JP3236336B2 - Dioxaborinane derivative compound, liquid crystal composition containing the same, and liquid crystal electro-optical element - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dioxaborinane derivative compound used for a liquid crystal electro-optical device, a liquid crystal composition containing the same, and a liquid crystal electro-optical device using the same.

[0002]

2. Description of the Related Art Liquid crystal display devices include watches, calculators,
In recent years, measuring instruments, automotive instruments, copiers, cameras, OA
It has begun to be used in various applications such as display devices for appliances and display devices for home appliances, and various performance requirements such as a wide operating temperature range, a low operating voltage, high-speed response, and chemical stability have been made.

[0003] However, at present, there is no material that satisfies all these characteristics with a single material, and a plurality of liquid crystals and
In this state, the required performance as a liquid crystal composition is satisfied by mixing non-liquid crystal materials. For this reason, it is desired to develop a liquid crystal or non-liquid crystal material having not only all the characteristics but also one or more characteristics. In such a situation, it is an important issue to provide a material which can be driven in a wide temperature range, has excellent compatibility with other liquid crystals or non-liquid crystals, and is chemically stable.

Further, among the liquid crystal display elements, the liquid crystal dot matrix display element has begun to be used in various office equipment such as an electronic desk calculator, a terminal display of an electronic computer, etc., so that it is easier to see and display more. A liquid crystal display device having a large number of pixels is required.

[0005]

The dot matrix display is for displaying information such as a figure or a character as a set of points. Since the number of display pixels increases, multiplex driving is required. TN (twisted nematic)
In the cell, a one-row display cell initially driven at 1/7 or 1/8 duty was generally used.
There is a demand for a / 32 duty, a 1/64 duty, and even a higher duty, and improving the multiplex drive characteristics of TN cells has become an important issue.

[0006]

Means for Solving the Problems The present invention has been made as a result of various studies to solve the above-mentioned problems, and has been made by the general formula (1)

[0007]

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(Wherein, R ₁ represents an alkyl group having 1 to 10 carbon atoms, and an oxygen atom is inserted between carbon-carbon bonds in the group or between carbon-carbon bonds between the group and the ring. R ₂ may be

[0009]

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[0010]

[0011]

[0012]

[0013]

Represents the following. here,

[0015]

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Represents a trans-1,4-cyclohexane ring, R ₃ represents an alkyl group having 1 to 10 carbon atoms, and a carbon atom between carbon-carbon bonds in the group or between the group and the ring. An oxygen atom may be inserted between carbon bonds . )
A dioxaborinane derivative compound represented by the formula: and a liquid crystal composition comprising at least one kind of the compound; and a liquid crystal composition sandwiched between substrates with electrodes. The present invention provides a liquid crystal electro-optical element characterized by the following.

The multiplex driving characteristic of the TN cell is as follows.
Although it is often expressed by a drive voltage, a voltage margin, a response speed, and the like, a voltage margin is the most important as a characteristic that directly affects display contrast. The voltage margin (M) is a value indicating how much fluctuation in the driving voltage is allowable. The minimum voltage (V _ON ) for sufficiently lighting the selected waveform and the maximum voltage (crosstalk) at which the half-selected waveform starts to occur in the half-selected waveform. V
_OFF ) is defined as the ratio to the drive voltage as follows:

M = (V _OFF −V _ON ) / V _D × 100% (a) V _D = (V _ON + V _OFF ) / 2 (b)

As the voltage margin increases, the number of scanning lines can be increased, that is, the duty ratio can be increased, and the display contrast can be improved.

In equations (a) and (b), V _ON and V _OFF
Has a different meaning depending on the applied waveform, the viewing angle, the temperature, the definition of the lighting state and the crosstalk state, and the like, and in the following description, it is defined as follows according to a common method.

First, since the TN cell operates according to the effective value of the applied voltage as is conventionally known, even if the duty ratio or the bias of the used waveform changes, it is necessary to make a relative comparison between the TN cells. Comparison with one type of waveform is sufficient.

Therefore, a comparison is made based on a voltage margin when a 1/3 duty 1/3 bias waveform is used. The viewing angle (θ) is assumed to be in the range of 10 ° to 40 ° in the low viewing angle clear viewing direction from the normal direction of the TN cell. The temperature is 25 ° C., and when θ = 10 °, the voltage at which the luminance change by voltage application reaches 50% of its saturation value is V _ON , θ = 4
It is considered that crosstalk occurs at 26% at 0 °, and is defined as V _OFF .

