JPH07309838A - Liquid crystalline compound, liquid crystal composition containing the same, liquid crystal element and liquid crystal device using the same and method for displaying using the same - Google Patents

Abstract

PURPOSE:To obtain the subject new compound, having a high speed of response, reducing the temperature dependence thereof, excellent in high contrast- properties, switching characteristics, etc., and useful as a liquid crystal element, especially a display element in combination with a light source, a driving circuit, etc. CONSTITUTION:This liquid crystalline compound is expressed by formula I {Q is quinoline-2,6-diyl: A1 is a group expressed by A2-R2 [A2 is a (substituted)1,4-phenylene, thiophene-2. etc.; R2 is F, CN, CF3, a 1-5C alkyl, etc.] or A3-R3 (A3 is pyrimidine-2,5-diyl, etc.; R3 is F, CN, CF3, a 1-20C alkyl, etc.); R) is same as R3}, e.g. 2-(4-pentylphenyl)-6-methoxyquinoline. This liquid crystal element is obtained by arranging a liquid crystal composition containing preferably 1-80wt.% compound expressed by formula I and, e.g. three kinds of compounds expressed by formulas II to IV as essential components as the compound expressed by formula I between a pair of opposite electrode substrates.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel liquid crystalline compound,
A liquid crystal composition containing the same, a liquid crystal device including the same, a liquid crystal device including a display device, and a display method using the same, and more specifically, a novel liquid crystal composition having improved response characteristics to an electric field, and The present invention relates to a liquid crystal display element using the same, a liquid crystal element used for a liquid crystal-optical shutter, and a liquid crystal device using the liquid crystal element for display.

[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 time (duty ratio) during which an effective electric field is applied to one selected point while scanning the entire screen (one frame) is reduced by 1 / N. Resulting in.

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, a reduction in image contrast and the occurrence of crosstalk are unavoidable drawbacks.

Such a phenomenon is caused by a liquid crystal having no bistability (that is, a stable state in which liquid crystal molecules are aligned horizontally with respect to the electrode surface, and while an electric field is effectively applied). This is an essentially unavoidable problem that occurs when driving (that is, repeatedly scanning) a liquid crystal that is vertically aligned only) by utilizing 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 from the driving side of the liquid crystal device has been proposed by Clark and Lagerwall. (JP-A-56-107216, US Pat. No. 4,
367,924 specification). In such a device, a bistable liquid crystal is generally a chiral smectic C
A ferroelectric liquid crystal having a phase (SmC ^* phase) or an H phase (SmH ^* phase) 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. In addition, 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, it is expected to be applied to high-speed optical optical shutters and high-density, large-screen displays. 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.

This point will be specifically described. Between the response time τ and the spontaneous polarization magnitude Ps 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.

Further, when the temperature range used as an actual display is, for example, about 5 to 40 ° C. in consideration of the use area difference, the change in response speed is generally about 20 times, and the adjustment depending on the drive voltage and frequency is required. The current situation is that the limit has been exceeded.

In general, in the case of a liquid crystal device utilizing the birefringence of liquid crystal, the transmittance under the crossed Nicols is expressed by the following equation (2).

[0021]

[Equation 2] In the equation (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
Will appear as the 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 during the non-selection period in matrix driving, so that 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.

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

[0028]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a device using a liquid crystal exhibiting a chiral smectic phase such as the above-mentioned ferroelectric liquid crystal, which has a particularly high response speed and can be put to practical use. A liquid crystal compound that is effective in reducing the temperature dependence and increasing the contrast,
A liquid crystal composition containing the same, particularly a liquid crystal composition exhibiting a ferroelectric chiral smectic phase, a liquid crystal element using the liquid crystal composition, a display method using the same, and a liquid crystal device are provided.

[0029]

The above-mentioned object of the present invention is solved by a liquid crystal compound represented by the following general formula (I).

[0030]

Embedded image R ₁ -Q-A ₁ (I)

(Wherein Q is quinoline 2,6-diyl, A
₁ shows a _-A 2 -R ₂ or _-A 3 -R _3.
A ₂ is 1,4-phenylene which may have one or two substituents arbitrarily selected from F, CH ₃ , CF ₃ , and CN, thiophene-2,5-diyl, indane-
2,5-diyl, 2-alkylindan-2,5-diyl (the alkyl group is a linear or branched alkyl group having 1 to 18 carbon atoms), coumarane-2,5-diyl, 2 -Alkylcoumaran-2,5-diyl (the alkyl group is a linear or branched alkyl group having 1 to 18 carbon atoms), benzofuran-2,5-diyl,
Selected from benzofuran-2,6-diyl, A ₃ is pyrimidine-2,5-diyl, pyridine-2,5-diyl, pyrazine-2,5-diyl, pyridazine-3,6-
Diyl, 1,4-cyclohexylene, 2,6-naphthylene, quinoxaline-2,6-diyl, quinoline-2,6
-Choose from each of the Jeil. R ₁ and R ₃ are F, CN, CF ₃ or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (one or more —CH ₂ in the alkyl group). -Is -O-, -S-, -CO-,-under the condition that heteroatoms are not adjacent.
^{_{* CY 1 Y 2 -, -}} CH = CH -, - C≡C- may be replaced with. Also one or two or more -CH ₃ in the alkyl group _-CH 2 F, -CH
It may be replaced with F ₂ or —CN. Y
₁ and Y ₂ are H, F, CH ₂ F, CHF ₂ and CF
₃ , CN or a linear alkyl group having 1 to 5 carbon atoms is shown. ^* C represents an asymmetric carbon atom. ) Is shown. R ₂ is F, CN, CF ₃ , or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (one or more -C in the alkyl group).
H ₂ - is ^{_{- * CY 1 Y 2 -,}} - CH = CH-,
It may be replaced with -C≡C-. In addition, one or two or more —CH ₃ in the alkyl group is —CH ₂
F, may be replaced by the -CHF ₂ or -CN,. )

The above object of the present invention is solved by a liquid crystal composition containing at least one liquid crystal compound represented by the general formula (I) as an essential component.

The divalent cyclic group defined in the above general formula (I) can be in any bonding state considered to be adjacent groups. Particularly, for Q (quinoline-2,6-diyl),

[0034]

[Chemical 11] Any structure of

The liquid crystalline compound as used in the present invention is not specified as to whether or not it exhibits liquid crystallinity by itself, and is any compound that can effectively function as a liquid crystal component in a liquid crystal composition. good.

Further, according to the present invention, there is provided a liquid crystal device in which the above liquid crystal composition is sandwiched between a pair of electrode substrates, and a liquid crystal device such as a display device using the device. In addition, according to the present invention, there is provided a display method using the above liquid crystal element or liquid crystal device.

In the liquid crystalline compound represented by the general formula (I), R ₁ is a preferable compound from the viewpoints of the temperature range of the liquid crystal phase and the response characteristics, viscosity, orientation when the liquid crystal composition is used as the compound. A compound which is any of (1) to (5), a compound wherein R ₂ is any of the following (6) to (10) or a compound whose R ₃ is any of the following (1) to (5) Can be mentioned.

