atom
X and z are 0 or 1. When x is 0, z is 0
Alternatively, it is 1, and when x is 1, z is 0. )
To the following reaction process formulas (1) and (2)
Therefore, or by repeating the process formula (2)
Synthesis of optically active alcohol or optically active carboxylic acid
it can. [0054] [Outside 22] (Where R₁ Is a linear or branched alkane having 1 to 18 carbon atoms.
A killed group, y is an integer from 0 to 8 and x is 0 or 1.
You. D is -OH, or [0055] [Outside 23] It is. ) [0056] [Outside 24] [0057] [Outside 25]Optically active alcohol synthesized in this way
Or optically active carboxylic acid
Derivatives of alcohols, thiols, etc. or carboxylic acids
The following general formula can be obtained by reacting with a conductor by a conventional method.
(8), (9) [0059] [Outside 26] Is shown. A_Two Is a divalent 6-membered member which may have a substituent
A cyclic group is shown, and as a substituent, an alkyl group or an alkoxy group is used.
Group, halogen atom (chlorine, bromine, fluorine), cyano group,
As a divalent 6-membered ring group [0060] [Outside 27]Is raised. R₁ Is a straight or branched chain having 1 to 18 carbon atoms
It is an alkyl group, y is an integer of 0 to 8 and x is 0 or 1.
It is. Y_Five Is -O- or -S-, and Y₆ Is simply
Bond, -CH = CH- or -CH_Two CH_Two -.
C^* Represents an asymmetric carbon atom. ), Ether
Optically active alcohol having a ruthenium or ester bond
And an optically active carboxylic acid can be obtained. (7), (8) and (9) are further described below
Formulas (10) and (11) [0063] [Outside 28] (Where R_Two Is a branched or straight-chain alkyl having 4 to 16 carbon atoms.
Represents a hydroxyl group. A₁ Is a divalent 6-membered member which may have a substituent
Represents a ring group, X₁ Is a single bond, -O-, [0064] [Outside 29] It is. Y₇ And Y₉ Is a single bond, -CH_Two CH_Two -Yes
I is -CH = CH- and Y₈ Is -O- or -S
-. ) Alcohol, thiol derivative,
Or reacting with a carboxylic acid derivative by a conventional method
Gives an optically active liquid crystalline compound represented by the general formula (2).
Things can be synthesized. The optically active full represented by the above general formula (3)
The oroalkane derivative is preferably Japanese Patent Application No. 60-23.
2-Fluoro-1 disclosed in the specifications such as 2886 publication
-Alkanol, p-hydroxybenzoic acid (2-full
Oroalkyl) ester, p-hydroxybiphenyl
Carboxylic acid (2-fluoroalkyl) ester, Hyde
Roquinone (2-fluoroalkyl) ether, 4-
[4 '-(2-fluoroalkyl) oxyphenyl] phenyl
It is synthesized from an optically active intermediate such as enol. For example, from these optically active intermediates,
Depending on the synthetic route, general formula (3) (especially Y_Two But [0067] [Outside 30] in the case of. ) A liquid crystalline compound is obtained. [0068] [Outside 31]The liquid crystal composition of the present invention is represented by the general formula (1).
A liquid crystal compound having an optically active group, preferably one
At least one liquid crystal compound represented by the general formula (2)
1 to 99% and an F-based liquid crystal compound, preferably a general formula
At least one kind of liquid crystal compounds represented by (3) 99
It is preferably formed by mixing ˜1%. Further, the liquid crystal composition of the present invention has a chiral carbon source.
Has an optically active group in which a fluorine atom is directly bonded to the child, and
A liquid crystal compound having an ester bond, wherein the optical activity is
Liquid crystal containing a polymerizable group as the carboxylic acid component of the ester bond
At least one kind of a photoactive compound and the optically active group
A small amount of liquid crystal compounds contained as an alcohol component of tel bonds
At least one kindYou may further contain. The optically active group is an ester-bonded carvone.
The liquid crystal compound contained as an acid component is preferably the following general
Formula (4) [0072] [Outside 32]And the optically active group is an ester-bonded alcohol.
The liquid crystal compound contained as a component is preferably the following general
Formula (5) [0073] [Outside 33] Is represented by The optically active group is an ester-bonded carvone.
A liquid crystal compound containing as an acid component, preferably a general formula
Specific examples of the liquid crystal compound represented by (4) are shown below.
