JP2937684B2 - Liquid crystal display device and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to TN, FLC, EC
The present invention relates to a polymer-dispersed liquid crystal display element which can be applied to modes such as B, STN, and PDLC and has a large number of liquid crystal droplets surrounded by a polymer wall, and a method of manufacturing the same.

[0002]

2. Description of the Related Art As a conventional liquid crystal display device, a device utilizing an electro-optic effect is known, and a TN type or STN type using a nematic liquid crystal has been put to practical use. Further, a display medium using a ferroelectric liquid crystal has been proposed. These require a polarizing plate and require an alignment treatment. On the other hand, liquid crystal display elements that do not require a polarizing plate include those using a dynamic scattering (DS) effect and those using a phase transition (PC) effect.

Recently, as a liquid crystal display element which does not require a polarizing plate and does not require an alignment treatment, a polymer dispersion type in which a large number of liquid crystal droplets are surrounded by a polymer wall functioning as a support medium has been proposed. Have been. Such a polymer-dispersed liquid crystal display element uses the birefringence of liquid crystal to electrically control a transparent or opaque state to perform display. Specifically, the ordinary light refractive index of the liquid crystal molecules is made to match the refractive index of the polymer wall, and a transparent state is displayed when the voltage is applied to align the liquid crystal molecules, and when no voltage is applied, the liquid crystal molecules are aligned. This indicates the state of light scattering due to the disturbance of light.

The following method has been proposed as a method of manufacturing the above-mentioned liquid crystal display element. Method of enclosing liquid crystal in polymer capsule (Japanese Patent Publication No. 58-501631) A liquid crystal is mixed with a photocurable or thermosetting resin, and the liquid crystal is precipitated by curing the resin to form liquid crystal droplets in the resin. Method (Japanese Patent Publication No. 61-502128) By removing a solvent from a mixture of a mixture of a polymer and a liquid crystal and a solvent that dissolves the mixture,
Method for Forming a Phase Separation State between Liquid Crystal and Polymer (Japanese Unexamined Patent Publication (Kokai) No. 59-226322) However, in the case of each of the above-mentioned proposed methods, unreacted liquid crystal droplets of the polymer dispersion type liquid crystal display device produced are not included. Monomers and oligomers remained, and the residuals increased the viscosity of the liquid crystal and reduced the response speed. In addition, most of the liquid crystal materials used in these proposed methods are cyanobiphenyl-based or cyanopyrimidine-based having a -CN group at a terminal of a liquid crystal molecule. Such a liquid crystal material is disclosed in, for example, JP-A-2-272422-27242.
4, JP-A-2-75688, JP-A-2-28284, JP-A-2-85822 and the like.

On the other hand, as a resin material surrounding liquid crystal droplets, an F (fluorine) resin material is used for the purpose of reducing the driving voltage and improving the electrical retention ratio.
-14015 and JP-A-4-168422. However, when a liquid crystal display element is manufactured using an F-based resin material, the response speed τ _r when a voltage is applied is increased due to the presence of F atoms at the interface between the liquid crystal and the resin.
Conversely, there is a problem that the response speed τ _d at the time of the voltage off becomes slow because the driving force (the force generated by the interaction between the liquid crystal material and the resin material) for returning the liquid crystal to the original state becomes weak.

[0006] In order to improve the shock resistance of a liquid crystal display device using a ferroelectric liquid crystal, a method of dispersing a liquid crystal material in a polymer material has been disclosed (Japanese Patent Application Laid-Open No. Sho 63-163).
264721 to 2647242). However, in the case of the disclosed method, it is difficult to maintain the orientation on the surface of the polymer material, and a complicated operation such as stretching is required for dispersion.

Further, a method of fixing a liquid crystal material to a polymer wall of a polymer dispersion type liquid crystal display device has been disclosed (Japanese Patent Laid-Open No. 2-116824). In this method, a liquid crystal material and a liquid crystalline polymer having a liquid crystal molecule in a side chain dissolved in a common solvent are applied to the substrate surface, and then the solvent is removed. This is a method of separating phases from molecules. However, in this case,
It is difficult to ensure conditions for phase separation, and it is difficult to completely remove the solvent.

[0008]

By the way, a method of manufacturing the above-mentioned polymer-dispersed liquid crystal display element (Japanese Patent Application Laid-Open No. 58-501).
631, JP-T-61-502128 and JP-A-59-2
26322), phase separation between the liquid crystal material and the resin material cannot be sufficiently performed, unreacted monomers and oligomers remain in the liquid crystal droplets, and the liquid crystal of the polymer at the polymer wall interface. Swelling, and the response speed could not be improved sufficiently. Further, -C is added to the terminal of the above-mentioned liquid crystal molecule.
Generally, a liquid crystal material having an N group is used, and the liquid crystal material has strong reactivity between the molecule itself and CN, and has high reactivity.
In addition, since it is easy to incorporate impurities in the entire system into the liquid crystal material,
In the manufacturing process, it was not possible to maintain a high retention of 90% or more in contact with other compounds. Further, in a method of curing a curable resin from a mixture of a photocurable or thermosetting resin and a liquid crystal to cause phase separation between the liquid crystal and the resin (Japanese Patent Application Laid-Open No. 61-502128), the reaction activity of the polymerization reaction is increased. Since the dots and the liquid crystal coexist, the liquid crystal is damaged and the retention rate is significantly reduced. Furthermore, a liquid crystal display device using a ferroelectric liquid crystal as a liquid crystal has a problem in shock resistance.

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art, and has as its object to provide a liquid crystal display element capable of sufficiently improving a response speed and maintaining a high retention, and a method of manufacturing the same. Aim.

[0010]

According to the liquid crystal display device of the present invention, a display medium provided between a pair of substrates disposed opposite to each other is formed for each picture element in a size corresponding to the picture element area. Was
Together with a liquid crystal droplets are surrounded by polymer walls has a structure in which liquid crystal compound in the vicinity of the interface between the <br/> polymer wall of the liquid crystal droplets is fixed, the objective accomplished by the Is done.

According to the method of manufacturing a liquid crystal display element of the present invention, there is provided a method of manufacturing a liquid crystal display element in which a display medium is provided between a pair of opposed substrates. A step of injecting a mixture of a layer material and a polymerizable compound comprising a liquid crystal compound having a polymerizable functional group in at least one kind of molecule, and causing the mixture to undergo a polymerization reaction and phase separation accompanying the reaction Allows liquid crystal droplets to correspond to pixel areas
And forming a display medium surrounded by a polymer wall for each picture element in a size as described above, whereby the object is achieved.

As the liquid crystalline compound, those having a polymerizable functional group and an F atom and / or a Cl atom in the molecule,
Alternatively, those having a polymerizable functional group and an optically active group in the molecule can be used. In the former case, it is preferable to use a material containing a liquid crystal material having an F and / or Cl element in a molecule as the liquid crystal droplet. In the latter case,
It is preferable to use a ferroelectric liquid crystal for the liquid crystal droplet.

