JPH0862559A - Tetrahydroquinazoline compound, liquid crystal composition containing same, liquid crystal element having same, and display method and display device using these - Google Patents

Abstract

PURPOSE: To obtain a liquid crystal compsn. which is effective to increase the response speed, to decrease the temp. dependency and to increase the contrast of a ferroelectric liquid crystal element by using a specified tetrahydroquinazoline compd. CONSTITUTION: This compd. is a new tetrahydroquinazoline compd. expressed by formula R1 -Q-Ph-R2 . In formula, R1 is a C1-C18 straight-chain, branched or cyclic alkyl group and one or more -CH2 - may be replaced by -O-, -S-, -CO-, -OCO-, -COO-, -CH=CH-, -C≡C- under the condition that heteroatoms are not adjacent to each other. R2 is a C10-C20 straight-chain, branched or cyclic alkyl group and one or more -CH2 - may be replaced by -O-, -S-, -CO, -OCO-, -COO-, -CH=CH-, -C≡C- under the condition that heteroatoms are not adjacent to each other. Q is 5,6,7,8-tetrahydroquinazolin-2,6-diyl and Ph is 1,4-phenylene.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel tetrahydroquinazoline compound, a liquid crystal composition containing the same, a liquid crystal device using the same, a display method using the same, and a display device, and more specifically, response characteristics to an electric field. And a liquid crystal display device using the same, a display method using the same, and a display device using the liquid crystal display device Is.

[0002]

2. Description of the Related Art Conventionally, liquid crystals have been applied as electro-optical elements in various fields. Most of the liquid crystal elements currently in practical use are, for example, M. Sch.
adt) and W. Helfri
ch) "Applied Physics Letters"
("Applied Physics Letter
s ") Vol. 18, No. 4 (1971.2.15)
P. 127-128 "Voltage Depend"
ent Optical Activity of a
Twisted Nematic Liquid Cr
TN (Twisted Nem)
atic) type liquid crystal is used.

These are based on the dielectric alignment effect of liquid crystals, and utilize the effect that the average molecular axis direction is directed in a specific direction by an applied electric field due to the dielectric anisotropy of liquid crystal molecules. The optical response speed limit of these devices is said to be milliseconds, which is too slow for many applications.

On the other hand, in the application to a large flat display, the simple matrix drive is the most effective in consideration of price, productivity and the like. The simple matrix method employs an electrode configuration in which a scan electrode group and a signal electrode group are arranged in a matrix, and in order to drive the scan electrode group, an address signal is sequentially and selectively selected and applied to the scan electrode group. Employs a time-division drive system in which a predetermined information signal is synchronized with an address signal and selectively applied in parallel.

However, when the above-mentioned TN type liquid crystal is adopted for the element of such a driving system, the scan electrode is selected and the signal electrode is not selected, or the scan electrode is not selected and the signal electrode is selected. An electric field is applied to a finite amount (so-called "half selection point").

If the difference between the voltage applied to the selection point and the voltage applied to the half selection point is sufficiently large and the voltage threshold value required to align the liquid crystal molecules perpendicularly to the electric field is set to an intermediate voltage value, The display element works normally,
When the number of scanning lines (N) is increased, the whole screen (1
The time (duty ratio) in which an effective electric field is applied to one selection point during scanning of a frame decreases at a rate of 1 / N.

For this reason, the voltage difference as the effective value applied to the selected point and the non-selected point in the case of repeating scanning is
As the number of scanning lines increases, the number becomes smaller, and as a result, deterioration of image contrast and crosstalk are inevitable drawbacks.

Such a phenomenon is caused by a liquid crystal having no bistability (a stable state in which liquid crystal molecules are aligned horizontally with respect to an electrode surface, and a vertical state only while an electric field is effectively applied). This is an essentially unavoidable problem that occurs when driving (that is, repeatedly scanning) using the temporal accumulation effect.

In order to improve this point, the voltage averaging method, 2
The frequency drive method and the multi-matrix method have already been proposed, but none of them is sufficient, and the increase in the screen size and the density of the display element are stopped because the number of scanning lines cannot be increased sufficiently. This is the current situation.

In order to improve the drawbacks of the conventional liquid crystal device, the use of a liquid crystal device having bistability is explained by Clark and Lagerwell.
11) (Japanese Patent Laid-Open No. 56-10721).
6 gazette, US Pat. No. 4,367,924, etc.). Bistable liquid crystals are generally chiral smectic C phase (SmC ^* phase) or H phase (SmH ^* phase).
A ferroelectric liquid crystal having is used.

This ferroelectric liquid crystal has a bistable state consisting of a first optical stable state and a second optical stable state with respect to an electric field, and therefore the optical modulation used in the above-mentioned TN type liquid crystal. Unlike the element, for example, the liquid crystal is oriented in the first optically stable state with respect to one electric field vector, and the liquid crystal is oriented in the second optically stable state with respect to the other electric field vector. Further, this type of liquid crystal has a property (bistability) of taking one of the two stable states described above in response to an applied electric field and maintaining that state when no electric field is applied.

In addition to the above-mentioned characteristic of having bistability, the ferroelectric liquid crystal has an excellent characteristic of high-speed response. This is because the spontaneous polarization of the ferroelectric liquid crystal and the applied electric field act directly to induce the transition of the alignment state.
It is 3 to 4 orders faster than the response speed due to the effect of the dielectric anisotropy and the electric field.

As described above, the ferroelectric liquid crystal potentially has extremely excellent characteristics, and by utilizing such characteristics, many of the problems of the conventional TN type element described above are solved. A fairly substantial improvement is obtained. In particular, application to high-speed optical optical shutters, high-density, large-screen displays is expected. For this reason, there has been extensive research on ferroelectric liquid crystal materials, but the ferroelectric liquid crystal materials that have been developed to date are sufficient for use in liquid crystal devices, including low-temperature operating characteristics, high-speed response, and contrast. It is hard to say that it has such characteristics.

Between the response time r, the magnitude Ps of spontaneous polarization and the viscosity η, the following equation [1]

[0015]

[Equation 1] (However, E is the applied electric field.)

Therefore, in order to increase the response speed, there are methods of (a) increasing the magnitude Ps of spontaneous polarization (b) decreasing the viscosity η (c) increasing the applied electric field E.

However, the applied electric field has an upper limit because it is driven by an IC or the like, and it is desirable that the applied electric field be as low as possible. Therefore, it is actually necessary to reduce the viscosity η or increase the value of the spontaneous polarization magnitude Ps.

Generally, in a ferroelectric chiral smectic liquid crystal compound having a large spontaneous polarization, the internal electric field of the cell caused by the spontaneous polarization is also large, and there is a tendency that there are many restrictions on the device structure capable of assuming a bistable state. Further, even if the spontaneous polarization is unnecessarily increased, the viscosity tends to increase accordingly, and as a result, the response speed may not be so fast.

When the operating temperature range of the actual display is, for example, about 5 to 40 ° C., the response speed generally changes about 20 times, which exceeds the limit of adjustment by the drive voltage and frequency. The current situation.

In general, in the case of a liquid crystal element utilizing the birefringence of liquid crystal, the transmittance under the crossed Nicols is expressed by the following formula [2].

[0021]

[Equation 2] In the formula [2], I ₀ is the incident light intensity, I is the transmitted light intensity, θ
_a is the apparent tilt angle defined below, Δn is the refractive index anisotropy, d is the thickness of the liquid crystal layer, and λ is the wavelength of the incident light.