You. [0075] [Outside 34][0076] [Outside 35][0077] [Outside 36]Optically active liquid represented by the above general formula (4)
The crystalline compound is preferably p-2-fluoroalkoxy
Benzoic acid, p'-2-fluoroalkoxybiphenyl-
It is synthesized from an optically active intermediate such as p-carboxylic acid. For example, from these optically active intermediates,
Depending on the synthetic route, the liquid crystalline compound represented by the general formula (4)
Things are obtained. [0080] [Outside 37](However, the symbols in the above formulas are the same as the symbols described above). Further, the optically active group may be an ester bond.
A liquid crystalline compound contained as a rucor component, preferably general
Specific examples of the liquid crystal compound represented by the formula (5) are shown below.
You. [0082] [Outside 38][0083] [Outside 39][0084] [Outside 40][0085] [Outside 41][0086] [Outside 42][0087] [Outside 43]Optically active liquid represented by the above general formula (5)
The crystalline compound is preferably Japanese Patent Application No. 60-232886.
2-fluoro-1-alkanol shown in the publication, p
-Hydroxybenzoic acid (2-fluoroalkyl) s
Tell, p-hydroxybiphenylcarboxylic acid (2-phenyl
Luoroalkyl) ester, hydroquinone (2-full
Oroalkyl) ether, 4- [4 '-(2-fluoro
Alkyl) oxyphenyl] phenol, etc.
Synthesized from interstitial bodies. For example, from these optically active intermediates,
Depending on the synthetic route, the liquid crystalline compound represented by the general formula (5)
Things are obtained. [0090] [Outside 44]FIG. 1 illustrates the structure of a ferroelectric liquid crystal device.
In order to improve the liquid crystal display device having a ferroelectric liquid crystal layer,
It is a cross-sectional schematic diagram. In FIG. 1, reference numeral 1 is a ferroelectric liquid crystal layer, 2
Is a glass substrate, 3 is a transparent electrode, 4 is an insulating orientation control layer,
5 is a spacer, 6 is a lead wire, 7 is a power supply, 8 is polarized light
A plate and 9 indicate a light source. In each of the two glass substrates 2, In_Two
O_Three , SnO_Two Alternatively, ITO (Indium-Tin)
  Oxide) and other thin film transparent electrodes are covered
I have. On top of that, a thin film of a polymer such as polyimide is used as gauze.
Rubbing the liquid crystal by rubbing with a cloth or acetate flocking cloth
An insulating alignment control layer is formed so as to be aligned in the direction. Also
As the insulating layer, for example, silicon nitride, a hydrogen-containing
Contains Recon Carbide, Silicon Oxide, Boron Nitride, Hydrogen
Having boron nitride, cerium oxide, aluminum oxide
Objects, zirconium oxide, titanium oxide and fluorinated magnesia
An inorganic insulating layer such as sium is formed, and a polyvinyl
Alcohol, polyimide, polyamide imide, poly
Sterimide, polyparaxylene, polyester, poly
Carbonate, polyvinyl acetal, polyvinyl chloride
Resin, polyvinyl acetate, polyamide, polystyrene, cell
Loin resin, melamine resin, urea resin, acrylic resin
Alignment control layer with organic insulating material such as photoresist or photoresist resin
Alternatively, the insulating orientation control layer may be formed of two layers.
Insulating alignment control layer or organic material
The insulating orientation control layer may be a single layer. This insulating composition
If the orientation control film is inorganic, it can be formed by vapor deposition, etc.
If so, a dissolved organic insulating material or its precursor
Solution (0.1 to 20% by weight in solvent, preferably 0.2 to
10 wt%), spinner coating method, dip coating
Application, screen printing method, spine coating method, roll coating method
Etc. and cured under specified curing conditions (for example, heating)
Can be formed. Thickness of insulating orientation control layer
The size is usually 50Å ~ 1μ, preferably 100Å ~ 5000
Å, more preferably 500 Å to 3000 Å
You. The two glass substrates 2 are used as spacers 5.