The compound of the general formula (1) of the present invention is obtained by mixing one or more compounds with another liquid crystal material and further with another non-liquid crystal material to form a liquid crystal composition having a desired liquid crystal temperature range. To use. In that case, the compound of the present invention is 1 to 50 wt%, more preferably 3 to 30 wt% in the mixture.
By being used, the multiplex drivability as a liquid crystal display element can be improved, and it is a chemically stable material.

The compound of the general formula (1) of the present invention is
Since it has a relatively large T _C (phase transition temperature), adding this compound to a liquid crystal composition has the effect of raising the clearing point (NI) of the composition. That is, it is an effective material when extending the drive temperature range.

The other material used in admixture with the compound of the general formula (1) of the present invention varies depending on the application and required performance, but includes a liquid crystal material and a main component having a similar structure to the liquid crystal material and, if necessary, And additional components to be added.

Specifically, a low-viscosity component, a component for improving dielectric anisotropy, another component for exhibiting liquid crystallinity at a high temperature, a component for imparting cholesteric properties, a component for exhibiting dichroism, and imparting conductivity. Components and other various additives.

Examples of the materials used in combination with the compound of the present invention include the following. R ₄ and R ₅ in the following formulas are different from R ₁ and R ₂ in the present invention, and represent an alkyl group, an alkoxy group, a halogen atom, a cyano group, or the like, and -Ph- is 1, 4-phenylene ring, -Cy-
Represents a trans-1,4-cyclohexylene ring.

R ₄ -Cy-Cy-R ₅ R ₄ -Cy-Ph-R ₅ R ₄ -Ph-Ph-R ₅ R ₄ -Cy-COO-Ph-R ₅ R ₄ -Ph-COO-Ph- _{R 5 R 4 -Cy-CH =} CH-Ph-R 5 R 4 -Ph-CH = CH-Ph-R 5 R 4 -Cy-CH 2 CH 2 -Ph-R 5 R 4 -Ph-CH 2 CH ₂ -Ph-R ₅ R ₄ -Ph-N = N-Ph-R ₅ R ₄ -Ph-NON-Ph-R ₅ R ₄ -Cy-COS-Ph-R ₅ R ₄ -Cy-Ph-Ph- R ₅ R ₄ -Cy-Ph-Ph-Cy-R ₅ R ₄ -Ph-Ph-Ph-R ₅ R ₄ -Cy-COO-Ph-Ph-R ₅ R ₄ -Cy-Ph-COO-Ph- R ₅ R ₄ -Cy-COO-Ph-COO-Ph-R ₅ R ₄ -Ph-COO-Ph-COO-Ph-R ₅ R ₄ -Ph-COO-Ph-OCO-Ph-R ₅

These compounds are merely examples, and substitution of hydrogen atoms in the ring structure or terminal groups with halogen atoms, cyano groups, methyl groups, etc., other six-membered rings of cyclohexane and benzene rings, and five-membered rings Substitution with a ring, for example, a pyrimidine ring, a dioxane ring, or the like, change of a bonding group between the rings, and the like are possible, and various materials may be selected and used in accordance with desired performance.

The composition of the present invention is injected into a liquid crystal cell as a liquid crystal composition, and is sandwiched between substrates with electrodes to form a liquid crystal electro-optical element. It can be used in various modes such as a TN mode, a guest-host (GH) mode, a dynamic scattering mode, a phase change mode, a DAP mode, a dual frequency drive mode, and a ferroelectric liquid crystal display mode.

As a typical liquid crystal cell, there is a TN type liquid crystal electro-optical element. Here, the expression “liquid crystal electro-optical element” means that the liquid crystal electro-optical element can be used not only for display but also for a light control window, an optical shutter, a polarization conversion element, and the like.

[0032] Plastics, on a substrate such as glass, of SiO _2, Al ₂ O undercoat layer or a color filter layer, such as ₃ to form _{optionally, In 2 O 3 -SnO 2 (} IT
O), after providing electrodes such as SnO ₂ and patterning,
If necessary, polyimide, polyamide, SiO ₂ , Al ₂
An overcoat layer of O ₃ or the like is formed, orientation treatment is performed, a seal material is printed on the overcoat layer, and the periphery is sealed by disposing the electrode surfaces to face each other, and the seal material is cured to form empty cells. .