[0038]

[Chemical 12]

(Where a is an integer from 1 to 16 and d and g
Is an integer of 0 to 7, b, e, h, j are integers of 1 to 10, and f is an integer of 0 or 1. However, b + d ≦ 1
6, e + f + g ≦ 16 is satisfied. Y ₃ is a single bond, —O—, —OCO—, —COO—, and Y ₄ is —CH _{2.
O -, - CH 2 -,} - COO- represents any. It may be optically active. )

Also preferably, in the compound of the general formula (I), A ₁ is —A ₂ —R ₂ and A ₂ is 1,4.
-A compound which is phenylene.

More preferably, as the liquid crystal compound represented by the general formula (I), R ₁ is the following (1), and R ₁ is
Examples of ₂ include the following compound (6).

[0042]

Embedded image _{(1) n-C a H} 2a + 1 -Y 3 - (6) n-C a H 2a + 1 -

(However, a is an integer of 1 to 16, Y ₃ is a single bond, -O-, -OCO-, -COO-.) Further, the liquid crystalline compound of the general formula (I) of the present invention. Can be more preferably used as a non-optically active compound.

Conventionally, liquid crystal compounds having quinoline-2,6-diyl are known from JP-A-4-316555 and JP-A-4-368370. However, the compounds described in these publications have different structures from the compounds represented by the general formula (I) of the present invention.

As a result of detailed examination of the liquid crystalline compound represented by the general formula (I), the present inventors have found that a composition containing the liquid crystalline compound of the present invention and the quinoline compound described in the above publication are included in the composition. Liquid crystal element using
It was found that various characteristics such as high-speed response, reduction of temperature dependence of response speed, and high contrast were improved, and good display characteristics were obtained.

Further, the liquid crystalline compound of the present invention has good compatibility with other compounds and has a chiral smectic C pitch, a cholesteric pitch as a liquid crystal mixture, a temperature range for taking a liquid crystal phase, a viscosity, an optical anisotropy and a tilt. It can also be used for adjusting the angle, dielectric anisotropy, and the like.

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

[0048]

[Chemical 14]

However, -A ₄ -R ₄ is -A ₂ -R
Shows a ₂ or _{-A 3 -R 3 (A 2,} A 3,
R ₂ and R ₃ are as defined above). R ₅ has 1 to 19 carbon atoms, and R ₆ and R ₇ each have a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms (one or 2 of the alkyl groups). One or more —CH ₂ — is —O under the condition that hetero atoms are not adjacent to each other.
-, - S -, - CO -, - * CY 1 Y 2 -, - C
It may be replaced with H = CH-, -C≡C-.
Further, one or more -CH ₃ in the alkyl group
MAY been replaced with _{-CH 2} F, -CHF 2 or -CN _(Y 1, Y ₂ are as defined above). X ₁ is a halogen atom such as iodine or bromine, X ₂
Represents a halogen atom such as iodine or bromine or a p-toluenesulfonyl group.

DCC is 1,3-dicyclohexylcarbodiimide and 9-BBN is 9-borabicyclo [3,3].
3, 1] is an abbreviation for nonane.

[0051]

[Chemical 15]

However, A ₁ and R ₁ are as defined above. In this example, it is also possible to allow a group capable of converting to A ₁ to be present at the 4-position of aniline, to close the quinoline ring, and then to substitute it with A ₁ .

Specific examples of the compound represented by formula (I) are shown below. Hereinafter, the cyclic group will be abbreviated by the following symbols.

[0054]

[Chemical 16]

[0055]

[Chemical 17]

[0056]

Embedded image _{(I-1) C 4 H} 9 -Q-Ph-C 5 H 11 (I-2) C 7 H 15 -Q-Ph-C 3 H 7 (I-3) C 10 H 21 - _{Q-Ph-C 5 H 11} (I-4) C 11 H 23 -Q-Ph-C 8 H 17 (I-5) C 14 H 29 -Q-Ph-C 6 H 13 (I-6) CH _{3 O-Q-Ph-C} 5 H 11 (I-7) C 4 H 9 O-Q-Ph-C 10 H 21 (I-8) C 5 H 11 O-Q-Ph-C 11 H 23 ( _{I-9) C 9 H 19} O-Q-Ph-C 8 H 17 (I-10) C 10 H 21 O-Q-Ph-C 5 H
_{11 (I-11) C 12} H 25 O-Q-Ph-C 9 H
₁₉ (I-12) C ₁₆ H ₃₃ -Q-Ph-CH ₃ (I-13) C ₆ H ₁₃ COO-Q-Ph-C _{10
H 21 (I-14) C} 8 H 17 COO-Q-Ph-C 5
H ₁₁ (I-15) C ₁₃ H ₂₇ COO-Q-Ph-C _{2
H 5 (I-16) C} 2 H 5 COO-Q-Ph-C 12
_{H 25 (I-17) CH} 2 = CH (CH 2) 6 O-Q-
_{Ph-C 4 H 9 (I} -18) C 8 H 17 * CH (F) CH 2 O-
_{Q-Ph-C 7 H 15} (I-19) C 3 H 7 * CH (CF 3) (CH 2) 2
_{O-Q-Ph-C 3} H 7 (I-20) C 2 H 5 * CH (CH 3) CH 2 O-Q
_{-Ph-C 8 H 17 (I} -21) C 2 H 5 OCH (CH 3) CH 2 O-Q
_{-Ph-C 6 H 13 (I} -22) C 6 H 13 * CH (F) COO-Q
_{-Ph-C 10 H 21 (I} -23) C 4 H 9 * CH (CF 3) COO-
_{Q-Ph-C 5 H 11} (I-24) C 6 H 13 -Q-Tn-C 6 H 13 (I-25) C 9 H 19 -Q-Tn-C 5 H 11

[0057]

Embedded image (I-26) C ₃ H ₇ O-Q-Tn-
C ₇ H ₁₅ (I-27) C ₇ H ₁₅ O-Q-Tn-C ₉ H
_{19 (I-28) C 5} H 11 COO-Q-Tn-C 4
_{H 9 (I-29) C} 11 H 23 COO-Q-Tn-C 8
_{H 17 (I-30) C} 5 H 11 -Q-Id-C 10 H 21 (I-31) C 8 H 17 -Q-Id-C 8 H 17 (I-32) C 6 H 13 O-Q _-Id-C 7 H
_{15 (I-33) C 10} H 21 O-Q-Id-C 2 H 5 (I-34) C 4 H 9 COO-Q-Id-C 6
_{H 13 (I-35) C} 8 H 17 -Q-Cm-C 8 H 17 (I-36) C 12 H 25 -Q-Cm-C 10 H 21 (I-37) C 5 H 11 O-Q _-Cm-C 9 H
_{19 (I-38) C 7} H 15 COO-Q-Cm-C 12
_{H 25 (I-39) C} 4 H 9 -Q-Ha-C 6 H 13 (I-40) C 10 H 21 -Q-Ha-C 11 H 23 (I-41) C 8 H 17 O-Q _{-Ha-C 10} H
_{21 (I-42) C 6} H 13 COO-Q-Ha-C 5
_{H 11 (I-43) C} 6 H 13 -Q-Hb-C 8 H 17 (I-44) C 12 H 25 -Q-Hb-C 4 H 9 (I-45) C 2 H 5 O-Q _-Hb-C 8 H
₁₇ (I-46) C ₉ H ₁₉ COO-Q-Hb-C _{6
^{H 13 (I-47) C}} 7 H 15 * CH (F) COO-Q
_{-Pyl-C 8 H 17 (I} -48) C 3 H 7 -Q-Pyl-C 10 H
_{21 (I-49) C 6} H 13 -Q-Pyl-C 6 H
_{13 (I-50) C 8} H 17 O-Q-Pyl-C 9 H
₁₉ (I-51) C ₉ H ₁₉ O-Q-Pyl-C ₁₁ H
₂₃

