JPH06222320A - Liquid crystal device - Google Patents

Abstract

PURPOSE:To provide the liquid crystal device which can lower a driving voltage, attains a high contrast and high voltage holding rate and is useful as a display device for a computer terminal and a display device of projection. CONSTITUTION:This liquid crystal device of a light scattering type is constituted by providing a light control layer clamped between two sheets of substrates which have a transparent electrode layer and at least one of which are transparent and incorporating a liquid crystal material and transparent solid material into this light control layer. The liquid crystal material contg. (1) 30 to 70wt.% first compd. group consisting of compds. having dielectric anisotropy DELTAepsilon in a -1 to 2 range, (2) 10 to 40wt.% second compd. group consisting of compds. having DELTAepsilon in an 8 to 18 range and (3) <=35wt.% third compd. group consisting of compds. having DELTAepsilon in a 19 to 45 range is used for the above-mentioned liquid crystal device. Further, the dielectric anisotropy DELTAepsilon of the above-mentioned liquid crystal is in an 8 to 17 range, the elastic constant K11 thereof in a 5.0 to 15.0 Newton range and the elastic constant ratio K33/K11 thereof in a 1.3 to 2.5 range.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal encapsulating thin film which does not use a polarizing plate, and more particularly to a liquid crystal display device capable of electrically or thermally controlling the blocking and transmission of a visual field. INDUSTRIAL APPLICABILITY The liquid crystal display device of the present invention is used as a screen for blocking a field of view in a window of a building or a show window, displays characters and figures, and switches the display electrically or thermally with high-speed response. It is used as a display device for decorative display boards such as advertising boards, clocks, calculators, and display devices that require a bright screen, particularly as a display device for computer terminals and a display device for projection.

[0002]

2. Description of the Related Art Conventionally, liquid crystal display elements of TN type or STN type using nematic liquid crystal have been put into practical use. Also, a liquid crystal device using a ferroelectric liquid crystal has been proposed. These require a polarizing plate to limit the brightening of the screen, and require an alignment treatment, so that there is a problem in that the yield at the time of manufacturing a display device decreases.

On the other hand, as a method for producing a liquid crystal device which does not require a polarizing plate or an alignment treatment and is bright and has good contrast, a method is known in which liquid crystal droplets are dispersed in a polymer and the polymer is formed into a film. Tokusho Sho-501
631 and U.S. Pat. No. 4,435,047 describe gelatin, gum arabic, as encapsulating substances,
Polyvinyl alcohol, etc. have been proposed, and in addition to these,
For example, Japanese Patent Publication No. 61-502128 and Japanese Patent Laid-Open No. 61-502128.
No. 305528, Japanese Patent Laid-Open No. 62-2231,
It is known from JP-A-63-144321. However, in the case of a liquid crystal device in which liquid crystal droplets are dispersed in a polymer, in addition to the inconvenience of optimizing the matching and non-matching of the individual refractive indices of the liquid crystal material and the polymer, 25 V or more is required to obtain sufficient transparency. Therefore, a high voltage is required, and it does not have a low driving voltage characteristic that is important in the practical application of a display device.

JP-A-1-1987 discloses a technique that enables low-voltage drivability, high contrast, and time-division drivability, which are important characteristics required for practical use of liquid crystal display devices.
Japanese Unexamined Patent Publication No. 25 discloses a liquid crystal device having a structure in which a liquid crystal material forms a continuous layer and a polymer substance is distributed in a three-dimensional network in the continuous layer.

Japanese Laid-Open Patent Publication No. 58-501631 mentioned above,
U.S. Pat. No. 4,435,047, JP-A-1-198725.
As typical liquid crystal materials used in the liquid crystal device described in JP-A No. 1994-331, those composed of a liquid crystal compound represented by the following general formula are shown. These compounds have a large dielectric anisotropy because they contain a cyano group, which was essential for obtaining a liquid crystal device with a lower driving voltage.

[0006]

[Chemical 17]

(In the formula, i represents a positive integer.)

However, a liquid crystal device manufactured by using a liquid crystal material containing the above-mentioned compound as a main component has a low resistance value, and therefore has a problem of weather resistance when used as a decorative display board such as an outdoor advertising board. Caused by a portable watch,
When used as a display device for a calculator, the durability was problematic due to the large power consumption, and it was used as a display device for a computer terminal or a projection display device characterized by having an active element in a transparent electrode layer. In this case, there is a problem that an image flickering and a decrease in contrast occur due to the low voltage holding ratio.

On the other hand, when a liquid crystal material containing a compound represented by the following general formula and having a small dielectric anisotropy as a main component is used,
There is a problem that the contrast deteriorates poorly and the driving voltage is too high, and it is impossible to use it for the display device of the computer terminal or the display device of the projection characterized by having the active element in the transparent electrode layer. Met.

[0010]

[Chemical 18]

In any case, the display characteristics required for a light-scattering liquid crystal device composed of a liquid crystal material and a transparent solid substance are in a trade-off relationship between low voltage driving and high resistance, and simply the dielectric property of the liquid crystal material is used. It cannot be achieved by a design that considers only anisotropy.

[0012]

As described above, the display characteristics required for a light-scattering type liquid crystal device characterized in that the light control layer contains a liquid crystal material and a transparent solid substance are currently widely used. In addition to characteristics such as being able to drive at a voltage low enough to use a driving circuit that is used, improving the contrast by blocking the field of view or improving the white turbidity, especially for decorative display boards such as advertising boards, watches and calculators. The following problems are emphasized in the use of a display device or a display device requiring a bright screen, particularly a display device of a computer terminal or a display device of a projection.

That is, the liquid crystal device having the light control layer having a low resistance value not only increases the power consumption and deteriorates the service life, but also has the electro-optical characteristics with respect to the temperature change and the frequency change, the driving voltage and the contrast. However, the steepness that determines the availability of time-division driving, the response speed, and the like are deteriorated. Furthermore, in the liquid crystal device characterized in that the transparent electrode layer is provided with an active element, it becomes a serious cause of deteriorating the voltage holding ratio, sufficient transparency of the display pixel is not obtained, and therefore the contrast is lowered. However, there was a problem that the display quality flickers. Therefore,
For example, a method using a conductive material such as a surfactant or an organometallic complex has been a lame liquid crystal device in which a serious defect is newly generated.

The reason why the light control layer has a low resistance value is as follows.
(1) The specific resistance value of the liquid crystal material, (2) the specific resistance value of the transparent solid substance, (3) the interaction which causes a decrease in the specific resistance of the mixture obtained by mixing the liquid crystal material and the transparent solid substance. ,
(4) It is conceivable that the light control layer may be damaged by light or heat used in forming the light control layer, or that water, organic solvent, or impurities remaining in the liquid crystal material may have an effect.

The problem to be solved by the present invention is to provide a liquid crystal device which achieves the problems of low voltage drivability, high contrast ratio and high retention ratio characteristic and is useful for computer terminal display devices and projection display devices. is there.

[0016]

Means for Solving the Problems As a result of intensive investigations by the present inventors, a liquid crystal material and a transparent solid substance constituting a liquid crystal device utilizing a light scattering opaque state and a transparent state,
It has been found that the problems (1), (3) and (4) can be solved by a combination of the dielectric anisotropy and the elastic constant of the liquid crystal material, and the problems of the present invention have been solved.

That is, according to the present invention, in order to solve the above problem, at least one of the transparent electrode layers is transparent.
A light-scattering liquid crystal device having a light control layer sandwiched between a plurality of substrates, wherein the light control layer contains a liquid crystal material and a transparent solid substance, wherein the liquid crystal material is (1) dielectric anisotropy. 30 to 70% by weight of a first compound group consisting of compounds having Δε in the range of −1 to 2; (2) 10 to 40% by weight of a second compound group consisting of compounds having Δε of 8 to 18;
And (3) 35% by weight or less, preferably 1 to 3, of the third compound group consisting of compounds having Δε in the range of 19 to 45.
35% by weight, the dielectric anisotropy Δε of the liquid crystal material is in the range of 8 to 17, the elastic constant K11 of the liquid crystal material is in the range of 5.0 to 15.0 Newton, and the elasticity of the liquid crystal material is There is provided a first liquid crystal device having a constant ratio K33 / K11 in the range of 1.3 to 2.5.

The electro-optical characteristics of the light-scattering type liquid crystal device according to the present invention are obtained by analogy with the known TN-LCD technology.
It has been supposed to be expressed by the following equation (a) using the physical property values of the liquid crystal material.

[0019]

[Equation 1]

(In the formula, Vth is a threshold voltage, Kii is an elastic constant, and Δε is a dielectric anisotropy.)

However, the liquid crystal device of the present invention is
The liquid crystal material is characterized by being sandwiched by a narrow boundary surface of several μm by a transparent solid substance. Therefore, the electro-optical characteristics cannot be discussed only by the relational expression of the above formula (a). However, as described later with the embodiment of the present invention, it was not actually suitable.

Another display characteristic that is not established in the conventional TN-LCD technology is a response characteristic. Generally, as the distance between electrodes increases,
The response speed increases in the TN-LCD. However, in the liquid crystal device of the present invention, the response speed is reduced and improved.

On the other hand, a technique for reducing the drive voltage by increasing the dielectric anisotropy of the liquid crystal material has been reported. However, as described above, the electric resistance of the liquid crystal device is often deteriorated, which poses a practical problem. are doing.

As a result of extensive studies on the relationship between the physical properties of the liquid crystal material and the display characteristics of the liquid crystal device, the present invention shows that the electro-optical characteristics of the light-scattering liquid crystal device according to the present invention are represented by the following equation (b). It is based on the findings. Here, ¹ Kii and ² Kii are elastic constants (hereinafter collectively referred to as Kii; i is 1, 2, or 3), Δε is dielectric anisotropy, and <γ> is a transparent solid. The average void spacing of the substance interface, A is the anchoring energy of the transparent solid substance to the liquid crystal molecules, and d is the distance between the substrates having transparent electrodes.

[0025]

[Equation 2]

This mathematical expression means that the regulating force applied to the liquid crystal molecules by the interface of the transparent solid substance changes depending on the ratio of the elastic constant Kii and the anchoring energy A. In particular, the effect is the actual average gap. From interval <γ>, Kii / A
It is shown that the driving voltage can be effectively reduced by the action of substantially expanding by the amount.