A composition containing the compound of the present invention is injected into the empty cell, and the injection port is sealed with a sealant to form a liquid crystal cell. A polarizing plate, a color polarizing plate, a light source, a color filter, a semi-transmissive reflector, a reflector,
Laminate light guide plate, UV cut filter, etc., letters,
A liquid crystal electro-optical element is obtained by printing a figure or the like, performing non-glare processing, or the like.

The above description merely shows the basic structure and manufacturing method of the liquid crystal electro-optical element. For example, a substrate using two-layer electrodes, a two-layer liquid crystal cell having two liquid crystal layers formed thereon, An active matrix element using an active matrix substrate on which active elements such as TFTs and MIMs are formed,
Various configurations can be used.

Further, modes other than the TN type described above, that is, a super twist nematic (ST) having a high twist angle
It can also be used for an N) type liquid crystal electro-optical element, a GH type liquid crystal electro-optical element using a polychromatic dye, a ferroelectric liquid crystal electro-optical element, and the like. In addition, it can be used for a type that performs writing by heat instead of electrically.

The compound of the general formula (1) of the present invention is produced, for example, according to the following method (wherein R ₁ ,
R ₂ has the same meaning as R ₁ and R ₂ in the formula (1), respectively.

[0037]

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That is, first, the 2-substituted diethyl malonate (2) is reduced with lithium aluminum hydride in anhydrous tetrahydrofuran solvent to give the 2-substituted-1,3-substituted.
Let it be propanediol (3).

On the other hand, a Grignard reagent synthesized from 1-bromo-4-substituted benzene (4) and metallic magnesium in anhydrous tetrahydrofuran is reacted with trimethyl borate and treated with an acid to give a 4-substituted phenylboronic acid (5). Get.

The 2-substituted-1,3-propanediol (3) obtained above and the 4-substituted phenylboronic acid (5) are subjected to a dehydration reaction in an azeotropically dehydrable inert organic solvent, whereby The dioxaborinane derivative compound (1) which is the compound of the present invention can be obtained. This manufacturing method is merely an example, and various manufacturing methods can be used.

[0041]

EXAMPLES Example 1 20 equipped with a stirrer, thermometer, dropping funnel and reflux condenser
A 00 ml four-necked flask was purged with nitrogen, charged with 49.7 g (1.31 mol) of lithium aluminum hydride and 650 ml of anhydrous tetrahydrofuran, and vigorously stirred to give a suspension of ethyl 2-propylmalonate 154.
A solution of 49 g (0.764 mol) dissolved in anhydrous tetrahydrofuran (150 ml) was added dropwise at room temperature. After stirring overnight at room temperature, sodium hydroxide 3
g of water in 190 ml of water and 600 ml of tetrahydrofuran were added dropwise to decompose excess lithium aluminum hydride. The resulting white solid was filtered off, the mother liquor was concentrated, and the residue was distilled under reduced pressure to give 2-propyl-1,2.
43.9 g (yield 50%) of 3-propanediol was obtained.

A 100 ml four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was purged with nitrogen, and 4.36 g (0.042 mol) of trimethyl borate and 20 ml of anhydrous tetrahydrofuran were charged and stirred. A solution was prepared and the internal temperature was kept at -60 ° C or lower in a dry ice bath.
To this solution, 60 ml of a tetrahydrofuran solution containing 0.04 mol of a Grignard reagent prepared from 1-bromo-4- (trans-4'-propylcyclohexyl) benzene in a conventional manner was added dropwise with stirring, followed by stirring at -60 ° C for 2 hours. Thereafter, 3 ml of water was added dropwise, and the internal temperature was gradually raised to −30 ° C. using the reaction heat. Next, the dry ice tank was removed, and while dropping 22 ml of 11% diluted sulfuric acid, the temperature was raised to room temperature to terminate the reaction. The desired product was solvent-extracted from the aqueous layer with 90 ml of ether, and the organic layer was washed with a small amount of saturated saline. The solid was further dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the precipitated solid was washed with n-hexane to remove impurities. This solid is purified water,
After washing with a mixed solvent of methyl alcohol and ethyl alcohol, 4- (trans-4′-propylcyclohexyl)
6.07 g (62% yield) of phenylboronic acid was obtained.