[0058]

Embedded image (I-52) C ₁₀ H ₂₁ -Q-Pyl-
OC ₉ H ₁₉ (I-53) C ₆ H ₁₃ -Q-Pyl-OC ₁₁ H
_{23 (I-54) C 5} H 11 O-Q-Pyl-OC 7
_{H 15 (I-55) C} 8 H 17 -Q-Prl-C 4 H 9 (I-56) C 11 H 23 O-Q-Prl-C 6 H
_{13 (I-57) C 7} H 15 -Q-Prl-OC 6 H
_{13 (I-58) C 6} H 13 -Q-Pr2-C 9 H
_{19 (I-59) C 10} H 21 -Q-Pr2-C 4 H 9 (I-60) C 3 H 7 O-Q-Pr2-C 8 H
_{17 (I-61) C 5} H 11 -Q-Cy-C 6 H 13 (I-62) C 12 H 25 O-Q-Cy-C 3 H 7 (I-63) C 9 H 19 -Q- _{Np-C 10 H 21 (I} -64) C 8 H 17 -Q-Np-OC 6 H
₁₃ (I-65) C ₁₀ H ₂₁ -Q-Ep-C ₈ H ₁₇ (I-66) C ₆ H ₁₃ O-Q-Ep-C ₁₀ H
₂₁ (I-67) C ₁₁ H ₂₃ -Q-Q-C ₅ H ₁₁ (I-68) CH ₃ O-Q-Q-C ₁₂ H ₂₅ (I-69) C ₄ H ₉ -Q-Ph2F- C ₁₀ H
₂₁ (I-70) C ₁₁ H ₂₃ O-Q-Ph2F-C _{11
H 23 (I-71) C} 9 H 19 -Q-Ph3F-C 5 H
_{11 (I-72) C 10} H 21 O-Q-Ph3F-C 9
H ₁₉ (I-73) C ₆ H ₁₃ O-Q-Ph23F-C _{3
H 7 (I-74) C} 8 H 17 O-Q-Ph3TF-C 6
_{H 13 (I-75) C} 12 H 25 O-Q-Ph3Cl-C 4
H ₉ (I-76) C ₉ H ₁₉ O-Q-Ph3M-C _{10
H 21 (I-77) C} 6 H 13 O-Q-Ph3CN-C
₁₂ H ₂₅

[0059]

Embedded image (I-78) C ₇ H ₁₅ O-Q-Ph-
_{CH 2 CH (CH 3) CH} 3 (I-79) C 6 H 13 -Q-Py2-CH 2 * C
_{H (F) C 6 H 13} (I-80) C 8 H 17 -Q-Np-OCOCH 2 *
_{CH (CF 3) C 8 H} 17 (I-81) C 12 H 25 -Q-Pa-C 10 H 21 (I-82) C 12 H 25 -Q-Pd-C 5 H 11 (I-83) ^{_{C 4 H 9 * C (CN}} ) (CH 3) COO
_{-Q-Ph3F-C 10 H 21} (I-84) C 10 H 21 -Q-Ph-F (I-85) C 12 H 25 O-Q-Ph3F-F (I-86) C 9 H 19 - _{Q-Ph-CF 3 (I} -87) C 8 H 17 O-Q-Ph-CN (I-88) C 9 H 19 O-Q-Ph-F (I-89) CF 3 -Q-Ph- _{C 5 H 11 (I-90} ) F-Q-Ph-C 10 H 21 (I-91) C 2 H 5 CH (CH 3) (CH 2) 3 -
_{Q-Ph-C 6 H 13} (I-92) C 4 H 9 -Q-Py2-C 6 H
₁₃ (I-93) C ₉ H ₁₉ -Q-Py2-C ₈ H
_{17 (I-94) C 4} H 9 -Q'-Ph-C 5 H
_{11 (I-95) C 7} H 15 -Q'-Ph-C 3 H 7 (I-96) C 10 H 21 -Q'-Ph-C 5 H
_{11 (I-97) C 11} H 23 -Q'-Ph-C 8 H
_{17 (I-98) C 14} H 29 -Q'-Ph-C 6 H
_{13 (I-99) C 16} H 33 -Q'-Ph-CH 3 (I-100) C 6 H 13 -Q'-Tn-C 6 H
_Thirteen

[0060]

Embedded image (I-101) C ₉ H ₁₉ -Q'-Tn-C ₅ H ₁₁ (I-102) C ₅ H ₁₁ -Q'-Id-C ₁₀ H
_{21 (I-103) C 8} H 17 -Q'-Id-C 8 H
_{17 (I-104) C 12} H 25 -Q'-Cm-C 10 H
_{21 (I-105) C 8} H 17 -Q'-Cm-C 8 H
_{17 (I-106) C 4} H 9 -Q'-Ha-C 6 H
_{13 (I-107) C 10} H 21 -Q'-Ha-C 11 H
_{23 (I-108) C 6} H 13 -Q'-Hb-C 8 H
_{17 (I-109) C 12} H 25 -Q'-Hb-C 4 H
_{9 (I-110) C 3} H 7 -Q'-Py1-C 10
_{H 21 (I-111) C} 6 H 13 -Q'-Py1-C 6
_{H 13 (I-112) C} 10 H 21 -Q'-Py1-OC 9
H ₁₉ (I-113) C ₆ H ₁₃ -Q'-Py1-OC
₁₁ H ₂₃ (I-114) C ₈ H ₁₇ -Q'-Pr1-C _{4
H 9 (I-115) C} 7 H 15 -Q'-Pr1-OC 6
_{H 13 (I-116) C} 5 H 11 -Q'-Cy-C 6 H
_{13 (I-117) C 9} H 19 -Q'-Np-C 10 H
_{21 (I-118) C 8} H 17 -Q'-Np-OC 6
_{H 13 (I-119) C} 4 H 9 -Q'-Ph3F-C
_{10 H 21 (I-120)} C 9 H 19 -Q'-Ph3F-C 5
_{H 11 (I-121) C} 8 H 17 -Q'-Np-OCOC
^{_{H 2 * CH (CF 3)}} C 8 H 17 (I-122) C 12 H 25 -Q'-Pa-C 10 H
_{21 (I-123) C 12} H 25 -Q'-Pd-C 5 H
_{11 (I-124) C 10} H 21 -Q'-Ph-F

[0061]