In order to explain the superiority of the technique of the present invention,
The simulation group of the formula (b) described later in the examples.
The rough is shown in FIG. FIG. 1 shows the average void spacing <γ> = 1
μm, the distance d between the substrates having transparent electrodes is d = 10 μm
When the elastic constant in Eq.
It shows the change. Where Kii = kii × 10 ^-12N
ewton, A = A × 10^-6Newton / μm, dimensionless
It will be described using kii and A. In the figure, curve (1-1)
Is the dielectric anisotropy Δε = 16, the elastic constant and the anchoring coefficient
The energy ratio is Kii / A = 0.01 × kiiμm (A = 10
^-Four), The curve (1-2) has Δε = 10,
Kii / A = 0.1 × kii μm (A = 10^-Five)
Respectively, as a comparative example, Δε = 20, Kii / A ≦
0.001 × kiiμm (A ≧ 10^-3) And the curve
It is represented by (1-ratio). It's clear from the results shown in Figure 1.
As described above, even if the dielectric anisotropy is small, the elastic constant and anchoring
Drive voltage is reduced by the existence of energy ratio Kii / A
Yes, greater elasticity for smaller dielectric anisotropy
Effective when it has a constant.

The present invention has found that the driving voltage can be improved also by the elastic constant ratio K33 / K11.
In order to show this, a description will be given with reference to FIG. 2 showing the results of Examples described later. FIG. 2 shows threshold voltages V ₁₀ and K 33.
This shows the relationship of / K11. Elastic constant ratio K33 / K
It is clear that increasing 11 can improve the drive voltage. This means that in the formula (b), ¹ Kii = ΣaiKii approximately K33, and ² Kii = ΣbiKii approximately K11 can be arranged and rearranged in response to electrical operation. Guessed.

On the other hand, the formula (b) in the present invention brings about the following effects. The white turbidity and transparency, which are important for the contrast characteristics, are determined by the average void spacing <γ>, and therefore can be used without impairing the display characteristics.
However, the transparency T ₁₀₀ when a voltage is applied is better when the elastic constant, especially K 11, is small. In order to show this, explanation will be given in FIG. 3 by using the result of the embodiment of the present invention described later. FIG. 3 shows the relationship in which the transparency T ₁₀₀ decreases as the elastic constant K11 increases. This shows that as a method for improving the decrease in contrast ratio or the deterioration in haze value in a wide viewing angle, it is achieved by reducing the elastic constant K11.

As described in detail above, the light-scattering liquid crystal device according to the present invention is a liquid crystal composed of a specified weight ratio with respect to the dielectric anisotropy (Δε) of the liquid crystal compound constituting the liquid crystal material. By using the composition, a high resistance liquid crystal device can be obtained, and the dielectric anisotropy Δ of the liquid crystal composition can be obtained.
Even if ε is small, the elastic constant K11 of the liquid crystal composition is 5.0 to
15.0 Newton, elastic constant ratio K33 / K11 of 1.3-2.
A liquid crystal device characterized by being able to be driven at a low voltage and having a wide viewing angle and a high contrast is set to 5.

Further, particularly preferable liquid crystal materials used in the first liquid crystal device of the present invention are shown below. This is an excellent technique for obtaining the above-mentioned physical properties of the liquid crystal material, that is, the dielectric anisotropy and elastic constant.

That is, (1) the first compound group is represented by the general formula (I)

[0033]

[Chemical 19]

(In the formula, R ¹ represents a linear alkyl group having 2 to 7 carbon atoms, R ² represents a linear alkyl group or alkoxyl group having 2 to 7 carbon atoms, and X ¹ Represents a hydrogen atom or a methyl group) and a compound represented by the general formula (II)

[0035]

[Chemical 20]

(In the formula, R ³ represents a linear alkyl group having 2 to 7 carbon atoms, R ⁴ represents a linear alkyl group or alkoxyl group having 2 to 7 carbon atoms, and X ³ Represents a hydrogen atom or a methyl group, X ³ represents a single bond, —C
H ₂ CH ₂ - or represent -COO-. ) Containing a compound selected from the group consisting of compounds represented by

(2) The second compound group is represented by the general formula (III)

[0038]

[Chemical 21]

(In the formula, R ⁵ is a linear alkyl group having 2 to 7 carbon atoms, an alkenyl group or the general formula R ⁶ —O—
(CH _{2) n} - (wherein, R ⁶ represents a straight-chain alkyl group having 1 to 3 carbon atoms, n represents an integer of 1 to 5.)
Represents a group represented by and p represents 0 or 1. )
Containing a compound represented by

(3) The third compound group is represented by the general formula (IV)

[0041]

[Chemical formula 22]

(Wherein R ⁷ represents a linear alkyl group or an alkoxyl group having 2 to 5 carbon atoms, and X ⁴ represents a hydrogen atom or a fluorine atom), a general formula (V )

[0043]

[Chemical formula 23]

(Wherein R ⁸ represents a linear alkyl group or alkenyl group having 2 to 7 carbon atoms, and X ⁵ represents a hydrogen atom or a fluorine atom) and a compound represented by the general formula (VI )

[0045]

[Chemical formula 24]

(In the formula, R ⁹ is a linear alkyl group having 2 to 7 carbon atoms, an alkenyl group or the general formula R ¹⁰ —O—
(CH _{2) m} - (wherein, R ¹⁰ represents a linear alkyl group having 1 to 3 carbon atoms, m is an integer of 2-5.)
Represents a group represented by and q represents 0 or 1. )
A liquid crystal material containing a compound selected from the group consisting of compounds represented by

The liquid crystal compounds represented by the general formulas (I) and (II) used in the first compound group have a refractive index anisotropy Δ.
It has a large n and is chemically stable to light and heat, but the most important property is that it is useful for adjusting the ratio Kii / A of the elastic constant Kii and the anchoring energy A, and It has the effect of modifying the interface obtained by curing the forming resin, and thus the anchoring energy A
Has the property of acting to bring the value of to approach the elastic constant Kii of the liquid crystal material.

General formula (III) used for the second compound group
The liquid crystal compound represented by the formula (1) is chemically stable to light and heat, and is most suitable for adjusting the elastic constant Kii and the elastic constant ratio K33 / K11 of the liquid crystal composition. More specifically, a liquid crystal compound having a large elastic constant ratio K33 / K11 is selected by selecting a liquid crystal compound in which R ⁵ represents an alkenyl group, or a liquid crystal compound in which R ⁵ represents R ⁶ —O— (CH ₂ ) n —. By choosing, it is possible to design a liquid crystal composition having a small K11.

General formula (IV) to be used for the third compound group
The liquid crystal compound represented by (VI) is chemically stable to light and heat and has excellent compatibility with the polymer-forming resin. Especially, the temperature of the liquid crystal phase at high temperature of the liquid crystal composition is high. It is useful for adjusting the driving voltage by improving the range.

The present invention further provides a compound represented by the general formula (VII) as the first compound group in order to adjust the temperature range of the liquid crystal phase and the driving voltage of the above-mentioned liquid crystal composition.

[0051]

[Chemical 25]

(Wherein R ¹¹ and R ¹² each independently represents a straight-chain alkyl group or alkoxyl group having 1 to 7 carbon atoms) and the compound represented by the general formula (VI
II)

[0053]

[Chemical formula 26]

(Wherein R ¹³ and R ¹⁴ each independently represents a straight-chain alkyl or alkoxyl group having 1 to 7 carbon atoms), and a compound selected from the group consisting of ,

(2) The third compound group is represented by the general formula (IX)

[0056]

[Chemical 27]

(Wherein R ¹⁵ represents a linear alkyl group or an alkoxyl group having 2 to 5 carbon atoms) and the general formula (X).

[0058]

[Chemical 28]

(In the formula, ring A represents a 1,4-cyclohexylene group or a 1,4-phenylene group, and R ¹⁶ represents a linear alkyl group having 2 to 7 carbon atoms). By mixing the compounds, a more suitable liquid crystal device can be provided.

The compounds represented by the general formulas (VII) and (VIII) can improve the fast response and the operating temperature range at low temperature, and have high white turbidity despite a small Δn. The liquid crystal device shows unique characteristics that can be obtained. The compounds represented by the general formulas (IX) and (X) are useful for reducing the driving voltage unless they are used frequently.

Further, in order to solve the above problems, the present invention has a light control layer sandwiched between two transparent substrates having at least one having a transparent electrode layer, wherein the light control layer is a liquid crystal material. And a light-scattering liquid crystal device containing a transparent solid substance, wherein the liquid crystal material has the general formula (XI)

[0062]

[Chemical 29]

(In the formula, R ¹⁷ represents a linear alkyl group having 2 to 7 carbon atoms, R ¹⁸ represents a linear alkyl group or alkoxyl group having 1 to 7 carbon atoms, and R ¹⁷ And at least one of R ¹⁸ represents a straight-chain alkyl group having an odd number of carbon atoms or an alkoxyl group having an even number of carbon atoms, and X ⁶ represents a hydrogen atom or a methyl group. Formula (XII)

[0064]

[Chemical 30]

(Wherein R ¹⁹ represents a linear alkyl group having 2 to 7 carbon atoms, R ²⁰ represents a linear alkyl group or alkoxyl group having 1 to 7 carbon atoms, and R ¹⁹ And R ²⁰ at least one represents a linear alkyl group having an odd number of carbon atoms or an alkoxyl group having an even number of carbon atoms, X ⁷ represents a hydrogen atom or a methyl group, X ⁸ represents a single bond, —CH A compound selected from the group consisting of compounds represented by ₂ CH ₂ — or —COO—)
The liquid crystal material has a dielectric anisotropy Δε in the range of 5 to 17 and an elastic constant K11 of the liquid crystal material in the range of 5.0 to 15.0 Newton. A second liquid crystal device is provided in which the elastic constant ratio K33 / K11 of the material is in the range of 1.3 to 2.5.

This liquid crystal device makes the combination of the dielectric constant anisotropy and the elastic constant of the liquid crystal material more excellent by specifying the alkyl groups of the compounds of the general formulas (XI) and (XII), The above-mentioned problems have been solved. That is, in the compounds represented by the general formulas (XI) and (XII), (i) R ¹⁷ and R ¹⁹ are alkyl groups having an odd number of carbon atoms, and (ii) R ¹⁸ and R ²⁰ are odd number carbon atoms. By selectively frequently using a compound having a number of alkyl groups or an alkoxyl group of an even number of carbon atoms,
It has been found that a liquid crystal material can be obtained in which the elastic constant Kii shown in the formula (b) or the ratio thereof is useful.

The compounds represented by the general formula (XI) and the general formula (XII) are the same effects as the compounds represented by the general formula (I) and the general formula (II) related to the first liquid crystal device of the present invention. In the case of (i), it is particularly preferable that the number of carbon atoms is 3 or 5, and in the case of (ii), the number of carbon atoms is 1. A linear alkyl group having 3 or 5 or an alkoxyl group having 2 or 4 carbon atoms is particularly preferable.