50 m with azeotropic dehydrator with reflux condenser
(1) in the eggplant flask of l, 2-propyl-1,
0.0084 mol of 3-propanediol and 0.0076 mol of 4- (trans-4′-propylcyclohexyl) phenylboronic acid were added together with 35 ml of toluene, and azeotropic dehydration was performed at a reflux temperature. The reaction was completed in 1 hour, toluene was distilled off under reduced pressure, and recrystallized from acetone to give 2-
[4 ′-(trans-4 ″ -propylcyclohexyl)
[Phenyl] -5-propyl-1,3,2-dioxaborinane (2.00 g, yield 80%) was obtained. (Melting point = 11
7.6 ° C)

[0044]

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FIG. 1 shows the IR spectrum of this compound.

Similarly, a compound as shown below can be synthesized by using another corresponding alkyl 2-substituted malonate in place of ethyl 2-propylmalonate.

2- [4 ′-(trans-4 ″ -propylcyclohexyl) phenyl] -5-methyl-1,3,2-dioxaborinane 2- [4 ′-(trans-4 ″ -propylcyclohexyl) phenyl ] -5-Ethyl-1,3,2-dioxaborinane 2- [4 '-(trans-4''-propylcyclohexyl) phenyl] -5-butyl-1,3,2-dioxaborinane 2- [4'-( Trans-4 ''-propylcyclohexyl) phenyl] -5-pentyl-1,3,2-dioxaborinane 2- [4 '-(trans-4''-propylcyclohexyl) phenyl] -5-heptyl-1,3, 2-dioxaborinane 2- [4 '-(trans-4''-propylcyclohexyl) phenyl] -5-decyl-1,3,2-dioxaborinane 2- [4'-(trans-4 ''-propylcyclohexyl) phenyl ] -5-Methoxy-1,3,2-dioxaborinane 2- [4 '-(trans-4''-propylcyclohexyl) phenyl] -5-ethoxy-1,3,2-dioxaborinane 2- [4'-( Trans-4``-propylcyclo Hexyl) phenyl] -5-methoxy-1,3,2-dioxaborinane

Similarly, by replacing 1-bromo-4- (trans-4'-propylcyclohexyl) benzene with the corresponding other 1-bromo-4- (trans-4'-substituted cyclohexyl) benzene. The following compounds can be synthesized.

2- [4 ′-(trans-4 ″ -methylcyclohexyl) phenyl] -5-methyl-1,3,2-dioxaborinane 2- [4 ′-(trans-4 ″ -methylcyclohexyl) phenyl ]
-5-ethyl-1,3,2-dioxaborinane 2- [4 '-(trans-4''-methylcyclohexyl) phenyl]
-5-propyl-1,3,2-dioxaborinane 2- [4 '-(trans-4''-methylcyclohexyl) phenyl]
-5-butyl-1,3,2-dioxaborinane 2- [4 '-(trans-4''-methylcyclohexyl) phenyl]
-5-pentyl-1,3,2-dioxaborinane 2- [4 '-(trans-4''-methylcyclohexyl) phenyl]
-5-heptyl-1,3,2-dioxaborinane 2- [4 '-(trans-4''-methylcyclohexyl) phenyl]
-5-decyl-1,3,2-dioxaborinane 2- [4 '-(trans-4''-methylcyclohexyl) phenyl]
-5-methoxy-1,3,2-dioxaborinane 2- [4 '-(trans-4''-methylcyclohexyl) phenyl]
-5-ethoxy-1,3,2-dioxaborinane 2- [4 '-(trans-4''-methylcyclohexyl) phenyl]
-5-methoxymethyl-1,3,2-dioxaborinane