Embedded image (I-125) C ₉ H ₁₉ -Q′-Ph-CF ₃ (I-126) C ₂ H ₅ CH (CH ₃ ) (CH
_{2) 3 -Q'-Ph-C} 6 H 13 (I-127) C 11 H 23 -Q-Id (8) -C 8
H ₁₇ (I-128) C ₁₇ H ₃₅ -Q-Ph-C ₅ H
₁₁ (I-129) C ₁₉ H ₃₉ -Q-Cy-CH ₃ (I-130) CN-Q-Np-OC ₆ H ₁₃ (I-131) Lc1 (8,0) -CHO-Q'-P
_{h-C 8 H 17 (I} -132) La1 (1,1) -OCO-Q'-I
_{d-C 10 H 21 (I} -133) Pla-COO-Q'-Ph-C 10
_{H 21 (I-134) C} 10 H 21 -Q-Cm (1) -C 5
_{H 11 (I-135) C} 18 H 37 -Q'-Tn-C 3 H
_{7 (I-136) C 20} H 41 -Q-Ph2F-F (I-137) Thf-COO-Q-Ph-C 9 H
_{19 (I-138) C 6} H 13 -Q-Py1-OCH-
Lc2 (5,5) (I-139) La2 (6,0) -Q-Ph-C _{6
H 13 (I-140) C} 8 H 17 -Q'-Np-O-Dp
(2)

The liquid crystal composition of the present invention can be obtained by mixing at least one liquid crystal compound represented by the general formula (I) and one or more other liquid crystal compounds in an appropriate ratio. The number of other liquid crystal compounds used in combination is 1 to 5
The range is 0, preferably 1 to 30, and more preferably 3 to 30.

The liquid crystal composition according to the present invention is preferably a chiral smectic liquid crystal composition containing at least one optically active compound, 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.

Further, the following general formulas (XIII) to (XVI
A liquid crystal compound represented by II) can also be used.

[0066]

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

[0067] 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. Further, the hydrogen atom in the alkyl group may be replaced with a fluorine atom.

[0068] Moreover R _'7, R' ₈ is preferably i below) -
vii).

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

[0070]

[Chemical 25] p: 0-5, q: 2-11 integer optically active

[0071]

[Chemical formula 26] r: 0 to 6, s: 0 or 1, t: 1 to 14 integer optically active

[0072]

[Chemical 27] w: 1 to 15 integer Optically active

[0073]

[Chemical 28] A: 0 to 2, B: 1 to 15 integer Optically active

[0074]

[Chemical 29] C: 0 to 2, D: 1 to 15 integer Optically active

[0075] vii) -H N, Q, R , T: 0 or _{1 Y '7, Y' 8} , Y '9: H
Or _{F A '4: Ph, Np} X' 7, X '8: single bond, -COO
-, - OCO -, - CH 2 O -, - OCH 2 -

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

[0077]

[Of 30] _{R '7 - [Py2] -} [Ph] -OCO- [T
n] -R ' ₈ (XIIIa)

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

[0079]

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

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

[0081]

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).

[0083]

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).

[0085]

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)

Ph, Tn, Pr1, Pr2, Py1, P
Abbreviations for y2, Pa, Cy, and Np are in accordance with the above definitions, and other abbreviations are the following groups.

[0087]

[Chemical 35]

When the liquid crystalline compound of the present invention is mixed with one or more of the above liquid crystalline compounds or the liquid crystal composition, the liquid crystalline compound of the present invention occupies in the liquid crystal composition obtained by mixing. It is desirable that the ratio is 1% by weight to 80% by weight. In particular, in order to put a device using a ferroelectric chiral smectic liquid crystal into practical use, it is essential to satisfy many characteristics such as liquid crystallinity in a wide temperature range, high-speed response, high contrast, and uniform switching. But
In order to set these properties appropriately, it is preferable to prepare and use a liquid crystal composition by blending the liquid crystal compound of the present invention and various compounds excellent in each property in an appropriate ratio. In this respect, the proportion of the liquid crystal compound of the present invention in the liquid crystal composition is particularly preferably 1% by weight to
The content is 60% by weight, and particularly preferably 1% by weight to 40% by weight, considering that the characteristics of the other liquid crystal compound are utilized. If it is less than 1% by weight, the effect of the compound of the present invention is too small and the characteristics may not be utilized. If it exceeds 80% by weight, problems such as precipitation at low temperature may occur.

When two or more liquid crystal compounds of the present invention are used, the proportion of the mixture of two or more liquid crystal compounds of the present invention in the liquid crystal composition obtained by mixing is from 1% by weight to. 80% by weight, preferably 1% by weight to a liquid crystal composition composed of various compounds as described above.
The content is 60% by weight, and more preferably 1% by weight to 40% by weight, considering that the characteristics of the other liquid crystal compounds are utilized depending on the type of the compound. If it is less than 1% by weight, the effect of the compound of the present invention is too small and the characteristics may not be utilized. If it exceeds 80% by weight, problems such as precipitation at low temperature may occur.

The liquid crystal composition of the present invention constitutes various liquid crystal devices. In particular, an element having a liquid crystal layer between a pair of electrode substrates can be constructed.

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

FIG. 1 is a schematic sectional view showing an example of a liquid crystal element (particularly a ferroelectric liquid crystal element) having a chiral smectic liquid crystal layer of the present invention.

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 alignment 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 each provided 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 alignment control layer 4 made of an insulating material for arranging the liquid crystal in the rubbing direction is formed thereon by rubbing a polymer thin film such as polyimide with gauze or acetate flocking cloth.

As the orientation control layer, for example, silicon nitride, silicon nitride containing hydrogen, silicon carbide, silicon carbide containing hydrogen, silicon oxide,
Boron nitride, hydrogen-containing boron nitride, cerium oxide, aluminum oxide, zirconium oxide, titanium oxide or an inorganic material insulating layer such as magnesium fluoride is formed, on which polyvinyl alcohol, polyimide, polyamide Orient 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 the insulating orientation control layer is an inorganic material, it can be formed by a vapor deposition method, and if it is an organic material, a solution in which an organic insulating material is dissolved or a precursor solution thereof (0.
1 to 20% by weight, preferably 0.2 to 10% by weight) is applied by a spinner coating method, a dip coating method, a screen printing method, a spray coating method, a roll coating method or the like under predetermined curing conditions ( For example, it can be cured and formed under heating.

The layer thickness of the insulating orientation control layer 4 is usually 1 nm to
1 μm, preferably 1 nm to 300 nm, more preferably 1 nm to 100 nm is 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. A liquid crystal exhibiting a chiral smectic phase, such as a ferroelectric liquid crystal, is enclosed between the two glass substrates.

The liquid crystal layer 1 in which the chiral smectic liquid crystal is enclosed is generally 0.5 to 20 μm, preferably 1 to 20 μm.
It is 5 μm.

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 the liquid crystal element utilizing the ferroelectricity applied in the present invention. 21a and 21b are In ₂
O ₃ , SnO ₂ or ITO (Indium Tin Oxide)
Is a substrate (glass plate) covered with a transparent electrode made of a thin film such as SmC ^* phase or SmH ^* phase, in which the liquid crystal molecular layer 22 is oriented perpendicular to the glass surface. 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. When a voltage of a certain threshold value or more is applied between the electrodes on the substrates 21a and 21b, the helical structure of the liquid crystal molecules 23 is unraveled, and the dipole moment (P⊥) 24 is entirely oriented in the electric field direction. Can be changed. 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 the liquid crystal layer becomes thinner in this way, as shown in FIG. 3, the helical structure of the liquid crystal molecules is unwound even when no electric field is applied, and the dipole moment Pa or Pb thereof 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 to change the orientation of the molecules, 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 drive waveforms 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 the 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.