As will be apparent from the examples described below, the composition ratio of the compounds of the general formulas (XI) and (XII) is preferably 15% by weight or more and 60% by weight or less.

Further, the second liquid crystal device of the present invention is
A liquid crystal material containing a compound represented by the general formula (XI) or (XII) has the general formula (XIII)

[0070]

[Chemical 31]

(In the formula, R ²¹ is a linear alkyl group having 2 to 7 carbon atoms, an alkenyl group or the general formula R ²² —O—
(CH _{2) s} - (wherein, R ²² represents a linear alkyl group having 1 to 3 carbon atoms, s represents an integer of 1 to 5.)
Represents a group represented by and r represents 0 or 1. )
A compound represented by the general formula (XIV)

[0072]

[Chemical 32]

(Wherein R ²³ represents a linear alkyl group or an alkoxyl group having 2 to 5 carbon atoms, and X ⁹ represents a hydrogen atom or a fluorine atom), a compound represented by the general formula (XV )

[0074]

[Chemical 33]

(Wherein R ²⁴ represents a linear alkyl group or alkenyl group having 2 to 7 carbon atoms, and X ¹⁰ represents a hydrogen atom or a fluorine atom), a compound represented by the general formula (XVI )

[0076]

[Chemical 34]

(In the formula, R ²⁵ is a linear alkyl group having 2 to 7 carbon atoms, an alkenyl group or a general formula R ²⁶ —O—
(CH _{2) u} - (wherein, R ²⁶ represents a linear alkyl group having 1 to 3 carbon atoms, u is an integer of 2-5.)
Represents a group represented by and t represents 0 or 1. )
Compounds selected from the group consisting of compounds represented by can be mixed and used. These compounds are represented by the general formulas (III) to (VI) related to the first liquid crystal device of the present invention.
It has the same effect as the compound of, and the total amount is 10
More preferably, the content is not less than 40% by weight.

The nematic liquid crystal composition according to the present invention is composed of the above-mentioned compounds, but other characteristics of the liquid crystal material, that is, the phase transition temperature between the isotropic liquid and the liquid crystal,
For the purpose of improving melting point, viscosity, Δn, solubility with a polymerizable composition and the like, and modification of the interface of a transparent solid substance,
A material generally recognized as a liquid crystal material in this technical field may be appropriately mixed. As such a liquid crystal, a nematic liquid crystal, a smectic liquid crystal and a cholesteric liquid crystal are preferable, and a nematic liquid crystal is particularly preferable.

The substrate used in the present invention may be a rigid material such as glass or metal, or a flexible material such as a plastic film. The two substrates are opposed to each other and are separated by an appropriate distance. Also, at least one of them
It has transparency, but complete transparency is not essential. If the liquid crystal device is used to act on light passing from one side of the device to the other, both substrates will be provided with appropriate transparency. Appropriate transparent or opaque electrodes may be provided on the entire surface or a part of the substrate depending on the purpose. It should be noted that a spacer for holding a space can be usually interposed between the two substrates, as in a known liquid crystal device. When the liquid crystal device of the present invention is used for a display device of a computer terminal, a display device of a projection or the like, it is preferable to provide a nonlinear element or an active element in the transparent electrode layer.

Typical structures of the liquid crystal material and the transparent solid substance in the liquid crystal device of the present invention are described below, but the liquid crystal device of the present invention is not limited to these.

(1) On a substrate having a transparent electrode layer, a layer having a uniform three-dimensional mesh-like transparent solid substance in a continuous layer of a liquid crystal material (hereinafter referred to as "PN-LC layer"), A liquid crystal device in which a transparent electrode layer and a substrate are sequentially laminated.

(2) P on the substrate having the transparent electrode layer
N-LC layer, liquid crystal layer (layer not containing transparent solid substance),
A liquid crystal device in which a transparent electrode layer and a substrate are sequentially laminated.

(3) On the substrate having the transparent electrode layer, P
A liquid crystal device in which an N-LC layer, a liquid crystal layer, a PN-LC layer, a transparent electrode layer, and a substrate are sequentially laminated.

These liquid crystal devices have a three-dimensional net-like solid substance that plays a role of causing optical scattering and sufficiently orienting the sandwiched liquid crystal material, and a light scattering opacity exhibited by the liquid crystal material. , A liquid crystal material that controls the transparency expressed by an electrical or thermal operation, and a structure characterized by separating the roles of the liquid crystal device from each other, thereby forming a material that constitutes the device. To improve the selectivity of the liquid crystal display device and further drastically improve the characteristics of the liquid crystal device.

That is, in these liquid crystal devices, the PN-LC layers facing each other or the layer between the PN-LC and the transparent electrode layer facing the PN-LC are in contact with each other without being structurally bonded except the sealing portion. Alternatively, it is essential to face each other at a certain distance. With this structure, it is possible to prevent the inclusion of bubbles in the liquid crystal layer when sandwiching the liquid crystal material,
The liquid crystal material can be sandwiched more easily and uniformly. In addition, it is possible to broaden the range of selection of materials without being caught by the difference in the coefficient of thermal expansion between the substrate and the three-dimensional mesh-like solid substance. It can play an important role in preventing the occurrence of cracks. The same applies to the following liquid crystal device.

(4) On the substrate having the transparent electrode layer, P
An N-LC layer, a liquid crystal layer, a vertical alignment layer, a transparent electrode layer, and a substrate are sequentially laminated, and liquid crystal molecules in the liquid crystal layer are randomly aligned on the PN-LC layer side, and the vertical alignment layer is formed. Liquid crystal device that is vertically aligned on the side.

(5) On a substrate having a transparent electrode layer, P
An N-LC layer, a liquid crystal layer, a horizontal alignment layer, a transparent electrode layer, and a substrate are sequentially laminated, and liquid crystal molecules are randomly aligned on the PN-LC layer side in the liquid crystal layer, and a vertical alignment layer. The liquid crystal device is horizontally aligned on the side.

The orientation of the liquid crystal molecules in the liquid crystal layer in these devices may be in a fixed direction, and may be in the middle between the vertical and horizontal directions.

Further, (6) the entire two light control layers having a transparent electrode layer and having a substrate feeling may be PN-LC layers.

When the average diameter of the shape of the three-dimensional network structure formed from the transparent solid substance in such a liquid crystal device is too large or too small as compared with the wavelength of light,
Since the light scattering property tends to deteriorate, the range of 0.2 to 2 μm is preferable. Also, the layer thickness of the PN-LC layer is in the range of 2 to 15 μm in order to obtain a sufficient contrast between the opacity due to light scattering and the transparency achieved electrically or thermally depending on the purpose of use. preferable. Substrate spacing is 2
The range of 30 μm is preferable, and the range of 5 to 20 μm is particularly preferable.

The liquid crystal composition according to the present invention is also useful for a device in which liquid crystal droplets in which a liquid crystal material is microencapsulated are dispersed in a transparent solid substance between two substrates having a transparent electrode layer. Is expected to be.

The transparent solid substance formed between the substrates may be a fibrous or particle-like dispersed substance or a film in which a liquid crystal material is dispersed in a droplet form, but has a three-dimensional network structure. It is more preferable to have Also,
It is preferable that the liquid crystal material forms a continuous layer, but it is essential for forming a disordered state of the liquid crystal material to form an optical boundary surface and to express light scattering.

Glass particles and synthetic resins are suitable as these transparent solid components. A thermosetting resin or an ultraviolet curable resin is preferable for dispersing the liquid crystal material in the form of droplets or providing a three-dimensional network structure. Also,
A synthetic resin soluble in an organic solvent and a synthetic resin soluble in water are also suitable.

Examples of the polymer-forming monomer that forms the transparent solid substance include styrene, chlorostyrene,
α-methylstyrene, divinylbenzene: As a substituent, methyl, ethyl, propyl, butyl, amyl, 2-
Ethylhexyl, octyl, nonyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, benzyl, methoxyethyl, butoxyethyl, phenoxyethyl, allyl, methallyl, glycidyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-chloro-2-hydroxypropyl, Acrylate, methacrylate or fumarate having a group such as dimethylaminoethyl, diethylaminoethyl and the like; ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-butylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, tri Mono (meth) acrylates such as methylolpropane, glycerin and pentaerythritol or poly (meth) acrylates ) Acrylate; vinyl acetate, vinyl butyrate or vinyl benzoate, acrylonitrile, cetyl vinyl ether, limonene, cyclohexene, diallyl phthalate, diallyl isophthalate, 2-, 3-
Or 4-vinyl pyridine, acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-hydroxymethyl acrylamide or N-hydroxyethyl methacrylamide and alkyl ether compounds thereof; 2 mol or more of ethylene oxide or propylene per mol of neopentyl glycol. Di (meth) acrylate of diol obtained by adding oxide; Di- or tri (meth) acrylate of triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane; Di (meth) acrylate of diol obtained by adding 2 mol or more of ethylene oxide or propylene oxide; 1 mol of 2-hydroxyethyl (meth) acrylate and phenol Le isocyanate or n-
The reaction product with 1 mol of butyl isocyanate; poly (meth) acrylate of dipentaerythritol and the like can be mentioned, but trimethylolpropane triacrylate, tricyclodecane dimethylol diacrylate,
Polyethylene glycol diacrylate, polypropylene glycol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tris- (acryloxyethyl) isocyanurate are particularly preferred.

Examples of the polymer-forming oligomer that forms the transparent solid substance include caprolactone-modified hydroxypivalic acid ester neopentyl glycol diacrylate.

Examples of the polymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one (“Darocur 1173” manufactured by Merck & Co., Inc.), 1-hydroxycyclohexylphenyl ketone (manufactured by Ciba Geigy Co., Ltd.). Irgacure 184 "), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-
On (Merck "Darocur 1116"), benzyl dimethyl ketal (Ciba Geigy "Irgacure 651"), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 (Ciba)・ Geigy's "Irgacure 907"), 2,4-diethylthioxanthone (Nippon Kayaku's "Kayacure DET"
X ”) and ethyl p-dimethylaminobenzoate (“ Kayacure EPA ”manufactured by Nippon Kayaku Co., Ltd.), isopropylthioxanthone (“ Cantacure ITX ”manufactured by Ward Prekinsop) and ethyl p-dimethylaminobenzoate. Examples thereof include a mixture and the like, and liquid 2-hydroxy-2-methyl-1-phenylpropan-1-one is particularly preferable in terms of compatibility with the liquid crystal material and the polymer-forming monomer or oligomer.