The tilt angle θ _a in the above-mentioned non-helical structure
Appears as an angle in the average molecular axis direction of the twisted liquid crystal molecules in the first and second alignment states.
According to the equation [2], the apparent tilt angle θ _a is 22.5.
The maximum transmittance is obtained at an angle of °, and the tilt angle θ _a in the non-helical structure that realizes the bistability needs to be as close as possible to 22.5 °.

However, when it is applied to the ferroelectric liquid crystal having a non-helical structure exhibiting the bistability announced by Clark and Lagerwall, it has the following problems and causes a decrease in contrast. Has become.

First, the apparent tilt angle θ _a in the ferroelectric liquid crystal having a non-helical structure obtained by orienting with a conventional rubbing-treated polyimide film (the angle formed by the molecular axes of two stable states is 1 / 2) is the tilt angle in the ferroelectric liquid crystal (angle θ that is 1/2 the apex angle of the triangular pyramid shown in FIG. 4 described later)
Since it is smaller than that, the transmittance is low.

Secondly, even if the contrast is high in the static state in which no electric field is applied, when driving display is performed by applying a voltage, liquid crystal molecules fluctuate due to a slight electric field in the non-selection period in matrix driving, and thus black is produced. It becomes pale.

As described above, in order to put the ferroelectric liquid crystal device into practical use, a liquid crystal composition having a chiral smectic phase having a high-speed response, a small temperature dependence of the response speed, and a high contrast. Is required.

Further, the spontaneous polarization of the liquid crystal composition, the chiral smectic C pitch, the cholesteric pitch, and the temperature at which the liquid crystal phase is taken for uniform switching of the display, good viewing angle characteristics, low temperature storage stability, and reduction of load on the driving IC. It is necessary to optimize the range, optical anisotropy, tilt angle, dielectric anisotropy and the like.

[0028]

SUMMARY OF THE INVENTION An object of the present invention is to have a high response speed, reduce its temperature dependence, and increase the contrast so that the above-mentioned ferroelectric liquid crystal device can be put to practical use. To provide a tetrahydroquinazoline compound effective for the use in a liquid crystal composition, a liquid crystal composition containing the same, particularly a ferroelectric chiral smectic liquid crystal composition, a liquid crystal element using the liquid crystal composition, and a display method and a display device using the same. It is in.

[0029]

That is, the present invention provides the following general formula (I):

[0030]

Embedded image R ₁ -Q-Ph-R ₂ (I)

(In the formula, R ₁ represents a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms.
One or more —CH ₂ — in the alkyl group is —O—, —S—, —CO under the condition that hetero atoms are not adjacent to each other.
-, -OCO-, -COO-, -CH = CH-, -C≡
It may be replaced with C-. R ₂ represents a linear, branched or cyclic alkyl group having 10 to 20 carbon atoms. However, one or more —CH ₂ — in the alkyl group may be —O—, under the condition that hetero atoms are not adjacent to each other.
-S-, -CO-, -OCO-, -COO-, -CH =
It may be replaced with CH-, -C≡C-. Q represents 5,6,7,8-tetrahydroquinazoline-2,6-diyl, and Ph represents 1,4-phenylene. )

A novel tetrahydroquinazoline compound represented by: a liquid crystal composition containing at least one of the compounds, a liquid crystal device comprising the liquid crystal composition arranged between a pair of electrode substrates, and a display method therefor, A display device is provided.

The tetrahydroquinazoline compound of the general formula (I) of the present invention is not particularly limited as to whether or not it is a liquid crystal by itself, and in a liquid crystal composition combined with another liquid crystal compound or the like. As one of the components, it exhibits an appropriate function and imparts excellent characteristics, but a liquid crystalline compound is preferable in terms of the characteristics and stability of the compound.

Among the tetrahydroquinazoline compounds represented by the general formula (I), the temperature range of the liquid crystal phase, miscibility, viscosity,
A compound in which R ₁ is a linear alkyl group having 1 to 10 carbon atoms is a preferable compound from the viewpoint of orientation and the like. Further, in view of the temperature width of the liquid crystal phase, the compatibility with other liquid crystals, the orientation, and the like, a more preferable compound is R ₂ having a linear alkyl group having 10 to 18 carbon atoms,
Examples thereof include compounds that are alkoxy groups and alkanoyloxy groups.

West German Laid-Open Patent Publication No. 2951099 discloses 6-alkyl-2- (4-alkylphenyl)-
5,6,7,8-Tetrahydroquinazoline is shown. However, the West German Published Patent Publication No. 2951099
In the compound shown in No. 4, the alkyl group bonded to the phenyl group has up to 8 carbon atoms, and the compounds specifically disclosed in Examples are compounds having only N phase. In addition, as an application, TNC (twisted ne
It is described that the compound is a compound for use in an electro-optical display device based on the principle of a matic cell or a cholesteric-nematic phase transition.

The inventors of the present invention produced a liquid crystal compound having a smectic phase by adjusting the number of carbon atoms of an alkyl group bonded to a phenyl group to 10 to 20 and containing at least one compound. Ferroelectric chiral smectic liquid crystal composition and liquid crystal device using the same are improved in various characteristics such as good orientation, high-speed response, and reduction of temperature dependence of response speed, and good display characteristics can be obtained. I found out.

Further, the tetrahydroquinazoline compound of the present invention has good compatibility with other compounds, and spontaneous polarization as a liquid crystal composition, chiral smectic C pitch, Ch pitch, temperature range of liquid crystal phase, optical anisotropy, It can also be used for adjusting the tilt angle, dielectric anisotropy, and the like.

Next, an example of a method for synthesizing the tetrahydroquinazoline compound represented by the general formula (I) will be shown below.

[0039]

[Chemical 5] (R ₃ is R ₂ or a group that is stable under condensation conditions and can be converted into R ₂ , and R ₁ , R ₂ , Q and Ph are as defined above.) Next, represented by general formula (I) The specific structural formula of the tetrahydroquinazoline compound is shown.

[0040]

Embedded image _{(1) C 2 H 5 -Q} -Ph-C 10 H 21 (2) C 5 H 11 -Q-Ph-C 10 H 21 (3) C 10 H 21 -Q-Ph-C 12 _{H 25 (4) C 5 H} 11 -Q-Ph-OC 10 H 21 (5) C 12 H 25 -Q-Ph-OC 18 H 37 (6) C 6 H 13 -Q-Ph-COOC 12 H 25 _{(7) C 8 H 17 -Q} -Ph-C 20 H 41 (8) C 10 H 21 -Q-Ph-OC 12 H 25 (9) C 18 H 37 -Q-Ph-C 18 H 37 (10 ) C ₅ H ₁₁ -Q-Ph-OCOC ₁₀ H ₂₁ (11) C ₄ H ₉ -Q-Ph-OC ₁₆ H ₃₃ (12) C ₁₀ H ₂₁ -Q-Ph-OCOC ₁₂ H ₂₅ (13) C ₆ H ₁₃ -Q-Ph-OCH ₂ CH ₂ OC ₈ H ₁₇ (14) C ₈ H ₁₇ -Q-Ph-OCOCH = CHC ₈ H ₁₇ (15) C ₁₀ H ₂₁ -Q-Ph-OCO (CH ₂ ) ₈ C≡CH

[0041]

(19) C ₂ H ₅ -Q-Ph-C ₁₁ H _{23 (21) CH 3 O (CH} 2) 4 -Q-Ph-C 12 H 25 (22) C 6 H 13 O (CH 2) 2 -Q-Ph-OCOC 16 H 33 (23) C 5 H 11 - Q-Ph-SC ₁₂ H _{25 (26) C 14 H 29 -Q} -Ph-C 16 H 33 (29) C ₁₆ H ₃₃ -Q-Ph-COOC ₁₈ H ₃₇ (30) C ₁₁ H ₂₃ -Q-Ph-C ₁₅ H ₃₁ (31) C ₅ H ₁₁ -Q-Ph-C ₁₈ H ₁₇ (32 _{) C 10 H 21 -Q-Ph} -COC 12 H 25

[0042]

Embedded image _{(35) C 10 H 21 -Q} -Ph-OC 10 H 21 (36) C 10 H 21 -Q-Ph-OCOC 10 H 21

The liquid crystal composition of the present invention can be obtained by mixing at least one kind of the tetrahydroquinazoline compound represented by the general formula (I) and one or more kinds of other liquid crystal compounds in an appropriate ratio. The number of other liquid crystal compounds used in combination is in the range of 1 to 50, preferably 1 to 30, and more preferably 3 to 30.

The liquid crystal composition according to the present invention is preferably a ferroelectric liquid crystal composition, particularly a ferroelectric chiral smectic liquid crystal composition.

Other liquid crystal compounds used in the present invention are disclosed in JP-A-4-272989 (23) to (39).
Compounds (III) to (XII), preferred compounds (IIIa) to (XIId), and more preferred compounds (IIIaa) to (XIIdb) described on the page are mentioned. Furthermore, liquid crystal compounds represented by the following general formulas (XIII) to (XVIII) can also be used.

[0046]

Embedded image R ′₇-[Py2] -X '₇-[Ph] -X '₈-([PhY '₇]))_N-[Tn] -R ' ₈ (XIII) R '₇-X '₉-[Py2]-[Ph] -OCO- [Ph4F] (XIV) R '₇-X '₉-[Py2]-[Ph] -OCO- [Ph34F] (XV) R '₇-([PhY '₇]))_Q-[Tz1]-[PhY '₈] -X '₇-([PhY '₉])_R-([Cy])_T-X '_Ten-R '₈ (XVI) R '₇-[Bo2] -A '_Four-X '₉-R '₈ (XVII) R '₇-[Bt2] -A '_Four-X '₉-R '₈ (XVIII)

[0047] wherein R _'7, R' ₈ is 1 the number hydrogen or C
To 18 linear or branched alkyl groups, one or two or more non-adjacent —CH in the alkyl group.
_2- is -O-, -CO unless hetero atoms are adjacent to each other.
-, - CH (CN) - , - C (CN) (CH 3) - may be replaced by.

[0048] Moreover R _'7, R' ₈ is preferably i below) -
viii).

I) a straight-chain alkyl group having 1 to 15 carbon atoms

[0050]

[Chemical 10] p: 0-5, q: 2-11 integer optically active

[0051]

[Chemical 11] r: 0 to 6, s: 0 or 1, t: 1 to 14 integer optically active

[0052]

[Chemical 12] w: 1 to 14 integer optically active

[0053]

[Chemical 13] A: 0 to 2, B: 1 to 15 integer Optically active

[0054]

Embedded image C: 0 to 2, D: 1 to 15 integer Optically active

Vii) -H

[0056]

[Chemical 15] u is an integer of 0, 1 and v is an integer of 1-15.

[0057]

Embedded image x represents an integer of 0 to 2 and y represents an integer of 1 to 15.

[0058] N, Q, R, T: 0 or 1 Y _{'7,
Y '8, Y' 9:} H or _{F A '4: Ph, Np} X' 7, X '8, X' 9: a single bond, -
COO -, - OCO -, - CH 2 O -, - OCH 2 -

Preferred compounds of (XIII) are (X
IIIa).

[0060]

[Of 17] _{R '7 - [Py2] -} [Ph] -OCO- [Tn] -R' 8 (XIIIa)

Preferred compounds of (XVI) are (XV
Ia) and (XVIb).

[0062]

Embedded image _{R '7 - [Tz1] -} [Ph] -X' 7 -R '8 (XVIa) R' 7 - [PhY '7] - [Tz1] - [PhY' 8] -X '7 - R _'8 (XVIb)

Preferred compounds of (XVII) are (X
VIIa) and (XVIIb).

[0064]

Embedded image _{R '7 - [Boa2] -} [Ph] -O-R' 8 (XVIIa) R '7 - [Boa2] - [Np] -O-R' 8 (XVIIb)

Preferred compounds of (XVIII) include (XVIIIa) to (XVIIIc).

[0066]

Embedded image _{R '7 - [Btb2] -} [Ph] -R' 8 (XVIIIa) R '7 - [Btb2] - [Ph] -O-R' 8 (XVIIIb) R '7 - [Btb2] - [Np] -OR ' ₈ (XVIIIc)

Preferred compounds of (XVIa) and (XVIb) include (XVIba) to (XVIbc).

[0068]

Embedded image _{R '7 - [Tz1] -} [Ph] -O-R' 8 (XVIaa) R '7 - [Ph] - [Tz1] - [Ph] -R' 8 (XVIba) R '7 - [Ph] - [Tz1] - [Ph] -O-R '8 (XVIbb) R' 7 - [Ph] - [Tz1] - [Ph] -OCO-R '8 (XVIbc)

Abbreviations such as Ph, Py2, Tn and the like are shown below.

[0070]

[Chemical formula 22]

When the tetrahydroquinazoline compound of the present invention is mixed with one or more of the above-mentioned liquid crystalline compounds or the liquid crystal composition, the tetrahydroquinazoline compound of the present invention occupying in the liquid crystal composition obtained by mixing is obtained. It is desirable that the proportion is 1% by weight to 80% by weight, preferably 1% by weight to 60% by weight, and more preferably 1% by weight to 40% by weight.

When two or more tetrahydroquinazoline compounds of the present invention are used, the proportion of the mixture of two or more tetrahydroquinazoline compounds of the present invention in the liquid crystal composition obtained by mixing is 1% by weight to 80%. It is desirable that the amount is 1% by weight, preferably 1% by weight to 60% by weight, and more preferably 1% by weight to 40% by weight.

Further, the ferroelectric liquid crystal layer in the ferroelectric liquid crystal device of the present invention is prepared by heating the ferroelectric liquid crystal composition prepared as described above in vacuum to an isotropic liquid temperature,
It is preferable that the liquid crystal layer is sealed in an element cell and gradually cooled to form a liquid crystal layer and then returned to normal pressure.

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

Referring to FIG. 1, in the liquid crystal element, a liquid crystal layer 1 exhibiting a chiral smectic phase is arranged between a pair of glass substrates 2 provided with a transparent electrode 3 and an insulating orientation control layer 4, respectively, and the layer is formed. The thickness is set by a spacer 5, and a voltage is applied between a pair of transparent electrodes 3 via a lead wire 6 so that a voltage can be applied from a power supply 7. Also, a pair of substrates 2
Are sandwiched between a pair of crossed Nicol polarizing plates 8, and a light source 9 is arranged outside one of them.

The two glass substrates 2 were coated with In ₂
A transparent electrode 3 made of a thin film of O ₃ , SnO ₂ or ITO (Indium Tin Oxide) is covered. An insulating alignment control layer 4 for arranging the liquid crystal in the rubbing direction is formed by rubbing a polymer thin film such as polyimide with gauze or acetate flocking cloth or the like.

As the insulating material, for example, silicon nitride, silicon nitride containing hydrogen, silicon carbide, silicon carbide containing hydrogen, silicon oxide,
An inorganic material insulating layer such as boron nitride, hydrogen-containing boron nitride, cerium oxide, aluminum oxide, zirconium oxide, titanium oxide or magnesium fluoride is formed, and polyvinyl alcohol, polyimide or polyamide is formed thereon. Align organic insulating materials such as imides, polyester imides, polyparaxylene, polyesters, polycarbonates, polyvinyl acetals, polyvinyl chlorides, polyvinyl acetates, polyamides, polystyrenes, cellulose resins, melamine resins, urea resins, acrylic resins and photoresist resins As the control layer, the insulating orientation control layer 4 may be formed of two layers, or may be an inorganic material insulating orientation control layer or an organic material insulating orientation control layer single layer.

If this insulating orientation control layer is an inorganic type, it can be formed by a vapor deposition method, and if it is an organic type, a solution in which an organic insulating substance is dissolved or a precursor solution thereof (0.1 to 20 in a solvent) is used.
% By weight, preferably 0.2 to 10% by weight) and applied by a spinner coating method, a dip coating method, a screen printing method, a spray coating method, a roll coating method, etc. under predetermined curing conditions (for example, under heating). ) And can be formed by curing.

The layer thickness of the insulating orientation control layer 4 is usually 10Å
1 μm, preferably 10 Å to 3000 Å, more preferably 10 Å to 1000 Å are suitable.

The two glass substrates 2 are held by the spacer 5 at arbitrary intervals. For example, there is a method in which silica beads and alumina beads having a predetermined diameter are sandwiched between two glass substrates as spacers, and the periphery is sealed with a sealing material, for example, an epoxy adhesive material. Other,
A polymer film or glass fiber may be used as the spacer. Ferroelectric liquid crystal is enclosed between the two glass substrates.

The ferroelectric liquid crystal layer 1 in which the ferroelectric liquid crystal is enclosed is generally 0.5 to 20 μm, preferably 1 to 5 μm.
m.

The transparent electrode 3 is connected to an external power source 7 by a lead wire. A polarizing plate 8 is attached to the outside of the glass substrate 2. The example of FIG. 1 is a transmissive type, and includes a light source 9.

FIG. 2 is a schematic drawing of an example of a cell for explaining the operation of a liquid crystal element utilizing ferroelectricity. 21a and 21b are In ₂ O ₃ and Sn, respectively.
O ₂ or ITO (indium tin oxide;
A substrate (glass plate) covered with a transparent electrode composed of a thin film such as Indium Tin Oxide), and liquid crystal of SmC ^* phase or SmH ^* phase in which the liquid crystal molecule layer 22 is oriented perpendicular to the glass surface is enclosed between them. Has been done. A thick line 23 represents a liquid crystal molecule, and this liquid crystal molecule 23 has a dipole moment (P⊥) 24 in a direction orthogonal to the molecule. Substrates 21a and 21b
When a voltage of a certain threshold value or more is applied between the upper electrodes, the helical structure of the liquid crystal molecules 23 is unwound, and the dipole moment (P
The alignment directions of the liquid crystal molecules 23 can be changed so that ⊥) 24 all face the electric field direction. The liquid crystal molecule 23 has an elongated shape and exhibits refractive index anisotropy in the major axis direction and the minor axis direction thereof. Therefore, for example, if crossed Nicol polarizers are placed above and below the glass surface, the voltage application polarity is increased. It can be easily understood that the liquid crystal optical modulation element changes its optical characteristics depending on the situation.

The liquid crystal cell preferably used in the optical modulator of the present invention has a sufficiently thin thickness (for example, 1
0 μ or less). As shown in FIG. 3, as the liquid crystal layer becomes thinner, the helical structure of the liquid crystal molecules unwinds even when no electric field is applied, and the dipole moment Pa or Pb of the liquid crystal molecule is directed upward (34a) or downward (34b). Take either state. When an electric field Ea or Eb having a polarity equal to or greater than a certain threshold is applied to such a cell by the voltage applying means 31a and 31b, the dipole moment corresponds to the electric field vector of the electric field Ea or Eb. The liquid crystal molecules are turned to the upward stable state 34a or the downward stable direction 34b, and accordingly, the liquid crystal molecules move to the first stable state 3
3a or the second stable state 33b.

As described above, there are two advantages of using such a ferroelectric liquid crystal element as an optical modulation element. The first is that the response speed is extremely fast, and the second is that the alignment of the liquid crystal molecules has bistability. The second point will be further explained with reference to FIG. 3, for example.
When a is applied, the liquid crystal molecules are aligned in the first stable state 33a, but this state is stable even when the electric field is cut off. When a reverse electric field Eb is applied, the liquid crystal molecules are oriented in the second stable state 33b and change their orientation, but they remain in this state even when the electric field is cut off. Further, as long as the applied electric field Ea or Eb does not exceed a certain threshold value, the previous alignment state is still maintained.

FIG. 5 shows an example of the drive waveform used in the present invention. In FIG. 5A, S _S is a selected scan waveform applied to the selected scan line, S _N is a non-selected scan waveform not selected, and I _S is selection information applied to the selected data line. waveform (black), I _N represents the non-selection information signal applied to the data line which is not selected (white). In the figure the _{(I S -S S) (I} N -S S) is the voltage waveforms applied to pixels on a selected scanning line, the voltage _{(I S} -S S) is applied pixel black take the display state, the pixel voltage (I N _{-S S)} is applied takes the display state of white.

FIG. 5B shows the drive waveform shown in FIG.
7 is a time series waveform when the display shown in FIG. 6 is performed. Figure 5
In the driving example shown in FIG. 3, the minimum application time Δt of the single polarity voltage applied to the pixel on the selected scan line is the writing phase t ₂
And the time of 1 line clear t ₁ phase is 2
It is set to Δt.

The values of the parameters V _S , V _I and Δt of the drive waveform shown in FIG. 5 are determined by the switching characteristics of the liquid crystal material used. Here, the bias ratio V _I / (V _I + V _S ) = 1/3 is fixed.

Although it is possible to increase the width of the appropriate driving voltage by increasing the bias ratio, increasing the bias ratio means increasing the amplitude of the information signal, and thus flicker in image quality increases. However, the contrast is lowered, which is not preferable. In our study, the bias ratio is 1/3 ~
About 1/4 was practical.

By using the liquid crystal device of the present invention in the display panel section and taking the communication information synchronizing means by the data format as the image information having the scanning line address information and the SYNC signal shown in FIGS. 7 and 8, the liquid crystal display device is obtained. To realize.

In the figure, the symbols are as follows. 101 ferroelectric liquid crystal display device 102 graphics controller 103 display panel 104 scanning line driving circuit 105 information line driving circuit 106 decoder 107 scanning signal generating circuit 108 shift register 109 line memory 110 information signal generating circuit 111 driving control circuit 112 GCPU 113 host CPU 114 VRAM

The image information is generated by the graphics controller 102 on the main body side, and transferred to the display panel 103 according to the signal transfer means shown in FIGS. The graphics controller 102 is a CP
U (central processing unit, abbreviated as GCPU 112 hereafter) and VRAM (memory for storing image information) 114 are at the core of management of image information and communication between the host CPU 113 and the liquid crystal display device 101, and control of the present invention. The method is mainly implemented on the graphics controller 102. A light source is arranged on the back surface of the display panel.

[0093]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 6-Pentyl-2- (4-decylphenyl) -5,6
7,8-Tetrahydroquinazoline (Exemplified Compound No.
2) Production (Step 1) Synthesis of 4-pentyl-2-hydroxymethylene-cyclohexanone 1.19 g (60% oiliness, 29.7 mmol) of sodium hydride in 35 ml of anhydrous ether
Was added and the mixture was stirred under ice-water cooling. Ethanol 0.17 there
After adding ml, 4-pentylcyclohexanone 5.0
0 g (29.7 mmol) and ethyl formate 3.30 g
(44.6 mmol) was added dropwise over 1 hour. After the dropping, the mixture was stirred at room temperature for 8 hours, poured into water and the ether layer was separated. The aqueous layer was extracted twice with ethyl acetate. The aqueous layer was acidified with 6N hydrochloric acid, extracted with ethyl acetate, washed with water, and dried over anhydrous sodium sulfate. After removing sodium sulfate by filtration, the solvent was distilled off to obtain 4.55 g of 4-pentyl-2-hydroxymethylene-cyclohexanone. Yield 78.0%.

(Step 2) Synthesis of 6-pentyl-2- (4-decylphenyl) -5,6,7,8-tetrahydroquinazoline 4-pentyl-2-hydroxymethylenecyclohexanone 0.7 g (3.56 mmol), 4-decylbenzamidine hydrochloride 1.06 g (3.56 mmol), sodium methoxide 0.48 g (8.88 mmol) and ethanol 12 ml were added, and the mixture was stirred under reflux for 6 hours. Then, the mixture was poured into water and extracted with ethyl acetate. After washing with water, it was dried over anhydrous sodium sulfate. Sodium sulfate was filtered off, and the solvent was distilled off under reduced pressure. The residue was purified by a silica gel column (developing solvent: toluene), recrystallized twice with ethanol, and 6-pentyl-2- (4-decylphenyl) -5,5.
0.58 g of 6,7,8-tetrahydroquinazoline was obtained. Yield 38.7%.

[0096]

(Equation 3)

Example 2 6-Pentyl-2- (4-decyloxyphenyl)-
Production of 5,6,7,8-tetrahydroquinazoline (Exemplified Compound No. 4) (Step 1) Synthesis of 6-pentyl-2- (4-hydroxyphenyl) -5,6,7,8-tetrahydroquinazoline 4- Pentyl-2-hydroxymethylenecyclohexanone 4.40 g (22.4 mmol), 4-hydroxybenzamidine hydrochloride 3.51 g (22.4 mmol),
Sodium methoxide 4.24 g (78.4 mmol)
And 60 ml of ethanol were added, and the mixture was stirred under reflux for 10 hours. Then, the mixture was poured into water, acidified with 6N hydrochloric acid, extracted with ethyl acetate, washed with water, and dried over anhydrous sodium sulfate.
After removing sodium sulfate by filtration, the solvent was distilled off, and the residue was subjected to a silica gel column (developing solvent: toluene / ethyl acetate = 2).
/ 1), crystallized with hexane, put in a freezer, filtered and washed with cold hexane. After drying, 6-pentyl-2- (4-hydroxyphenyl) -5,6,7,8-
2.12 g of tetrahydroquinazoline was obtained. Yield 31.
9%.

(Step 2) Synthesis of 6-pentyl-2- (4-decyloxyphenyl) -5,6,7,8-tetrahydroquinazoline 6-pentyl-2- (4-hydroxyphenyl) -5
0.12 g of 6,7,8-tetrahydroquinazoline (0.
40 mmol), 0.11 g of iododecane (0.40 m
mol), 0.03 g of potassium hydroxide (85%, 0.4
5 mmol) and DMF (N, N-dimethylformamide) 5 ml were added, and the mixture was stirred at 110 ° C. for 5 hours. After the reaction, the mixture was poured into water, extracted with toluene, washed with water, and dried over anhydrous sodium sulfate. After sodium sulfate was filtered off, the solvent was distilled off and the residue was purified by a silica gel column (developing solvent: toluene) and recrystallized from ethanol to give 6-pentyl-2- (4-decyloxyphenyl) -5,6. , 7, 8
-0.1 g of tetrahydroquinazoline was obtained. Yield 57.
1%.

[0099]

[Equation 4]

Example 3 Preparation of 6-pentyl-2- (4-undecanoyloxyphenyl) -5,6,7,8-tetrahydroquinazoline (Exemplified Compound No. 10) 6-pentyl-2- (4- Hydroxyphenyl) -5,
0.20 g of 6,7,8-tetrahydroquinazoline (0.
67 mmol), undecanoic acid 0.12 g (0.67 m
mol), dicyclohexylcarbodiimide 0.13 g
(0.67 mmol), N, N-dimethylaminopyridine 0.02 g and methylene chloride 20 ml were added, and the mixture was stirred at room temperature for 5 hours. The produced dicyclohexylurea was filtered off, washed with methylene chloride, combined with the filtrate, and concentrated under reduced pressure. The residue is a silica gel column (developing solvent: toluene)
And recrystallized from ethanol to give 6-pentyl-2- (4-undecanoyloxyphenyl) -5,
0.18 g of 6,7,8-tetrahydroquinazoline was obtained. Yield 58.1%.

[0101]

(Equation 5)

Example 4 6-decyl-2- (4-decyloxyphenyl) -5, -5
6,7,8-Tetrahydroquinazoline (Exemplified Compound N
o. Preparation of 35) (Step 1) Synthesis of 4-decyl-2-hydroxymethylene-cyclohexanone 0.84 g (60% oiliness, 21.0 mmol) of sodium hydride was added to 50 ml of anhydrous ether, and the mixture was stirred under ice-water cooling. Ethanol 0.17 there
After adding ml, 4-decylcyclohexanone 5.00
g (21.0 mmol) and ethyl formate 2.33 g
(31.5 mmol) was added dropwise over 40 minutes. After the dropping, the mixture was stirred at room temperature for 8 hours, poured into water, and the ether layer was separated. The aqueous layer was extracted twice with ethyl acetate. Then 6 water layers
The mixture was acidified with N hydrochloric acid, extracted with ethyl acetate, washed with water, and dried over anhydrous sodium sulfate. After removing sodium sulfate by filtration, the solvent was distilled off to obtain 4.2 g of 4-decyl-2-hydroxymethylenecyclohexanone. Yield 75.0
%.

(Step 2) Synthesis of 6-decyl-2- (4-hydroxylphenyl) -5,6,7,8-tetrahydroquinazoline 4-decyl-2-hydroxymethylenecyclohexanone 2.0 g (7.5 mmol), 4-Hydroxybenzamidine hydrochloride 1.18 g (7.5 mmol), sodium methoxide 1.42 g (26.3 mmol) and ethanol 50 ml were added, and the mixture was stirred under reflux for 10 hours.
Then, the mixture was poured into water, acidified with 6N hydrochloric acid, extracted with ethyl acetate, washed with water, and dried over anhydrous sodium sulfate. After removing sodium sulfate by filtration, the solvent was distilled off, and the residue was purified by a silica gel column (developing solvent: toluene / ethyl acetate = 2/1), crystallized with hexane, put into a freezer and collected by filtration, and with cold hexane. washed. After drying, 6-decyl- (2-
1.07 g of hydroxyphenyl) -5,6,7,8-tetrahydroquinazoline was obtained. Yield 38.9%.

(Step 3) Synthesis of 6-decyl-2- (4-decyloxyphenyl) -5,6,7,8-tetrahydroquinazoline 6-decyl-2- (4-hydroxyphenyl) -5
0.2 g of 6,7,8-tetrahydroquinazoline (0.5
5 mmol), 0.15 g of iododecane (0.55 mm
ol), 0.05 g of potassium hydroxide (85%, 0.76)
mmol) and 8 ml of DMF were added, and the mixture was stirred at 110 ° C. for 6 hours. After the reaction, the mixture was poured into water, extracted with toluene, washed with water, and dried over anhydrous sodium sulfate. After sodium sulfate was filtered off, the solvent was distilled off and the residue was purified by a silica gel column (developing solvent: toluene) and recrystallized from ethanol to give 6-decyl-2- (4-decyloxyphenyl)-.
0.14 g of 5,6,7,8-tetrahydroquinazoline was obtained. Yield 50.1%.

[0105]

(Equation 6)

Example 5 6-decyl-2- (4-dodecyloxyphenyl)-
Production of 5,6,7,8-tetrahydroquinazoline (Exemplified Compound No. 8) 6-decyl-2- (4-hydroxyphenyl) -5,5
0.25 g of 6,7,8-tetrahydroquinazoline (0.
68 mmol), 0.19 g of iodododecane (0.68
mmol), 0.05 g of potassium hydroxide (85%, 0.
75 mmol) and 8 ml of DMF were added, and the mixture was stirred at 110 ° C. for 6 hours. After the reaction, pour into water and extract with toluene,
After washing with water, it was dried over anhydrous sodium sulfate. After sodium sulfate was filtered off, the solvent was distilled off, the residue was purified with a silica gel column (developing solvent: toluene), and recrystallized from ethanol to give 6-decyl-2- (4-dodecyloxyphenyl) -5. , 6,7,8-Tetrahydroquinazoline 0.
17 g was obtained. Yield 48.0%.

[0107]

(Equation 7)

Example 6 Preparation of 6-decyl-2- (4-undecanoyloxyphenyl) -5,6,7,8-tetrahydroquinazoline (Exemplified Compound No. 36) 6-decyl-2- (4- Hydroxyphenyl) -5,
0.2 g of 6,7,8-tetrahydroquinazoline (0.5
5 mmol), undecanoic acid 0.1 g (0.55 mmo
l), 0.11 g of dicyclohexylcarbodiimide
(0.55 mmol), N, N-dimethylaminopyridine (0.02 g) and methylene chloride (20 ml) were added, and the mixture was stirred at room temperature for 5 hours. The produced dicyclohexylurea was filtered off, washed with methylene chloride, combined with the filtrate, and concentrated under reduced pressure. The residue was purified with a silica gel column (developing solvent: toluene), recrystallized from ethanol, and 6-decyl-2-
(4-Undecanoyloxyphenyl) -5,6,7,
0.16 g of 8-tetrahydroquinazoline was obtained. Yield 5
4.4%.

[0109]

[Equation 8]

Example 7 The following compounds were mixed in the following parts by weight to prepare a liquid crystal composition A.

[0111]

[Chemical formula 23]

Further, with respect to this liquid crystal composition A, the following exemplary compounds were mixed in the respective parts by weight shown below to prepare a liquid crystal composition B.

[0113]

[Chemical formula 24]

Example 8 Two 0.7 mm thick glass plates were prepared, an ITO film was formed on each glass plate, and voltage application electrodes were prepared.
Further, SiO ₂ was vapor-deposited on this to form an insulating layer. Silane coupling agent on glass plate [K manufactured by Shin-Etsu Chemical Co., Ltd.
BM-602] 0.2% isopropyl alcohol solution was rotated at a rotation speed of 2000 r.p.m. p. m spinner applied for 15 seconds and surface-treated. After that, heat drying treatment was performed at 120 ° C. for 20 minutes.

A polyimide resin precursor [Toray Industries, Inc. SP-
510] Rotate the 1.5% dimethylacetamide solution at a rotation speed of 2
000r. p. m spinner for 15 seconds. After the film formation, the film was subjected to heat condensation baking treatment at 300 ° C. for 60 minutes.
At this time, the film thickness of the coating film was about 250Å.

The coating film after firing was rubbed with an acetate flocked cloth, then washed with an isopropyl alcohol solution, and silica beads having an average particle diameter of 2 μm were dispersed on one glass plate, and then each rubbed treatment was performed. The axes were made parallel to each other, and glass plates were laminated using an adhesive sealant [Rixon Bond (Chisso Corporation)] and dried by heating at 100 ° C. for 60 minutes to prepare a cell.

The liquid crystal composition B mixed in Example 7 was injected into this cell in an isotropic liquid state and gradually cooled from the isotropic phase to 25 ° C. at 20 ° C./h to obtain a ferroelectric liquid crystal element. Created. When the cell thickness of this cell was measured with a Berek phase plate, it was about 2 μm.

Using this ferroelectric liquid crystal device, the optical response (transmission light amount change 0 to 90%) under orthogonal Nicols was detected by applying a voltage of peak-to-peak voltage Vpp = 20 V, and the response speed ( Hereinafter, the optical response speed) was measured. The measurement results are shown below.

[0119]

[Table 1] 10 ° C. 25 ° C. 40 ° C. Response speed 411 μsec 214 μsec 120 μsec

Comparative Example 1 A ferroelectric liquid crystal device was prepared in the same manner as in Example 8 except that the liquid crystal composition A mixed in Example 7 was injected into the cell, and the optical response speed was measured. The measurement results are shown below.

[0121]

[Table 2] 10 ° C 25 ° C 40 ° C Response speed 668 μsec 340 μsec 182 μsec

Example 9 A liquid crystal composition C was prepared by mixing the exemplified compounds shown below instead of the exemplified compound used in Example 7 in the weight parts shown below.

[0123]

[Chemical 25]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 8 except that the liquid crystal composition C was injected into the cell.
The optical response speed was measured and the switching state was observed.
The uniform alignment in this liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown below.

[0125]

[Table 3] 10 ° C 25 ° C 40 ° C Response speed 402 μsec 209 μsec 116 μsec

Example 10 The following compounds were mixed in the following parts by weight to prepare a liquid crystal composition D.

[0127]

[Chemical formula 26]

Further, with respect to this liquid crystal composition D, the following exemplary compounds were mixed in the respective parts by weight shown below to prepare a liquid crystal composition E.

[0129]

[Chemical 27]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 8 except that the liquid crystal composition E was injected into the cell.
The optical response speed was measured and the switching state was observed.
The uniform alignment in this liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown below.

[0131]

[Table 4] 10 ° C 25 ° C 40 ° C Response speed 508 μsec 249 μsec 140 μsec

Comparative Example 2 A ferroelectric liquid crystal device was prepared in the same manner as in Example 8 except that the liquid crystal composition E mixed in Example 10 was injected into the cell, and the optical response speed was measured. The results are shown below.

[0133]

[Table 5] 10 ° C 25 ° C 40 ° C Response speed 784 μsec 373 μsec 197 μsec

Example 11 Liquid crystal composition F was prepared by mixing the following compounds in the weight parts shown below instead of the exemplified compounds mixed in Example 10.
It was created.

[0135]

[Chemical 28]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 8 except that the liquid crystal composition F was injected into the cell.
The optical response speed was measured and the switching state was observed.
The uniform alignment in this liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown below.

[0137]

[Table 6] 10 ° C. 25 ° C. 40 ° C. Response speed 489 μsec 242 μsec 139 μsec

Example 12 The following compounds were mixed in the following parts by weight to prepare a liquid crystal composition G.

[0139]

[Chemical 29]

Further, with respect to this liquid crystal composition G, the following exemplary compounds were mixed in the respective parts by weight shown below to prepare a liquid crystal composition H.

[0141]

[Chemical 30]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 8 except that the liquid crystal composition H was injected into the cell.
The optical response speed was measured and the switching state was observed.
The uniform alignment in this liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown below.

[0143]

[Table 7] 10 ° C 25 ° C 40 ° C Response speed 422 μsec 214 μsec 114 μsec

Comparative Example 3 A ferroelectric liquid crystal device was prepared in the same manner as in Example 8 except that the liquid crystal composition G mixed in Example 12 was injected into the cell, and the optical response speed was measured. The measurement results are shown below.

[0145]

[Table 8] 10 ° C 25 ° C 40 ° C Response speed 653 μsec 317 μsec 159 μsec

Example 13 A liquid crystal composition I was prepared by mixing the exemplified compounds shown below instead of the exemplified compound used in Example 12 in the respective parts by weight shown below.

[0147]

[Chemical 31]

A ferroelectric liquid crystal device was prepared in the same manner as in Example 8 except that the liquid crystal composition I was injected into the cell.
The optical response speed was measured and the switching state was observed.
The uniform alignment in this liquid crystal element was good, and a monodomain state was obtained. The measurement results are shown below.

[0149]

[Table 9] 10 ° C. 25 ° C. 40 ° C. Response speed 401 μsec 202 μsec 110 μsec

As is clear from Examples 7 to 13, the ferroelectric liquid crystal elements containing the liquid crystal compositions B, C, E, F, H and I according to the present invention have operating characteristics at low temperature and high speed response. It has been improved and the temperature dependence of the optical response speed has been reduced.

Example 14 Except that the polyimide resin precursor 1.5% dimethylacetamide solution used in Example 8 was replaced with a 2% aqueous solution of polyvinyl alcohol resin [PUA-117 manufactured by Kuraray Co., Ltd.]. Create a ferroelectric liquid crystal element by the method of
The optical response speed was measured in the same manner as in Example 8. The measurement results are shown below.

[0152]

[Table 10] 10 ° C 25 ° C 40 ° C Response speed 408 μsec 211 μsec 118 μsec

Example 15 A ferroelectric liquid crystal device was prepared and manufactured in exactly the same manner as in Example 8 except that the alignment control layer was prepared only with a polyimide resin without using SiO ₂ used in Example 8. The optical response speed was measured in the same manner as in Example 8. The measurement results are shown below.

[0154]

[Table 11] 10 ° C 25 ° C 40 ° C Response speed 412 μsec 214 μsec 121 μsec

As is clear from Examples 14 and 15, even when the element structure was changed, the element containing the ferroelectric liquid crystal composition according to the present invention had much improved low-temperature operating characteristics as in Example 8. Moreover, the temperature dependence of the response speed is reduced.

Example 17 Liquid Crystal Composition J was prepared by mixing the following compounds in the following parts by weight.

[0157]

[Chemical 32]

Further, with respect to the liquid crystal composition J, the exemplified compounds shown below were mixed in the respective parts by weight shown below to prepare a liquid crystal composition K.

[0159]

[Chemical 33]

Next, the optical response was observed using a cell prepared by the following procedure from these liquid crystal compositions. Two 0.7 mm-thick glass plates were prepared, an ITO film was formed on each glass plate, a voltage application electrode was prepared, and SiO ₂ was further vapor-deposited on this to form an insulating layer. Silane coupling agent on glass plate [KBM manufactured by Shin-Etsu Chemical Co., Ltd.
-602] A 0.2% isopropyl alcohol solution was rotated at a rotation speed of 2000 r.p. p. m spinner for 15 seconds,
A surface treatment was applied. After that, heat drying treatment was performed at 120 ° C. for 20 minutes.

Further, a polyimide resin precursor [Toray Industries, Inc. SP-
510] Rotate the 1.0% dimethylacetamide solution at a rotation speed of 3
000r. p. m spinner for 15 seconds. After the film formation, the film was subjected to heat condensation baking treatment at 300 ° C. for 60 minutes.
The film thickness of the coating film at this time was about 120Å.

The coating film after firing was rubbed with an acetate flocked cloth, washed with an isopropyl alcohol solution, and silica beads having an average particle size of 1.5 μm were dispersed on one glass plate. The rubbing axes were made parallel to each other, the glass plates were laminated using an adhesive sealant [Rixon Bond (Chisso Corporation)], and heated and dried at 100 ° C. for 60 minutes to prepare a cell.

The cell thickness of this cell was measured by a Berek phase plate and found to be about 1.5 μm. The liquid crystal composition K was injected into this cell in an isotropic liquid state, and the
A ferroelectric liquid crystal element was prepared by gradually cooling to 25 ° C at a rate of ° C / h.

When the ferroelectric liquid crystal element was used and the driving waveform (1/3 bias ratio) shown in FIG. 5 was used to measure the contrast at the time of driving at 30 ° C., it was 12.2.

Comparative Example 4 A ferroelectric liquid crystal device was prepared in the same manner as in Example 16 except that the liquid crystal composition J mixed in Example 16 was injected into the cell, and the same driving waveform was used at 30 ° C. The contrast at the time of driving was measured. As a result, the contrast was 6.7.

Example 17 A liquid crystal composition L was prepared by mixing the exemplified compounds shown below instead of the exemplified compound used in Example 16 with the respective parts by weight shown below.

[0167]

Embedded image

A ferroelectric liquid crystal device was prepared in the same manner as in Example 16 except that this liquid crystal composition was used, and the contrast at the time of driving at 30 ° C. was measured using the same driving waveform as in Example 16. did. As a result, the contrast is 1
It was 1.7.

Example 18 A liquid crystal composition M was prepared by mixing the exemplified compounds shown below instead of the exemplified compound used in Example 16 in the respective parts by weight shown below.

[0170]

Embedded image

A ferroelectric liquid crystal element was prepared in the same manner as in Example 16 except that this liquid crystal composition was used, and the contrast at the time of driving at 30 ° C. was measured using the same driving waveform as in Example 16. did. As a result, the contrast is 1
It was 0.8.

As is clear from Examples 16 to 18, the ferroelectric liquid crystal elements containing the liquid crystal compositions K, L and M according to the present invention have high contrast during driving.

Example 19 A polyimide resin precursor 1.0% dimethylacetamide solution used in Example 16 was replaced with a 2% aqueous solution of polyvinyl alcohol resin [PUA-117 manufactured by Kuraray Co., Ltd.]. A ferroelectric liquid crystal device was produced by the same method as in Example 16, and the contrast during driving at 30 ° C. was measured by the same method as in Example 16 and as a result, the contrast was 14.9.

Example 20 Except that the SiO ₂ used in Example 16 was not used and the alignment control layer was formed only with a polyimide resin, Example 1 was carried out at all.
A ferroelectric liquid crystal device was prepared in the same manner as in Example 6, and Example 1
As a result of measuring the contrast at the time of driving at 30 ° C. by the same method as in 6, the contrast was 15.3.

Example 21 A polyamic acid (LQ1802, manufactured by Hitachi Chemical Co., Ltd.) 1% NMP solution was used in place of the polyimide resin precursor 1.0% dimethylacetamide solution used in Example 16.
A ferroelectric liquid crystal device was prepared in the same manner as in Example 16 except that it was baked at 270 ° C. for 1 hour, and the contrast during driving at 30 ° C. was measured in the same manner as in Example 16. As a result, the contrast was 17.6.

As is apparent from Examples 19, 20 and 21, even when the element structure was changed, the element containing the ferroelectric liquid crystal composition according to the present invention showed high contrast as in Example 16. There is. Further, as a result of detailed examination even when the drive waveform was changed, it was found that a liquid crystal element containing the ferroelectric liquid crystal composition of the present invention similarly provided higher contrast.

[0177]

The liquid crystal composition containing the tetrahydroquinazoline compound of the present invention can be operated by utilizing the ferroelectricity of the liquid crystal composition. The ferroelectric liquid crystal element of the present invention that can be used in this manner is a liquid crystal element having excellent switching characteristics, high-speed response, temperature dependence of optical response speed, and high contrast. be able to.

A display device in which the liquid crystal device of the present invention is used as a display device in combination with a light source, a drive circuit, etc. is a good device.

[Brief description of drawings]

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

FIG. 2 is a perspective view schematically showing an example of an element cell for explaining the operation of a liquid crystal element utilizing the ferroelectricity of liquid crystal.

FIG. 3 is a perspective view schematically showing an example of an element cell for explaining the operation of a liquid crystal element utilizing the ferroelectricity of liquid crystal.

FIG. 4 is an explanatory diagram showing a tilt angle (θ).

FIG. 5 is a waveform diagram of a driving method of a liquid crystal element used in the present invention.

6 is a schematic diagram of a display pattern when actual driving is performed with the time-series driving waveform shown in FIG. 5 (B).

FIG. 7 is a block configuration diagram showing a liquid crystal display device having a liquid crystal element utilizing ferroelectricity and a graphics controller.

FIG. 8 is a timing chart of image information communication between the liquid crystal display device and the graphics controller.

[Explanation of symbols]

1 Liquid Crystal Layer Having Chiral Smectic Phase 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 Liquid Crystal Having Chiral Smectic Phase 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 101 Ferroelectric liquid crystal display device 102 Graphics controller 103 Display panel 104 Scan line drive circuit 105 Information line drive circuit 106 Decoder 107 Scan signal generation circuit 108 Shift register 109 Line memory 110 Information signal generation circuit 11 Drive control circuit 112 GCPU 113 host CPU 114 VRAM

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07D 333/38 C09K 19/34 9279-4H // C07D 213/55 (72) Inventor Yoko Yamada Tokyo 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Shinichi Nakamura 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (23)

[Claims] 1. A tetrahydroquinazoline compound represented by the following general formula (I). Embedded image R ₁ -Q-Ph-R ₂ (I) (In the formula, R ₁ represents a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. And one or more —CH ₂ — are —O—, —S—, —CO—, —OCO under the condition that hetero atoms are not adjacent to each other.
It may be replaced with-, -COO-, -CH = CH-, -C≡C-. R ₂ represents a linear, branched or cyclic alkyl group having 10 to 20 carbon atoms. However, one or two or more —CH ₂ in the alkyl group
-Is -O-, -S-,-under the condition that heteroatoms are not adjacent.
CO-, -OCO-, -COO-, -CH = CH-,-
It may be replaced by C≡C-. Q is 5, 6,
7,8-tetrahydroquinazoline-2,6-diyl is shown, and Ph is 1,4-phenylene. ) 2. The tetrahydroquinazoline compound according to claim 1, wherein in the general formula (I), R ₁ is a linear alkyl group having 1 to 10 carbon atoms. 3. The tetrahydroquinazoline compound according to claim 1, wherein in the general formula (I), R ₂ is a linear alkyl group having 10 to 18 carbon atoms, an alkoxy group or an alkanoyloxy group. 4. A liquid crystal composition containing at least one tetrahydroquinazoline compound according to claim 1. 5. The liquid crystal composition according to claim 4, wherein the tetrahydroquinazoline compound represented by the general formula (I) is contained in an amount of 1 to 80% by weight based on the liquid crystal composition. 6. The liquid crystal composition according to claim 4, wherein the tetrahydroquinazoline compound represented by the general formula (I) is contained in an amount of 1 to 60% by weight based on the liquid crystal composition. 7. The liquid crystal composition according to claim 4, wherein the tetrahydroquinazoline compound represented by the general formula (I) is contained in an amount of 1 to 40% by weight based on the liquid crystal composition. 8. The liquid crystal composition according to claim 4, wherein the liquid crystal composition has a chiral smectic phase. 9. A liquid crystal device comprising the liquid crystal composition according to claim 4 disposed between a pair of electrode substrates. 10. The liquid crystal element according to claim 9, wherein an alignment control layer is provided on the electrode substrate. 11. The liquid crystal device according to claim 10, wherein the alignment control layer is a layer that has been subjected to a rubbing treatment. 12. The liquid crystal element according to claim 9, wherein the pair of electrode substrates are arranged with a film thickness in which a spiral formed by an arrangement of liquid crystal molecules is released. 13. A display device comprising the liquid crystal element according to claim 9. 14. The display device according to claim 13, further comprising a drive circuit for the liquid crystal element. 15. The display device according to claim 13, further comprising a light source. 16. A display method using a liquid crystal composition containing at least one tetrahydroquinazoline compound represented by the following general formula (I). Embedded image R ₁ -Q-Ph-R ₂ (I) (In the formula, R ₁ represents a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. , - - -O Under the conditions heteroatoms are not adjacent - one or two or more -CH ₂ in the S -, - CO -, - OC
It may be replaced with O-, -COO-, -CH = CH-, -C≡C-. R ₂ has 10 to 20 carbon atoms
Represents a linear, branched or cyclic alkyl group. However, one or two or more —CH ₂ in the alkyl group
-Represents -O-, -S-, under the condition that heteroatoms are not adjacent
-CO-, -OCO-, -COO-, -CH = CH-,
It may be replaced with -C≡C-. Q is 5, 6,
7,8-tetrahydroquinazoline-2,6-diyl is shown, and Ph is 1,4-phenylene. ) 17. The general formula (I), wherein R ₁ is a linear alkyl group having 1 to 10 carbon atoms.
How to display the description. 18. The display method according to claim 16, wherein in the general formula (I), R ₂ is a linear alkyl group having 10 to 18 carbon atoms, an alkoxy group or an alkanoyloxy group. 19. The display method according to claim 16, wherein the tetrahydroquinazoline compound represented by the general formula (I) is contained in an amount of 1 to 80% by weight based on the liquid crystal composition. 20. The display method according to claim 16, wherein the tetrahydroquinazoline compound represented by the general formula (I) is contained in an amount of 1 to 60% by weight based on the liquid crystal composition. 21. The display method according to claim 16, wherein the tetrahydroquinazoline compound represented by the general formula (I) is contained in an amount of 1 to 40% by weight based on the liquid crystal composition. 22. The display method according to claim 16, wherein the liquid crystal composition has a chiral smectic phase. 23. A display method using a liquid crystal element in which a liquid crystal composition containing at least one tetrahydroquinazoline compound represented by the following general formula (I) is arranged between a pair of electrode substrates. Embedded image R ₁ -Q-Ph-R ₂ (I) (In the formula, R ₁ represents a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. , - - -O Under the conditions heteroatoms are not adjacent - one or two or more -CH ₂ in the S -, - CO -, - OC
It may be replaced with O-, -COO-, -CH = CH-, -C≡C-. R ₂ has 10 to 20 carbon atoms
Represents a linear, branched or cyclic alkyl group. However, one or two or more —CH ₂ in the alkyl group
-Represents -O-, -S-, under the condition that heteroatoms are not adjacent.
-CO-, -OCO-, -COO-, -CH = CH-,
It may be replaced with -C≡C-. Q is 5, 6,
7,8-tetrahydroquinazoline-2,6-diyl is shown, and Ph is 1,4-phenylene. )