The liquid crystal element of the present invention constitutes various liquid crystal devices as a functional element. For example, the liquid crystal device of the present invention is used in a display panel section, and the data format and S as image information having the scanning line address information shown in FIGS.
A liquid crystal display device is realized by using a communication synchronizing means based on the YNC signal.

The image information is generated by the graphics controller 102 on the main unit side and transferred to the display panel 103 according to the signal transfer means shown in FIGS. 7 and 8. The graphics controller 102 is a CP
U (central processing unit, hereinafter abbreviated as GCPU 112) and VRAM (memory for storing image information) 114 are used as cores for managing image information and communication between the host CPU 113 and the liquid crystal display device 101, and controlling 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.

[0110]

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 Preparation of 2- (4-pentylphenyl) -6-methoxyquinoline (I-6) 4-pentyliodobenzene 6.45 g (23.5 mm)
ole), dry tetrahydrofuran 40 ml to 200 m
1 ml in a 3-necked flask and 1.6M butyllithium hexane solution with stirring while maintaining the internal temperature at -75 to -60 ° C in a dry ice-acetone bath under a nitrogen stream.
(27.7 mmole) was added dropwise over 15 minutes. After completion of dropping, the mixture was stirred at the same temperature for 1 hour.

Further, at the same temperature, a solution prepared by dissolving 2.18 ml (15.8 mmole) of 6-methoxyquinoline in 13 ml of dry tetrahydrofuran was added dropwise over 30 minutes. After completion of dropping, the cooling bath was removed and the mixture was stirred at room temperature for 1 hour and 40 minutes. The reaction product was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water, dried over sodium sulfate and dried under reduced pressure. 5 ml of nitrobenzene was added to the residue, and the mixture was stirred under reflux for 5 minutes. Nitrobenzene was distilled off as much as possible from the reaction product under reduced pressure, the residue was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 100/1), and recrystallized from methanol to give 2- (4-pentylphenyl)-. 2.16 g of 6-methoxyquinoline (yield 44.8%) was obtained. The phase transition temperature of this compound is shown below.

[0113]

[Equation 3]

Example 2 Preparation of 2- (4-pentylphenyl) -6-decyloxyquinoline (I-10) 0.70 g (2.29 mmole) of 2- (4-pentylphenyl) -6-methoxyquinoline, acetic acid 4.6 ml,
4.3 ml of 47% hydrobromic acid was placed in a 30 ml eggplant flask, and the mixture was stirred under reflux for 33 hours. Pour the reaction product into ice water,
The precipitated crystals were collected by filtration. The crystals were dispersed in water, ethyl acetate was added, and 1.5 g of sodium hydrogen carbonate was added little by little while stirring at room temperature. The ethyl acetate layer was washed with water, dried over sodium sulfate, and dried under reduced pressure. Hexane was added to the residue, and the precipitated crystals of 2- (4-pentylphenyl) -6-hydroxyquinoline were collected by filtration. Yield 0.58 g (yield 86.8
%) 2- (4-pentylphenyl) -6-hydroxyquinoline 0.23 g (0.79 mmole), 1-bromodecane 0.17 ml (0.82 mmole), potassium hydroxide butanol solution 2.6 ml (butanol solution 1 ml)
(Containing 0.02 g of potassium hydroxide) was placed in a 20 ml round-bottomed flask and stirred under reflux for 2 hours and 50 minutes. The reaction product was left in a freezer at -20 ° C overnight, and the precipitated crystals were collected by filtration and washed successively with methanol and water. This crystal was purified by silica gel column chromatography (eluent: toluene) and recrystallized from a toluene-methanol mixed solvent to give 2-
0.23 g (yield 67.5%) of (4-pentylphenyl) -6-decyloxyquinoline was obtained. The phase transition temperature of this compound is shown below.

[0115]

[Equation 4]

Example 3 The following compounds were mixed in the following parts by weight to prepare a liquid crystal composition A.

[0117]

[Chemical 36]

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.

[0119]

Embedded image Exemplified Compound No. Structure parts _{I-3 C 10 H 21 -Q} -Ph-C 5 H 11 5 I-39 C 4 H 9 -Q-Ha-C 6 H 13 2 I-88 C 9 H 19 O-Q-Ph -F 2 liquid crystal composition A 91

Prepare two 0.7 mm thick glass plates,
Form an ITO film on each glass plate and apply a voltage
Create a pole, and further on this SiO_Two Insulation
Layered. Silane coupling agent on glass plate [Shin-Etsu
Gaku Co., Ltd., KBM-602] 0.2% isopropyl acetate
Lucor solution, rotation speed 33s^-1 (2000 rpm)
It was applied with a spinner for 15 seconds and surface-treated. this
After that, a heat drying treatment was performed at 120 ° C. for 20 minutes.

With the surface-treated ITO film
Polyimide resin precursor on glass plate [Toray Industries, Inc., S
P-510] Rotate 1.5% dimethylacetamide solution
Number 33s^-1 (2000 rpm) spinner for 15 seconds
Applied. After film formation, heat condensation baking at 300 ° C for 60 minutes
Treated. The film thickness of the coating film at this time is about 25 nm.
It was.

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

A liquid crystal element (actually a ferroelectric liquid crystal element) was prepared by injecting the liquid crystal composition B into this cell in an isotropic liquid state and gradually cooling from the isotropic phase to 25 ° C. at 20 ° C./h. did. When the cell thickness of this cell was measured with a Berek phase plate, it was about 2 μm. The uniform alignment in this liquid crystal element was good, and a monodomain state was obtained.

By applying a voltage of peak-to-peak voltage Vpp = 20V using this liquid crystal element, an optical response (transmission light amount change 0 to 90%) under orthogonal Nicols is detected and a response speed (hereinafter , Optical response speed) was measured. The measurement results are shown below.

[0125]

Table 1 10 ° C. 25 ° C. 40 ° C. Optical response speed 627 μsec 310 μsec 171 μsec Temperature dependence (10 ° C./40° C.) 3.7

Comparative Example 1 A ferroelectric liquid crystal device was prepared in the same manner as in Example 3 except that the liquid crystal composition A mixed in Example 3 was injected into the cell, and the optical response speed was measured. The measurement results are shown below.

[0127]

Table 2 10 ° C. 25 ° C. 40 ° C. Optical response speed 784 μsec 373 μsec 197 μsec Temperature dependence (10 ° C./40° C.) 4.0

Example 4 Exemplified compounds I-3, I-39, I- used in Example 3
Instead of 88, the following exemplary compounds were mixed in the respective weight parts shown below to prepare a liquid crystal composition C.

[0129]

Embedded image Exemplified Compound No. Structure parts _{I-13 C 6 H 13 COO} -Q-Ph-C 10 H 21 3 I-31 C 8 H 17 -Q-Id-C 8 H 17 2 I-49 C 6 H 13 -Q-Pyl -C ₆ H ₁₃ 4 liquid crystal composition A 91

A liquid crystal element was prepared in the same manner as in Example 3 except that this liquid crystal composition was used, 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 of the optical response speed are shown below.