As a method for forming a layer containing a transparent solid substance having a uniform three-dimensional network structure on a substrate, for example, (1) a liquid crystal material and a polymer-forming monomer or oligomer A uniform solution of the photopolymerization initiator depending on the requirements, or (2) a uniform solution of the solvent and the polymer-forming monomer or oligomer and, if necessary, the photopolymerization initiator are provided on the two transparent electrode layers. It may be sandwiched between the substrates, or it may be coated on a substrate having one transparent electrode layer by using a coater such as a spin coater, and then the other auxiliary plate may be superposed, and is irradiated with ultraviolet rays. Alternatively, it is thermally polymerized and cured to form a three-dimensional mesh-like synthetic resin layer. Next, one of the two substrates sandwiching the transparent solid substance having the three-dimensional network structure thus obtained or the auxiliary plate is peeled off, and then the transparent solid having the three-dimensional network structure is obtained. The uncured monomer or oligomer, liquid crystal material, and solvent are washed and removed from the substance. If the release agent is applied on one of the substrates or the auxiliary plate in advance, the peeling step becomes easy.

The liquid crystal device of the present invention can be manufactured according to the following method, for example, using the substrate on which the layer having the uniform three-dimensional network solid substance obtained by the above method is formed.

That is, (1) a substrate having two transparent electrode layers in which at least one substrate has a layer having a uniform three-dimensional network solid substance on the transparent electrode layer is a known liquid crystal device. Similarly, they are laminated and fixed with a sealant to form a panel. A method of injecting a liquid crystal material by evacuating the inside of this panel in vacuum, immersing the liquid crystal injection port of this panel in the liquid crystal material, and then returning to normal atmospheric pressure, (2) a uniform tertiary layer on the transparent electrode layer. After applying the liquid crystal material on the substrate on which the layer having the original net-like solid substance is formed, the same substrate or a substrate having a normal transparent electrode layer is stacked and sufficiently degassed under reduced pressure in vacuum to remove both substrates. There is a method of manufacturing a liquid crystal device by fixing the periphery with a sealant.

With respect to the liquid crystal device manufactured as described above, the inventors of the present invention diligently studied the liquid crystal material and the transparent solid substance which compose the liquid crystal device utilizing the light scattering opaque state and the transparent state, and examined the dielectric property of the liquid crystal material. It is the result of finding that it can be improved by the combination of anisotropy and elastic constants, compared with the conventional light scattering type liquid crystal device,
It achieves the problems of low voltage drivability, high contrast ratio, and high retention ratio characteristics, and is useful for computer terminal display devices and projection display devices.

[0101]

EXAMPLES The present invention will now be described more specifically by showing examples of the present invention. Examples 1 to 22 and Comparative Examples 1 to 3 relate to the first liquid crystal device of the present invention, and Examples 23 to 33
Comparative Examples 4 and 5 relate to the second liquid crystal device of the present invention. However, the invention is not limited to these examples.

In the following Examples and Comparative Examples, "%" means "% by weight". Further, each of the evaluation characteristics in each example and comparative example means the following symbols and contents.

(1) V ₉₀ , V ₁₀ : transmittance when the light transmittance (T ₀ ) of the device when no voltage is applied is 0% and the light transmittance does not change as the applied voltage increases. (T ₁₀₀ )
Is set to 100%, the applied voltage (volt) at which the light transmittance is 90% is V ₉₀ , and the applied voltage at which the light transmittance is 10% is V ₁₀ .

(2) Contrast: With the device removed from the light metering state, the light transmittance of the light source is 100% when the light source is on, and the light transmittance is 0% when the light source is off, the device when no voltage is applied. Where T ₀ is the light transmittance of T ₀ and T ₉₀ is the light transmittance obtained when the applied voltage is V ₉₀ , contrast = T ₉₀ / T
Represented by ₁₀ .

(3) Response speed: ON from an applied voltage of 0V
When switching to the ON state, the time until the light transmittance reaches 90% is the rising time τ _r, and when switching from the ON state to 0 V, the time when the light transmittance reaches 10% is the falling time τ _d. As, by changing the voltage of the ON state,
The response speed is the time when τ _r = τ _d .

(4) Retention rate: A frame frequency of 60 Hz, a peak voltage V ₉₀ , a rectangular wave of 67 μsec in the ON state is applied, the electric charge accumulated in the ON state is Q ₀ , and the leakage current in the OFF state is high impedance. When measured with a voltmeter and the residual charge is Q, it is expressed as retention rate = (Q / Q ₀ ) × 100.

The V described in the physical properties of each composition
_th is the threshold voltage measured by the 8 μm TN-LCD.

(Example 1) "HX-620" (caprolactone-modified hydroxypivalic acid ester neopentyl glycol diacrylate manufactured by Nippon Kayaku Co., Ltd.) as a polymer-forming oligomer and 19.8% as a polymerization initiator.
Hydroxy-2-methyl-1-phenylpropane-1-
On% 0.2%, and the following liquid crystal composition (A) as a liquid crystal material
A light control layer forming material of a uniform solution mixed with 80% is sandwiched between two ITO glass plates of 5 × 5 cm in which a small amount of spacers having an average particle size of 10 μm are sprinkled on the transparent electrode layer and irradiated with ultraviolet rays, The molecule-forming oligomer was cured.

As curing conditions, a metal halide lamp (80 W / cm ² ) was passed under a speed of 3.5 m / min, and ultraviolet rays having an energy equivalent to 500 mJ / cm ² were irradiated.

When the light control layer of the obtained liquid crystal device was observed by a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device are
It was as follows. _{V 10: 6.7 V V 90:} 14.0 V T 0: 2.4% T 100: 82.1% _{Contrast: 1:34 τ r = τ d:} 11.0 ms retention: 85.6 %

[0111]

[Chemical 35]

Physical Properties of Liquid Crystal Composition (A): Transition Temperature T _NI = 80.1 ° C. Refractive Index Δn = 0.194 Dielectric Constant Δε = 16.4 Threshold Voltage V _th = 1.51 V Elastic Constant K 11 = 9.0 x 10 ^-12 Newton K33 = 18.3 x 10 ^-12 Newton K33 / K11 = 2.03

(Example 2) "HX-620" (caprolactone-modified hydroxypivalic acid ester neopentyl glycol diacrylate manufactured by Nippon Kayaku Co., Ltd.) as a polymer-forming oligomer 19.8%, and 2- as a polymerization initiator
Hydroxy-2-methyl-1-phenylpropane-1-
ON 0.2%, and the following liquid crystal composition (XVI
I) A polycarbonate solution plate (made by Mitsubishi Gas Chemical Co., Ltd.) of the same size as a 5 × 5 cm ITO glass plate in which a small amount of spacers having an average particle size of 10 μm are dispersed on a transparent electrode layer with a uniform solution of a dimming control material mixed with 80%. It was sandwiched between "Iupilon") and irradiated with ultraviolet rays from the ITO glass plate side to cure the polymer-forming oligomer.

The curing conditions are as follows: pass under a metal halide lamp (80 W / cm ² ) at a speed of 3.5 m / min,
It was irradiated with ultraviolet light having an energy equivalent to 500 mJ / cm ² . When a cross section of the cured product formed between the substrates was observed with a scanning electron microscope, a three-dimensional network structure of the transparent polymer was recognized.

The ITO glass plate obtained by peeling off the polycarbonate plate from the UV-irradiated product and having the three-dimensional network solid substance uniformly attached thereto was dipped in ethanol and subjected to an ultrasonic cleaning step, followed by vacuum heating and drying. It was

An ITO glass plate on which this three-dimensional mesh-like solid substance was evenly attached and an ITO glass plate of 5 × 5 cm were bonded together, and “DSA-001” (Epoxy resin manufactured by Rodik Co.) was used as a sealant. It was immobilized and an empty cell was prepared.
This cell was placed under vacuum pressure reduction, and the injection port was set to the liquid crystal (A)
Then, the liquid crystal device of the present invention was obtained by returning to normal atmospheric pressure. The characteristics of the obtained liquid crystal device were as follows. V ₁₀ : 3.6 V V ₉₀ : 15.7 V T ₀ : 5.7% T ₁₀₀ : 83.1% Contrast: 1:15 τ _r = τ _d : 6.6 ms Retention rate: 96.5 %

[0117]

[Chemical 36]

Physical Properties of Liquid Crystal Composition (XVII): Transition Temperature 68.5 ° C. (NI) Refractive Index Δn = 0.254 Dielectric Constant Δε = 26.9

Example 3 A liquid crystal device of the present invention was obtained in the same manner as in Example 1 except that the following liquid crystal composition (B) was used instead of the liquid crystal composition (A). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. _{V 10: 6.7 V V 90:} 14.9 V T 0: 1.2% T 100: 81.9% _{Contrast: 1:68 τ r = τ d:} 10.0 ms retention: 89.7 %

[0120]

[Chemical 37]

Physical Properties of Liquid Crystal Composition (B): Transition Temperature T _NI = 63.1 ° C. Refractive Index Δn = 0.202 Dielectric Constant Δε = 11.9 Threshold Voltage V _th = 1.47 V Elastic Constant K11 = 8.3 × 10 ^-12 Newton K33 = 14.6 × 10 ^-12 Newton K33 / K11 = 1.77

Example 4 A liquid crystal device of the present invention was obtained in the same manner as in Example 1 except that the following liquid crystal composition (C) was used instead of the liquid crystal composition (A). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. V ₁₀ : 7.1 V V ₉₀ : 16.3 V T ₀ : 2.8% T ₁₀₀ : 81.6% Contrast: 1:29 τ _r = τ _d : 10. 3 ms Retention rate: 85.6 %

[0123]

[Chemical 38]

[0124] Physical properties of liquid crystal composition (C): transition temperature T _NI = 69.9 ° C. refractive index [Delta] n = 0.194 Dielectric constant [Delta] [epsilon] = 12.6 threshold voltage V _th = 1.50 V elastic constant K11 = 9.3 × 10 ^-12 Newton K33 = 14.9 × 10 ^-12 Newton K33 / K11 = 1.60

Example 5 A liquid crystal device of the present invention was obtained in the same manner as in Example 1 except that the following liquid crystal composition (D) was used instead of the liquid crystal composition (A). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. _{V 10: 6.2 V V 90:} 14.0 V T 0: 1.4% T 100: 82.6% _{Contrast: 1:59 τ r = τ d:} 9.8 ms retention: 84.3 %

[0126]

[Chemical Formula 39]