Therefore, it is kept at an arbitrary interval. For example, given diameter
With silica beads and alumina beads as spacers
It is sandwiched between two glass substrates and the periphery is sealed with a sealing material such as
There is a method of sealing using a poxy adhesive. Others
Polymer films, glass fibers, etc. as spacers
May be used. Ferroelectricity between these two glass substrates
Liquid crystal is enclosed. Ferroelectric liquid crystal filled with ferroelectric liquid crystal
The electric liquid crystal layer is generally 0.5 μm to 20 μm, preferably
It is 1 μ to 5 μ. From the transparent electrode 3, an external electric power is supplied by a lead wire.
Connected to the source 7. In addition, the outside of the glass substrate 2 is biased.
The light plate 8 is attached. Since FIG. 1 is a transmissive type, a light source 9 is provided.
You. FIG. 2 illustrates the operation of the ferroelectric liquid crystal device.
Therefore, an example of the cell is schematically drawn. 21a and
21b is In_Two O_Three , SnO_Two Or IT
From thin films such as O (Indium-Tin Oxide)
Is a substrate (glass plate) covered with a transparent electrode
Align the liquid crystal molecule layer 22 so that it is perpendicular to the glass surface between
SmC^* Phase or SmH^* Phase liquid crystal is enclosed
You. The thick line 23 represents the liquid crystal molecules.
Liquid crystal molecule 23 of the dipole mode is in the direction orthogonal to the molecule.
Ment (P⊥) 24. Substrates 21a and 21b
When a voltage above a certain threshold is applied between the upper electrodes, the liquid crystal
The spiral structure of the molecule 23 is unwound, and the dipole moment (P
⊥) The liquid crystal molecules 23 are set so that all 24 are oriented in the direction of the electric field.
The orientation direction can be changed. The liquid crystal molecules 23 are elongated
It has a large shape, and its refractive index is
Exhibits anisotropy, and therefore, for example above and below the glass surface,
If a crossed Nicol polarizer is placed,
It is easy to become a liquid crystal optical modulator with changing optical characteristics.
Understood. It is preferably used in the optical modulator of the present invention.
The liquid crystal cell has a sufficiently small thickness (for example, 10 μm or less).
Below) As the liquid crystal layer becomes thinner like this
Therefore, no electric field is applied as shown in FIG.
However, the spiral structure of the liquid crystal molecule is unraveled, and the dipole
The component Pa or Pb faces upward (34a) or downward (3a).
4b) is taken. In a cell like this,
As shown in 3, electric fields Ea or
Applies Eb by the voltage applying means 31a and 31b
And the dipole moment is the electric field vector of the electric field Ea or Eb.
Depending on the tor, face up 34a or down 34b
The liquid crystal molecules accordingly change to the first stable state 33a.
Or oriented in either of the second stable states 33b
You. Such ferroelectricity as an optical modulator
As described above, there are two advantages of using them. The first is that the response speed is extremely fast.
The second is that the orientation of liquid crystal molecules has bistability.
You. The second point will be further described with reference to FIG.
When the electric field Ea is applied, the liquid crystal molecules are in the first stable state 33a.
However, this state is stable even when the electric field is cut off.
Moreover, when an electric field Eb in the opposite direction is applied, the liquid crystal molecules are
Orients to stable state 33b and changes the orientation of the molecule,
After all, even if the electric field is turned off, it remains in this state. Also,
As long as the electric field Ea or Eb that is obtained does not exceed a certain threshold value.
In each case, the previous alignment state is maintained. [0101] EXAMPLES The present invention will be described in more detail below with reference to examples.
I do. In the following examples, the spontaneous polarization is K.K. Miyasa
To et al. "Direct measurement of spontaneous polarization of ferroelectric liquid crystal using triangular wave"
Law "(Journal of Japan Society of Applied Physics)22No. 10, L (661)
1983, ("Direct Method with
  Triangular Waves for Mea
suring Spontaneous Polari
zation in Ferroelectric L
liquid Crystal ”, as describ
ed by K.D. Miyasato et al. (J
ap. J. Appl. Pyhys. 22, no. 10,
L661 (1983))). Regarding the polarity of Ps, it is clear
Et al. (NA Clark and S. T. La.
gerwell, Ferroelectrics,59
  P. 25 (1984)). By itself, the chiral smectic phase
The liquid crystal compounds not shown show a smectic C phase and P
Mix with a liquid crystal compound without s at a ratio of 10:90
To have a chiral smectic C phase by
After that, Ps was measured, and it was set as 10% of the original value, and 10
The Ps value was determined based on the 0% conceptual value. Example 1 Liquid crystalline compounds 15 and liquids shown in Tables 1 and 2 above
Liquid crystal composition by mixing crystalline compound 41 at a ratio of 84:16
I got something. This liquid crystal composition showed the following phase transitions. [0106] [Outside 45] That is, this liquid crystal composition has a single liquid crystallinity.