[0131]

[Table 3] 10 ° C. 25 ° C. 40 ° C. Optical response speed 605 μsec 304 μsec 168 μsec Temperature-dependent characteristics (10 ° C./40° C.) 3.6

Example 5 The following compounds were mixed in the following parts by weight to prepare a liquid crystal composition D.

[0133]

Embedded image Structural part by weight C₈H₁₇-Py2-Ph-OC₆H₁₃ 10 C₈H₁₇-Py2-Ph-OC₉H₁₉ 5 C_TenH_{twenty one}-Py2-Ph-OCOC₆H₁₃ 7 C_TenH_{twenty one}-Py2-Ph-O (CH₂)₃CH (CH₃) OC₃H₇ 7 C₁₂H_{twenty five}-Py2-Ph-O (CH₂)_FourCH (CH₃) OC H₃ 6 C_FiveH₁₁-Py2-Ph-Ph-C₆H₁₃ 5 C₇H₁₅-Py2-Ph-Ph-C₆H₁₃ 5 C_FourH₉-Cy-COO-Ph-Py1-C₁₂H_{twenty five} 8 C₃H₇-Cy-COO-Ph-Py1-C_TenH_{twenty one} 8 C₉H₁₉O-Ph-COO-Ph-OC_FiveH₁₁ 20 C₈H₁₇-Ph-COO-Ph-Ph-OCH₂CH (CH₃) C₂H_Five 5 C₈H₁₇-Ph-OCO-Ph-Ph-^*CH (CH₃) OCOC₆H₁₃ 5 C₆H₁₃O-Ph-OCH₂-Ph-Ph-C₇H₁₅ 6 C₁₂H_{twenty five}-Py2-Ph-OCH₂ ^*CH (F) C₆H₁₃ 3 (^*C represents an optically active asymmetric carbon atom)

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.

[0135]

Embedded image Exemplary Compound No. Structure parts ^{_{I-18 C 8 H 17 *}} CH (F) CH 2 O-Q-Ph-C 7 H 15 2 I-25 C 9 H 19 -Q-Tn-C 5 H 11 4 I-62 C _{12 H 25 O-Q-Cy} -C 3 H 7 2 liquid crystal composition D 92

A ferroelectric liquid crystal device was prepared in the same manner as in Example 3 except that this liquid crystal composition was used, 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 of the optical response speed are shown below.

[0137]

Table 4 10 ° C. 25 ° C. 40 ° C. Optical response speed 525 μsec 265 μsec 142 μsec Temperature dependence (10 ° C./40° C.) 3.7

Comparative Example 2 A liquid crystal element was prepared in the same manner as in Example 3 except that the liquid crystal composition D mixed in Example 3 was injected into the cell, and the optical response speed was measured. The measurement results are shown below.

[0139]

Table 5 10 ° C. 25 ° C. 40 ° C. Optical response speed 653 μsec 317 μsec 159 μsec Temperature dependence (10 ° C./40° C.) 4.1

Example 6 Exemplified Compounds I-18, I-25, I used in Example 5
A liquid crystal composition F was prepared by mixing the following exemplary compounds in place of −62 in the amounts shown below.

[0141]

Embedded image Exemplified Compound No. Structure parts _{I-35 C 8 H 17 -Q} -Cm-C 8 H 17 2 I-56 C 11 H 23 O-Q-Prl-C 6 H 13 4 I-71 C 9 H 19 -Q-Ph3F -C ₅ H ₁₁ 3 The liquid crystal composition D 91

A ferroelectric liquid crystal device was prepared in the same manner as in Example 3 except that this liquid crystal composition was used, 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 of the optical response speed are shown below.

[0143]

Table 6 10 ° C. 25 ° C. 40 ° C. Optical response speed 530 μsec 271 μsec 144 μsec Temperature dependence (10 ° C./40° C.) 3.7

As is clear from Examples 3, 4, and 5, the liquid crystal devices using the liquid crystal compositions B, C, E, and F according to the present invention have improved operating characteristics and high-speed responsiveness at low temperatures, and have a response. The temperature dependence of speed is also reduced.

Example 7 A 2% aqueous solution of polyvinyl alcohol resin [Kuraray Co., Ltd., PUA-117] was used in place of the 1.5% dimethylacetamide solution of the polyimide resin precursor used in Example 3. A liquid crystal element was prepared by the same method, and the optical response speed was measured by the same method as in Example 3. The measurement results are shown below.

[0146]

Table 7 10 ° C. 25 ° C. 40 ° C. Optical response speed 630 μsec 312 μsec 175 μsec Temperature dependence (10 ° C./40° C.) 3.6

Example 8 A liquid crystal element was prepared in the same manner as in Example 3 except that the alignment control layer was prepared only with a polyimide resin without using SiO ₂ used in Example 3, and the optical response speed was changed. It was measured. The measurement results are shown below.

[0148]

Table 8 10 ° C. 25 ° C. 40 ° C. Optical response speed 592 μsec 292 μsec 160 μsec Temperature-dependent characteristics (10 ° C./40° C.) 3.7

As is clear from Examples 7 and 8, even when the element structure was changed, the element using the liquid crystal composition according to the present invention had much improved low-temperature operating characteristics as in Example 3.
Moreover, the temperature dependence of the response speed is reduced.

Example 9 Liquid crystal composition G was prepared by mixing the following compounds in the following parts by weight.

[0151]

[Chemical 42]

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.

[0153]

Embedded image Exemplified Compound No. Structure parts _{I-9 C 9 H 19 O} -Q-Ph-C 8 H 17 3 I-10 C 10 H 21 O-Q-Ph-C 5 H 11 4 I-63 C 9 H 19 -Q- _np-C 10 _{H 21} 3 The liquid crystal composition G 90

Next, the following procedure was carried out for this liquid crystal composition.
The optical response was observed using the cell prepared in. Two
Prepare 0.7 mm thick glass plates and
The ITO film is formed on the plate and the voltage application electrode is created.
SiO on top of this_Two Was evaporated to form an insulating layer. Gala
Silane coupling agent on the plate [Shin-Etsu Chemical Co., Ltd., K
BM-602] 0.2% isopropyl alcohol solution
Number of revolutions 33 s^-1Apply for 15 seconds with the spinner
Reasoned. After this, heat drying treatment at 120 ° C. for 20 minutes
Reasoned.

Further, a polyimide resin precursor [Toray Industries, Inc., S
P-510] 1.0% dimethylacetamide solution was applied for 15 seconds by a spinner having a rotation speed of 50 s ^-1 . After film formation,
A heat-condensation baking treatment at 300 ° C. was performed for 60 minutes. The film thickness of the coating film at this time was about 12 nm.

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 diameter of 1.5 μm were dispersed on one glass plate, and then each of the glass beads was sprayed. The rubbing axes were made parallel to each other, and the glass plates were laminated using an adhesive sealant [Rixon Bond, manufactured by Chisso Corporation], and dried by heating at 100 ° C. for 60 minutes to form a cell.

A liquid crystal element (ferroelectric liquid crystal element) was prepared by injecting the liquid crystal composition H into this cell in an isotropic liquid state and gradually cooling from the isotropic phase to 25 ° C. at 20 ° C./h. . When the cell thickness of this cell was measured with a Berek phase plate, it was about 1.5 μm. Using this liquid crystal element, the drive waveform (1/3 bias ratio) shown in FIG.
As a result of measuring the contrast at the time of driving at 30 ° C., it was 25.5.