Physical Properties of Liquid Crystal Composition (D): Transition Temperature T _NI = 58.7 ° C. Refractive Index Δn = 0.198 Dielectric Constant Δε = 12.7 Threshold Voltage V _th = 1.37 V Elastic Constant K11 = 7.2 x 10 ^-12 Newton K33 = 14.4 x 10 ^-12 Newton K33 / K11 = 2.01

Example 6 A liquid crystal device of the present invention was obtained in the same manner as in Example 1 except that the following liquid crystal composition (E) was used instead of the liquid crystal composition (A). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. _{V 10: 5.8 V V 90:} 12.6 V T 0: 1.4% T 100: 82.1% _{Contrast: 1:59 τ r = τ d:} 9.9 ms retention: 85.3 %

[0129]

[Chemical 40]

Physical Properties of Liquid Crystal Composition (E): Transition Temperature _TNI = 62.9 ° C. Refractive Index Δn = 0.195 Dielectric Constant Δε = 14.9 Threshold Voltage _Vth = 1.27 V Elastic Constant K11 = 8.6 × 10 ^-12 Newton K33 = 15.7 × 10 ^-12 Newton K33 / K11 = 1.84

Example 7 A liquid crystal device of the present invention was obtained in the same manner as in Example 1 except that the following liquid crystal composition (F) was used instead of the liquid crystal composition (A). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. V ₁₀ : 6.0 V V ₉₀ : 15.0 V T ₀ : 3.5% T ₁₀₀ : 82.4% Contrast: 1:24 τ _r = τ _d : 10. 3 ms Retention rate: 92.5 %

[0132]

[Chemical 41]

Physical Properties of Liquid Crystal Composition (F): Transition Temperature T _NI = 70.3 ° C. Refractive Index Δn = 0.197 Dielectric Constant Δε = 13.4 Threshold Voltage V _th = 1.45 V Elastic Constant K11 = 9.2 x 10 ^-12 Newton K33 = 18.3 x 10 ^-12 Newton K33 / K11 = 1.98

Example 8 A liquid crystal device of the present invention was obtained in the same manner as in Example 1 except that the following liquid crystal composition (G) was used instead of the liquid crystal composition (A). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. _{V 10: 7.9 V V 90:} 14.9 V T 0: 3.0% T 100: 81.4% _{Contrast: 1:27 τ r = τ d:} 11.6 ms retention: 89.7 %

[0135]

[Chemical 42]

Physical Properties of Liquid Crystal Composition (G): Transition Temperature T _NI = 73.1 ° C. Refractive Index Δn = 0.194 Dielectric Constant Δε = 11.3 Threshold Voltage V _th = 1.54 V Elastic Constant K11 = 9.7 x 10 ^-12 Newton K33 = 14.8 x 10 ^-12 Newton K33 / K11 = 1.53

Example 9 A liquid crystal device of the present invention was obtained in the same manner as in Example 1 except that the following liquid crystal composition (H) was used in place of the liquid crystal composition (A). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. _{V 10: 5.9 V V 90:} 16.3 V T 0: 1.9% T 100: 80.2% _{Contrast: 1:42 τ r = τ d:} 9.9 ms retention: 88.9 %

[0138]

[Chemical 43]

Physical Properties of Liquid Crystal Composition (H): Transition Temperature _TNI = 77.5 ° C. Refractive Index Δn = 0.196 Dielectric Constant Δε = 16.9 Threshold Voltage _Vth = 1.37 V Elastic Constant K11 = 9.0 x 10 ^-12 Newton K33 = 18.2 x 10 ^-12 Newton K33 / K11 = 2.03

Example 10 A liquid crystal device of the present invention was obtained in the same manner as in Example 1 except that the following liquid crystal composition (I) was used in place of the liquid crystal composition (A). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows.

V ₁₀ : 6.1 V V ₉₀ : 13.4 V T ₀ : 1.4% T ₁₀₀ : 80.9% Contrast: 1:58 τ _r = τ _d : 12.0 ms Retention rate: 89.7%

[0142]

[Chemical 44]

Physical Properties of Liquid Crystal Composition (I): Transition Temperature T _NI = 67.6 ° C. Refractive Index Δn = 0.200 Dielectric Constant Δε = 14.9 Threshold Voltage V _th = 1.39 V Elastic Constant K11 = 8.4 × 10 ^-12 Newton K33 = 16.1 × 10 ^-12 Newton K33 / K11 = 1.91

(Example 11) A liquid crystal device of the present invention was obtained in the same manner as in Example 1 except that the following liquid crystal composition (J) was used in place of the liquid crystal composition (A). When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows.

V ₁₀ : 7.8 V V ₉₀ : 16.5 V T ₀ : 1.4% T ₁₀₀ : 82.4% Contrast: 1:59 τ _r = τ _d : 11.0 ms Retention rate: 88.3%

[0146]

[Chemical formula 45]

Physical Properties of Liquid Crystal Composition (J): Transition Temperature _TNI = 60.1 ° C. Refractive Index Δn = 0.188 Dielectric Constant Δε = 12.0 Threshold Voltage _Vth = 1.36 V Elastic Constant K11 = 8.0 × 10 ^-12 Newton K33 = 10.8 × 10 ^-12 Newton K33 / K11 = 1.35

Example 12 A liquid crystal device of the present invention was obtained in the same manner as in Example 1 except that the following liquid crystal composition (K) was used instead of the liquid crystal composition (A). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. V ₁₀ : 4.7 V V ₉₀ : 16.0 V T ₀ : 2.8% T ₁₀₀ : 80.5% Contrast: 1:29 τ _r = τ _d : 10.9 milliseconds Retention rate: 84.0 %

[0149]

[Chemical formula 46]

Physical Properties of Liquid Crystal Composition (K): Transition Temperature _TNI = 81.9 ° C. Refractive Index Δn = 0.189 Dielectric Constant Δε = 16.8 Threshold Voltage _Vth = 1.46 V Elastic Constant K11 = 10.1 x 10 ^-12 Newton K33 = 22.1 x 10 ^-12 Newton K33 / K11 = 2.19

(Example 13) A liquid crystal device of the present invention was obtained in the same manner as in Example 1 except that the following liquid crystal composition (L) was used in place of the liquid crystal composition (A). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. _{V 10: 8.1 V V 90:} 16.3 V T 0: 2.6% T 100: 83.1% _{Contrast: 1:32 τ r = τ d:} 8.9 ms retention: 95.0 %

[0152]

[Chemical 47]

Physical Properties of Liquid Crystal Composition (L): Transition Temperature T _NI = 50.0 ° C. Refractive Index Δn = 0.170 Dielectric Constant Δε = 8.2 Threshold Voltage V _th = 1.57 V Elastic Constant K11 = 6.7 × 10 ^-12 Newton K33 = 10.3 × 10 ^-12 Newton K33 / K11 = 1.54

(Embodiment 14) FIG. 1 is a graph in which the change of the driving voltage with respect to the increase of the elastic constant in the equation (b) is calculated and is plotted. Here, the average amount of the gaps γ between the surfaces of the transparent solid material formed in a three-dimensional mesh is set to an average gap distance <γ> = 1 μm, the distance d between the substrates having transparent electrodes is 10 μm, and the elastic constant is Kii = kii × 10
^-12 Newton, the anchoring energy A = A × 10 ^-6 Ne
The dimensionless kii, A was used as wton / μm. In the figure, (1-1) shows the dielectric anisotropy Δε = 16 and the ratio of the elastic constant and the anchoring energy is Kii / A = 0.01 × kii.
What is [μm] (A = 10 ⁻⁴ ), (1-2) is
Δε = 10, Kii / A = 0.1 × kii [μm] (A = 10
^-5 ), and Δε = 20 as a comparative example,
The value of Kii / A ≦ 0.001 × kii [μm] (A ≧ 10 ⁻³ ) is represented by (1-ratio). As is clear from the results shown in FIG. 1, even if the dielectric anisotropy is small, the drive voltage can be reduced by the existence of the ratio Kii / A of the elastic constant and the anchoring energy. Is effective when it has a larger elastic constant.

FIG. 2 shows the relationship between the elastic constant ratio K33 / K11 and the threshold voltage V ₁₀ of the light scattering type liquid crystal device using the results of Example 1 and Examples 3 to 13.
From this, it can be understood that the drive voltage can be improved by increasing K33 / K11. Using this result, equation (b)
The content of the elastic constant of is ¹ Kii = ΣaiKii approximately K33
It is presumed that the liquid crystal molecules are rearranged so that ² Kii = ΣbiKii approximately becomes K11 and that the liquid crystal molecules are rearranged in response to electrical operation.

FIG. 3 shows the relationship between the transparency T ₁₀₀ and the elastic constant K 11 when a voltage is applied, using the results of Example 1 and Examples 3 to 13. The white turbidity and the transparency, which are important for the contrast characteristics, are the birefringence index Δn of the liquid crystal material when the transparent solid substance is formed into a three-dimensional network.
It is known that it is determined by the average void spacing <γ>. However, from FIG. 3, the transparency T when voltage is applied
It was found that ₁₀₀ also depends on the elastic constant, and it was revealed that the one with a smaller K11 was more excellent. This shows that as a method for improving the decrease in contrast ratio or the deterioration in haze value in a wide viewing angle, it is achieved by reducing the elastic constant K11.

FIG. 4 shows the relationship between the right side of the formula (b) according to the present invention and the threshold voltage V ₁₀ of the light scattering type liquid crystal device, using the results of Example 1 and Examples 3 to 13. It is a thing. Here, the average void spacing <γ> was 1 μm, the distance d between the substrates having transparent electrodes was 10 μm, and the anchoring energy was A = 10 ⁻⁴ Newton / m. On the other hand, FIG.
FIG. 4 shows the relationship between the right side of the conventionally described formula (a) and the threshold voltage V ₁₀ of the light scattering type liquid crystal device, using the results of Example 1 and Examples 3 to 13. Similarly, FIG. 6 shows the relationship between the right side of the formula (a) and the threshold voltage V _th of the TN-LCD using the polarizing plate other than the present invention. Here, Kii is (K11 + 1 / 4K3
3)

Comparing FIG. 4 and FIG. 5, the electro-optical characteristics of the liquid crystal device according to the present invention can be found from the equation (a) to the equation (b).
It turns out that the relationship is more effective. That is, by positively utilizing this effect, it is possible to reduce the driving voltage and improve the holding ratio, which are in a trade-off relationship. Further, from FIG. 6, the liquid crystal composition according to the present invention does not have a special relation of the dielectric anisotropy and elastic constants related to the known TN-LCD.
Therefore, it can be said that this known technique has an unexpected effect that cannot be easily analogized to the effect of the present invention.