2- [4 ′-(trans-4 ″ -methoxycyclohexyl) phenyl] -5-methyl-1,3,2-dioxaborinane 2- [4 ′-(trans-4 ″ -methoxycyclohexyl) phenyl ] -5-Ethyl-1,3,2-dioxaborinane 2- [4 '-(trans-4''-methoxycyclohexyl) phenyl] -5-propyl-1,3,2-dioxaborinane 2- [4'-( Trans-4 ''-methoxycyclohexyl) phenyl] -5-butyl-1,3,2-dioxaborinane 2- [4 '-(trans-4''-methoxycyclohexyl) phenyl] -5-pentyl-1,3, 2-dioxaborinane 2- [4 '-(trans-4''-methoxycyclohexyl) phenyl] -5-heptyl-1,3,2-dioxaborinane 2- [4'-(trans-4 ''-methoxycyclohexyl) phenyl ] -5-decyl-1,3,2-dioxaborinane 2- [4 '-(trans-4''-methoxycyclohexyl) phenyl] -5-methoxy-1,3,2-dioxaborinane 2- [4'-( Trans-4 ''-methoxycyclohe Sill) phenyl] -5-ethoxy-1,3,2-dioxaborinane 2- [4 '- (trans-4''- methoxyphenyl) phenyl] -5-methoxy-1,3,2-dioxaborinane

2- [4 ′-(trans-4 ″ -methoxymethylcyclohexyl) phenyl] -5-methyl-1,3,2-dioxaborinane 2- [4 ′-(trans-4 ″ -methoxymethylcyclohexyl) )
Phenyl] -5-ethyl-1,3,2-dioxaborinane 2- [4 '-(trans-4''-methoxymethylcyclohexyl)
Phenyl] -5-propyl-1,3,2-dioxaborinane 2- [4 '-(trans-4''-methoxymethylcyclohexyl)
Phenyl] -5-butyl-1,3,2-dioxaborinane 2- [4 '-(trans-4''-methoxymethylcyclohexyl)
Phenyl] -5-pentyl-1,3,2-dioxaborinane 2- [4 '-(trans-4''-methoxymethylcyclohexyl)
Phenyl] -5-heptyl-1,3,2-dioxaborinane 2- [4 '-(trans-4''-methoxymethylcyclohexyl)
Phenyl] -5-decyl-1,3,2-dioxaborinane 2- [4 '-(trans-4''-methoxymethylcyclohexyl)
Phenyl] -5-methoxy-1,3,2-dioxaborinane 2- [4 '-(trans-4''-methoxymethylcyclohexyl)
Phenyl] -5-ethoxy-1,3,2-dioxaborinane 2- [4 '-(trans-4''-methoxymethylcyclohexyl)
Phenyl] -5-methoxymethyl-1,3,2-dioxaborinane

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

Example 2 The liquid crystal composition ZLI-1565 manufactured by Merck & Co., Ltd.
I) is 85.8 ° C., and this ZLI-1565 is injected into a cell having a thickness of 8 μm formed by combining a silicon oxide-coated and rubbed indium oxide transparent electrode, and a 1/3 duty 1/3 When driven at 25 ° C. with a bias waveform, V _D is 4.64 V and the voltage margin is 3.
9.2%. When 90 wt% of this composition was added with 10 wt% of the compound of Example 1 of the present invention, the clear point (NI) of the composition was 90.1 ° C., and the V _D was 4.77.
V and the voltage margin were 40.6%, and the physical properties could be improved on both the clearing point and the voltage margin.

[0070]

As described above, the present invention provides a novel dioxaborinane derivative compound of the general formula (1), a liquid crystal composition containing the compound, and the liquid crystal composition sandwiched between substrates with electrodes. By providing a liquid crystal electro-optical element, it is possible to improve the multiplex driving property as a liquid crystal display element, and it is excellent in that it is capable of forming a liquid crystal composition which is chemically stable and has a high clearing point. It is.

[Brief description of the drawings]

FIG. 1 is an IR spectrum of a compound of an example of the present invention.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C07F 5/04 C09K 19/40

Claims (3)

(57) [Claims] 1. A compound of the general formula (1) (In the formula, R ₁ represents an alkyl group having 1 to 10 carbon atoms, wherein an oxygen atom is inserted between carbon-carbon bonds in the group or between carbon-carbon bonds between the group and the ring. R
₂ is Represents Where: Represents a trans-1,4-cyclohexane ring, R ₃
Represents an alkyl group having 1 to 10 carbon atoms, and an oxygen atom may be inserted between carbon-carbon bonds in the group or between carbon-carbon bonds between the group and the ring . Dioxaborinane derivative compound, characterized by being represented by). 2. A liquid crystal composition comprising at least one dioxaborinane derivative compound according to claim 1. 3. A liquid crystal electro-optical element comprising the liquid crystal composition according to claim 2 sandwiched between substrates with electrodes.