Comparative Example 3 A liquid crystal element was prepared in the same manner as in Example 9 except that the liquid crystal composition G mixed in Example 9 was injected into the cell, and the same driving waveform was used to obtain contrast at 30 ° C. It was measured. As a result, the contrast was 6.7.

Example 10 Exemplified Compounds I-9, I-10, I- Used in Example 9
Liquid Crystal Composition J was prepared by mixing the following Exemplified Compounds in place of 63 in the respective parts by weight shown below.

[0160]

Embedded image Exemplified Compound No. Structure parts _{I-4 C 11 H 23 -Q} -Ph-C 8 H 17 3 I-50 C 8 H 17 O-Q-Pyl-C 9 H 19 3 I-85 C 12 H 25 O-Q- Ph3F-F2 liquid crystal composition G92

A liquid crystal element was prepared in the same manner as in Example 9 except that this liquid crystal composition was used, and the same driving waveform as in Example 9 was used to measure the contrast during driving at 30 ° C. As a result, the contrast was 21.4.

As is clear from Examples 9 and 10, the liquid crystal elements using the liquid crystal compositions H and J according to the present invention have high contrast during driving.

Example 11 The polyimide resin precursor 1.0% dimethylacetamide solution used in Example 9 was replaced with a polyvinyl alcohol resin [Kuraray Co., Ltd., PUA-117] 2% aqueous solution. A liquid crystal device was produced by the same method, and the contrast at the time of driving at 30 ° C. was measured by the same method as in Example 9 and the result was 28.0.

Example 12 A liquid crystal element was prepared in the same manner as in Example 9 except that the alignment control layer was formed only by a polyimide resin without using SiO ₂ used in Example 9, and by the same method as in Example 9. As a result of measuring the contrast at the time of driving at 30 ° C., 20.6
Met.

Example 13 In place of the polyimide resin precursor 1.0% dimethylacetamide solution used in Example 9, a polyamic acid (LQ1802, manufactured by Hitachi Chemical Co., Ltd.) 1% NMP solution was used. A liquid crystal element was prepared by the same method, and the contrast was measured by the same method as in Example 9. As a result, the contrast was 37.9.

As is clear from Examples 11, 12 and 13, the device using the liquid crystal composition according to the present invention, even when the device structure was changed, had a high contrast as in Example 9. Further, as a result of detailed examination even when the drive waveform was changed, it was found that similarly a device using the liquid crystal composition of the present invention can obtain higher contrast.

Example 14 A liquid crystal composition K was prepared by mixing the following compounds including the exemplified compound (I-10) produced in Example 2 in the following parts by weight.

[0168]

[Chemical formula 45]

The phase transition temperature (° C.) of this composition K is shown below.

[0170]

[Equation 5]

Subsequently, a liquid crystal element was prepared in the same manner as in Example 3 except that the liquid crystal composition K was injected into the cell, and the optical response speed was measured. The measurement results are shown below.

[0172]

Table 9 15 ° C. 35 ° C. 55 ° C. Optical response speed 140 μsec 58 μsec 21 μsec Temperature dependence (15 ° C./55° C.) 6.7

Comparative Example 4 Production of 6-decyl-2- (4-pentyloxyphenyl) quinoline Step 1 Production of 6-decylquinoline 12.5 g of 6-decylaniline, 5.0 g of 3-nitrobenzenesulfonic acid, iron sulfide ( II) 1.5 g, sulfuric acid 10
ml and boric acid 2.8 g were dissolved in glycerin 13 ml, and the mixture was stirred at 140 ° C. for 6 hours. After the reaction was completed, the product was poured into water, an aqueous sodium hydroxide solution was added to make the mixture alkaline, and the mixture was extracted with diethyl ether. The obtained organic layer was washed with water, dried over anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography. Yield 2.0g.

Step 2 Preparation of 6-decyl-2- (4-methoxyphenyl) quinoline To a solution of 3.5 g of 4-bromoanisole in 7 ml of dry benzene was added 1.6 mol / 1 butyllithium-hexane. 11 ml of the solution was added, and the mixture was stirred overnight at room temperature. After completion of the reaction, the solvent was removed by decantation to obtain a solid. This was thoroughly dried, dissolved in dry tetrahydrofuran, cooled to 0 ° C in an ice bath, and 12 ml.
1.8 g of 6-decylquinoline dissolved in the dry tetrahydrofuran of 1 was added and stirred. After 2 hours, the temperature was returned to room temperature, the mixture was further stirred for 1 hour, poured into water, and extracted with diethyl ether. The obtained organic layer is washed with water,
The extract was dried over anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography and recrystallization. Yield 2.5g.

Step 3 Preparation of 6-decyl-2- (4-hydroxyphenyl) quinoline 2.5 g 6-decyl-2- (4-methoxyphenyl) quinoline and 15 ml 47% hydrobromic acid in 35 ml acetic acid.
Was added, and the mixture was stirred at 100 ° C. for 12 hours, and further stirred at room temperature overnight. Next, the reaction mixture was poured into water and extracted with chloroform. The obtained organic layer was washed with water, dried over anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 1.7 g of the desired product.

Step 4 Preparation of 6-decyl-2- (4-pentyloxyphenyl) quinoline 0.8 g of 6-decyl-2- (4-hydroxyphenyl) quinoline obtained in Step 3 and 170 mg of potassium hydroxide were added to 2 g.
0.5 g of pentyl bromide was added to a solution dissolved in ml butanol, and the mixture was heated under reflux for 4 hours. After the reaction,
The reaction mixture was poured into water and extracted with toluene. The obtained organic layer was washed with water and dried over anhydrous sodium sulfate,
The solvent was distilled off and the residue was purified by silica gel column chromatography. Further, recrystallization was performed to obtain 0.8 g of the desired product. The phase transition temperature of this compound is shown below.

[0177]

[Equation 6]

The IR chart of the compound is shown in FIG.

In the liquid crystal composition K used in Example 14, 6-, which was produced here instead of the exemplified compound (I-10), was used.
A liquid crystal composition L was prepared in the same manner as in Example 14 except that decyl-2- (4-pentyloxyphenyl) quinoline was used.

[0180]

[Chemical formula 46]

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

[0182]

[Equation 7]

Then, a ferroelectric liquid crystal device was prepared in the same manner as in Example 3 except that the liquid crystal composition L was injected into the cell, and the optical response speed was measured. The measurement results are shown below.

[0184]

Table 10 15 ° C. 35 ° C. 55 ° C. Optical response speed 170 μsec 66 μsec 22 μsec Temperature dependence (15 ° C./55° C.) 7.7

The liquid crystal composition used for the display is required to have a low temperature dependence of its response speed. As is clear from Example 14 and Comparative Example 4, the liquid crystal composition containing the liquid crystalline compound of the present invention has a small temperature dependence of the response speed, and particularly has a fast response at a low temperature (small decrease in the response speed), A liquid crystal composition having good characteristics.

[0186]

The liquid crystal composition (particularly the chiral smectic liquid crystal composition) containing the liquid crystal compound of the present invention can be operated by utilizing the ferroelectricity exhibited by the liquid crystal composition. The liquid crystal element of the present invention that can be used in this manner, particularly the ferroelectric liquid crystal element, has excellent switching characteristics, and has excellent characteristics such as high-speed response, reduction of temperature dependence of optical response speed, and high contrast. It can be a liquid crystal element.

The liquid crystal element of the present invention constitutes various liquid crystal devices, and particularly a display device in which a light source, a driving circuit and the like as display elements are combined 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 a chiral smectic liquid crystal.

FIG. 3 is a perspective view schematically showing an example of an element cell for explaining the operation of the liquid crystal element utilizing the ferroelectricity of the chiral smectic 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 device using a chiral smectic liquid crystal and a graphics controller.

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

9 is an IR chart diagram of 6-decyl-2- (4-pentyloxyphenyl) quinoline used in Comparative Example 4. FIG.

[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 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 111 Drive control Circuit 112 GCPU 113 Host CPU 114 VRAM

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09K 19/34 9279-4H G02F 1/13 500 (72) Inventor Goji Kadoka Shimomaruko Ota-ku, Tokyo 3-30-2 Canon Inc. (72) Inventor Shinichi Nakamura 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (27)

[Claims] 1. A liquid crystal compound represented by the following general formula (I). R ₁ -Q-A ₁ (I) (In the formula, Q is quinoline-2,6-diyl and A ₁ is -A _2-.
Shows the R ₂ or -A ₃ -R _3. A ₂ is F, CH ₃ , C
F _3, 1 or 2 substituents may have a 1,4-phenylene which optionally selected from CN, thiophene -2,
5-diyl, indane-2,5-diyl, 2-alkylindan-2,5-diyl (the alkyl group is a linear or branched alkyl group having 1 to 18 carbon atoms), coumarane-2 , 5-diyl, 2-alkylcoumarane-2,5-diyl (the alkyl group is a linear or branched alkyl group having 1 to 18 carbon atoms), benzofuran-2,5-diyl , Benzofuran-2,6-diyl, A ₃ is pyrimidine-2,5-diyl,
Pyridine-2,5-diyl, pyrazine-2,5-diyl, pyridazine-3,6-diyl, 1,4-cyclohexylene, 2,6-naphthylene, quinoxaline-2,6-
Each is selected from diyl and quinoline-2,6-diyl. R ₁ and R ₃ are F, CN, CF ₃ , or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (one or more of the alkyl group-
CH ₂ — is —O—, —S under the condition that hetero atoms are not adjacent to each other.
^{-, - CO -, - *} CY 1 Y 2 -, - CH = CH -, -
It may be replaced by C≡C-. In addition, one or two or more -CH ₃ in the alkyl group is -CH ₂ F,
-CHF _2, or may be replaced with -CN,. Y ₁ and Y ₂ are H, F, CH ₂ F, CHF ₂ and CF
₃ , CN or a linear alkyl group having 1 to 5 carbon atoms is shown. ^* C represents an asymmetric carbon atom. ) Is shown. R ₂ is F, CN, CF ₃ , or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (one or more —CH ₂ in the alkyl group).
- is ^{_{- * CY 1 Y 2 -,}} - CH = CH -, - C≡C- may be replaced with. Further, one or two or more -CH ₃ in the alkyl group is -CH ₂ F or -CHF.
₂ or -CN may be substituted. ) Is shown. ) 2. The liquid crystalline compound according to claim 1, which satisfies at least one or more of the following three items in the general formula (I). (A) R ₁ is any of the following (1) to (5). (B) R ₂ is any of the following (6) to (10). (C) R ₃ is any of the following (1) to (5). [Chemical 2] (However, a is an integer from 1 to 16, d and g are integers from 0 to 7, b, e, h, and j are integers from 1 to 10, and f is 0 or an integer. B + d ≦ 16 , E + f + g
The condition of ≦ 16 is satisfied. Y ₃ is a single bond, —O—, —O
CO -, - COO-, _{Y 4} is _-CH 2 O -, - CH
Indicates either _2- or -COO-. It may be optically active. ) 3. In the general formula (I), A ₁ is -A.
The liquid crystal compound according to claim 1, which is _2- R ₂ . 4. In the general formula (I), A ₂ is 1,
It is 4-phenylene, The liquid crystalline compound of Claim 3 characterized by the above-mentioned. 5. The liquid crystalline compound according to claim 2, wherein in the general formula (I), R ₁ is the following (1) and R ₂ is the following (6). Embedded image _{(1) n-C a H} 2a + 1 -Y 3 - (6) n-C a H 2a + 1 - ( where, a is an integer from 1 to 16, Y ₃ is a single bond, -O
-, -OCO-, and -COO- are shown. ) 6. A compound represented by the general formula (I) is 2-
The liquid crystalline compound according to claim 1, which is (4-pentylphenyl) -6-methoxyquinoline. 7. The compound represented by the general formula (I) is 2-
The liquid crystalline compound according to claim 1, which is (4-pentylphenyl) -6-decyloxyquinoline. 8. A liquid crystal composition comprising at least one liquid crystal compound represented by the general formula (I) according to claim 1. 9. The liquid crystal composition according to claim 8, containing 1 to 80% by weight of the liquid crystal compound represented by the general formula (I). 10. The liquid crystal composition according to claim 8, containing 1 to 60% by weight of the liquid crystal compound represented by the general formula (I). 11. The liquid crystal composition according to claim 8, containing 1 to 40% by weight of the liquid crystal compound represented by the general formula (I). 12. The liquid crystal composition according to claim 8, which has a chiral smectic phase. 13. A compound represented by the general formula (I): 9. The liquid crystal composition according to claim 8, which contains the three types as essential components. 14. A compound represented by the general formula (I): 9. The liquid crystal composition according to claim 8, which contains the three types as essential components. 15. A compound represented by the general formula (I): 9. The liquid crystal composition according to claim 8, which contains the three types as essential components. 16. A compound represented by the general formula (I): 9. The liquid crystal composition according to claim 8, which contains the three types as essential components. 17. A compound represented by the general formula (I): 9. The liquid crystal composition according to claim 8, which contains the three types as essential components. 18. A compound represented by the general formula (I): 9. The liquid crystal composition according to claim 8, which contains the three types as essential components. 19. A liquid crystal device comprising the liquid crystal composition according to claim 8 disposed between a pair of opposing electrode substrates. 20. The liquid crystal device according to claim 19, further comprising an alignment control layer provided on the facing surface of at least one of the electrode substrates. 21. The liquid crystal device according to claim 20, wherein the alignment control layer is a layer subjected to a rubbing treatment. 22. The liquid crystal device according to claim 19, wherein the pair of electrode substrates are arranged with a film thickness in which a helix formed by alignment of liquid crystal molecules is released. 23. A display method comprising: controlling the liquid crystal composition according to claim 8 according to image information to obtain a display image. 24. A liquid crystal device having the liquid crystal element according to claim 19. 25. The liquid crystal device according to claim 24, which is a display device. 26. The liquid crystal device according to claim 24, further comprising a drive circuit for the liquid crystal element. 27. The method according to claim 24, further comprising a light source.
6. The liquid crystal device according to any one of item 6.