From compound 15, the temperature range of the chiral smectic C phase is
Spreads to both high and low temperature side, SmC even at supercooling temperature^*
Keep relatively stable. The relationship between the spontaneous polarization and the response speed of the above liquid crystal composition.
The fruits are shown in Table 3 below. [0109] [Table 12] The response speed is the same as the polyimide coating covering the electrodes.
The liquid crystal is formed between a pair of electrode substrates whose film is rubbed.
The composition is sandwiched, and the liquid crystal layer thickness is set to 2 μm.
Applying a voltage of 20 V as the peak voltage causes orthogonal
The optical response under the
(Up to 90%) to measure the response speed
Was. As can be seen, the mixing according to the invention
The liquid crystal composition has a SmC content higher than that of a single liquid crystal compound.^* phase
Temperature range is widened, and the large F-type liquid crystal compound has
Spontaneous polarization is reflected in the mixed liquid crystal composition and
The answer speed has been improved. Example 2 The liquid crystalline compounds 5, 6, and 10 shown in Table 1 were mixed with 1:
Liquid crystal composition mixed at 1: 2AIndicates the following phase transition: [0113] [Outside 46] Further, the liquid crystal compositionALiquid crystallinity of each
The values of the spontaneous polarization of compounds 5, 6, and 10 and the spiral winding
Show. [0115] [Outside 47] Further, the liquid crystal compounds 44 shown in Table 2 above.
And 48 mixed in 1: 3 liquid crystal compositionBIs the following phase transition
Is shown. [0117] [Outside 48] Further, a liquid crystal compoundBLiquid crystallinity of each
The results for compounds 44 and 48 are also shown. [0119] [Outside 49] These two liquid crystal compositionsAas well asBCan be mixed
Liquid crystal compositionABOf phase transition temperature (temperature rising process)
Figure as a phase diagram4Shown in Figure4As is clearer, A:
Chiral smectic near B = 80: 20
The temperature range of C is particularly widened to the low temperature side. Also, this compositionABOf whichA ₈₀ -B ₂₀
(A: B = 80: 20 mixture) was the same as in Example 1.
Similarly, create the element and measure the response speed under exactly the same conditions
The composition was 550 μsec at 25 ° C.A
_100%The response characteristics were improved compared to the case of using
(Note that the response speed of the liquid crystal composition A at 25 ° C. was 61
It is 0 μsec. ). In this liquid crystal element (measurement conditions are
Similar to Example 11 below) Tilt angle is 15 °, maximum transmission
The rate was 13%. Example 3 The liquid crystalline compounds 1, 4, 10, 15 and
16 and the liquid crystal compound 41 shown in Table 2 above.
A liquid crystal composition was obtained by mixing in the proportions shown in Table 4 below. [0124] [Table 13] This liquid crystal composition showed the following phase transitions.
Was. [0126] [Outside 50] Using the above composition, the same as Example 1.
The optical response was measured under exactly the same conditions by using
The speed was 220 μsec at 25 ° C. That is, this liquid crystal composition has a single liquid crystallinity.
The temperature range of the chiral smectic C phase is more
It spreads to the low temperature side and remains stable at room temperature.
Response speed has been improved. Example 4 The liquid crystalline compounds 10, 15, 16 shown in Table 1 and the above
The liquid crystalline compounds 33, 44 and 46 listed in Table 2 are
Liquid mixed with 35, 20, 5, 5, 10, 25% of each
Phase transition was investigated using a crystalline composition, and light was emitted in the same manner as in Example 3.
It was confirmed that the response speed was higher than that of a single liquid crystalline compound.
Improved response speed due to smectic C phase spreading to low temperature side
It was possible to obtain a good liquid crystal element. Example 5 Liquid crystalline compounds 22 and 30 described in Table 1 above and Table 2 above
And the liquid crystalline compounds 33, 44, 46 and 47 described in 1.
15, 5, 10, 15, 35, and 20% mixed respectively
The same results as in Example 4 can be obtained by using the liquid crystal composition.