Example 15 A liquid crystal device of the present invention was obtained in the same manner as in Example 1 except that spacers having an average particle size of 14 μm were used. When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope,
A three-dimensional mesh-like transparent polymer substance was confirmed. The response speed of the obtained liquid crystal device and the device using the average particle diameter of 10 μm of Example 1 due to temperature change were measured. The results were as follows. From this, it was found that the light-scattering liquid crystal device of the present invention does not exhibit the response characteristics (the response speed proportional to the square of the distance between the electrodes) represented by the known TN-LCD.

Τ _r = τ _d measurement temperature of liquid crystal device using spacer having average particle diameter of 14 μm 20 ° C .: 8.0 ms 0 ° C .: 38.4 ms −20 ° C .: 750 ms

Τ _r = τ _d measurement temperature of the liquid crystal device of Example 1 using spacers having an average particle diameter of 10 μm 20 ° C .: 11.0 milliseconds 0 ° C .: 51.3 milliseconds −20 ° C .: 1040 milliseconds

Example 16 A liquid crystal device of the present invention was obtained in the same manner as in Example 1 except that the liquid crystal composition (A) was replaced with the following liquid crystal composition (M). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. V ₁₀ : 5.9 V V ₉₀ : 9.1 V T ₀ : 2.9% T ₁₀₀ : 82.0% Contrast: 1:28 τ _r = τ _d : 10. 3 ms Retention rate: 83.9 %

[0163]

[Chemical 48]

Physical Properties of Liquid Crystal Composition (M): Transition Temperature T _NI = 76.1 ° C. Refractive Index Δn = 0.209 Dielectric Constant Δε = 13.6 Threshold Voltage V _th = 1.52 V Elastic Constant K11 = 9.6 x 10 ^-12 Newton K33 = 18.4 x 10 ^-12 Newton K33 / K11 = 1.92

Example 17 A liquid crystal device of the present invention was obtained in the same manner as in Example 1 except that the following liquid crystal composition (N) was used instead of the liquid crystal composition (A). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. V ₁₀ : 5.1 V V ₉₀ : 10.8 V T ₀ : 3.2% T ₁₀₀ : 82.8% Contrast: 1:26 τ _r = τ _d : 11.3 milliseconds Retention rate: 86.9 %

[0166]

[Chemical 49]

Physical Properties of Liquid Crystal Composition (N): Transition Temperature T _NI = 74.0 ° C. Refractive Index Δn = 0.201 Dielectric Constant Δε = 10.5 Threshold Voltage V _th = 1.66 V Elastic Constant K11 = 7.4 x 10 ^-12 Newton K33 = 18.4 x 10 ^-12 Newton K33 / K11 = 2.48

(Example 18) A liquid crystal device of the present invention was obtained in the same manner as in Example 1 except that the following liquid crystal composition (O) was used in place of the liquid crystal composition (A). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. V ₁₀ : 5.3 V V ₉₀ : 9.9 V T ₀ : 3.8% T ₁₀₀ : 83.5% Contrast: 1:22 τ _r = τ _d : 12.1 milliseconds Retention rate: 85.0 %

[0169]

[Chemical 50]

Physical Properties of Liquid Crystal Composition (O): Transition Temperature T _NI = 66.9 ° C. Refractive Index Δn = 0.189 Dielectric Constant Δε = 11.0 Threshold Voltage V _th = 1.58 V Elastic Constant K 11 = 7.0 x 10 ^-12 Newton K33 = 14.7 x 10 ^-12 Newton K33 / K11 = 2.10

Example 19 A liquid crystal device of the present invention was obtained in the same manner as in Example 1 except that the following liquid crystal composition (P) was used instead of the liquid crystal composition (A). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were excellent with V ₁₀ of 4.0 V and a retention rate of 85.0%.

[0172]

[Chemical 51]

Physical Properties of Liquid Crystal Composition (P): Transition Temperature T _NI = 97.4 ° C. Refractive Index Δn = 0.174 Dielectric Constant Δε = 14.0 Threshold Voltage V _th = 1.57 V

(Example 20) A liquid crystal device of the present invention was obtained in the same manner as in Example 1 except that the following liquid crystal composition (Q) was used in place of the liquid crystal composition (A). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were excellent with low V ₁₀ and high retention.

[0175]

[Chemical 52]

Physical Properties of Liquid Crystal Composition (Q): Transition Temperature T _NI = 70.9 ° C. Refractive Index Δn = 0.220 Dielectric Constant Δε = 15.7

(Example 21) A liquid crystal device of the present invention was obtained in the same manner as in Example 1 except that the following liquid crystal composition (R) was used in place of the liquid crystal composition (A). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were excellent with low V ₁₀ and high retention.

[0178]

[Chemical 53]

Physical Properties of Liquid Crystal Composition (R): Transition Temperature T _NI = 72.8 ° C. Refractive Index Δn = 0.219 Dielectric Constant Δε = 13.7

(Example 22) A liquid crystal device of the present invention was obtained in the same manner as in Example 1 except that the following liquid crystal composition (S) was used in place of the liquid crystal composition (A). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were excellent with low V ₁₀ and high retention.

[0181]

[Chemical 54]

Physical Properties of Liquid Crystal Composition (S): Transition Temperature T _NI = 80.8 ° C. Refractive Index Δn = 0.201 Dielectric Constant Δε = 12.5

(Comparative Example 1) In the same manner as in Example 1, except that the following liquid crystal composition (e) other than the present invention was used in place of the liquid crystal composition (A) in Example 1, the results other than the present invention were obtained. A liquid crystal device was obtained. When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. V ₁₀ : 41.8 V V ₉₀ : 74.4 V T ₀ : 44.8% T ₁₀₀ : 86.6% Contrast: 1: 2 τ _r = τ _d : 18.0 ms Retention rate: High drive voltage Cannot be measured with own device because of

The liquid crystal composition (e) does not contain the liquid crystal compounds represented by the general formulas (I) and (II) as the first component according to the present invention, and the second component as the general formula (III). Of the liquid crystal compounds of ⁵ are compounds in which R ⁵ represents an alkyl group, which has a poor effect of optimizing the elastic constant.
It is a high content of 0%.

Therefore, this device cannot solve the problems to be used for the screen for blocking the visual field, the computer, and the display device for the projection because the driving voltage is high and the contrast is poor.

[0186]

[Chemical 55]

Physical Properties of Liquid Crystal Composition (e): Transition Temperature T _NI = 99.0 ° C. Refractive Index Δn = 0.113 Dielectric Constant Δε = 11.4

(Comparative Example 2) In the same manner as in Example 1 except that the following liquid crystal composition (f) other than the present invention was used in place of the liquid crystal composition (A) in Example 1, the results other than the present invention were obtained. A liquid crystal device was obtained. When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. V ₁₀ : 8.9 V V ₉₀ : 17.9 V T ₀ : 1.8% T ₁₀₀ : 81.1% Contrast: 1:45 τ _r = τ _d : 13.0 milliseconds Retention rate: 18.0 %

The liquid crystal composition (f) does not contain the liquid crystal compound represented by the general formula (III) as the second component according to the present invention, and the third component has a large dielectric anisotropy and a high retention rate. General formula (IX) having a property of poor improvement effect
The liquid crystal compound (1) is contained as much as 50%.

Therefore, the resistance value and the voltage holding ratio of this liquid crystal device are not improved, and the problem to be applied to the display device of the computer and the projection, which is characterized in that the nonlinear electrode or the active element is provided in the transparent electrode layer, is solved. It does not lead to.

[0191]

[Chemical 56]

Physical Properties of Liquid Crystal Composition (f): Transition Temperature T _NI = 70.1 ° C. Refractive Index Δn = 0.224 Dielectric Constant Δε = 12.8 Threshold Voltage V _th = 1.39 V

(Comparative Example 3) In the same manner as in Example 1, except that the following liquid crystal composition (g) other than the present invention was used in place of the liquid crystal composition (A) in Example 1, the results other than those of the present invention were obtained. A liquid crystal device was obtained. When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. _{V 10: 6.8 V V 90:} 12.2 V T 0: 1.7% T 100: 82.6% _{Contrast: 1:49 τ r = τ d:} 10.0 ms retention: 10.3 %

The liquid crystal composition (g) does not contain the liquid crystal compound represented by the general formula (III) as the second component according to the present invention, and the third component has a large dielectric anisotropy and a high retention rate. A large amount of pyridine-based liquid crystal compound having a property of poor improvement effect is contained at 50%. Therefore, the resistance value and the voltage holding ratio of the liquid crystal device are not improved, and the problem to be solved for use in a display device for a computer or a projection, which is characterized by providing a non-linear element or an active element in a transparent electrode layer, has been solved. There is no such thing.

[0195]

[Chemical 57]

Physical Properties of Liquid Crystal Composition (g): Transition Temperature T _NI = 67.5 ° C. Refractive Index Δn = 0.233 Dielectric Constant Δε = 12.7 Threshold Voltage V _th = 1.35 V

The characteristics of the liquid crystal devices in the above-mentioned Examples and Comparative Examples are shown in Tables 1 and 2 below.

[0198]

[Table 1]

[0199]

[Table 2]

(Example 23) "HX-620" (caprolactone-modified hydroxypivalic acid ester neopentyl glycol diacrylate manufactured by Nippon Kayaku Co., Ltd.) as a polymer-forming oligomer 19.8%, and a polymerization initiator 2-
Hydroxy-2-methyl-1-phenylpropane-1-
ON of 0.2% and the following liquid crystal composition (T) 80% as a liquid crystal material, a uniform solution of the light control layer forming material,
A spacer having an average particle diameter of 10 μm was sandwiched between two ITO glass plates having a size of 5 × 5 cm and a small amount of which was scattered on the transparent electrode layer, and ultraviolet rays were irradiated to cure the polymer-forming oligomer. Curing conditions are metal halide lamp (80W / c
m ² ), at a speed of 3.5 m / min, 500 mJ
It was irradiated with ultraviolet light having an energy equivalent to / cm ² .