The polymer wall is preferably in a liquid crystal state. In this case, due to the presence of the alignment film, the polymer wall and the liquid crystal droplet can be in the same alignment state. Further, it is preferable that the liquid crystal droplets and the polymer wall include a dichroic dye.

In the formation of the above-mentioned display medium, when the polymerizable compound has photocurability, it is preferable to irradiate the mixture with light having a regular intensity.

[0015]

In the present invention, a mixture of a liquid crystal material and a polymerizable compound containing a liquid crystal compound having a polymerizable functional group in at least one kind of molecule is polymerized. Phase separation occurs with this reaction, and liquid crystal droplets
A display medium surrounded by a polymer wall is formed for each pixel with a corresponding size, but the liquid crystal droplet structure is such that a liquid crystalline compound is fixed near the interface with the polymer wall. . In such a state, the interface between the liquid crystal droplet and the polymer wall is driven when a voltage is applied, and the driving force is increased when the voltage is turned off because the fixed liquid crystal molecules are bonded to the polymer wall. , Τr and τd are both improved,
The response speed increases . Further, since the liquid crystalline compound is fixed at the interface with the polymer wall, phase separation is clearly performed. Change
The display medium has a size corresponding to the picture element area.
Liquid crystal droplets formed every time are surrounded by polymer walls
In the picture element compared with the conventional polymer dispersion type liquid crystal display element
Scattering of liquid crystal, greatly increasing the contrast of the liquid crystal display
It can be improved.

In addition, the liquid crystal material has a chemically stable F
In the case of using a liquid crystal material of a liquid crystal or Cl system, the liquid crystal molecules have chemical stability by using a liquid crystal compound having an F atom or a Cl atom in the molecule.

Further, when a ferroelectric liquid crystal is used as a liquid crystal material, a liquid crystal compound having a polymerizable functional group and an optically active group in a molecule is used, so that an optical interface is formed at the interface with the polymer wall. Liquid crystal molecules having an active functional group can be present. Due to the presence of the liquid crystal molecules, not only the alignment regulating force from the substrate subjected to the alignment treatment, but also the regulating force from the polymer wall having a component perpendicular to the substrate surface acts on the liquid crystal droplet.

Further, when the polymer wall is cured in a liquid crystal state, the polymer portion is also in an aligned state, and the liquid crystal region is aligned in the alignment direction of the substrate, thereby making use of the alignment regulating force of the substrate. The orientation direction can be determined. In addition, when the liquid crystal droplet and the polymer wall include a dichroic dye, if the liquid crystal droplet and the polymer wall are in the same alignment state, the liquid crystal droplet and the polymer wall may Both can be used as translucent regions.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments.

(Embodiment 1) FIG. 1 is a sectional view showing a liquid crystal display device of this embodiment. This liquid crystal display element has a configuration in which a display medium is provided between two opposing substrates 1 and 2, and the display medium has a liquid crystal droplet 8 surrounded by a polymer wall 7 formed in a matrix. I have. In the substrate 1, a plurality of electrode lines 3 are formed in parallel on the substrate 2 side of the base substrate 1a, and an alignment film 5 is formed so as to cover the electrode lines 3. On the other substrate 2, a plurality of electrode lines 4 are formed in parallel on the substrate 1 side of the base substrate 2 a, and further, an alignment film 6 is formed so as to cover the electrode lines 4. The electrode lines 4 formed on the substrate 2 are arranged to intersect, for example, orthogonally to the electrode lines 3 formed on the substrate 1 as shown in FIG. The intersecting portions constitute picture elements 10 to be displayed. The electrode wires 3 and 4 do not need to be orthogonal to each other, but only need to intersect. Furthermore, the counter electrode is TF
In the case of T, one counter electrode may be used.

The display medium comprising the polymer walls 7 and the liquid crystal droplets 8 is a mixture of a liquid crystal material and a polymerizable compound containing a liquid crystal compound having a polymerizable functional group in at least one kind of molecule. It is formed by polymerization reaction and phase separation accompanying this reaction. The liquid crystal droplet 8 has a structure in which a liquid crystalline compound 9 is present in the vicinity of the interface with the polymer wall 7.

Next, a method of manufacturing the liquid crystal display device having such a configuration will be described.

First, it is prepared by synthesizing a liquid crystalline compound having a polymerizable functional group in a molecule. As the liquid crystal compound, for example, the following compound X was used.

[0024]

Embedded image

The above compound X is prepared as follows. 4'-Hydroxy-4-fluorobiphenyl is converted to an excess of 1,10-
Esterification is performed using dibromodecane. Then
After purification using column chromatography, the purified product is mixed with an equimolar amount of tetramethylene ammonium-hydroxypentahydrate and esterified with acrylic acid. Note that the liquid crystal compound is
It may be prepared in advance.

Next, a cell is manufactured. The fabrication is performed, for example, as follows. That is, PE having a thickness of 0.25 mm
The electrode wires 3 and 4 shown in FIG.
A set of substrates is obtained. The electrode wires 3 and 4 are ITO
(A mixture of indium oxide and tin oxide)
Formed to a thickness of 500 angstroms and have a width of 200μ
m, the interval was 50 μm, and the number of lines was 20 lines. A polyimide obtained by adding 5% of a reaction initiator ( Irgacure e184) to SE150 (manufactured by Nissan Chemical Industries, Ltd.) is applied to the obtained pair of substrates by spin coating, and the coating is rubbed using a nylon cloth. Was done. Subsequently, the two substrates subjected to the above treatment were combined so that the electrode wires were orthogonal to each other, and a cell having a constant cell thickness was formed by interposing a 6 μm spacer therebetween. Thereafter, as shown by hatching in FIG. 2, a light-shielding portion 11 is formed for each picture element 10 on the formed cell, that is, a photomask in which the light-shielding portion 11 is formed in a dot pattern is formed by It was arranged so as to be shielded from light, and a uniform mixture prepared in advance was injected into the cell. The mixture comprises 0.1 g of trimethylolpropane trimethacrylate, 0.35 g of 2-ethylhexyl acrylate, 0.45 g of isobornyl acrylate,
0.2 g of the compound X to which 0.3% of N (cholesteric nonanate) was added, and a liquid crystal material ZLI-479.
2 (manufactured by Merck), 3.8 g, total 4 g of compound X
And ZLI-4792, and 0.15 g of an initiator Ir
gacur e184 is uniformly mixed.
That is, the mixture includes a polymer material, a liquid crystal compound as compound X, a liquid crystal material, and a reaction initiator. Subsequently, using a high-pressure mercury lamp capable of obtaining parallel rays, the mixture was cured by irradiating ultraviolet rays at 10 mW / cm ² from the photomask side for 5 minutes. In addition, for another cell manufactured in this way,
When the cell was peeled off in liquid nitrogen and the liquid crystal material was washed away with acetone, the horizontal section of the polymer wall was observed with an SEM (scanning electron microscope). ), And it was confirmed that liquid crystal droplets having the same size and uniformity were formed. In the observation of the polymer matrix described above, there were portions where the structure was destroyed at the time of preparing the sample. Therefore, 20 liquid crystal droplet regions having the best regularity in the sample were selected and observed. Therefore, the photomask is required to have the same regularity.

Next, a polarizing plate was adhered to the produced cell so that the polarization direction was adjusted in the direction along the alignment direction, thereby producing a TN mode polymer-dispersed liquid crystal display device.

Table 1 shows the electro-optical characteristics of the liquid crystal display element according to the first embodiment, together with Comparative Examples 1 and 2. In Comparative Example 1, glass with ITO (ITO-50 manufactured by Nippon Sheet Glass) was used instead of the substrate in Example 1.
A cell is manufactured in the same manner as in Example 1 using (flint glass with 0 Å). Further, only the same liquid crystal material as in Example 1 was injected into the prepared cell, and a polarizing plate was attached to the prepared cell so that the polarization direction was aligned in the direction along the alignment direction. It is a display element. Further, in Comparative Example 2, as in Example 1, T
An N-type cell was prepared, and a mixture of the same liquid crystal material as in Example 1 and a photocurable resin excluding the compound X was used. After the mixture was injected into the cell, the photomask was not covered on the cell. This is a polymer-dispersed liquid crystal display device manufactured by performing UV irradiation similarly to 1.

[0029]

[Table 1]

As can be seen from Table 1 above, Example 1
Can use a film substrate without inferior in electro-optical characteristics to Comparative Example 1 which has been conventionally used. Also,
Compared with the polymer-dispersed liquid crystal display device (Comparative Example 2), which has been studied in the past, the contrast is significantly higher due to less scattering in the picture element. Furthermore, the response speed is about five times faster than that of Comparative Example 2, and is faster than that of the TN liquid crystal display element (Comparative Example 1) due to the effect of the liquid crystal compound fixed on the polymer wall. Has become. In the present invention, the response speed (τ _r ) when the saturation voltage is applied and the OF
The sum of the response speed at time F (τ _d ) was taken as the response speed.

Further, in Example 1, since ZLI-4792 having fluorine is used as the liquid crystal material, the liquid crystal compound X contains a fluorine atom as shown in the above chemical formula 1. As a result, the liquid crystal molecules existing in the vicinity of the interface between the liquid crystal droplet and the polymer wall have chemical stability, and as a result, the TFT or the like can be used without lowering the electrical retention of the entire liquid crystal display element. An effect that can be applied to the liquid crystal display element of the charge retention type is obtained. This effect is obtained when the liquid crystal material has Cl and the liquid crystal compound has C
It is also obtained when 1 atom is contained.

Example 2 In Example 2, a liquid crystal display device was manufactured by changing the type of liquid crystal compound used. As the liquid crystal compound, a ferroelectric compound Y shown below was used as a liquid crystal, vol. 9, No. 5, pp 635-641,
Those prepared as shown in 1991 were used.

[0033]

Embedded image

First, the two substrates subjected to the uniaxial orientation treatment in the same manner as in Example 1 are bonded together so that the rubbing directions are the same, and a 2 μm silica bead is interposed therebetween to form a cell. did. Subsequently, a homogeneous mixture was injected into the cell. The mixture comprises 0.018 g of trimethylolpropane methacrylate, 0.060 g of lauryl acrylate, 0.020 g of compound Y,
0.002 g of initiator ( Irgacure 65)
1) and 0.400 g of a ferroelectric liquid crystal material (ZLI-4)
237-000). That is, the mixture contains a polymer material, a liquid crystal compound as compound Y, a reaction initiator, and a ferroelectric liquid crystal material.

Thereafter, using the same photomask as in Example 1, the resin was irradiated with ultraviolet light (UV light) continuously for 20 minutes at 10 mW / cm ² under a high-pressure mercury lamp capable of obtaining parallel rays from the photomask side. Cured.

Table 2 shows the measurement results of the electro-optical characteristics and the shock resistance of the manufactured cell according to Example 2, together with Comparative Examples 3 and 4. The measurement related to the electro-optical characteristics was performed for the response speed, the memory pulse width, the contrast, and the pressure application test, and the measurement related to the shock resistance was performed for the impact test. In Comparative Example 3, the same ferroelectric liquid crystal ZLI-4003 as in Example 2 and the compound Y
Using a mixture with a photocurable resin except for the above, and after injecting this mixture into the cell, UV irradiation was performed in the same manner as in Example 1 without covering the cell with a photomask, to obtain a polymer-dispersed liquid crystal display element. Produced.

In Comparative Example 4, a cell was produced by injecting only the ferroelectric liquid crystal ZLI-4003 between the substrates produced in the same manner as in Example 2.

[0038]

[Table 2]

The above-mentioned electro-optical characteristics were measured under the following conditions. That is, the cell was placed between the polarizing plates of the optical property measurement system under the crossed Nicols, and 100 Hz, ± 10 V
When a rectangular wave is applied, the angle at which the maximum value of the photodetector corresponding to the transmitted light intensity with respect to the positive and negative electric fields is almost equal to 0 degree, and the direction of the polarity of the electric field matches the polarity of the signal from the photodetector. The measurement was performed in a state of being tilted at 22.5 degrees. Each measurement value was obtained as follows.

(Response speed) The change in the optical light amount of the cell is 10% to 90% with respect to the rise / fall of the pulse when a rectangular wave of 100 Hz and ± 10 V is applied.
The average value of the time required to change to?

(Memory pulse width) The pulse width of a bipolar pulse of ± 10 V capable of memory switching of all picture elements.

(Contrast) A photo detector signal in a completely dark state in a state where all the picture elements are subjected to memory switching is used as a reference (V _D ), and a photo detector signal in a bright state with respect to a signal (V _off ) from the photo detector in a dark state. the ratio of (V _on), ie, _{(V on -V D) / (} V o ff -V
The value of _D ) was used.

(Pressure test) AGS is used as a pressure tester.
This was performed by a compression test using -100A (manufactured by Shimadzu Corporation). The cell was placed on a horizontal table and closely contacted with the upper surface of the cell, having a diameter of 8 mm and a cross-sectional area of 0.670.
A load was applied to the cell through a stainless steel rod of cm ² , and the load when the orientation changed was examined.

(Impact Test) A change in the orientation state when the cell was dropped horizontally from 50 cm above a linoleum-clad desk surface was examined. In the table, は indicates that some disturbance of the alignment occurred in the boundary region between the liquid crystal and the polymer material, but there was no practical problem, and × indicates that there was the disturbance of the alignment in the picture element part. ing.

As understood from Table 2 above, Example 2
Is superior in the pressure application test and the impact test as compared with Comparative Example 3 using the same ferroelectric liquid crystal. In addition, when compared with Comparative Example 4 having the conventional configuration, Comparative Example 4 did not have a sufficient alignment of the liquid crystals, had low contrast, and could not be evaluated in the impact test because the alignment was insufficient from the beginning. On the other hand, in Example 2, good results were obtained.

As described in detail above, in the present invention,
A mixture of a liquid crystal material and a polymerizable compound containing a liquid crystal compound having a polymerizable functional group in at least one molecule is polymerized. A phase separation occurs due to this reaction, and a display medium in which liquid crystal droplets are surrounded by the polymer wall is formed. As a structure of the liquid crystal droplet, a liquid crystalline compound is fixed near an interface with the polymer wall. State. In such a state, the interface between the liquid crystal droplet and the polymer wall is driven when a voltage is applied, and the driving force is increased when the voltage is turned off because the fixed liquid crystal molecules are bonded to the polymer wall. , Τ _r , τ _d are both improved. Further, since the liquid crystalline compound is fixed at the interface with the polymer wall, phase separation is clearly performed.

When a ferroelectric liquid crystal is used as the liquid crystal material, the liquid crystal compound having a polymerizable functional group and an optically active group in a molecule is used, so that an optical interface is formed at the interface with the polymer wall. There is a liquid crystal molecule having an active functional group. Due to the presence of the liquid crystal molecules, not only the alignment regulating force from the substrate subjected to the alignment treatment, but also the regulating force from the polymer wall having a component perpendicular to the substrate surface acts on the liquid crystal droplet. Therefore, the orientation state is stabilized and the shock resistance is improved.

Further, in the present invention, when a chemically stable F-based or Cl-based liquid crystal material is used as the liquid crystal material, a liquid crystal compound having an F atom or a Cl atom in the molecule is used. Thereby, the liquid crystal molecules have chemical stability. Due to this chemical stability, the present invention can be applied to a charge retention type device such as a TFT without lowering the electrical retention of the entire display device.

(Embodiment 3) Embodiment 3 is directed to a case where the alignment regulating force of the resin material with respect to the liquid crystal is increased. in this case,
By adding a polymerizable material having a liquid crystalline functional group, a mixture of a curable resin and a liquid crystal can be phase-separated in a liquid crystal phase, and the whole is brought into an alignment state.

Hereinafter, a method for manufacturing the liquid crystal display element according to the third embodiment will be described. First, the compound X used in Example 1 is synthesized. Next, ITO (a mixture of indium oxide and tin oxide, 5
A vertical alignment film JALS-203-R6 (manufactured by Nippon Synthetic Rubber Co., Ltd.) was applied by spin coating on a substrate having a transparent electrode (00 angstrom) as a transparent electrode, followed by firing.
A cell was formed by disposing two substrates subjected to the above-described processing in opposition, and maintaining a cell thickness of 6 μm by interposing a spacer between the two substrates.

A pitch of 250 μm was formed on the prepared cell.
Then, a photomask in which a rectangular light-shielding portion with a separation interval of 50 μm is arranged is arranged so that the pixel portion is shielded from light, and 0.1 g of bifunctional acrylate is further placed in the cell.
And Oh Ru R-684 (manufactured by Nippon Kayaku Co., Ltd.), and styrene 0.05 g, and Compound X 0.85 g, 4g crystal material ZL of
I-2806 (Δε <0: manufactured by Merck) and 0.002
A mixture was prepared by mixing 5 g of the photoinitiator Irgacure 651. When the prepared mixture was observed while changing the temperature under a polarizing microscope, the crystal-nematic transition temperature was 45 ° C and the nematic-homogeneous liquid transition temperature was 78 ° C.
Met. The mixture was injected at 48 ° C. (nematic state), and then maintained under the same temperature under a high-pressure mercury lamp capable of obtaining parallel light from the dot pattern side of the photomask.
At mW / cm ² (irradiation for 1 second, no irradiation for 30 seconds)
Was repeated 20 times, followed by continuous irradiation for 10 minutes, followed by removing the photomask and irradiating with ultraviolet rays for 10 minutes to cure the resin material .

After the fabricated cell was peeled off in liquid nitrogen and the liquid crystal material was washed away with acetone, the horizontal section of the polymer wall was observed by SEM (scanning electron microscope). It was confirmed that liquid crystal droplets having the same regularity as those of the picture elements) and having substantially the same size and being uniformly arranged were produced.

Before and after the manufactured cell, two polarizing plates were attached so as to be orthogonal to each other, and E was surrounded by a polymer wall.
A CB display element was manufactured.

Table 3 shows the electro-optical characteristics of the manufactured cells. In Table 3, in the item of the reversal phenomenon in the halftone,
The mark “○” indicates a state where the reversal phenomenon does not occur, the mark “X” indicates a state where the reversal phenomenon can be easily observed, and the mark “△” indicates a state where the reversal phenomenon is barely observed.

[0055]

[Table 3]

In Comparative Example 5, a similar alignment film was formed on the same substrate as in Example 3, and then rubbed with a nylon cloth to obtain an antiparallel state. The substrates were bonded together, and the same liquid crystal material ZLI-2806 as in Example 3 was injected between the substrates, and two polarizing plates were bonded to the cell thus manufactured before and after the cell so as to be orthogonal to each other. In this case, a conventional ECB display element is manufactured. In Comparative Example 6, a cell was prepared in the same manner as in Example 3, and the mixture was injected into the cell using the same mixture as in Example 3, and then the same as in Example 3 without covering the cell with a photomask. In this case, a UV-irradiation is performed to attach a polarizing plate to produce a polymer dispersed liquid crystal element. Example A
Is included in the range of the above-mentioned Example 1 or 2. After preparing a cell in the same manner as in Example 3, using the same mixture as in Example 3, and injecting the mixture into the cell Example 3 while maintaining the temperature of the mixture at 100 ° C.
In the same manner as described above, ultraviolet irradiation was performed with a photomask covered. After producing the cell, a polarizing plate was bonded in the same manner as in Example 3.

As can be seen from Table 3, the voltage of of Example 3 of the present invention was high because the polymer portion was also vertically oriented.
The light-shielding state at f is excellent, the electro-optical characteristics are comparable to those of Comparative Example 5 conventionally used, and a film substrate can be used. On the other hand, compared with the polymer-dispersed liquid crystal display device (Comparative Example 6), the contrast is higher due to less scattering in the picture element.

Further, in the third embodiment, since the liquid crystal molecules fall in various directions due to the interaction with the polymer when the liquid crystal molecules fall, the refractive index becomes uniform from any direction and the viewing angle characteristics are improved. Have been. On the other hand, in Comparative Example 5,
The rubbing process in one direction causes the liquid crystal molecules to fall in one direction when a voltage is applied, and the refractive index differs depending on the direction in which the liquid crystal molecules are viewed. And the viewing angle characteristics are very poor. In Comparative Example 6, a granular liquid crystal region was formed, and the display was entirely rough.

When the cell of Example A was observed with a polarizing microscope, the liquid crystal region was almost vertically aligned, but light leakage was observed in the polymer portion under crossed Nicols.
The contrast is slightly reduced as compared with.

Next, the reason why the viewing angle characteristics are improved in the third embodiment will be described. That is, the conventional liquid crystal display device using a polarizing plate has poor viewing angle characteristics and is not suitable for a liquid crystal display device viewed at a wide angle. For example, ECB
When the initial alignment is a homeotropic alignment in a liquid crystal display device of the type (electric field birefringence type), an alignment treatment is performed on the alignment film so that the alignment film falls in the same direction when a voltage is applied. Therefore, when the liquid crystal molecules are tilted in the halftone, the liquid crystal molecules tilt in the same direction. Therefore, when the liquid crystal molecules a are viewed from the A direction and the B direction as shown in FIG. Since they are different, the contrast viewed from each direction is greatly different, and in extreme cases, display abnormalities such as inversion phenomenon appear. Thus, in the conventional display mode, there is a problem that the viewing angle characteristics are poor. On the other hand, a liquid crystal display device (with a polarizing plate) in which a liquid crystal and a polymer material are regularly phase-separated using a photomask, as shown in FIG. Since the liquid crystal molecule a falls down in the direction of each polymer wall f due to the interaction with f, the apparent refractive index becomes almost the same in the C direction and the D direction, which has a great effect on improving the viewing angle characteristics. However, even in a vertical alignment film having an excellent alignment regulating force, an extremely thin polymer material layer enters between liquid crystal molecules in a liquid crystal region and a substrate, thereby weakening the vertical alignment effect on the substrate. As a result, a slight fluctuation occurs in the vertical alignment of the liquid crystal molecules, light leakage occurs under crossed Nicols, and the contrast is slightly reduced. Furthermore, in the mode using the vertical alignment film, fine liquid crystal droplets are formed in the polymer wall, and the alignment state on the substrate is not reflected by the alignment of the liquid crystal molecules, and is in a random state. Transmission occurs, and the apparent contrast is significantly reduced. A ferroelectric liquid crystal element has a problem in shock resistance, and is improved by dispersing liquid crystal droplets in a polymer. However, phase separation is not clearly performed and it is difficult to control alignment.

On the other hand, in Example 3, a polymerizable compound was cured in a liquid crystal state from a homogeneous mixture of a liquid crystal material and a polymerizable compound (polymerizable compound having liquid crystallinity), and the liquid crystal and the polymer material were subjected to phase separation. In this method, the liquid crystal and the polymer material can be in the same alignment state. When the curing is performed in the liquid crystal state, the alignment state of the polymer material region as well as the liquid crystal region is maintained, so that the liquid crystal region has a stronger orientation. In particular, in the case of a normal ECB element, light is transmitted under crossed Nicols to reduce contrast because small liquid crystal molecules confined in a polymer wall are randomly aligned. In the case of the example, the liquid crystal compound is contained in the polymer material and the liquid crystal material is in the same alignment state as the liquid crystal material, so that light does not easily transmit. Furthermore, in the case of the ECB element (with a polarizing plate) to which the embodiment is applied, the direction in which the liquid crystal molecules fall due to the electric field becomes random due to the interaction between the polymer wall and the liquid crystal molecules.
Since the state is the same in any direction, the viewing angle characteristics are excellent even in the halftone.

(Embodiment 4) In Embodiment 4, as in Embodiment 3, in addition to bringing the whole into an alignment state, the contrast is improved, and a dichroic dye is used. Hereinafter, a method for manufacturing the liquid crystal display element according to the fourth embodiment will be described.

A cell was manufactured so as to have a cell thickness of 9 μm in the same manner as in Example 3, and the liquid crystal material was different from that of Example 3,
Specifically, dichroic dye S-301 is added to ZLI-2806.
Using a liquid crystal material containing 4% (manufactured by Mitsui Toatsu Dye),
A liquid crystal cell was manufactured in the same manner as in Example 3. When the transition temperature of the mixed mixture was examined by DSC (differential thermal balance), the result was almost the same as that of Example 3. Therefore, the mixture was injected at 48 ° C. and irradiated with light through a photomask to be cured.

A substrate on which Al was vapor-deposited was placed behind the fabricated cell, and a light source and an observation unit were placed at an angle of 30 ° from the vertical direction of the cell, and electro-optical characteristics were measured as a reflection type liquid crystal display device.

The fabricated cell according to the fourth embodiment is shown in FIG.
As shown in (a), when the voltage is turned off, the liquid crystal molecules a and the dichroic dye b in the liquid crystal droplet g and the polymer and the dichroic dye b in the polymer wall f are all oriented in the same direction. Is in a decolored state, and as shown in FIG.
By applying a voltage in between, only the liquid crystal droplet g changed its direction and became colored. In FIG. 5, d is a substrate, and h is an alignment film. The contrast of the liquid crystal display device of Example 4 was 7, and the driving saturation voltage was around 7 V.
In addition, the contrast from all directions was uniform because the molecules fell down when a voltage was applied in all directions.

On the other hand, the following liquid crystal display device was manufactured for comparison. That is, as in Example 4, the substrate was rubbed in one direction with a nylon cloth, and the two substrates were bonded together so that the processing directions were antiparallel, thereby producing a cell.
ZLI-2806 (containing 4% of a two-color dye S-301) was injected into the cell to produce a conventional GH mode liquid crystal display device. In this device, the contrast was changed depending on the viewing angle direction because the molecules were tilted in one direction when a voltage was applied, and the display characteristics were poor.

As described in detail above, in the case of Examples 3 and 4, since the curing reaction is performed in the liquid crystal state, the polymer portion is also in the alignment state, and the liquid crystal region is aligned in the alignment direction of the substrate. Since the alignment direction can be artificially determined by utilizing the alignment regulating force, the following advantages can be obtained.
That is, when a curing reaction is performed in a state that is not in a liquid crystal state as in Examples 1 and 2, a very thin resin may enter between the substrate and the liquid crystal layer, so that the alignment regulating force of the substrate is weakened. Artificial orientation was difficult. In addition, since the polymer did not align, the liquid crystal in the minute liquid crystal droplets that entered the polymer was oriented along the polymer wall and was in a random state, which caused inconvenience. For example, when using a vertical alignment film and using it under crossed Nicols,
Since the inside of the minute liquid crystal droplets is randomly oriented, light leakage occurs and the contrast is reduced. On the other hand, the third and fourth embodiments have an advantage that such a disadvantage can be solved.

Further, in the case of Examples 3 and 4, the conventional liquid crystal display elements (TN, GH, STN, EC
B, FLC, etc.), but ECB, GH, FL
Particularly effective for C. For example, when applied to an ECB element, the ECB mode is a vertical orientation in an initial state (a black state under orthogonal Nicols), and a molecule is collapsed (white state due to birefringence) by applying a voltage. When the liquid crystal molecules fall, interaction with the polymer causes the liquid crystal molecules to fall in various directions, so that the refractive index becomes uniform from any direction and the viewing angle characteristics are improved.

However, even in an ECB element (without a polarizing plate) to which a dichroic dye is added, if the polymer wall is not in the alignment state, the dye material contained in the polymer wall is colored in a random alignment state. Since the state is not responded to the electric field, the overall contrast is reduced. However, when the polymer material can be made to be in the alignment state as in Examples 3 and 4, the dichroic dye in the polymer wall is also in the homeotropic alignment state, and the liquid crystal is changed from a state almost entirely transparent to the liquid crystal. Only the portion becomes colored, and the dichroic ratio of the dichroic dye can be maximized. Furthermore, in the case of curing using a photomask, light is less likely to leak to the light-shielding portion of the photomask because the mixture contains a dye, and the location where the polymer wall can be produced can be clearly limited,
Furthermore, since the liquid crystal molecules are oriented in a horizontal direction and randomly in a plane with respect to the cell by the electric field from the vertical state and the alignment force of the polymer wall and the liquid crystal, the reflection type liquid crystal having excellent viewing angle characteristics. An element can be manufactured.

When applied to a GH (host guest) mode, the GH mode is, for example, a mode in which a dichroic dye is added to the device, and the vertical and horizontal directions of molecules are electrically used. The dichroic dye's dichroic ratio can be used to the maximum extent possible. Furthermore, since the dichroic dye in the polymer wall is oriented vertically, the molecules are oriented in the color erasing direction, and the state is changed from a state where the entire color is erased to a state where only the liquid crystal droplet portion is colored. Be able to control. Furthermore, FL
When applied to a C (ferroelectric liquid crystal) element, the polymer can be more strongly aligned by uniaxially oriented polymer. This makes it possible to improve the impact resistance, which is the greatest drawback of FLC, with the polymer wall. In addition, photocurable resin materials
When a material that becomes an FLC polymer is used as a material, this portion also responds to a voltage, and since a driving voltage is different between the FLC and the FLC polymer, gradation display can be realized.

In Examples 3 and 4, the mixture is cured in a liquid crystal state, which corresponds to a nematic phase, a smectic phase or a cholesteric phase.

In Examples 1, 3 and 4, the compound X is used as the liquid crystal compound, and in Example 2, the compound Y is used. However, the present invention is not limited to this. Can be used.

[0073]

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A in Chemical Formula 3 represents a polymerizable functional group, and CH ₂
＝ CH—, CH ₂ ＣＨCH—COO—, an unsaturated bond such as a structure represented by the following formula 4, or a functional group having a strained heterocyclic structure. LC represents a liquid crystal compound, and corresponds to a compound represented by the following formula 5, a cholesterol ring and a derivative thereof, and the like. B is a linking group that connects the polymerizable functional group and the liquid crystal compound, and specifically includes an alkyl chain (— (CH ₂ ) —), an ester bond (—COO—), an ether bond (—O—), and polyethylene glycol. Chain (-
CH ₂ CH ₂ O—) and a bonding group obtained by combining these bonding groups, and the like. In particular, in order to easily move in response to an electric field on a polymer wall, a liquid crystal molecule is converted from a polymerizable functional group. Is preferably a connecting group having a length having 6 or more bonds up to the rigid portion. In the case where the polymer wall is also in the alignment state, it is preferable to exhibit liquid crystallinity when mixed with a liquid crystal material.

[0075]

Embedded image

[0076]

Embedded image

D in Chemical Formula 5 is a functional group that binds to B in Chemical Formula 3, and has a function of determining the magnitude of the dielectric anisotropy and the refractive index anisotropy of the liquid crystal molecules. Specifically, a paraphenyl ring, a 1,10-diphenyl ring, a 1,4-cyclohexane ring, a 1,10-phenylcyclohexane ring, a naphthalene ring, a terphenyl ring and the like are applicable. G is a polar group that expresses the dielectric anisotropy of the liquid crystal, etc., -CN, -OC
_{H 3, -F, -Cl, -OCF} 3, -OCCl 3, -H,
A benzene ring, a cyclohexane ring, a paradiphenyl ring, a phenylcyclohexane ring and the like having a functional group such as —R (R: alkyl group) are applicable. E is a functional group for connecting D, and G, a single _{bond, -CH 2 -, - CH 2} CH 2 -,
—O—, a carbon-carbon triple bond, —CH ＝ CH— and the like correspond.

Further, as the polymer material which can be used in the present invention, a photocurable resin, a thermosetting resin, or the like corresponds. As the photocurable resin material , for example, acrylic acid and acrylate having a long-chain alkyl group or a benzene ring of C3 or more, specifically, isobutyl acrylate, stearyl acrylate, lauryl acrylate, isoamyl acrylate, n- Butyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, 2-ethylhexyl acrylate, n-stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-phenoxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate and the like are applicable. Further, polyfunctional compounds having two or more functionalities to increase the physical strength of the polymer, for example, bisphenol A dimethacrylate, bisphenol A diacrylate, 1,4-butanediol dimethacrylate,
1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, neopentyl diacrylate and the like can be used. More preferably, these monomers are halogenated, especially chlorinated or fluorinated compounds , for example, 2,2,3,4,4,4-hexafluorobutyl methacrylate, 2,2,3,4,4 2,4-hexachlorobutyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, perfluorooctylethyl methacrylate, perchlorooctylethyl methacrylate, perfluorooctylethyl acrylate And perchlorooctylethyl acrylate.

As the thermosetting compound, the photocurable resin material described above can be used, and a compound having an epoxy group in the molecule can be used. Specifically, for example, bisphenol A type epoxy compound, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hexahydrobisphenol A diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, diglycyl phthalate , triglycidyl isocyanate, a tetra- glycidyl meta-xylene diamine and the like, these monomers may be used alone or may be a mixture of two or more.

As the dichroic dye which can be used in the present invention, both N-type and P-type dyes can be used.
Specifically, for example, a merocyanine-based, anthraquinone-based, styryl-based, azobenzene-based, or the like can be appropriately selected and used. The amount of the dichroic dye added is preferably in the range of 0.5% to 10% by weight relative to the liquid crystal, and is preferably about 1% to 5%. In addition to the purpose of improving the contrast by the light absorption effect, a combined use of a dye effect for colorization may be used.

The liquid crystal which can be used in the present invention corresponds to a liquid crystal which is an organic mixture showing a liquid crystal state at around normal temperature. That is, a nematic liquid crystal including a two-frequency driving liquid crystal or a liquid crystal with Δε <0, a cholesteric liquid crystal (in particular, a liquid crystal having a selective reflection characteristic for visible light), a smectic liquid crystal (including a ferroelectric liquid crystal), and a discotic liquid crystal. A liquid crystal or a mixture of two or more of these liquid crystals is applicable. In particular, a nematic liquid crystal, a cholesteric liquid crystal, a nematic liquid crystal to which a chiral agent is added, or a ferroelectric liquid crystal is preferable in terms of characteristics. Furthermore, a liquid crystal having a functional group such as a fluorine atom in a compound is preferable because the compound is accompanied by a photopolymerization reaction during processing and has excellent chemical reaction resistance. Specifically, Z
LI-4801-000, ZLI-4801-001,
ZLI-4792 (manufactured by Merck) and the like. In selecting a liquid crystal material and a liquid crystal compound having a polymerizable functional group in a molecule, it is preferable that the portions exhibiting liquid crystal properties are similar from the viewpoint of compatibility. In particular, for an F or Cl liquid crystal material having a specific chemical environment, a liquid crystal compound having a polymerizable functional group is preferably an F or Cl liquid crystal material. Also, when a ferroelectric liquid crystal is used, it is preferable to use a polymerizable compound having a ferroelectric liquid crystal in a molecule in order to form a stable smectic phase.

The weight ratio of mixing the liquid crystal and the polymerizable compound is such that the ratio of the liquid crystal to the polymerizable compound is 50:50 to 97: 3.
And more preferably 70:30 to 90:10. When the content of the liquid crystal material is less than 50%, the effect of the polymer wall is enhanced, the driving voltage of the cell is significantly increased, and practicality is lost. Conversely, if the content of the liquid crystal material exceeds 97 %, the physical strength of the polymer wall decreases and stable performance cannot be obtained.

Further, when the compound having liquid crystallinity and the polymerizable compound having non-liquid crystallinity are mixed, the polymerization ratio is within the above-mentioned weight ratio and the compound having liquid crystallinity is 0.5% or more. I just need. In particular, when using a ferroelectric liquid crystal,
By making the compound having liquid crystallinity 70% or more,
By generating two regions of a low-molecular liquid crystal and a high-molecular liquid crystal and setting the voltage to a voltage value driven by each compound, a ferroelectric liquid crystal display element capable of gradation display can be manufactured.

[0084] Also, the includes a photoinitiator and a thermal initiator such as a reaction initiator (or catalyst), if the photoinitiator, I
rgacure 184, 651, 907, Darocu
re 1173, 1116, 2959, etc. can be used. As the thermal initiator, peroxides such as biphenyl peroxide and t-butyl peroxide, and radical generators such as ABIN can be used. Furthermore, the addition amount of these polymerization initiators depends on the reactivity of each compound and is not particularly limited in the present invention. In the case of a photoinitiator, the amount of the liquid crystal and the photocurable resin (including the liquid crystalline photocurable resin) It is preferably 0.01% to 5% based on the mixture. If it is 5% or more, the phase separation speed of the liquid crystal and the polymer is too fast to control, the liquid crystal droplet becomes small, the driving voltage becomes high, and the alignment control force of the alignment film on the substrate becomes weak. The liquid crystal region is reduced in the element (when a photomask is used, liquid crystal droplets are formed in the light shielding portion), and the contrast is reduced. On the other hand, if it is less than 0.01%, the polymer cannot be cured sufficiently. The material of the alignment film that can be used in the present invention is polyimide (specifically, SE150).
(Nissan Chemical Co., Ltd.), Cytop (produced by Asahi Glass Co., Ltd.), or other organic films, inorganic films such as SiO, and the like, and if necessary, alignment treatment such as rubbing may be performed.

In the first and second embodiments, a photomask in which a light-shielding portion is formed for each picture element is used. However, the present invention is not limited to this, and as shown in FIG. A photomask in which a light-shielding portion is formed over the picture elements may be used, or a photomask in which a light-shielding portion is formed for each set of several picture elements as shown in FIG.

The present invention is not limited to the photomask, and the illuminance distribution may be given to the UV light by using a micro lens, an interference plate or the like. In the case where the illuminance distribution is given to the UV light in this way, the diameter of the necessary liquid crystal droplet (picture element)
When regular strengths of the same degree are provided, photopolymerization occurs regularly and uniform liquid crystal droplets can be regularly arranged in a plane. In other words, in the portion where the UV illuminance is high, the polymerization speed is high, and the phase separation speed between the liquid crystal and the polymer is also fast, so that the polymer is quickly precipitated and the liquid crystal is extruded to the low illuminance portion, and as a result, the UV illuminance is low. Liquid crystal droplets can be formed in portions. At this time, if a curing reaction is performed in a liquid crystal state, the polymer and the liquid crystal layer generated are in a liquid crystal state, so that curing and phase separation can be performed while maintaining the alignment state regulated by the alignment. As the liquid crystal phase, a nematic phase or a smectic phase can be used, but a nematic phase rich in fluidity is more preferable in consideration of mass transfer of a photocurable resin or the like during light irradiation time.

In the present invention, the position where the photomask is installed may be either inside or outside the cell.
It suffices if irregularities can be created in the light regularly. When the photomask is separated from the cell, the image on the photomask is blurred and the effect of the present invention is reduced. Therefore, it is desirable that the photomask be as close as possible to a mixture of a liquid crystal-photocurable resin. Also, it is desirable that the UV light source be as parallel as possible. However, in order to improve the shock resistance of the ferroelectric liquid crystal element, it is effective to arrange small liquid crystal droplets for buffering around liquid crystal droplets of the same size as a picture element. For this purpose, the edge of the light-shielding portion such as a photomask may be intentionally blurred, the photomask may be intentionally separated from the cell body, or a light source having a slightly poor parallelism may be used as a UV light source. According to the study results of the present inventors, it is preferable that the size of the uneven illuminance (low illuminance region) is larger than 30% of the size of the picture element.
When a liquid crystal droplet having a size of 30% or less is used, the size of the liquid crystal droplets generated is also 30% or less of the size of the pixel, and the number of interfaces between the liquid crystal and the polymer increases in the pixel and the contrast is greatly reduced due to scattering. Become. Further, it is preferable that a weak illuminance region larger than the size of the picture element is provided so that the interface between the liquid crystal and the polymer is extremely reduced in the picture element. It is preferable to use a photomask or the like.

Further, the shape of the weak illuminance region (such as a photomask) may be one that covers more than 30% of the picture elements and locally reduces the UV intensity in a mode that does not use scattering between the polymer and the liquid crystal material. I just need. Although not particularly limited in the present invention, a circle, a square, a trapezoid, a rectangle, a diamond, a character, a hexagon, a figure delimited by a curve and a straight line,
These figures are obtained by partially cutting these figures, figures combining these figures, and aggregations of these small figures. More preferably, a photomask or the like in which the picture element portion is in a low illuminance region is preferable because it reduces the scattering intensity in the picture element and improves the contrast of the element. In the present invention, at least one type may be selected from these figures and used. However, in order to increase the uniformity of the liquid crystal droplets, it is preferable to limit the shapes to one type as much as possible.

The low-illuminance areas do not need to be independent from each other, and may be connected at the end, and the area where UV light is most effectively cut has the above-described shape and arrangement. I just need.

In the case of the method of the present invention, by combining the fabricated cell with a polarizing plate or the like, liquid crystal droplets of each of the conventional display methods such as TN, STN, FLC (SSF), ECB and the like can be polymerized. A liquid crystal display element which is confined in a wall or partially connected can be manufactured, and a large screen, a film, and the like can be formed. In addition, the created cells are simple matrix drive, TFT, MIM
, Etc., and is not particularly limited in the present invention.

[0091]

As described above in detail, according to the present invention, the display medium has a size corresponding to the picture element area,
The liquid crystal droplets formed on the surface are surrounded by polymer walls
In the picture element compared with the conventional polymer dispersion type liquid crystal display element
Scattering of liquid crystal, greatly increasing the contrast of the liquid crystal display
Can be improved. Furthermore, the polymer of this liquid crystal droplet
The liquid crystal compound is fixed near the interface with the wall.
Therefore, when a voltage is applied, the interface between the liquid crystal droplet and the polymer wall is driven, and when the voltage is turned off, the driving force increases because the fixed liquid crystal molecules are bonded to the polymer wall, and τr and τd And improve response speed
It is possible, it can be clearly performed phase separation.

The liquid crystal material has a chemically stable F
When a liquid crystal material of a liquid crystal system or Cl system is used, it is possible to provide liquid crystal molecules with chemical stability by using a liquid crystal compound having an F atom or a Cl atom in a molecule. The present invention can be applied to a charge holding type liquid crystal display device such as a TFT without lowering the electrical holding ratio of the entire display device.

Further, when a ferroelectric liquid crystal is used as a liquid crystal material, a liquid crystal compound having a polymerizable functional group and an optically active group in a molecule is used, so that an optical interface is formed at the interface with the polymer wall. Liquid crystal molecules having an active functional group can be present. As a result, not only the alignment control force from the alignment-treated substrate but also the control force from the polymer wall having a direction component orthogonal to the substrate surface can be applied to the liquid crystal droplets to stabilize the alignment state. And shock resistance can be improved.

When the polymer wall is also cured in a liquid crystal state, the molecules in the polymer wall are also solidified in an oriented state,
It can be made perpendicular to the cell, and the contrast can be improved. In addition, if a dichroic dye is present in the liquid crystal droplets or polymer walls, the entire display surface can be in a light transmitting state when the voltage is off, so that the contrast can be further improved.

Further, the liquid crystal display device of the present invention can be used for flat display devices such as projection televisions and personal computers,
It can be used for a display plate, a window, a door, a wall, and the like using a shutter effect.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a liquid crystal display device of Example 1.

FIG. 2 is a plan view showing a state of intersecting electrode lines 3 and 4 in the liquid crystal display element of Example 1.

FIGS. 3A and 3B are plan views each showing an example of a photomask applicable to the present invention.

FIG. 4A is a diagram illustrating a state in which a conventional ECB element displays a halftone, and FIG. 4B is a diagram illustrating the EC of the third embodiment.
FIG. 7 is a diagram illustrating a state in which a B element displays a halftone.

5A is a diagram illustrating a molecular orientation state of the GH mode liquid crystal display device according to Example 4 when a voltage is off, and FIG. 5B is a diagram illustrating a molecular orientation state of the GH mode liquid crystal display device when a voltage is applied. FIG.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1, 2 Substrate 1a, 2a Substrate 3, 4 Electrode wire 5, 6 Alignment film 7 Polymer wall 8 Liquid crystal drop 9 Liquid crystalline compound 10 Picture element 11 Shielding part a Liquid crystal molecule b Dichroic dye c Electrode d Substrate f Polymer Wall g liquid crystal droplet h alignment film

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-5-257134 (JP, A) JP-A-4-218024 (JP, A) JP-A-4-338923 (JP, A) JP-A-3-338 278024 (JP, A) JP-A-4-84121 (JP, A) JP-A-5-313142 (JP, A) JP-T-61-502128 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G02F 1/1333 610

Claims (10)

(57) [Claims] A display medium provided between a pair of substrates disposed opposite to each other has a size corresponding to a pixel region and is provided for each pixel.
A liquid crystal display device liquid crystal droplets formed together with the surrounding by the polymer walls, a structure in which liquid crystalline compound is fixed in the vicinity of the interface between the polymer wall of the <br/> liquid crystal droplets. 2. The liquid crystalline compound has an F atom and / or a Cl atom in a molecule, and the liquid crystal droplet has an F atom and / or a Cl atom in the molecule.
2. The liquid crystal display device according to claim 1, comprising a liquid crystal material containing a Cl element. 3. The liquid crystal display device according to claim 1, wherein the liquid crystal compound has an optically active group in a molecule, and the liquid crystal droplet is made of a ferroelectric liquid crystal. 4. The liquid crystal display device according to claim 1, wherein the polymer wall is formed of a compound having a liquid crystal. 5. When the polymer wall is formed of a compound having a liquid crystal and the display medium is in a state where no voltage is applied, the polymer wall and the liquid crystal droplet are placed on the display medium side of the pair of substrates. 2. The liquid crystal display device according to claim 1, wherein the same alignment state is provided based on the provided alignment film. 6. The liquid crystal display device according to claim 4, wherein the liquid crystal droplet and the polymer wall are formed to contain a dichroic dye. 7. A method for manufacturing a liquid crystal display device in which a display medium is provided between a pair of opposed substrates, wherein a liquid layer material and at least one kind of molecule are interposed between the pair of opposed substrates. Injecting a mixture with a polymerizable compound comprising a liquid crystalline compound having a polymerizable functional group therein, and causing the mixture to undergo a polymerization reaction, and by phase separation accompanying the reaction
Forming a display medium in which liquid crystal droplets are sized to correspond to the picture element regions and surrounded by a polymer wall for each picture element. 8. A liquid crystal having a polymerizable functional group and an F atom and / or a Cl atom in the molecule as the liquid crystal compound, wherein the liquid crystal droplet has an F and / or Cl element in the molecule. The method for manufacturing a liquid crystal display element according to claim 7, wherein a material containing the material is used. 9. The production of a liquid crystal display device according to claim 7, wherein the liquid crystal compound has a polymerizable functional group and an optically active group in a molecule, and a ferroelectric liquid crystal is used as the liquid crystal droplet. Method. 10. The display medium according to claim 7, wherein, when the polymerizable compound has photocurability, the mixture is irradiated with light in a state of having regular intensity to form the display medium. 5. A method for manufacturing a liquid crystal display device according to any one of the above.