It was confirmed that. Example6 The following liquid crystal compounds are mixed in the following composition ratio to obtain a liquid crystal composition
HI got [0132] [Outside 51][0133] [Outside 52]Next, the compositionHUsing2Liquid crystal film thickness of μm
A liquid crystal element having6). [0135]2The structure of the substrate of the μm cell is 0.7 m
Glass (m) thick glass plate with 1000 liters of ITO (Indium)
  Tin Oxide) and 200Å P (Polyimide)
A coating is provided, and the PI coating is suitable for rubbing treatment.
More uniaxial alignment treatment is performed, and each rubbing axis direction
Two substrates were assembled into cells so that they were parallel to each other. The cell thickness (distance between upper and lower substrates) is2μm bee
It was held with a spacer. This liquid crystal cell was mixed with the above-mentioned mixed liquid crystal under an isotropic phase.
After vacuum injecting at 30 ℃ at 0.5 ℃ / h from the isotropic phase
It was possible to orient by slow cooling to. After that
The experiment was conducted at 30 ° C. Observing this cell under crossed Nicols,
A uniform, defect-free monodomain is obtained, with contrast
High white and black domain bistable states exist.
It turned out. Using this liquid crystal element 6, while applying an electric field
When observed under a microscope, the tilt angle was 18 °.
Was. The transmittance was measured and found to be 16%, which was extremely low.
A high transmittance was obtained. Next, the threshold characteristic due to the pulsed electric field is measured.
When set, 6 V at 500 μs, 1.3 at 100 ms
It has been found that it exhibits a very excellent threshold value characteristic of V. Example7 The following liquid crystal compounds are mixed in the following composition ratio to obtain a liquid crystal composition.I
I got [0143] [Outside 53][0144] [Outside 54]Example6And cell thickness (1.2μ) and PI coverage
In addition to changing the film to PVA (polyvinyl alcohol) film
Is a cell having exactly the same structure, and the above liquid crystal compositionITo
A liquid crystal element 7 was obtained by using the above. Observing this cell under crossed Nicols,
A uniform and defect-free monodomain was obtained. To rotate the cell under crossed Nicols
Therefore, when it is adjusted to the darkest position, almost the entire surface is in the darkest state.
Was. Using this liquid crystal element 7, an example6Similar to
The tilt angle measured by the method was 15 °.
In addition, the transmittance was measured and was 13%, which was extremely high.
was gotten. [0149] As described above, according to the present invention, the temperature
A liquid crystal composition with a wide range can be obtained, and at the same time, it can be used in a low temperature range.
It is excellent in answering, and it has a rapid change in response speed due to temperature.
It is possible to obtain a liquid crystal element with excellent display characteristics.
Was. Further, according to the present invention, Ps ≧ 8 nc / c
m^Two Chiral smectic of (| Tc-T | = 15 ° C)
At least one liquid crystal compound and Ps ≧ −8 nc / c
m^TwoChiral smectic of (| Tc-T | = 15 ° C)
Liquid crystal group containing at least one liquid crystal compound
By using a ferroelectric liquid crystal device composed of
More preferably | Ps | ≧ 10 nc / cm^Two , More preferably
| Ps | ≧ 20 nc / cm^Two However, | Tc−T | = 15
℃), the tilt angle of the bistable state is expanded to
Blessed with trust, high-speed response, pixel density and large area
It is possible to realize a doubled display element or shutter element.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a sectional view schematically showing an example of a chiral smectic liquid crystal device of the present invention. FIG. 2 is a perspective view showing an alignment state of a chiral smectic liquid crystal having a helical structure. FIG. 3 is a perspective view showing an orientation state of a chiral smectic liquid crystal having a non-helical molecular arrangement. 4 is a phase diagram showing a relationship between a compounding ratio and a phase transition temperature in a mixed system of the liquid crystal composition A and the liquid crystal composition B according to Example 2. FIG. FIG. 5 is a plan view schematically showing liquid crystal molecules twisted and aligned along a normal line of a substrate. [Description of Reference Signs] 1 ferroelectric liquid crystal layer 2 glass substrate 3 transparent electrode 4 insulating alignment control layer 5 spacer 6 lead wire 7 power supply 8 polarizing plate 9 light source I ₀ incident light I transmitted light 21a substrate 21b substrate 22 ferroelectric Liquid crystal layer 23 Liquid crystal molecule 24 Dipole moment (P⊥) 31a Voltage applying means 31b Voltage applying 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 81 uniaxial alignment axis formed on upper and lower substrates 82 axis of liquid crystal molecules adjacent to upper substrate 83 axis of liquid crystal molecules adjacent to lower substrate