When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device are
It was as follows. V ₁₀ : 3.7 V V ₉₀ : 8.2 V T ₀ : 1.8% T ₁₀₀ : 82.8% Contrast: 1:46 τ _r = τ _d : 11.0 ms Retention rate: 91.8 %

[0202]

[Chemical 58]

Physical Properties of Liquid Crystal Composition (T): Transition Temperature T _NI = 70.4 ° C. Refractive Index Δn = 0.222 Dielectric Constant Δε = 15.5 Threshold Voltage V _th = 1.37 V Elastic Constant K 11 = 8 .2 × 10 ^-12 Newton K33 = 16.4 × 10 ^-12 Newton K33 / K11 = 2.00

Example 24 A liquid crystal device of the present invention was obtained in the same manner as in Example 23 except that the following liquid crystal composition (U) was used instead of the liquid crystal composition (T). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. V ₁₀ : 3.9 V V ₉₀ : 7.1 V T ₀ : 2.1% T ₁₀₀ : 81.9% Contrast: 1:39 τ _r = τ _d : 10.0 milliseconds Retention rate: 89.2 %

[0205]

[Chemical 59]

Physical Properties of Liquid Crystal Composition (U): Transition Temperature T _NI = 67.7 ° C. Refractive Index Δn = 0.210 Dielectric Constant Δε = 15.1 Threshold Voltage V _th = 1.31 V Elastic Constant K 11 = 8 .4 × 10 ^-12 Newton K33 = 16.1 × 10 ^-12 Newton K33 / K11 = 1.92

(Example 25) A liquid crystal device of the present invention was obtained in the same manner as in Example 23 except that the liquid crystal composition (V) shown below was used in place of the liquid crystal composition (T). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. V ₁₀ : 3.8 V V ₉₀ : 8.0 V T ₀ : 1.6% T ₁₀₀ : 83.2% Contrast: 1:52 τ _r = τ _d : 10. 3 ms Retention rate: 89.7 %

[0208]

[Chemical 60]

Physical Properties of Liquid Crystal Composition (V): Transition Temperature _TNI = 70.3 ° C. Refractive Index Δn = 0.216 Dielectric Constant Δε = 15.2 Threshold Voltage _Vth = 1.35V Elastic Constant K11 = 8 .5 × 10 ^-12 Newton K33 = 15.4 × 10 ^-12 Newton K33 / K11 = 1.82

(Example 26) A liquid crystal device of the present invention was obtained in the same manner as in Example 23 except that the liquid crystal composition (W) shown below was used in place of the liquid crystal composition (T). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. V ₁₀ : 4.0 V V ₉₀ : 8.4 V T ₀ : 2.8% T ₁₀₀ : 81.9% Contrast: 1:29 τ _r = τ _d : 18.0 milliseconds Retention rate: 93.3 %

[0211]

[Chemical formula 61]

Physical Properties of Liquid Crystal Composition (W): Transition Temperature T _NI = 64.7 ° C. Refractive Index Δn = 0.202 Dielectric Constant Δε = 14.2

(Example 27) A liquid crystal device of the present invention was obtained in the same manner as in Example 23 except that the liquid crystal composition (X) was used instead of the liquid crystal composition (T). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. V ₁₀ : 3.8 V V ₉₀ : 7.8 V T ₀ : 4.3% T ₁₀₀ : 82.4% Contrast: 1:19 τ _r = τ _d : 13.0 ms Retention rate: 93.3 %

[0214]

[Chemical formula 62]

Physical Properties of Liquid Crystal Composition (X): Transition Temperature T _NI = 65.7 ° C. Refractive Index Δn = 0.199 Dielectric Constant Δε = 14.3 Threshold Voltage V _th = 1.30 V

Example 28 A liquid crystal device of the present invention was obtained in the same manner as in Example 23 except that the liquid crystal composition (Y) shown below was used instead of the liquid crystal composition (T). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. V ₁₀ : 3.2 V V ₉₀ : 7.6 V T ₀ : 2.0% T ₁₀₀ : 81.4% Contrast: 1:40 τ _r = τ _d : 10.0 milliseconds Retention rate: 85.0 %

[0217]

[Chemical formula 63]

Physical Properties of Liquid Crystal Composition (Y): Transition Temperature T _NI = 66.6 ° C. Refractive Index Δn = 0.211 Dielectric Constant Δε = 15.6 Threshold Voltage V _th = 1.30 V

(Example 29) A liquid crystal device of the present invention was obtained in the same manner as in Example 23 except that the liquid crystal composition (Z) shown below was used in place of the liquid crystal composition (T). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. V ₁₀ : 3.0 V V ₉₀ : 6.6 V T ₀ : 4.1% T ₁₀₀ : 82.1% Contrast: 1:20 τ _r = τ _d : 10.0 milliseconds Retention rate: 86.6 %

[0220]

[Chemical 64]

Physical Properties of Liquid Crystal Composition (Z): Transition Temperature T _NI = 62.2 ° C. Refractive Index Δn = 0.206 Dielectric Constant Δε = 14.2 Threshold Voltage V _th = 1.28 V

(Example 30) A liquid crystal device of the present invention was obtained in the same manner as in Example 23 except that the liquid crystal composition (AA) described below was used instead of the liquid crystal composition (T). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. V ₁₀ : 4.0 V V ₉₀ : 7.8 V T ₀ : 4.6% T ₁₀₀ : 82.6% Contrast: 1:18 τ _r = τ _d : 10.0 ms Retention rate: 93.3 %

[0223]

[Chemical 65]

Physical Properties of Liquid Crystal Composition (AA): Transition Temperature T _NI = 65.5 ° C. Refractive Index Δn = 0.199 Dielectric Constant Δε = 14.4 Threshold Voltage V _th = 1.30V

(Comparative Example 4) A device other than the present invention was obtained in the same manner as in Example 23 except that the following liquid crystal composition (h) was used in place of the liquid crystal composition (T). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. V ₁₀ : 3.0 V V ₉₀ : 6.6 V T ₀ : 5.9% T ₁₀₀ : 83.1% Contrast: 1:14 τ _r = τ _d : 10.0 milliseconds Retention rate: 83.5 %

Since this device has a poor contrast, it has not been possible to solve the problem of using it for a screen for blocking a visual field, a computer, and a display device for projection.

[0227]

[Chemical formula 66]

Physical Properties of Liquid Crystal Composition (h): Transition Temperature T _NI = 57.7 ° C. Refractive Index Δn = 0.198 Dielectric Constant Δε = 13.2 Threshold Voltage V _th = 1.18 V

(Comparative Example 5) A device other than the present invention was obtained in the same manner as in Example 23 except that the liquid crystal composition (i) shown below was used instead of the liquid crystal composition (T). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. V ₁₀ : 3.7 V V ₉₀ : 7.3 V T ₀ : 4.9% T ₁₀₀ : 83.3% Contrast: 1:17 τ _r = τ _d : 10.0 milliseconds Retention rate: 81.3 %

Since this device has a poor contrast, it has not been possible to solve the problem of using it for a screen for blocking a visual field, a computer, and a display device for projection.

[0231]

[Chemical formula 67]

Physical Properties of Liquid Crystal Composition (i): Transition Temperature T _NI = 63.1 ° C. Refractive Index Δn = 0.193 Dielectric Constant Δε = 14.8 Threshold Voltage V _th = 1.27 V (Example 31) In Example 23, the liquid crystal composition (T)
A liquid crystal device of the present invention was obtained in the same manner as in Example 1 except that the following liquid crystal composition (AB) was used instead. When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. V ₁₀ : 3.5 V V ₉₀ : 7.5 V T ₀ : 3.2% T ₁₀₀ : 81.9% Contrast: 1:26 τ _r = τ _d : 10.0 milliseconds Retention rate: 97.0 %

[0233]

[Chemical 68]

Physical Properties of Liquid Crystal Composition (AB): Transition Temperature T _NI = 86.7 ° C. Refractive Index Δn = 0.217 Dielectric Constant Δε = 13.3 Threshold Voltage V _th = 1.67 V

Example 32 A liquid crystal device of the present invention was obtained in the same manner as in Example 23 except that the liquid crystal composition (T) was replaced with the following liquid crystal composition (AC). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. V ₁₀ : 3.8 V V ₉₀ : 7.8 V T ₀ : 1.2% T ₁₀₀ : 81.9% Contrast: 1:68 τ _r = τ _d : 10.0 milliseconds Retention rate: 95.0 %

[0236]

[Chemical 69]

Physical Properties of Liquid Crystal Composition (AC): Transition Temperature _TNI = 70.9 ° C. Refractive Index Δn = 0.220 Threshold Voltage _Vth = 1.40V

(Example 33) A liquid crystal device of the present invention was obtained in the same manner as in Example 23 except that the following liquid crystal composition (AD) was used instead of the liquid crystal composition (T). . When the light control layer of the obtained liquid crystal device was observed with a scanning electron microscope, a transparent polymer substance having a three-dimensional network was confirmed. The characteristics of the obtained liquid crystal device were as follows. V ₁₀ : 3.4 V V ₉₀ : 5.7 V T ₀ : 2.4% T ₁₀₀ : 88.4% Contrast: 1:37 τ _r = τ _d : 12.0 ms Retention rate: 95.0 %

[0239]

[Chemical 70]

Physical Properties of Liquid Crystal Composition (AD): Transition Temperature T _NI = 79.9 ° C. Refractive Index Δn = 0.215 Dielectric Constant Δε = 15.8 Threshold Voltage V _th = 1.40 V

The liquid crystal compositions (T) to (Z), (AA) used in Examples 23 to 30 and Comparative Examples 4 and 5 above.
(H) and (i) are the following base liquid crystal compositions

[0242]

[Chemical 71]

70% by weight and 30% by weight of each of the compounds (1) to (8), (c) and (d) shown in Table 3 below. The compounds (1) to (3) are
In the general formula (XI), (i) has 3 or 5 carbon atoms.
And (ii) the number of carbon atoms is 1, 3 or 5
A straight-chain alkyl group having 2 or 4 carbon atoms
The compound (4) to (8) is a compound satisfying both of the above (i) and (ii). The compounds (c) and (d) are examples of the compound relating to the first liquid crystal device of the present invention.

[0244]

[Table 3]

Regarding the liquid crystal devices produced by using these compositions described in Examples 23 to 30 and Comparative Examples 4 and 5, the contrast ratio (CR), the driving voltage (V ₉₀ ), and the voltage holding ratio were obtained. (HR) is shown in Table 4 below.

[0246]

[Table 4]

From Table 4, compounds (1) to (2) satisfying both the above-mentioned (i) and (ii) in the general formula (XI) are described.
It is recognized that the liquid crystal device of the present invention using (3) has a very high contrast ratio and voltage holding ratio.
Moreover, it was driven at a voltage low enough to use a commonly used drive circuit. Similarly, the liquid crystal device of the present invention using the compounds (4) to (8) satisfying one of the above (i) or (ii) in the general formula (XI) has a very high contrast ratio and voltage holding ratio. It was driven at a voltage low enough to use a commonly used drive circuit.

Further, regarding the liquid crystal devices manufactured by using the liquid crystal compositions (AB) to (AD) described in Examples 31 to 33, the contrast ratio (CR), driving voltage (V ₉₀ ), voltage holding The rate (HR) is shown in Table 5 below.

[0249]

[Table 5]

As is clear from Table 5, the liquid crystal device of the present invention using the liquid crystal composition (AB) has a particularly high voltage holding ratio, and the liquid crystal composition (AC)
The liquid crystal device of the present invention using and (AD) has a particularly high contrast ratio and low voltage drivability.

[0251]

INDUSTRIAL APPLICABILITY The liquid crystal device of the present invention does not require a polarizing plate and is a light-scattering type with bright image quality, and has a large transparent-opaque contrast. The liquid crystal composition disclosed in the present invention is excellent in obtaining a liquid crystal device that has a low retention voltage and a high retention rate despite a relatively small dielectric anisotropy.

Furthermore, by using a liquid crystal composition containing a compound having a side chain group specified in the compound represented by the general formula (XI) or (XII), the compound of the present invention having a high contrast in a wide viewing angle can be obtained. It is possible to obtain the second liquid crystal device of the present invention in which the characteristics of the first liquid crystal device are improved, and it is possible to drive at a low voltage and achieve a high voltage holding ratio.

Therefore, the liquid crystal device of the present invention is useful as a display device for computer terminals and a display device for projection.

[Brief description of drawings]

FIG. 1 is a diagram simulating a relationship between an elastic constant of formula (b) and a threshold voltage in a liquid crystal device of the present invention.

FIG. 2 shows the elastic constant ratio K33 / of the liquid crystal composition according to the present invention.
9 is a chart showing the relationship between K11 and the threshold voltage V ₁₀ of a liquid crystal device.

FIG. 3 is a table showing the relationship between the elastic constant K11 of the liquid crystal composition according to the present invention and the transparency T ₁₀₀ of the liquid crystal device when a voltage is applied.

FIG. 4 is a chart showing the relationship between the right side of formula (b) and the threshold voltage V ₁₀ of the light-scattering liquid crystal device, using the results of Example 1 and Examples 3 to 13 in the present specification. .

FIG. 5 is a chart showing the relationship between the right side of known formula (a) and the threshold voltage V ₁₀ of a light-scattering liquid crystal device, using the results of Example 1 and Examples 3 to 13 in the present specification. Is.

FIG. 6 is a chart showing the relationship between the right side of the known formula (a) and the threshold voltage V _th in the TN-LCD of the liquid crystal compositions described in Example 1 and Examples 3 to 13 of the present invention. is there.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location G02F 1/1333 9225-2K

Claims (11)

[Claims] 1. A light scattering type having a transparent electrode layer, at least one of which has a light control layer sandwiched between two transparent substrates, the light control layer containing a liquid crystal material and a transparent solid substance. In the liquid crystal device of (1), the liquid crystal material is (1) 30 to 70 wt% of a first compound group consisting of compounds having a dielectric anisotropy Δε in the range of −1 to 2, and (2) Δε of 8 to 18
Second compound group 10 to 40 consisting of compounds in the range
% And (3) 35% by weight or less of a third compound group consisting of compounds having Δε in the range of 19 to 45, and the dielectric anisotropy Δε of the liquid crystal material is in the range of 8 to 17,
The elastic constant K11 of the liquid crystal material is 5.0 to 15.0 Newton
And the elastic constant ratio K33 / K11 of the liquid crystal material is in the range of 1.3 to 2.5. (1) The first compound group is represented by the general formula (I): (In the formula, R ¹ represents a linear alkyl group having 2 to 7 carbon atoms, R ² represents a linear alkyl group or alkoxyl group having 2 to 7 carbon atoms, and X ¹ represents a hydrogen atom. Or a compound represented by the general formula (II): (In the formula, R ³ represents a linear alkyl group having 2 to 7 carbon atoms, R ⁴ represents a linear alkyl group or alkoxyl group having 2 to 7 carbon atoms, and X ² represents a hydrogen atom. Or a methyl group, X ³ represents a single bond, —CH ₂ CH ₂ — or —COO—), and (2) the second compound group contains , The general formula (III): (In the formula, R ⁵ is a linear alkyl group having 2 to 7 carbon atoms, an alkenyl group or the general formula R ⁶ —O— (CH ₂ ) _n —
(In the formula, R ⁶ represents a linear alkyl group having 1 to 3 carbon atoms, and n represents an integer of 1 to 5), and p represents 0 or 1. ), The third compound group (3) has the general formula (I
V) [Chemical 4] (In the formula, R ⁷ represents a linear alkyl group or an alkoxyl group having 2 to 5 carbon atoms, and X ⁴ represents a hydrogen atom or a fluorine atom.) A compound represented by the general formula (V): 5] (Wherein R ⁸ represents a linear alkyl group or alkenyl group having 2 to 7 carbon atoms, and X ⁵ represents a hydrogen atom or a fluorine atom), and a compound represented by the general formula (VI): Chemical 6] (In the formula, R ⁹ is a linear alkyl group having 2 to 7 carbon atoms, an alkenyl group or a general formula R ¹⁰ —O— (CH ₂ ) _m —
(In the formula, R ¹⁰ represents a straight-chain alkyl group having 1 to 3 carbon atoms, m represents an integer of 2 to 5), and q represents 0 or 1. 3. The liquid crystal device according to claim 1, further comprising a compound selected from the group consisting of compounds represented by 3. (1) The first compound group has the general formula (VI
I) [Chemical 7] (In the formula, R ¹¹ and R ¹² each independently have 1 carbon atom.
Represents a straight-chain alkyl group or an alkoxyl group. ) And a compound represented by the general formula (VIII): (In the formula, R ¹³ and R ¹⁴ each independently have a carbon atom number of 1 to
7 represents a linear alkyl group or an alkoxyl group. ) Containing a compound selected from the group consisting of compounds represented by the formula (2), the second compound group (2) is represented by the general formula (IX): The liquid crystal device according to claim 2, further comprising a compound represented by the formula: wherein R ¹⁵ represents a linear alkyl group or an alkoxyl group having 2 to 5 carbon atoms. 4. A third compound group is a compound represented by the general formula (IV), a compound represented by the general formula (V), a compound represented by the general formula (VI), or the general formula (IX). ) And a compound represented by the general formula (X): (In the formula, ring A is a 1,4-cyclohexylene group or 1,
It represents a 4-phenylene group, and R ¹⁶ has 2 to 7 carbon atoms.
Represents a linear alkyl group. 4. The liquid crystal device according to claim 2 or 3, comprising a compound represented by the formula (4). 5. A light scattering type having a transparent electrode layer, at least one of which has a light control layer sandwiched between two transparent substrates, the light control layer containing a liquid crystal material and a transparent solid substance. In the liquid crystal device of, the liquid crystal material has the general formula (X
I) [Chemical 11] (In the formula, R ¹⁷ represents a linear alkyl group having 2 to 7 carbon atoms, R ¹⁸ represents a linear alkyl group or alkoxyl group having 1 to 7 carbon atoms, and R ¹⁷ and R ¹⁸ At least one of them represents a straight-chain alkyl group having an odd number of carbon atoms or an alkoxyl group having an even number of carbon atoms, and X ⁶ represents a hydrogen atom or a methyl group, and a compound represented by the general formula (XII ) [Chemical 12] (In the formula, R ¹⁹ represents a linear alkyl group having 2 to 7 carbon atoms, R ²⁰ represents a linear alkyl group or alkoxyl group having 1 to 7 carbon atoms, and R ¹⁹ and R ²⁰ At least one represents a linear alkyl group having an odd number of carbon atoms or an alkoxyl group having an even number of carbon atoms, X ⁷ represents a hydrogen atom or a methyl group, X ⁸ represents a single bond, —CH ₂
Represents CH ₂ — or —COO—. 15% by weight in total of the compound selected from the group consisting of compounds represented by
60 wt% or less, the dielectric anisotropy Δε of the liquid crystal material is in the range of 5 to 17, the elastic constant K11 of the liquid crystal material is in the range of 5.0 to 15.0 Newton, A liquid crystal device having an elastic constant ratio K33 / K11 in the range of 1.3 to 2.5. 6. The liquid crystal material has the general formula (XIII): (In the formula, R ²¹ is a linear alkyl group having 2 to 7 carbon atoms, an alkenyl group or the general formula R ²² —O— (CH ₂ ) _s—
(In the formula, R ²² represents a straight-chain alkyl group having 1 to 3 carbon atoms, s represents an integer of 1 to 5), and r represents 0 or 1. 6. The liquid crystal device according to claim 5, wherein the compound represented by the formula (4) is contained in a total amount of 10% by weight or more and 40% by weight or less. 7. The liquid crystal material has the general formula (XIV): (Wherein R ²³ represents a straight-chain alkyl group or alkoxyl group having 2 to 5 carbon atoms, and X ⁹ represents a hydrogen atom or a fluorine atom), a compound represented by the general formula (XV): 15] (Wherein R ²⁴ represents a linear alkyl group or alkenyl group having 2 to 7 carbon atoms, and X ¹⁰ represents a hydrogen atom or a fluorine atom), and a compound represented by the general formula (XVI): Chemical 16] (In the formula, R ²⁵ is a linear alkyl group having 2 to 7 carbon atoms, an alkenyl group or the general formula R ²⁶ —O— (CH ₂ ) _u—
(In the formula, R ²⁶ represents a linear alkyl group having 1 to 3 carbon atoms, and u represents an integer of 2 to 5), and t represents 0 or 1. 7. The liquid crystal device according to claim 5, further comprising a compound selected from the group consisting of compounds represented by the formula (10) in a total amount of 10% by weight or more and 40% by weight or less. 8. The general formula (VII), the general formula (VII
8. The liquid crystal device according to claim 7, further comprising a compound selected from the group consisting of I), the compound represented by the general formula (IX) and the compound represented by the general formula (X). 9. A transparent electrode layer on at least one of the substrates, wherein a layer having a uniform three-dimensional mesh-like transparent solid substance in a continuous layer of a liquid crystal material is provided.
The liquid crystal device according to 2, 3, 4, 5, 6, 7 or 8. 10. A transparent electrode layer of one substrate is provided with a layer having a uniform three-dimensional mesh-like transparent solid substance in a continuous layer of liquid crystal material, and the transparent electrode layer or the transparency of the other substrate is provided. Providing a liquid crystal layer in contact with the liquid crystal alignment layer provided on the electrode layer,
The liquid crystal device according to claim 9, wherein liquid crystal molecules in the liquid crystal layer are aligned in a fixed direction. 11. The liquid crystal device according to claim 9, wherein the entire light control layer is a layer having a transparent solid substance having a uniform three-dimensional network in a continuous layer of the liquid crystal material.