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Shunji Utsumi               3-30-2 Shimomaruko, Ota-ku, Tokyo               Non Corporation (72) Inventor Masataka Yamashita               3-30-2 Shimomaruko, Ota-ku, Tokyo               Non Corporation (72) Inventor Yoko Yamada               3-30-2 Shimomaruko, Ota-ku, Tokyo               Non Corporation (72) Inventor Takashi Iwaki               3-30-2 Shimomaruko, Ota-ku, Tokyo               Non Corporation (72) Inventor Chieko Hioki               3-30-2 Shimomaruko, Ota-ku, Tokyo               Non Corporation (72) Inventor Ichiharu Katagiri               3-30-2 Shimomaruko, Ota-ku, Tokyo               Non Corporation

Claims (1)

(57) [Claims] The following general formula (2) [External 1] A ₁ and A ₂ represent a divalent 6-membered ring group which may have a substituent. R ₂ and R ₁ are linear or branched alkyl groups having 4 to 16 and 1 to 18 carbon atoms, y is an integer of 0 to 8 and x is 0 or 1. C ^* represents an asymmetric carbon atom. ) And at least one of the optically active liquid crystalline compounds represented by the following general formula (3) R ₃ and R ₄ are linear or branched alkyl groups having 1 to 16 carbon atoms, alkoxyalkyl groups, or halogenated alkyls, and may have asymmetric carbon atoms. a, b, c and d are 0, 1 or 2 and e is 0 or 1. C
^* Represents an asymmetric carbon atom. And at least one kind of optically active liquid crystalline compound represented by the formula (1). 2. The substituent of A ₁ and A _{2 in} the general formula (2) is an alkyl group, an alkoxy group, a halogen atom (chlorine, bromine or fluorine) or a cyano group, and the divalent 6-membered ring group is [external 3] The liquid crystal composition according to claim 1, which is 3. The following general formula (2) [External 4] A ₁ and A ₂ represent a divalent 6-membered ring group which may have a substituent. R ₂ and R ₁ are linear or branched alkyl groups having 4 to 16 and 1 to 18 carbon atoms, y is an integer of 0 to 8 and x is 0 or 1. C ^* represents an asymmetric carbon atom. ) And at least one of the optically active liquid crystalline compounds represented by the following general formula (3) R ₃ and R ₄ are linear or branched alkyl groups having 1 to 16 carbon atoms, alkoxyalkyl groups, or halogenated alkyls, and may have asymmetric carbon atoms. a, b, c and d are 0, 1 or 2 and e is 0 or 1. C
^* Represents an asymmetric carbon atom. And at least one kind of optically active liquid crystalline compound represented by the formula (1). 4. The substituent of A ₁ and A _{2 in} the general formula (2) is an alkyl group, an alkoxy group, a halogen atom (chlorine, bromine or fluorine) or a cyano group, and the divalent 6-membered ring group is The liquid crystal element according to claim 3, wherein 5. The following general formula (2) [External 7] A ₁ and A ₂ represent a divalent 6-membered ring group which may have a substituent. R ₂ and R ₁ are linear or branched alkyl groups having 4 to 16 and 1 to 18 carbon atoms, y is an integer of 0 to 8 and x is 0 or 1. C ^* represents an asymmetric carbon atom. ) And at least one of the optically active liquid crystalline compounds represented by the following general formula (3) R ₃ and R ₄ are linear or branched alkyl groups having 1 to 16 carbon atoms, alkoxyalkyl groups, or halogenated alkyls, and may have asymmetric carbon atoms. a, b, c and d are 0, 1 or 2 and e is 0 or 1. C
^* Represents an asymmetric carbon atom. And at least one kind of optically active liquid crystalline compound represented by the formula (1), wherein the liquid crystalline compound is Ps ≧
8 nc / cm ² (| Tc−T | = 15) or Ps ≦ −8
nc / cm ² (| Tc−T | = 15), and at least one liquid crystal compound is contained each satisfying the relationship of Ps ≧ 8 nc / cm ² and Ps ≦ −8 nc / cm ^2. The liquid crystal composition according to claim 1, wherein the liquid crystal composition comprises: