JPH06301015A - Liquid crystal display element and its production - Google Patents

Abstract

(57) [Abstract] [Purpose] Liquid crystal regions having a uniform diameter can be regularly arranged in the direction along the substrate surface, whereby the threshold characteristics are steep and the contrast is excellent. [Structure] Mixture 4 of photocurable polymer resin and liquid crystal
Is injected between two substrates 1 and 3 at least one of which is transparent, the irradiation light intensity is reduced at a portion corresponding to an area of at least 30% or more of the size of a pixel, and a light 10 is added to the mixture 4.
Irradiate. The irradiation direction is preferably from the side where the photomask 7 is provided. Then, in the portion of the mixture 4 which is strongly exposed to light, the polymer resin is cured to form the wall 8 that reaches both substrates 1 and 3, and the liquid crystal region 9 is formed in the portion surrounded by the wall 8. Become.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal display device in which a display medium having a liquid crystal region surrounded by a polymer wall is sandwiched between two substrates facing each other, and a manufacturing method thereof.

[0002]

2. Description of the Related Art Liquid crystal display devices are available in various display modes. For example, as a liquid crystal display element utilizing the electro-optical effect, a TN (twisted nematic) mode using nematic liquid crystal molecules or an STN (super twisted nematic) mode has been put into practical use. Further, a liquid crystal display device using a ferroelectric liquid crystal (FLC) has also been proposed. These require polarizing plates and alignment treatments.

On the other hand, there is a liquid crystal display element which utilizes a light scattering of liquid crystal without using a polarizing plate and which utilizes a dynamic scattering (DS) mode or a phase transition (PC) mode.

In recent years, as a liquid crystal display device which does not require a polarizing plate and does not require an alignment treatment, a liquid crystal display device utilizing a birefringence of liquid crystal and electrically controlling a transparent or cloudy state has been proposed. There is. This liquid crystal display element
When a liquid crystal is aligned by applying a voltage, the ordinary refractive index of the liquid crystal molecules is matched with the refractive index of a supporting medium such as a polymer that supports the liquid crystal to form a transparent state. The basic method is to display by setting the state in which light scattering occurs due to the disorder of the molecular orientation.

The following five methods have been proposed as a method of manufacturing a scattering type liquid crystal display element of this type.

As a first method, there is a method in which a liquid crystal is contained in a polymer capsule to provide a display medium (Japanese Patent Publication No. 58-501631).

As a second method, a mixture of a photo-curable or thermo-curable resin and a liquid crystal is used, only the resin is deposited and cured, and a droplet-shaped liquid crystal region is provided between the cured resins. There is a method of forming
issue).

As a third method, there is a method of controlling the diameter of the liquid crystal region in the form of drops (Japanese Patent Laid-Open No. 3-72317).

As a fourth method, there is a method of impregnating a polymer porous film with liquid crystal (Japanese Patent Laid-Open No. 3-59515, etc.).

As a fifth method, there is disclosed a liquid crystal structure in which polymer beads, which are light scattering sources, are suspended in a liquid crystal provided between two transparent electrodes arranged apart from each other (special feature). Kaihei 3-46621).

[0011]

However, in the case of the above-mentioned first method, since the liquid crystal contained in the polymer capsule is an independent liquid crystal region in the form of droplets, the orientation of the liquid crystal molecules is changed. The drive voltage for generating is different for each liquid crystal region, and as a result, the drive voltage for simultaneously operating all liquid crystal regions is high, and the range that can be used as a liquid crystal display element is narrow.

Although the phase separation method is used in the second and third methods, it is difficult to arrange the liquid crystal droplets in a plane precisely in the former case, and in the latter case, the position of the liquid crystal droplet is changed. It was difficult to control precisely.

In the case of the fourth method, since phase separation is not used when forming the liquid crystal region, the degree of freedom in selection of applicable resin materials and liquid crystals is very large, and sufficient purification of the polymer porous membrane is possible. Although it has the advantage of being possible, on the other hand, at present, there is a drawback that the diameter of the liquid crystal region is not sufficiently controlled and the position of the liquid crystal region in the direction along the substrate surface cannot be precisely arranged. Have.

In the case of the fifth method, although the light scattering intensity is large, it is difficult to uniformly disperse the beads,
It is difficult to generate the same degree of scattering in each picture element, and display unevenness is likely to occur.

Therefore, each so-called polymer dispersion type liquid crystal display element using the polymer type liquid crystal in which the liquid crystal region is dispersed as described above has a non-uniform shape of the liquid crystal region due to its manufacturing method, and It has been difficult to accurately control the position of the liquid crystal region in the direction along the surface of the substrate. Therefore, liquid crystal regions having different diameters exist, and the distribution thereof is not uniform. Further, since the position of the liquid crystal region cannot be accurately arranged, the driving voltage is different for each liquid crystal region, so that the steepness of the threshold in the electro-optical characteristics is lacking and the driving voltage is relatively high. Further, since there are many small liquid crystal regions having low light scattering ability, there is a problem that the contrast becomes relatively low.

Further, as described above, the shape of the liquid crystal region is not uniform, and it is difficult to regulate the positional arrangement of the liquid crystal region in the direction along the surface of the substrate. Therefore, a large screen can be obtained in a high-definition state. I couldn't. In addition, when the method of driving the liquid crystal display element is the duty driving method of driving the signal on / off and by an averaged value, the duty ratio cannot be increased.

Further, each polymer dispersion type liquid crystal display element is
There is a problem that it is difficult to perform the alignment treatment. The reason will be described below.

As an alignment treatment method, a method of applying a magnetic field or an electric field during polymer polymerization in the production of a liquid crystal display element has been proposed (Japanese Patent Laid-Open No. 3-528).
43, and Liquid crystal, Vol.5, No5, pp1477,
(1989)). However, according to this method, since the polymer surface is not directly subjected to the alignment treatment, the alignment regulating force is weak, and the liquid crystal molecules can be aligned only in one direction.
It cannot be applied to modes that require alignment in different directions on both sides of two substrates sandwiching a liquid crystal, such as TN mode and STN mode.

Another proposed alignment treatment method is to use a substrate that has been subjected to an alignment treatment and indirectly align it through a polymer wall formed on the substrate (17th Liquid Crystal Symposium Lecture Presentation Collection 320). However, when this method is used, it is unavoidable that the polymer remains on the surface of the alignment film on the pixel electrode, and it is difficult to directly align the liquid crystal molecules. The force is significantly reduced, which is a big problem for practical use.

Further, as described above, in the liquid crystal display element using the polarizing plate and the ferroelectric liquid crystal which requires the alignment treatment as the liquid crystal, the SmC ^* (smectic) phase is used for expressing the spontaneous polarization. Since the regularity is closer to that of a crystal than that of a nematic phase, there is a problem that it is weak against impact. In order to solve this problem, it has been considered to disperse the ferroelectric liquid crystal in a polymer to reduce the impact, but it is difficult to perform the alignment treatment in the polymer and it has not been put to practical use.

Therefore, as a method for orienting the ferroelectric liquid crystal in the polymer, a liquid crystal in which the ferroelectric liquid crystal is dispersed is processed into a film and stretched in one direction. A method for orienting has been proposed (JP-A-63-264721 to 264724). But,
In the case of this method, since there are many interfaces between the liquid crystal region and the polymer in one picture element, incident linearly polarized light is scattered and a part of the light is depolarized. There is a problem that the white turbidity level of the device is lowered and the contrast is lowered. This problem is caused by other display modes that require a polarizing plate, such as TN mode, STN mode, and EC.
The same occurs in the B (Electrically Controlled Birefringence) mode.

In addition, when the liquid crystal dispersed in the polymer is pseudo-solidified, the alignment of the liquid crystal is controlled and the contrast is lowered due to depolarization due to scattering occurring at the interface between the liquid crystal and the polymer. And becomes a problem. That is, regarding the orientation, in the polymer dispersion type liquid crystal display element, the orientation processing cannot be performed on the substrate because the polymer exists between the substrate and the liquid crystal. On the other hand, with respect to the scattering that occurs at the interface between the liquid crystal and the polymer, it is sufficient to reduce the interface between the liquid crystal and the polymer in the pixel, but it is difficult to produce the liquid crystal region by the conventional method. Further, in the liquid crystal display device using the ferroelectric liquid crystal, there is another problem that the impact resistance becomes weak due to the high regulation of the liquid crystal phase (smectic phase) used.

The liquid crystal display element obtained by the above-mentioned first to fifth methods is a scattering type, and is applied to a non-scattering type liquid crystal display element such as TN mode, STN mode, ECB mode. Absent.

The present invention has been made in order to solve the problems of the prior art, and the liquid crystal region in the form of droplets has a uniform diameter and can be regularly arranged in the direction along the substrate surface. Accordingly, it is a first object of the present invention to provide a scattering type liquid crystal display device having a sharp threshold characteristic and excellent contrast, and a manufacturing method thereof. Also,
A second object is to provide a non-scattering type liquid crystal display device in which the size of the liquid crystal region is adjusted with respect to the picture element to form the liquid crystal region, and a manufacturing method thereof.

[0025]

The liquid crystal display device of the present invention is a polymer dispersion type liquid crystal display device in which picture elements are arranged in a matrix and is a scattering type liquid crystal display device. At least one of the substrates is transparent, the two substrates are disposed so as to face each other with the electrode side facing inward, and between the two substrates facing each other, a wall mainly made of a polymer reaching both substrates, A display medium composed of a liquid crystal region mainly composed of liquid crystal surrounded by the walls is sandwiched, and a distance (pitch) a in the direction along the substrate surface from one liquid crystal region to an adjacent liquid crystal region is in that direction. Within the pixel size, and 3b / 2>a> b with respect to the average value b of the distance
Since there is a regularity of 80% or more of the whole of the liquid crystal regions of / 2, the first object can be achieved by that.

The liquid crystal display device manufacturing method of the present invention is of a polymer dispersion type in which picture elements are arranged in a matrix, and
In a method of manufacturing a scattering type liquid crystal display element, a photocurable polymer material and a liquid crystal material are provided between two substrates, at least one of which is transparent, and a pair of substrates having electrodes serving as picture elements are opposed to each other. And injecting a mixture of
At least one place in one picture element irradiates light with a light intensity distribution of 90% or less with respect to the maximum illuminance within a circle 10 times the area of the picture element centered around the picture element. The first object described above is achieved.

In the method for manufacturing a liquid crystal display device of the polymer dispersion type and the scattering type, a photomask having a regular pattern smaller than the size of the picture element is used.
A transparent substrate side of a liquid crystal display element composed of a pair of substrates having electrodes, at least one of which is transparent, is placed on the transparent substrate side, and a mixture of the photocurable polymer and liquid crystal material is injected between the liquid crystal display elements. However, light may be irradiated from the photomask side.

In addition, in a liquid crystal display element composed of a substrate provided with a photomask having a regular pattern as compared with the size of the picture element under the electrode serving as the picture element, and a substrate having electrodes, A mixture of the photocurable polymer and a liquid crystal material may be injected, and light may be irradiated from the side of the substrate provided with the photomask.

As the photomask, a regular pattern is formed continuously or independently, and the regular pattern is formed so as to cover at least 30% or more of the area of each picture element. It is possible. Or
A regular pattern is formed continuously or independently, and the minimum repeating unit portion of the pattern is 1 μm or more and 50 μm.
It is possible to use those having a size within a circle having a diameter of m or less and having a separation distance from the center of the unit portion to the center of the nearest unit portion of 1 μm or more and 50 μm or less.

The liquid crystal display element of the present invention is a liquid crystal display element in which picture elements are arranged in a matrix, and at least one of two substrates each having an electrode is transparent, and the two substrates have electrode sides. Facing inside,
A display medium sandwiched between two opposing substrates is composed of a polymer-based wall and a liquid crystal-based liquid crystal region. The wall reaches both substrates and is formed. The second object is achieved by having a parallel portion which is surrounded by the wall and which is close to both substrates and whose approaching portions are parallel to the substrates.

The liquid crystal region may be provided for one or more picture elements. Further, the size of at least one liquid crystal region included in each pixel may be 30% or more of the area of each pixel.

When the long side dimension of the picture element is long, for example, 200 μm or more, two or more liquid crystal regions are present in one picture element so that the whole or a part thereof is included. You may

The liquid crystal region may have a plurality of liquid crystal domains, and the alignment direction of each liquid crystal domain may be concentric along the polymer wall on a plane substantially parallel to the substrate surface. . Further, the liquid crystal region is formed by enclosing the inner liquid crystal domain located at the center, the polymer region surrounding the inner liquid crystal domain, and the polymer region surrounding the outer region of the polymer region. The outer liquid crystal domains may be separated from each other and the directions of the respective outer liquid crystal domains may be radial on a plane substantially parallel to the substrate surface. The liquid crystal region may be composed of a plurality of liquid crystal domains separated by disclination, and the liquid crystal domains may be oriented in different directions on a plane substantially parallel to the substrate surface. Further, the liquid crystal region is composed of a polymer region located at the center and a plurality of liquid crystal domains that are formed so as to surround the outside of the polymer region and are separated by disclination. You may make it radial on the surface substantially parallel to the substrate surface.

A plurality of liquid crystal molecules included in the liquid crystal region may have a spiral pitch of 15 μm or more and 100 μm or less. Also, the product of the thickness between both parallel parts of the liquid crystal region and the refractive index anisotropy is 0.4 μm or more and 1.1 μm or less, and the separation distance between both substrates is 3 μm or more and 10 μm.
It may be as follows.

Further, a light-shielding mask may be provided on one of the substrates, and the light-shielding mask may cover at least 50% or more of the wall portion reaching the substrate. In addition, an alignment film may be formed on each of the electrodes provided on the two substrates. The alignment film may be a uniaxial alignment film. The uniaxial alignment film corresponds to an alignment film that has been subjected to a uniaxial alignment treatment such as an oblique deposition film on the electrode or an organic alignment film that has been subjected to a rubbing treatment. At this time, an electrically insulating layer may be formed between the alignment film and the electrodes in order to prevent a short circuit between the electrodes of the upper and lower substrates.

Further, the two substrates may or may not be provided with a polarizing plate depending on the display mode. Even when the two substrates are provided, a polarizing plate is provided outside one or both substrates depending on the display mode. It may be provided.

The method for producing a liquid crystal display element of the present invention is the same as the method for producing a liquid crystal display element in which picture elements are arranged in a matrix, and a mixture containing at least a photocurable polymer material and a liquid crystal material is used as an electrode. A step of injecting between the two substrates each having, and a wall made of a material containing a polymer formed by reaching the both substrates by irradiating the mixture with light by reducing the light intensity in the liquid crystal region forming part of the mixture; Forming a display medium between the two substrates, the display medium being surrounded by the wall and approaching both substrates, and a liquid crystal region having a parallel portion in which the approaching portions are parallel to the substrates. As a result, the above object is achieved.

In the above manufacturing method, the mixture portion for reducing the light intensity and irradiating the light is defined as a range extending over one or more picture elements, and the liquid crystal region is arranged for one or more picture elements. You may

In addition, the size of the picture element is 30 with respect to the mixture.
At least one liquid crystal region included in a pixel may have a size of 30% or more of the area of a pixel by reducing the light intensity and irradiating light to a portion corresponding to the area of 100% or more.

Further, the alignment direction of each liquid crystal molecule in the liquid crystal region may be formed radially. The formation uses a photomask in which a light-transmitting hole is provided in the center of a plurality of light-shielding portions for liquid crystal region formation, or has a light-transmitting hole in the center of the light-shielding portion for liquid crystal region formation, and It is possible to use a photomask having a light-transmitting slit radially provided from a light-transmitting hole in the light-shielding portion, and irradiate the mixture with light from the photomask side. Further, it is possible to reduce the light intensity in the liquid crystal region forming part of the mixture and to irradiate the mixture with light by alternately providing the light irradiation period and the light non-irradiation period.

It is also possible to use a mixture containing a compound having a photopolymerization-inhibiting effect.

In addition, the step of injecting the mixture between the two substrates is as follows.
It may be performed by bonding two substrates.

When a photomask is used as a means for reducing the light intensity, the photomask formed on one liquid crystal layer side of the two substrates can be used.

[0044]

In the present invention, a mixture containing at least a photo-curable polymer material and a liquid crystal material is used in each case having two electrodes.
It is injected between two substrates, and the mixture is irradiated with light while reducing the light intensity in the liquid crystal region forming part of the mixture.

As a result, first, the photo-curable polymer in the light irradiation region reacts to form nuclei for the polymer wall, and thereafter, the concentration of the polymer decreases in the light irradiation portion, so that the polymer of the polymer is reduced. A concentration gradient is formed, and along the concentration gradient, the unreacted polymer in the weak irradiation region gathers in the light irradiation region and polymerizes to form a polymer wall. Further, a liquid crystal region is formed in a portion where the polymer wall is not formed.

In this case, when the position of the weak irradiation region is set according to the formation position of the liquid crystal region on the display medium and the mixture is irradiated with light, the liquid crystal region is formed in the set weak irradiation region. At this time, when the mixture is irradiated with light using a photomask or the like having a comparatively small weak irradiation region, a substantially spherical liquid crystal region is formed in the weak irradiation region, and the obtained liquid crystal display element becomes a scattering type. The liquid crystal region in the scattering mode is shown in FIG. A large number of the liquid crystal regions d are formed for one picture element b and have a very small diameter.

The scattering mode is a liquid crystal display element that electrically controls the scattering and transmission states of liquid crystal surrounded by polymers. The principle is set so that the refractive index of the liquid crystal molecules and the refractive index of the polymer material are substantially matched when a voltage is applied. In that case, when voltage is applied, the transparent state,
When no voltage is applied, the liquid crystal molecules become randomly aligned due to the interaction with the polymer wall, the apparent refractive index of the liquid crystal increases, and the scattering state occurs due to the mismatch of the refractive index with the polymer wall. Is.

In such a case, at least one of the mixture of the photocurable polymer material and the liquid crystal is transparent.
At least 3 times the size of a pixel is injected between two electrode substrates.
Reduce the irradiation light intensity in the area corresponding to the area of 0% or more,
Illuminate the mixture with light. Note that a photomask or the like corresponds to the means for reducing the irradiation light intensity, and light may be irradiated from the side of the photomask or the like.

Then, in the portion of the mixture that is strongly exposed to light, the polymer material is cured to form a wall shape that reaches both substrates, and a liquid crystal region is formed in the portion surrounded by the walls. That is, the liquid crystal regions are formed in a dispersed state.

On the other hand, when the mixture is irradiated with light using a photomask or the like having a comparatively large weak irradiation region, the liquid crystal region is widened, and parallel portions parallel to the substrate surface are provided in portions close to the substrates on both sides. The liquid crystal region is formed, and the obtained liquid crystal display element is of non-scattering type. In the non-scattering mode, the scattering caused by the difference in the refractive index as described above is reduced as much as possible, and the display is performed only by the change of the molecular orientation of the liquid crystal. As a method for extracting the change in the molecular orientation of the liquid crystal, a method for detecting the change in the refractive index using a polarizing plate (T
(N, ECB, etc.) and a GH (guest host) mode in which a dichroic dye is added to the liquid crystal without using a polarizing plate.

In this non-scattering type liquid crystal display element, each liquid crystal region is set to one picture element by setting a suitable means such as a photomask for reducing the irradiation light intensity.
Alternatively, it can be provided for two or more picture elements. Also,
Even if the picture element is large, one picture element can hold one or more whole or part of the liquid crystal region.

In addition, a uniform mixture of a photocurable polymer material and a liquid crystal material is dropped or applied on one of two opposing substrates, the two substrates are bonded together, and then the polymer material is cured. You may do it.

Further, a liquid crystal region is provided for each picture element, and a light-shielding mask provided on one side of the liquid crystal layer is provided, and the wall portion where the light-shielding mask reaches one of the substrates is defined as the wall portion. By covering at least 50% or more of the area, the light scattered at the interface between the wall and the liquid crystal region can be prevented from leaking to the outside. In particular, when the light-shielding mask is provided on the light incident side of the liquid crystal region, it is possible to suppress the incident light itself from scattering at the interface between the wall and the liquid crystal region.

In particular, when a photomask is used, the irradiation area can be limited in advance, and the liquid crystal area can be preferentially produced for each picture element of the liquid crystal display element. Also in the case of producing individual liquid crystal regions, a large amount of polymer material can be arranged outside the picture element, and it is easy to improve the contrast, which is preferable.

In the production of a non-scattering type liquid crystal display device, the photopolymerization rate is changed by changing the material of the mixture, the light irradiation conditions, etc. to adjust the phase separation rate between the polymer and the liquid crystal. .

When the phase separation rate, that is, the photopolymerization rate is high, light leaking from the light irradiation region causes a photopolymerization reaction in the polymer material even in the weak irradiation region, and a plurality of liquid crystal regions are generated even in the weak irradiation region. In this case, as shown in FIG. 23, each liquid crystal region d existing in the picture element b is circular when viewed from above one substrate, and its orientation direction is concentric along the polymer wall, and It is almost parallel to the substrate surface.
When an electric field is applied to such a display medium, the liquid crystal molecules rise omnidirectionally in the halftone when the electric field is applied, the apparent refractive index is almost the same from any direction, and the viewing angle characteristics are improved. As a result, the contrast is improved.

When the phase separation rate, that is, the photopolymerization rate is slow: The polymerization reaction in the weak irradiation region is reduced, and the shape of the liquid crystal region is close to the shape of the light-shielding portion of the photomask. The polymer of Fig. 24 cannot reach the location where the polymer wall is polymerized by mass transfer.
As shown in (b), (c), or (d), a liquid crystal region d is generated substantially in the center of a pixel (weakly irradiated region) b, and a polymer region f and another liquid crystal region are provided outside the liquid crystal region d. d is formed with another liquid crystal region d as an outer side, and another liquid crystal region d is
For example, it is formed into a donut shape or a C-shaped shape with a part cut off.

The liquid crystals in the formed liquid crystal region are oriented in the same manner as above in the circular liquid crystal region in the central portion, but there are a plurality of C-shaped liquid crystal regions in the donut shape or a part of the peripheral liquid crystal region. It is composed of individual liquid crystal domains (indicates regions where polymer-like walls do not exist between liquid crystal regions, but has different alignment states, and is distinguished by disclination lines between the domains). They are arranged in a shape close to a radial shape from the central portion of the donut shape or a C-shaped shape with a part cut off.

This phenomenon occurs because the liquid crystal molecules try to align perpendicularly to the polymer wall due to the polymerization reaction of the photocurable polymer during mass transfer, and when the liquid crystal region becomes larger. But the same phenomenon can be seen. When an electric field is applied to the display medium in such an alignment state,
With respect to the circular liquid crystal region in the central portion, the same phenomenon as described above is performed. On the other hand, in the donut-shaped or partially cut C-shaped portion, the rising direction of the liquid crystal molecules is different between the domains, and the same as above. In principle, the viewing angle characteristics, so-called viewing angle characteristics, are dramatically improved. Note that when the photopolymerization rate is a little faster than in this case, a liquid crystal region as shown in FIG. 25 is obtained. In FIG. 25, there is a liquid crystal region d2 in which a plurality of circular liquid crystal units are in contact with each other at a portion corresponding to the edge portion of the weakly illuminated region b of the photomask, and a large number of circular liquid crystal units d1 are surrounded by the liquid crystal region d2. .

When the phase separation rate, that is, the photopolymerization rate is slower, the residual amount of the polymer in the weak irradiation region is further reduced, and a liquid crystal region similar to the weak irradiation region is produced. In this case, the orientation of the liquid crystal molecules in the liquid crystal region is as shown in FIG.
As shown in (b), (c), or (d), the disclination line h is composed of a plurality of domains g and the domains g are perpendicular to the polymer wall.
Since there are no islands in the center of the liquid crystal region d, they are random. At this time, if a light-transmitting hole is provided in the center of the weakly illuminated region (light-shielding part) b of the photomask, a polymer island i can be formed in the center of the liquid crystal region d as shown in FIG. 27. The liquid crystal domains g can be arranged radially in the center.

When an electric field is applied to such a display medium, the movement of the liquid crystal molecules is similar to the above, the refractive index is almost the same when viewed from all directions at a constant angle from the vertical direction of the substrate surface, and the viewing angle characteristics are Be improved. In this case, the occupancy of the liquid crystal region with respect to the picture element is increased, and the contrast can be increased, which is preferable.

Further, in the above cases and, as an example, when a chiral agent is added to the mixture, a plurality of liquid crystal molecules contained in the liquid crystal region becomes as shown in FIG. That is, when the liquid crystal region d is viewed from the substrate side as shown in FIG. 28B, the plurality of domains g are radial, but as shown in FIG. 28A, each liquid crystal molecule j is relative to the substrate surface. It is in a state of being helically oriented around the substantially vertical spiral axis k. More specifically, when the I layer portion of FIG. 28C is viewed from the substrate side, I of FIG.
28A, the layers II, III, and IV in FIG. 28A are viewed from the substrate side, and the layers II and III in FIG.
When the layers IV and IV are viewed from the substrate side, II in FIG.
Layer, III layer, IV layer. In addition, l shown in FIG. 28A indicates a disclination line.

On the other hand, when no chiral agent is added,
The plurality of liquid crystal molecules are as shown in FIG. That is, when the liquid crystal region d is viewed from the substrate side as shown in FIG. 29B, the plurality of domains g are radial, but FIG.
As shown in (a), each liquid crystal molecule j is aligned in a fixed direction around an axis substantially perpendicular to the substrate surface.
More specifically, when the I layer portion of FIG. 29A is viewed from the substrate side, it becomes like the I layer of FIG. 29C, and the II layer, the III layer of FIG. When the IV layer is viewed from the substrate side, it becomes like the II layer, the III layer, and the IV layer in FIG.

However, in the case where the chiral agent is added too much, when the liquid crystal region d is viewed from the substrate side as shown in FIG.
As shown in 0 (a), the helical axis is parallel to the substrate surface even when the liquid crystal molecules are oriented in a helical state. Incidentally, such a phenomenon occurs not only when the chiral agent is added to the mixture but also when the cholesteric liquid crystal is added to the nematic liquid crystal.

[0065]

EXAMPLES The present invention will be specifically described below based on examples.

(Example 1) A case where the present invention is applied to a scattering type liquid crystal display element will be described.

FIG. 1 is a sectional view showing the liquid crystal display element of this embodiment. In this embodiment, two substrates 12 and 13 are arranged opposite to each other with a spacer (not shown) interposed therebetween. One of the substrates 12 is made of glass, and the pixel electrode 11 made of ITO is formed on the substrate 12. The other substrate 13
Is made of glass, a photomask 14 is arranged on one surface, and a counter electrode 15 made of ITO is formed on the other surface.

A mixture of a liquid crystal material and a photo-curable polymer material is enclosed between the two substrates 12 and 13, and the mixture is irradiated with ultraviolet light 20 to emit the polymer material. Was cured. A liquid crystal layer having a liquid crystal region 16 surrounded by a polymer wall 17 was obtained between the two substrates 12 and 13 after curing.

The polymer-dispersed liquid crystal display device thus produced was observed as follows. That is, the polymer-dispersed liquid crystal display device was divided, the cell was peeled off in liquid nitrogen, and the horizontal section of the polymer wall 17 after rinsing the liquid crystal material with acetone was observed by SEM (scanning electron microscope). However, it was confirmed that a liquid crystal region 16 having the same regularity as the dot pattern, and a substantially spherical liquid crystal region 16 of the same size and uniform shape was formed.

In the first embodiment, the distance a in the direction along the substrate surface from one liquid crystal area to the adjacent liquid crystal area is within the pixel size in the same direction, and the average value of the distances is used. One feature is that the liquid crystal regions satisfying the condition of 3b / 2>a> b / 2 with respect to b have a regularity of 80% or more of the whole.

According to the examination results of the present inventors, when the period size of the weak illuminance region is smaller than 2 μm among the strong illuminance region and the weak illuminance region which constitute the illuminance change, the liquid crystal region diameter is also smaller than 2 μm. Therefore, there are many liquid crystal regions that are less likely to be scattered by visible light, and light scattering when no voltage is applied is reduced. In addition, the thickness between the substrates is also subtly related, and when the weak illuminance region is smaller than the thickness between the substrates, the liquid crystal region has a circular honeycomb structure, which also causes a decrease in light scattering. Further, there is a problem that the film does not become sufficiently transparent even when a voltage is applied.

On the other hand, when the weak illuminance region is larger than 50 μm, the liquid crystal region is also larger than 50 μm, and the liquid crystal region occupies most of the space between the substrates, which is one of the light scattering characteristics when no voltage is applied. It was found to be unfavorable because of the decrease in the property.

Therefore, considering the above-mentioned results, in the first embodiment, the average range of the weak illuminance region is preferably 2 μm or more and 50 μm or less, and more preferably. It should be 3 μm or more and 20 μm or less. When the thickness is 20 μm or less, the scattering intensity can be increased as the scattering source is closer to the wavelength of light, and the scattering ability can be improved.

By limiting in this way, the distance a in the direction along the substrate surface from one liquid crystal region to the adjacent liquid crystal region is within the pixel size in the same direction, and the average value b of the distances is On the other hand, 3b / 2>a> b / 2
The liquid crystal regions having the regularity have a regularity of 80% or more of the whole. That is, the regularity of the liquid crystal region is increased. As a result, the liquid crystal layer is regularly arranged in the picture element portion, and depolarization due to scattering is suppressed. The regularity of the liquid crystal regions is preferably 90% or more of the entire liquid crystal regions satisfying 3b / 2>a> b / 2.

Further, the mixture is irradiated with light such that at least one spot in one picture element is 90% or less with respect to the maximum illuminance within a circle 10 times the area of the picture element centered around the picture element. It is preferred to use light with an intensity distribution.

Regarding the shape of the weak illuminance area, UV
Any material that locally reduces the strength may be used. In the present embodiment, although not particularly limited, circular, rectangular, trapezoidal, hexagonal,
A figure delimited by a rectangle, a rhombus, a character type, a curved line, and a straight line is applicable. Also, some of these figures are cut, figures that combine these figures, or
A collection of these small figures corresponds to this. However, in the case of an aggregate, the average diameter of the weak illuminance area is the distance from the center of the aggregate to the outermost contour. In addition, when implementing
It is only necessary to select one or more types from these figures and use them.
It is preferable to limit the number to the seeds and arrange them.

Another feature of this embodiment is that the liquid crystal regions are regularly arranged in the horizontal direction along the surface of the substrate. In this case, the arrangement of the weak illuminance area becomes a problem. As for the arrangement of the weak illuminance regions, when the distance between the regions is shorter than 1 μm, the weak illuminance regions are continuous and the illuminance portion becomes dot-like, and the effect of regulating the liquid crystal region of the present invention is lost. .

On the contrary, when the distance between the respective regions is longer than 50 μm, the regions in which the UV light is cut and the liquid crystal region cannot be controlled increase, and the liquid crystal regions having the random diameter similar to the conventional ones increase. The effect of this embodiment is diminished.

Therefore, in the first embodiment, the distance between the regions is 1 μm to 50 μm. More preferably, it is from 5 μm to 20 μm. Similar regularity is required for the photomask.

The weak illuminance areas need not be independent of each other, and may be connected at the ends.
It is sufficient that the region that cuts the most UV light has the above-mentioned shape and arrangement.

The liquid crystal is an organic mixture which exhibits a liquid crystal state near room temperature, and includes nematic liquid crystal (including dual frequency driving liquid crystal and liquid crystal with Δε <0) and cholesteric liquid crystal (especially selective reflection for visible light). Liquid crystal having characteristics), smectic liquid crystal, ferroelectric liquid crystal (SmC ^* ), and discotic liquid crystal. These liquid crystals may be mixed, and nematic liquid crystals or nematic liquid crystals to which cholesteric liquid crystals are added are particularly preferable in terms of characteristics.
More preferably, a liquid crystal having excellent compounding reactivity is preferable because it is accompanied by a photopolymerization reaction during processing. Specifically, it is a liquid crystal having a functional group such as a fluorine atom in the compound,
I-4801-000, ZLI-4801-001, Z
LI-4792 and the like.

The selection of the polymer material is important because it is a substance that is mixed with the liquid crystal material to form a mixture and finally becomes a wall that supports the two substrates and the liquid crystal region. The polymer material that can be used in this embodiment corresponds to a photo-curable resin monomer, and may be another polymer substance or the like. Examples of the photocurable resin monomer include acrylic acid and acrylic acid ester having a C3 or longer long-chain alkyl group or an aromatic ring. Further, isobutyl acrylate, steric acrylate, lauryl acrylate, isoamyl acrylate, n-butyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, 2-ethylhexyl acrylate, n-
There are stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate and 2-phenoxyethyl methacrylate.

Further, in order to increase the physical strength of the polymer, a polyfunctional resin having two or more functional groups such as bisphenol A dimethacrylate, bisphenol A diacrylate, 1,4-butanediol dimethacrylate, 1, 6
-Hexanediol dimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, etc. can also be used.

Further, usable resins include resins obtained by halogenating, especially chlorinating or fluorinating, the above-mentioned monomers. As such a material, for example, 2, 2, 3,
4,4,4-hexafluorobutyl methacrylate, 2,
2,3,4,4,4-hexachlorobutyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, perfluorooctylethyl methacrylate, perchlorooctylethyl Methacrylate, perfluorooctylethyl acrylate, and perchlorooctylethyl acrylate may be mentioned.

The polymer materials described above may be used alone or in combination of two or more. Moreover, you may mix and use the polymer and oligomer which were chlorinated and fluorinated with the above-mentioned monomer as needed.

As a switching element, a TFT (thi
When using an n film transistor), the electrical resistance of not only the liquid crystal material but also the polymer resin is required, so the specific resistance of the polymer resin is 1 x 10 ¹² Ω · c even in the uncured state.
It is preferable to use those having a size of m or more.

In combining these liquid crystal materials and polymer materials, when a polymer dispersion type liquid crystal display element was prepared by the conventional photopolymerization phase separation method, the diameter of the prepared liquid crystal region was It is preferable to make it larger than the dot diameter of the photomask to be used.
It can be used by weakening the V light intensity or suppressing the addition amount of the photocuring catalyst. The position of the photomask may be inside or outside the display element as long as it can regularly form unevenness in the UV light.

A specific example of the first embodiment will be described below.

[Specific Example 1] A glass substrate 12 (ITO-5 manufactured by Nippon Sheet Glass Co., Ltd.) on which a pixel electrode 11 having ITO (a mixture of indium oxide and tin oxide) on one side is formed.
Flint glass with 00 angstrom), and the other has a photomask 14 having a dot pattern made of aluminum (a circle having a diameter of 10 μm and a center-to-center distance of 15 μm and a square pattern) shown in FIG. 1 on one surface of the glass substrate 13. Then, using two substrates, which are glass substrates, on the other surface of which opposite electrodes 15 formed by vapor-depositing ITO to 500 angstroms were formed, a cell was produced through a spacer of 12 μm.

Next, 0.1 g of trimethylolpropane trimethacrylate and 0.9 g of 2 were added to the prepared cell.
-Ethylhexyl acrylate and 4g ZLI-47
92 (Merck) 0.03 g of photocurable catalyst Irgacu
A mixture of re184 (manufactured by Ciba Geigy) is uniformly mixed and then injected. Then, using a high pressure mercury lamp that can obtain parallel rays from the photomask 14 side, 20 mW
The resin was cured by irradiating with ultraviolet rays 20 for 2 minutes at an illuminance of / cm ² to obtain a polymer dispersion type liquid crystal display device. Liquid crystal regions 16 controlled by the photomask 14 were regularly formed on the polymer wall 17 in the cell.

As a result of observing the produced polymer-dispersed liquid crystal display device, the distance a in the direction along the substrate surface from one liquid crystal region to an adjacent liquid crystal region, which is an index of uniformity, is the same in the same direction. 95% of the total distance between the liquid crystal regions was 3b / 2>a> b / 2 within the pixel size and the average value b of the distances.

The electro-optical characteristics of this polymer-dispersed liquid crystal display element are values obtained by subtracting the transmittance T ₀ when no voltage is applied from the saturated transmittance T _s when the light transmittance is set to an excessively high voltage. Applied voltage V ₁₀ when the 10% transmittance of the
V, 90% transmittance increased, and the applied voltage V ₉₀ at that time was 5.1.
V, the driving voltage is lower than that of the conventional polymer-dispersed liquid crystal display device, and the sensitivity is excellent (α = V ₉₀ / V
₁₀ = 1.18). Further, polarizing plates were arranged in front of and behind the polymer-dispersed liquid crystal display device so as to form crossed Nicols. As a result, a black state was obtained when a voltage was applied and a white state was obtained when no voltage was applied, and a good black and white display was achieved.

In contrast to this Concrete Example 1, a liquid crystal display device of Comparative Example 1 was prepared as follows. The liquid crystal display element of Comparative Example 1 was replaced with the substrate 13 with the photomask 14 of Example 1, and the same glass with ITO as the other substrate 12 (printed glass with ITO-500 angstrom made by Nippon Sheet Glass) was used. Similarly, a polymer-dispersed liquid crystal display device was produced.

The liquid crystal display device of Comparative Example 1 was observed by SEM, and it was confirmed that the liquid crystal region diameter and shape were random. The distance a in the direction along the substrate surface from one liquid crystal region to the adjacent liquid crystal region, which is an index of uniformity, is within the pixel size in the same direction, and 3b with respect to the average value b of the distance. / 2>a> b / 2
65% of the entire liquid crystal region was. As for electro-optical characteristics, V ₁₀ was 7.5 V, V ₉₀ was 13.7 V, and α was 1.83.

[Specific Example 2] Both glass substrates 12 and 13 of Specific Example 1 were replaced with a PET film with ITO having a thickness of 125 μm, and a 12 μm spacer was put between two PET films to form a cell. The same material as 1 was injected into the cell. Subsequently, a photomask having the same dot pattern as in Example 1 was placed so that the mask image was in contact with the PET film, and UV light irradiation was performed through the mask in the same manner as in Example 1 to display a polymer-dispersed liquid crystal display. The device was obtained.

The obtained polymer-dispersed liquid crystal display device was SE
The horizontal cross section of the polymer wall was observed after the cell was peeled off in liquid nitrogen and the liquid crystal material was washed off with acetone. As a result, it was confirmed that a liquid crystal region having the same regularity as the dot pattern and the same size and uniform alignment was produced. It is also an index of uniformity,
The distance a in the direction along the substrate surface from one liquid crystal region to the adjacent liquid crystal region is within the pixel size in the same direction, and 3b / 2 with respect to the average value b of the distance.
97% of the entire liquid crystal regions were>a> b / 2. Further, the electro-optical characteristic is that V ₁₀ is 4.6 V, and 9
The applied voltage V ₉₀ when the 0% transmittance increased was 5.8V. Therefore, the driving voltage is lower than that of the conventional polymer-dispersed liquid crystal display device, and the sharpness (α = V ₉₀
/ V ₁₀ = 1.26) could be secured.

In contrast to Concrete Example 2, the following liquid crystal display device of Comparative Example 2 was produced. In the liquid crystal display element of Comparative Example 2, a polymer dispersed liquid crystal display element was produced in the same manner as in Example 2 except that UV light irradiation was performed without covering the photomask 14. The polymer matrix in the produced polymer-dispersed liquid crystal display element has a random shape. The distance (pitch) a in the direction along the substrate surface from one liquid crystal region to the adjacent liquid crystal region, which is an index of uniformity, is within the pixel size in the same direction, and the average value b of the distance is On the other hand, 3b / 2>a>
67% of the entire liquid crystal region was b / 2. The electro-optical characteristics of V ₁₀ are 7.7 V and V ₉₀ is 14.3.
V and α = 1.85.

As the photomask, its regular pattern is formed continuously or independently, and the minimum repeating unit portion of the pattern is of a size that can be accommodated within a circle having a diameter of 1 μm or more and 50 μm or less. The separation distance from the center of the unit portion to the center of the closest unit portion is 1 μm
It is possible to use those having a thickness of 50 μm or more and 50 μm or less.

As described above, according to the first embodiment,
A polymer-dispersed liquid crystal display device in which liquid crystal regions having a uniform diameter are regularly arranged along the surface of a substrate can be manufactured with a good yield in a small number of steps. This method enables the alignment treatment of the liquid crystal by the alignment treatment of the substrate, can produce the liquid crystal liquid crystal device which can be operated in various display modes which have been used conventionally, and has a very wide range of application.

Further, the obtained liquid crystal display element has performance comparable to that of a conventional liquid crystal display element which is not a polymer dispersion type. Furthermore, since the number and shape of the liquid crystal regions with respect to the pixel electrodes can be freely changed, it is possible to control the light scattering intensity that occurs at the interface between the liquid crystal region and the polymer wall, which is not possible with the conventional polymer dispersed liquid crystal display device. It is possible to control, adjust the driving voltage, and increase the definition of the screen. Furthermore, since the diameter of the liquid crystal region is uniform, the threshold characteristic becomes steep, and high-definition and high-contrast display is possible. In addition, when the light-shielding mask is provided as described above, the scattering generated at the interface can be suppressed, and the contrast characteristic can be further improved. Furthermore, it may be used for a simple matrix drive with a high duty ratio. Such a liquid crystal display device can be used, for example, in a projection television, a surface display device such as a personal computer, a display plate using a shutter effect, a window, a door, a wall, and the like. In particular, it can also be used for a direct-view type polymer dispersion type liquid crystal display device that does not use a backlight.

(Second Embodiment) The second and subsequent embodiments relate to the case where the present invention is applied to a non-scattering type liquid crystal display device.

A method of manufacturing the liquid crystal display element according to the second embodiment will be described with reference to FIG. First, as shown in FIG. 2A, the active matrix substrate 1 and the counter substrate 3 are opposed to each other, and the liquid crystal material is provided between the two opposed substrates 1 and 3.
A mixture 5 made of a photocurable polymer raw material is enclosed. The upper active matrix substrate 1 shown in the figure is transparent, and the pixel electrodes 2 are formed on the inner surface side thereof. A counter electrode 4 is formed on the entire inner surface of one counter substrate 3.

Next, a glass plate 6 having a photomask 7 formed thereon is placed on the active matrix substrate 1, and ultraviolet (UV) light 10 is irradiated toward the mixture 5 from the photomask 7 side. . As a result, as shown in FIG. 2B, a wall 8 made of a polymer resin and a liquid crystal region 9 surrounded by the wall 8 are formed. This formation is UV
The polymerization rate is high in the portion having high strength and the polymer is rapidly deposited, and coexisting liquid crystal molecules are pushed out to the portion having low light intensity, and as a result, the liquid crystal region 9 is generated in the portion having low UV intensity. The liquid crystal region 9 has a parallel portion in which the portions close to the substrates 1 and 3 are parallel to the surfaces of the substrates 1 and 3.

In the liquid crystal display element according to the present invention manufactured as described above, the liquid crystal region 9 is formed in the portion covered with the photomask 7, and the portion not covered with the photomask 7 is made of polymer resin. A wall 8 is formed. That is, the liquid crystal region 9 and the wall 8 made of polymer resin are formed so as to be clearly separated.

As described above, the parallel portion is provided in the liquid crystal region 9 only in the liquid crystal region 9 in which the boundary between the liquid crystal region and the polymer wall is located outside the picture element and the refractive index in each portion is little changed. This is to reduce the scattering power by allowing incident light to pass through. In this case, the larger the parallel part, the more effective.

Further, since the wall 8 is formed so as to reach both the substrates 1 and 3, both the substrates 1 and 3 are firmly held by the wall 8 and the shock resistance is improved. Further, even when the liquid crystal display element is used in a state where the substrates 1 and 3 are erected, it is possible to prevent the upper gap between the substrates 1 and 3 from becoming wider than the lower gap due to the weight of the liquid crystal. This is particularly effective when a film-shaped substrate is used as the substrate.

The shape of the liquid crystal region actually formed in Example 2 was as follows: the liquid crystal display element was peeled into two pieces, the liquid crystal molecules were removed with a solvent, and the polymer matrix consisting of the remaining walls 8 was SEM (scanning electron). It can be observed and confirmed with a microscope. Since there is a portion where the structure is destroyed during the preparation of the SEM observation sample, it is preferable to select the 20 liquid crystal regions having the most regularity in the sample and observe the polymer matrix. FIG. 3 is a diagram obtained by observing a state where the wall 8 and the liquid crystal region 9 are phase-separated with a microscope. As can be understood from this figure, the polymer-made wall 8 is not formed in the region shielded by the photomask, while the wall 8 is formed in the region irradiated with ultraviolet rays and its vicinity. It was confirmed. However, a small liquid crystal region may be formed on the wall 8.

The configuration of each part applied to the present embodiment, modifications and the like will be described below. (Light regulating means such as photomask) According to the results of the study by the present inventors, the size of the weak illuminance region is 30% or less of the area of the picture element among the high illuminance region and the weak illuminance region forming the illuminance unevenness. It has been found that the size of the liquid crystal region to be generated is 30% or less of the area of the picture element when the size is used.
In this case, a large number of interfaces between the liquid crystal region and the polymer wall are present in one picture element, and the reduction in contrast due to scattering becomes large, which is not practical.

Therefore, the size of at least one liquid crystal region included in each picture element is limited to 30% or more of the area of the picture element.

Therefore, in this embodiment, as shown in FIG. 2B, the size of the liquid crystal region 9 is set to the same size as the pixel electrode 2. By doing so, only the liquid crystal region 9 can be formed in the pixel portion, and the alignment direction of the liquid crystal region 9 can be set by providing the substrate with an alignment film. This is also preferable from the viewpoint of aperture ratio.

Further, in this embodiment, it is preferable to arrange the liquid crystal regions 9 regularly along the surface of the substrate, that is, corresponding to each picture element. In this case, as shown in FIG. 4, the arrangement of the weak illuminance regions for forming the liquid crystal region 9 is preferably matched with the arrangement pitch of the picture elements 9a, and one weak illuminance area is arranged within one picture element. Is preferred. Alternatively, as shown in FIG. 5, the weak illuminance area may extend over two picture elements 9a or three or more picture elements 9a.
You may arrange over a. Furthermore, each weak illuminance area is
It is not necessary for the respective regions to be completely separated, and they may be connected at the end portion as long as the regions for effectively blocking the UV irradiation light have the shape and arrangement described later.

Further, as shown in FIG. 6, in order to reduce the interface between the liquid crystal region 9 and the polymer wall 8 which causes scattered light in the picture element, the picture element electrode 2 It is preferable to create a weak illuminance region that is larger than the size. At this time, it is advisable to use a light control unit that irradiates only the portion other than the picture element with UV light. In particular, a photomask may be used as the light regulating means, and it is possible to reduce the light scattering intensity in the picture element and improve the contrast of the liquid crystal display element.

The shape of the weak illuminance region of the photomask may be such that the UV intensity of 30% or more of the picture element can be locally reduced. Although not particularly limited, circular, rectangular, trapezoidal, hexagonal,
A rectangle, a rhombus, a character type, a figure delimited by a curved line and a straight line, and the like correspond. In addition, a figure obtained by cutting a part of these figures, a figure obtained by combining these figures, and an aggregate of these small figures are also equivalent. In practice, one or more of these figures may be selected and used, and it is preferable to limit the shape to one in order to improve the uniformity of the liquid crystal region.

In this embodiment, other light regulating means can be used instead of the photomask. For example, a microlens, an interference plate or the like that can form a regular UV intensity distribution can be used. Further, such a light regulating means may be present inside or outside the liquid crystal display element as long as it can regularly impart strength to UV irradiation light. However, when the photomask is used, if the distance between the liquid crystal layer and the photomask is increased, the image is blurred by the light passing through the photomask and the weak illuminance region becomes unclear, and the effect of the present invention is reduced, so that the liquid crystal layer is as much as possible. It is preferable to bring them closer.

(Irradiation Light) As the UV light used in this embodiment, a beam light, a line light or the like can be used, but it is desirable that the UV light is a parallel light beam. However, in the case of a liquid crystal display device using a ferroelectric liquid crystal, irradiation light with a slightly poor parallelism may be used. That is, in the case of a liquid crystal display device using a ferroelectric liquid crystal, it is necessary to improve impact resistance, and for that purpose, it is effective to dispose a smaller liquid crystal region around the liquid crystal region as a buffer. Because it is. Instead of using irradiation light with a little poor parallelism, blur the end of light control means such as a photomask,
The photomask may be intentionally separated from the cell body.
In this embodiment, not only UV light but also general light containing UV light can be used.

Further, in the present embodiment, in the case of irradiating with light having a distribution having a regular weak illuminance region approximately the same as the required liquid crystal region diameter, the polymer resin is regularly photopolymerized. Thus, it becomes possible to arrange uniform liquid crystal regions regularly in the direction along the substrate surface.

(Optimal Thickness of Liquid Crystal Layer) The optimal thickness of the liquid crystal layer varies depending on the display mode.

(Method of Injecting Mixture Between Substrates) In the present embodiment, a method of putting a mixture of a liquid crystal material and a photocurable polymer resin between the substrates is a conventional general method. After the two substrates are bonded together, the mixture may be injected between the two substrates. Alternatively, before the two substrates are bonded together, the mixture is dropped or applied on one substrate, and in that state, UV light is irradiated to cure the polymer resin, and then the two substrates are bonded. You may adopt the method. The latter method has an advantage that a spacer or the like for controlling the thickness of the liquid crystal layer can be eliminated.

Alternatively, FIG. 7 (front view) and FIG. 8 (cross-sectional view)
The injection method shown in can be used. According to this injection method, at least two opening holes 5 are formed in one substrate 52 in a cell in which a space between two substrates 51 and 52 arranged opposite to each other is shielded.
2a and 52b are provided, suction is performed from one of the opening holes 52a and 52b, and the suction is performed to the other opening hole 52a.
The mixture for injection from b may be inserted into the cell by using the injector 53 shown in FIG. In this case, one or more openings may be provided on one side of the substrate, and the rest may be provided on the shield part.
Further, vacuuming may be performed from the outside of the opening hole for suction. In this case, the degree of pressure reduction is preferably 200 Pa or more and less than atmospheric pressure in the opening hole for suction. Further, the pressure may be applied from one of the opening holes, and the mixture may be injected from the pressing opening hole. Regarding the degree of pressurization in that case, it is preferable to use an arbitrary pressure from atmospheric pressure to 10 ⁶ Pa.

(Orientation Treatment Method) As an orientation treatment method that can be used in this embodiment, for example, a rubbing method in which a polymer material such as polyimide or an inorganic material is applied to the surface of a substrate and then rubbed with a cloth, or a surface tension is low A vertical alignment method in which a surface-active compound is applied, or an oblique alignment method by oblique deposition of SiO ₂ or the like corresponds.

(Alignment Film) In this embodiment, a substrate having an alignment film can be used. In this case, as shown in FIGS. 10A and 10B, the alignment film 8a and the liquid crystal molecules in the liquid crystal region 9 can be in direct contact with each other, which allows the alignment of the liquid crystal molecules. (Polymer Material) The polymer material to be mixed with the liquid crystal material to form the mixture is a substance that finally becomes a wall that supports the two substrates and the liquid crystal region, and therefore its selection is important.

The polymer material that can be used in this embodiment corresponds to a photo-curable resin monomer, and other polymerizable polymer substances may be used. Examples of the photocurable resin monomer include acrylic acid and acrylic acid ester having a C3 or longer long-chain alkyl group or an aromatic ring. Furthermore, isobutyl acrylate, steric acrylate, lauryl acrylate, isoamyl acrylate, n
-Butyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, 2-ethylhexyl acrylate, n-stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-
There is phenoxyethyl methacrylate.

In order to increase the physical strength of the polymer, a polyfunctional resin having two or more functional groups, such as bisphenol A dimethacrylate, bisphenol A diacrylate, 1,4-butanediol dimethacrylate, 1,6
-Hexanediol dimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, etc. can also be used.

Further, usable resins include resins obtained by halogenating, especially chlorinating or fluorinating, the above-mentioned monomers. As such a material, for example, 2, 2, 3,
4,4,4-hexafluorobutyl methacrylate, 2,
2,3,4,4,4-hexachlorobutyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, perfluorooctylethyl methacrylate, perchlorooctylethyl Methacrylate, perfluorooctylethyl acrylate, and perchlorooctylethyl acrylate may be mentioned.

The polymeric materials described above may be used alone or in combination of two or more. In addition, chlorine and fluorinated polymers or oligomers, or a photopolymerization initiator may be mixed with the above-mentioned monomer, if necessary.

As a switching element, a TFT (thi
When using an n film transistor), the electrical resistance of not only the liquid crystal material but also the polymer resin is required, so the specific resistance of the polymer resin is 1 x 10 ¹² Ω · c even in the uncured state.
It is preferable to use those having a size of m or more.

(Liquid Crystal) The liquid crystal usable in the present embodiment is an organic substance or a mixture of organic substances which shows a liquid crystal state at around room temperature, such as nematic liquid crystal, cholesteric liquid crystal or smectic liquid crystal, ferroelectric liquid crystal and discotic liquid crystal. Is included.

As the ferroelectric liquid crystal, a linear molecule having a rigid core portion and an optically active portion in the molecule can be used. Furthermore, by providing a guest-host type liquid crystal display device in which a polychromatic dye is added to these ferroelectric liquid crystal materials, a liquid crystal display device can be constructed by combining the device with one polarizing plate. it can. Further, as the ferroelectric liquid crystal prepolymer, a compound in which a polymerizable functional group is bonded to a part of the ferroelectric liquid crystal can be used. As the polymerizable functional group, acrylate, methacrylate, epoxy group and the like can be used. Specific examples of the ferroelectric liquid crystal prepolymer include JP-A-63-28074.
2, JP-A-63-264629, JP-A-62-27.
7412 and the like. Further, a curable resin that is not liquid crystalline may be added to the extent that the response speed of the device is not impaired.

These liquid crystal materials may be a mixture of two or more liquid crystals, and nematic liquid crystal or nematic liquid crystal to which cholesteric liquid crystal is added is particularly preferable in terms of characteristics. Furthermore, since a photopolymerization reaction is involved in the production of the liquid crystal region, it is preferable that the liquid crystal material has excellent chemical reactivity resistance and does not undergo modification during the polymerization reaction. For example, an inert substituent such as a fluorine atom in the compound. Liquid crystals with are preferred. Although not particularly limited to those having such properties, ZLI-4801-000 and ZLI-4801-00 commercially available from Merck & Co., Inc.
1, ZLI-4792 and the like.

(Conditions for Forming Liquid Crystal Region) Although it is difficult to separately form the liquid crystal region in the scattering mode and the non-scattering mode, basically, the liquid crystal region is smaller than 20 μm in the cell and is uniformly formed in the picture element. In this case, the liquid crystal display device suitable for the scattering mode becomes a liquid crystal display device. On the other hand, in the case of the non-scattering mode liquid crystal display device, the non-scattering mode liquid crystal display can be obtained by making the parallel part parallel to the substrate large. It can be an element.

The size of the liquid crystal region mutually depends on the shape of the weakly illuminated region (photomask), the light beam parallelism of the light irradiation device, and the photopolymerization reaction rate. The shape of the weak irradiation area is
This is an important factor that determines the size of the liquid crystal region, and the contour of the liquid crystal region is almost determined by the shape setting of the weak irradiation region.

The light beam parallelism of the light irradiation device is a factor that determines whether or not the shape of the photomask can be faithfully irradiated to the mixture of the liquid crystal, the photocurable resin and the photoinitiator, and at the same time, from the light irradiation region. Affects the amount of light leakage to the weak irradiation area. Due to such leaked light, the photo-curable resin existing in the weak irradiation region undergoes a curing reaction before moving to the light irradiation region, and as a result, a small liquid crystal region suitable for the scattering mode is formed in the weak irradiation region. Will end up.

Regarding the photopolymerization reaction rate, when the polymerization rate is extremely high, the polymerization reaction occurs even with weak leakage light, and a polymer wall is formed in the weak irradiation region. As the factors that determine the polymerization reaction rate, the amount of photoinitiator added,
Examples include the light irradiation intensity and the type of polymer resin.

(Display Mode) In the present embodiment, the manufactured liquid crystal display element is sandwiched between two polarizing plates, so that a high contrast and a steep driving voltage characteristic can be obtained.
N-mode, STN-mode, ECB-mode, guest-host-mode liquid crystal display devices, ferroelectric liquid crystal display devices, and the like can be manufactured. One polarizing plate may be provided only on one substrate side. That is, in the liquid crystal in which the dichroic dye is added to the ferroelectric liquid crystal, when the polarization plane of light is changed by electrically controlling the alignment direction, the polarizing plate on one substrate side can be omitted.

(Orientation Controlling Power) When a mixture of liquid crystal molecules and a photo-curable resin is irradiated with light with varying intensity as in the present invention, a thin polymer film may remain on the substrate surface even in the liquid crystal region. Therefore, the alignment control ability of the alignment film on the substrate is weakened. In the case where the alignment control ability of the alignment film on the substrate is completely lost, the alignment form is caused by the light irradiation conditions, as will be specifically described in a specific example. Specifically, the structure is such that the domains in the liquid crystal region are radially or randomly aligned, and the rising directions of the liquid crystal molecules are almost the same when viewed from any direction when a voltage is applied. There is. In this case, the alignment film is
The manufacturing process (application of the alignment film, rubbing treatment, cleaning, etc.) can be largely omitted, which is industrially significant.

When a vertical alignment film having a high alignment regulating ability is used, the alignment regulating force remains, and the liquid crystal molecules are in a homeotropic state in which they stand vertically to the cell. Also in this case, the liquid crystal molecules interact with the polymer material when a voltage is applied, so that the rise of the liquid crystal molecules is in each wall direction, and the refractive index is almost the same when viewed from any direction, thus improving the viewing angle characteristics. Is effective.

It has been confirmed that when a material having a high liquid crystal alignment ability such as a ferroelectric liquid crystal is used, the alignment is performed according to the alignment state of the substrate even in the case of the present invention in which the alignment control ability is weakened.

(Others) The liquid crystal display device of this embodiment is not particularly limited, but the drive system may be a simple matrix drive system or an active drive system such as TFT or MIM.

Further, in the liquid crystal display element of the present embodiment, it is possible to arrange a color filter on the picture element for color display.

A specific example of the second embodiment will be shown below.

[Specific Example 3] A plurality of electrode wires made of ITO (a mixture of indium oxide and tin oxide) having a thickness of 50 nm were formed on a PET film having a thickness of 0.25 mm, and 2
A set of substrates is prepared. The width of this electrode wire was 200 μm, the gap between adjacent electrode wires was 50 μm, and the number of electrode wires was 20. Polyimide (SE150: manufactured by Nissan Kagaku Co., Ltd.) was applied to the set of substrates by a spin coating method, and rubbed in one direction with a nylon cloth to form an alignment film.

The two substrates thus treated were combined so that the electrode lines were orthogonal to each other, a spacer of 6 μm was inserted between them, and a cell was produced with the gap between both substrates being kept constant.

As shown in FIG. 4, a photomask was placed on the produced cell in a state where each pixel 9a was shielded from light. In the cell, 0.1 g of trimethylolpropane trimethacrylate and 2-ethylhexyl acrylate were used.
0.9g, 4g of a mixture of liquid crystal material ZLI-3700-000 (manufactured by Merck & Co.) with 0.3% of CN (cholesteric nonanate), and Irgacure184 which is a photocurable catalyst.
(Ciba Geigy) 0.03g and a uniform mixture is poured.

Next, using a high-pressure mercury lamp capable of producing parallel rays, ultraviolet rays were irradiated from the photomask side for 2 minutes at an irradiation intensity of 10 mW / cm ² to cure the mixture of the liquid crystal material and the polymer material. .

The liquid crystal display element manufactured as described above was divided, the liquid crystal display element was peeled off in liquid nitrogen, the liquid crystal material was washed off with acetone, and then the liquid crystal layer portion was observed by SEM (scanning electron microscope). I observed. As a result, it has the same regularity as the dot pattern and pixel pattern of the photomask,
In addition, it was confirmed that liquid crystal regions having a size similar to the dot pattern and uniformly aligned were formed.

Further, a polymer matrix type TN liquid crystal display device was produced by laminating a polarizing plate on another liquid crystal display device produced in the same manner with the alignment direction and the polarization direction of the polarizing plate being aligned.

Table 1 shows the contrast characteristics of the produced liquid crystal display element together with Comparative Examples 3 and 4 produced by the conventional method. In the liquid crystal display element of Comparative Example 3, a cell was prepared in the same manner as in Example 3 using glass with ITO (flint glass with ITO-50 nm made by Nippon Sheet Glass) instead of the substrate of Example 3. It is a conventional TN liquid crystal display device manufactured by injecting the same liquid crystal material as in Example 3 into a cell and aligning the polarization direction with the orientation direction of the cell and laminating a polarizing plate. Further, in the liquid crystal display element of Comparative Example 4, a cell was prepared in the same manner as in Example 3, and the same mixture of liquid crystal and photocurable resin as in Example 3 was injected, and then, as in Example 3, without a photomask. TN produced by performing similar UV irradiation
Type polymer dispersion type liquid crystal display device.

[0148]

[Table 1]

As can be seen from Table 1, Example 3 of the present invention was found to be comparable in electro-optical characteristics to Comparative Example 3 which is a conventional TN type liquid crystal display device. Compared with Comparative Example 4, which is a conventional polymer-dispersed liquid crystal display element, the contrast is high because the scattering within the picture element is extremely small. Further, in the liquid crystal display element of Example 3, since the two substrates are firmly held by the wall as described above, the substrate using the PET film can be used. Even if another plastic film or a glass substrate was used instead of this PET film, the effect was exactly the same. [Specific Example 4] The same substrate as in Specific Example 3 was used, and Cytop (manufactured by Asahi Glass Co., Ltd.) was applied to this substrate by spin coating so as to have a thickness of 0.2 μm. Next, as in the third specific example, 2
A cell was produced by inserting a spacer between the sheets. Next, a photomask similar to that in Example 3 was set in the same manner as in Example 3. In the cell, 0.1 g of trimethylolpropane trimetacrate and 0.9 g of n-lauryl acrylate.
Then, a uniform mixture of 4 g of a liquid crystal material (ZLI-4788-000: manufactured by Merck & Co., Inc.) and 0.03 g of a photocurable catalyst Irgacure184 (manufactured by Ciba-Geigy) was injected.

Next, using a high-pressure mercury lamp capable of producing parallel rays, ultraviolet rays were irradiated from the photomask side for 2 minutes at an irradiation intensity of 10 mW / cm ² to cure the mixture.

The obtained cell was divided, the cell was peeled off in liquid nitrogen, the liquid crystal material was washed off with acetone, and the liquid crystal layer was observed by SEM (scanning electron microscope). It was confirmed that a liquid crystal region having the same regularity as the elementary pattern and having the same size as the dot pattern and uniformly aligned was produced. Further, a polarizing plate was attached to another liquid crystal display element manufactured in the same manner so that the polarization planes thereof were orthogonal to each other, to manufacture a polymer dispersion type ECB liquid crystal display element.

A normal ECB liquid crystal display device is shown in FIG.
As shown in FIG. 11A, the liquid crystal molecules e are aligned homeotropically with a tilt angle of several degrees when no voltage is applied. Therefore, as shown in FIG. Since they fall in the same direction, the apparent refractive index differs depending on the direction, and the retensionation (Δn · d: Δn
Is the birefringence of the liquid crystal molecules, d is the thickness of the liquid crystal cell),
An inversion phenomenon in which the black and white state is inverted depending on the viewing position and uneven contrast occur. On the other hand, when the mixture of the liquid crystal and the photocurable resin is cured by the light having the irradiation intensity distribution as in the present invention, a very thin polymer layer is formed between the substrate and the liquid crystal to control the orientation of the substrate. Although the force is weakened, it was confirmed that when a vertical alignment film having a strong alignment regulating force as in this example is used, the liquid crystal molecules have homeotropic alignment. That is, it was observed that the liquid crystal molecules e stood upright with respect to the cell as shown in FIG. Further, when an electric field is applied to the cell, FIG.
As shown in Fig. 5, the liquid crystal molecules e are tilted in the respective wall directions due to the interaction between the liquid crystal and the polymer walls, so that the directionality of the liquid crystal molecules e is randomized, and the refractive index is almost the same when viewed from all directions at a constant angle from the vertical direction of the cell. As a result, the viewing angle characteristics are greatly improved.

Table 2 shows the contrast characteristics of the manufactured liquid crystal display element together with those of Comparative Examples 5 and 6 by the conventional method. In addition, the liquid crystal display element of Comparative Example 5 was replaced with the substrate of Concrete Example 4 by glass with ITO (IT manufactured by Nippon Sheet Glass).
O-50 nm flint glass) was used to fabricate a cell in the same manner as in Example 4, and the same liquid crystal material ZLI-47 as in Example 4 was used.
It is a conventional ECB liquid crystal display device manufactured by injecting 88-000 and laminating polarizing plates so that the polarizing directions of the polarizing plates are orthogonal to each other. Further, in the liquid crystal display element of Comparative Example 6, a cell was prepared in the same manner as in Example 4, and the same mixture of liquid crystal and photocurable resin as in Example 4 was injected, and then, as in Example 4 without a photomask. It is an ECB type polymer dispersion type liquid crystal display device produced by performing similar UV irradiation.

[0154]

[Table 2]

As can be seen from Table 2, it was confirmed that Example 4 of the present invention is comparable in electro-optical characteristics to Comparative Example 5 which is an ECB liquid crystal display device according to the conventional method. Compared with Comparative Example 6, which is a conventional polymer-dispersed liquid crystal display device, the contrast is high because the scattering in the picture element is extremely small. Regarding the viewing angle characteristics, in Comparative Example 5, the reversal phenomenon occurs when the angle is changed, and in Example 4, the viewing angle does not occur and the viewing angle is wide. In addition, in Example 4, PET
A substrate using a film can be used. This P
The effect was exactly the same even if another plastic film or a glass substrate was used instead of the ET film.

[Specific Example 5] An ITO film having a thickness of about 100 nm was formed on two glass substrates by a vapor deposition method, and a substrate having a plurality of electrode lines arranged in parallel was formed by a wet etching method. A polyimide alignment film with a thickness of about 50 nm was applied on the surface of the glass substrate on which the electrode wire was formed by spin coating, baked at 190 ° C for 1 hour, and then uniaxially rubbed to form an alignment film. Granted.

This rubbing treatment is performed such that the two substrates have the same rubbing direction when the electrode wire forming surfaces of the two substrates are faced to each other and the electrode wires are bonded so as to be orthogonal to each other. It was 2 μm silica beads were dispersed as spacers on this substrate to control the cell thickness, and two substrates were bonded together to form a cell.

Next, the ferroelectric liquid crystal composition ZLI-400 was used.
3 (manufactured by Merck) and 0.80 g of polyethylene glycol diacrylate (trade name NK ester) as a polymer precursor
A-200, Shin-Nakamura Chemical Co., Ltd. 0.02 g, and lauryl acrylate (trade name NK ester LA, Shin-Nakamura Chemical Co., Ltd.) 0.18 g were uniformly mixed, and a mixture was injected between the substrates. did. This liquid crystal-polymer precursor mixture is in a nematic phase or an isotropic liquid phase state at normal pressure. The phase transition temperatures of this liquid crystal-polymer precursor mixture are shown below.

SmC ← 25 ° C. → SmA ← 31 ° C. → Ch ← 35 ° C. → Iso Next, a light-shielding photomask was installed as in Example 3.
While the liquid crystal-polymer precursor mixture was in the nematic phase or the isotropic liquid phase, ultraviolet irradiation was performed from the photomask side for 2 minutes at an irradiation intensity of 10 mW / cm ² using a high pressure mercury lamp capable of obtaining parallel rays. This irradiation photocured the liquid crystal-polymer precursor mixture and caused phase separation of the mixture of liquid crystal and polymer.

Observation of this phase-separated state with a polarization microscope revealed that, similar to FIG. 3 described above, the polymer-made wall 8 was not formed in the region shielded by the photomask.
It was confirmed that the wall 8 was formed in the region irradiated with the ultraviolet rays and its vicinity.

When this cell is observed with a polarizing microscope having a crossed Nicols, in the central portion of the liquid crystal region formed in the region shielded from ultraviolet rays, a normal SSF (surface stabilized ferroelectric) type is formed in the rubbing direction of the substrate. It has been confirmed that the orientation is changed, and the orientation changes sharply in the vicinity of the wall made of the polymer to show the vertical orientation. On the other hand, it was confirmed that light scattering occurs in the polymer region in the region irradiated with ultraviolet rays.

When the mixture of the liquid crystal and the photocurable resin is cured by the light having the irradiation intensity distribution as in this example, even if the alignment film is a horizontal alignment film and the alignment regulating force is weak, When a liquid crystal material such as FLC having excellent regulation power is used, liquid crystal molecules can be aligned in the alignment direction of the substrate.

Further, when the ferroelectric liquid crystal cell thus manufactured was placed under a microscope having a crossed Nicols and a memory pulse was applied, in a liquid crystal region shielded from ultraviolet rays, a normal SSF type cell was obtained. It was confirmed that the same switching that occurs was done. Further, when the extinction phase of the cell and the polarizing plate are matched so that switching occurs between the complete extinction state and the light transmission state, the region irradiated with ultraviolet rays is in a state where no electric field is applied, It was observed that there was light leakage due to light scattering and disordered alignment of the liquid crystal, and the brightness was in the middle of the on / off state.

Regarding the plurality of observation results described above,
It was exactly the same even if another plastic film or the like was used instead of the glass substrate.

Table 3 shows the contrast characteristics of the manufactured liquid crystal display element together with those of Comparative Examples 7 and 8 by the conventional method. The liquid crystal display element of Comparative Example 7 is manufactured by injecting the liquid crystal material ZLI-4003 into a cell manufactured under the same conditions as those manufactured in Example 5 and sealing the cell.
In addition, the liquid crystal display element of Comparative Example 8 is manufactured by using the same procedure and the same material as in Concrete Example 5, except that a photomask is not used in the ultraviolet irradiation step.

[0166]

[Table 3]

As can be seen from Table 3, it was confirmed that Example 5 of the present invention was comparable in electro-optical characteristics to Comparative Example 7. Compared with Comparative Example 8, the contrast is high because the scattering within the picture element is extremely small. Further, although the glass substrate is used in Example 5, the same effect can be obtained by using a plastic film or the like instead of the glass substrate.

In the liquid crystal display device of Comparative Example 8, the liquid crystal-polymer precursor mixture was cured almost uniformly in the cell by irradiation with ultraviolet rays, and phase separation between the liquid crystal and the polymer composition occurred. When the portion where this phase separation has occurred is observed with a microscope, as shown in FIG. 13, the liquid crystal region 9 has a structure in which it is randomly divided by polymer walls 8 on almost the entire surface. In addition, when observing this cell with a polarizing microscope having a crossed Nicols, light scattering occurs in the polymer region, and in the central part of the liquid crystal region, the orientation is almost SSF type in the rubbing direction of the substrate. It was confirmed that the orientation was gradually randomized as approached.

Further, when the ferroelectric liquid crystal cell thus obtained was sandwiched by crossed Nicols and a memory pulse was applied, it was confirmed that the switching was almost similar to that of a normal SSF type cell. But in reverse switching,
It did not completely extinguish, and it appeared that a part had an irregular orientation. Examination of this irregular part with a polarizing microscope revealed that light scattering occurred at the polymer wall, and light leakage occurred around the polymer wall due to disordered alignment of the liquid crystal. .

Table 4 shows that a pressure of 5 kg / cm ² was applied to the three liquid crystal display elements of Example 5, Comparative Example 7 and Comparative Example 8,
The result of having evaluated shock resistance by observing the change of orientation is shown. Further, Table 5 shows changes in the alignment state when the above three liquid crystal display elements are dropped from a height of 30 cm.

[0171]

[Table 4]

[0172]

[Table 5]

As can be understood from both these tables, there was no problem in both the pressure test and the drop test in the case of Example 5, but in the cases of Comparative Examples 7 and 8, both had problems. There is.

[Specific Example 6] Similar to Specific Example 5, a plurality of electrode lines were formed and two substrates subjected to the same rubbing treatment were prepared. Ferroelectric liquid crystal composition ZLI on one substrate
-4003 (Merck) 0.80 g, high molecular weight precursor polyethylene glycol diacrylate (trade name NK ester A-200, Shin Nakamura Chemical Co., Ltd.) 0.02 g, lauryl acrylate (trade name NK ester LA) , Shin-Nakamura Chemical Co., Ltd.) and 2 μm of silica beads are uniformly mixed, and the composition is applied under normal pressure in a nematic phase or in an isotropic liquid state. A cell was produced by laminating the cells so as to be the same as the above.
The phase transition temperatures of this liquid crystal-polymer precursor mixture are shown below.

SmC ← 25 ° C. → SmA ← 31 ° C. → Ch ← 35 ° C. → Iso Next, a light-shielding photomask is arranged in the same manner as in Example 5, and ultraviolet rays are irradiated from the side of the photomask under the same conditions as in Example 5. Then, the liquid crystal-polymer precursor mixture was cured to cause phase separation between the liquid crystal and the polymer composition.

When the cured mixture portion was observed with a microscope, no polymer wall was formed in the region shielded from light by the photomask, and a polymer wall was formed in the region irradiated with ultraviolet light and its vicinity. It was confirmed.

As described above, the liquid crystal display element of Example 6 was prepared by mixing a liquid crystal-polymer precursor mixture with a nematic phase or an isotropic liquid on one of two glass substrates provided with electrodes and an alignment film layer. It is manufactured by applying in a state and then bonding glass substrates together. In the case of Example 6 produced in this way, there was no disorder in the orientation. However, as in the specific example 5 described above, after bonding the two glass substrates provided with the electrodes and the alignment film layer and then injecting the liquid crystal-polymer precursor mixture in a nematic phase or an isotropic liquid state, A clear disorder of orientation was observed under the microscope near the injection hole and near the seal.

In the second embodiment, one liquid crystal region is provided for one picture element or for two or more picture elements.
The present invention is not limited to this. For example, the present invention includes a state where at least one liquid crystal region is included in one picture element, and one or more other liquid crystal regions or a part thereof are included in the same picture element. I'm out. That is, such an arrangement structure is effective when the size of each picture element is increased to increase the screen size. In particular, it is effective when the long side of the picture element exceeds 200 μm, aiming for a large screen. The reason is that if a photomask that completely covers the picture elements is used, unreacted monomer remains in the center of the picture element when exposed to light, and the residual monomer leaks out and a polymerization reaction occurs in the central section due to the light , Or polymer islands are formed,
This is because it is possible to prevent the contrast from being extremely reduced because it becomes a scattering source. Therefore, in the present invention, when the long side of the picture element exceeds 200 μm, a plurality of weak illuminance areas are present in the picture element so that a plurality of liquid crystal areas where no polymer exists are present in the picture element. It will be made. In this case, regarding the size of the weak illuminance region, the maximum diameter of the region is 500 to 20 μm. More preferably, it is 200 to 50 μm. When the thickness is 20 μm or less, a large number of polymer walls are present in the picture element and the contrast is significantly lowered. When it exceeds 500 μm, it becomes difficult to move the photo-curable resin in the central portion of the light-shielding portion of the photomask to the end portion, and it becomes substantially impossible to make the liquid crystal region in conformity with the shape of the photomask. As the arrangement of the low illuminance area,
It is preferable that the maximum diameter condition is set to a pitch that is as small as possible.

(Third Embodiment) The third embodiment is a case of providing a liquid crystal display device capable of improving the viewing angle characteristics and the contrast. The liquid crystal display element will be described below based on a specific example.

[Specific Example 7] First, polyimide (SE150: SE150 :) was formed on a glass substrate (flint glass: 1.1 mm thick) on which ITO (a mixture of indium oxide and tin oxide) having a thickness of 500 angstrom was attached. Nissan Chemical Industries, Ltd.) was applied by a spin coating method to form an alignment film.

Between the two substrates that have been subjected to the above processing, 5 μm
The spacer was inserted, and the gap between both substrates was kept constant to produce a cell.

As shown in FIG. 14, a photomask 43 was placed on the produced cell, which is likened to square picture elements having a pitch of 250 μm. 43a is a light shielding part. In the cell, 0.9 g of isobornyl methacrylate and R-
684 (Nippon Kayaku Co., Ltd.) 0.1 g and liquid crystal material Z
A uniform mixture of 4 g of a mixture of LI-4792 (manufactured by Merck) with 0.3% of S-811 (manufactured by Merck) and 0.02 g of Irgacure184 (manufactured by Ciba-Geigy) which is a photocurable catalyst. Infuse.

Next, using a high-pressure mercury lamp capable of obtaining parallel rays, irradiation was performed for 1 second at an irradiation intensity of 15 mW / cm ² .
20 cycles of non-irradiation for 30 seconds were repeated, and then ultraviolet rays were continuously irradiated for 5 minutes to cure the resin.

When the cell manufactured as described above was observed with a polarization microscope, as shown in FIG. 24 (a) (b) (c) or (d), the regularity (pixels and The outer liquid crystal regions d having the same regularity) and the same size and uniform are produced, and the liquid crystal domains g in the outer liquid crystal regions d are omnidirectional on a plane parallel to the surface of the substrate. Oriented liquid crystal region d in the center
It was confirmed that the structure had.

A polarizing plate was attached to the produced cell to produce a liquid crystal display element.

The electro-optical characteristics of the prepared cell are shown in Table 6.

[0187]

[Table 6]

The contrast was measured by combining a cell and a polarizing plate in a normally white state and using a liquid crystal evaluation device LC-
6000 (manufactured by Otsuka Electronics Co., Ltd.), using a lens having a cell collecting angle of 24 ° from the vertical direction, the light transmittance T _o when the voltage is OFF and the light transmittance T _sut. The ratio T _o / T _{sut. Was} defined. In Table 6, ∘ indicates a state where the inversion phenomenon hardly occurs, X indicates a state where the inversion phenomenon is easily observed, and Δ indicates a state where the inversion phenomenon is barely observed.

In Comparative Example 9, a cell was prepared in the same manner as in Concrete Example 7, and the same liquid crystal material (S-8 as in Concrete Example 7 was used in the prepared cell.
11: 0.3% added) was injected, and the polarization direction of the polarizing plate was aligned in the direction along the alignment direction in the prepared cell, and the polarizing plate was bonded to the cell to manufacture a conventional TN display element. Comparative Example 1
0 is the same as in Example 7 except that a cell was prepared in the same manner as described above, and the same liquid crystal, photocurable resin, and photoinitiator mixture as in Example 7 was injected into the prepared cell, and the cell was not covered with a photomask. Photocuring was performed under the conditions of. Polarizing plates were attached to the prepared cell so that the polarizing directions of the polarizing plates were orthogonal to each other, and a device in which a conventional polymer-dispersed liquid crystal display device was sandwiched between the polarizing plates was manufactured.

As can be seen from Table 6, Example 7 of the present invention is comparable in electro-optical characteristics to the conventionally used TN cell (Comparative Example 9), and is particularly seen in the TN cell in the halftone. No reversal phenomenon is observed when the viewing angle is changed, and the contrast observed from the direction tilted by 40 degrees from the vertical direction is hardly changed. In addition, compared with the polymer dispersion type liquid crystal display device (Comparative Example 10) that has been conventionally studied,
The contrast is high because there is little scattering within the picture element. Note that, as shown in FIG. 22, a large number of liquid crystal regions d of Comparative Example 10 are formed for one picture element and are of a scattering type having a very small diameter.

[Specific Example 8] 0.9 g of isobornyl methacrylate and 0.1 g of R-684 (manufactured by Nippon Kayaku Co., Ltd.)
And liquid crystal material ZLI-4792 (made by Merck) S-8
4 g of a mixture containing 11% (Merck) 0.3%,
Irgacure184, a photocurable catalyst (manufactured by Ciba Geigy)
A cell prepared in the same manner as in Example 7 is injected with a mixture of 0.02 g and 0.02 g.

Next, using a high-pressure mercury lamp capable of obtaining parallel rays, the resin was cured by continuously irradiating ultraviolet rays for 5 minutes at an irradiation intensity of 15 mW / cm ² while covering the photomask shown in FIG.

When the cell manufactured as described above was observed with a polarization microscope, as shown in FIG. 25, a plurality of circular liquid crystal portions were in contact with each other at the portion corresponding to the edge portion of the weak irradiation region b of the photomask. Such a liquid crystal region d2 and a large number of circular liquid crystal parts d1 are present in a region surrounded by the liquid crystal region d2. In the former d2 of the liquid crystal portion, each circular portion is divided into one to several liquid crystal domains, and each domain is radial. The latter d1 is still 1
~ It is divided into several liquid crystal domains, and the orientation of the domains is random as a whole. When a voltage is applied in such a state, the rising directions of the liquid crystal molecules are different for each liquid crystal domain. Therefore, when all directions are viewed at a constant angle from the vertical direction, the apparent refractive index becomes almost constant, and the halftone The viewing angle characteristics at are improved. Polarizing plates were attached to both sides of the cell so that the planes of polarization were orthogonal to each other. Table 7 shows the electro-optical characteristics of the manufactured cell.

[0194]

[Table 7]

[Specific Example 9] 0.9 g of isobornyl methacrylate and 0.1 g of R-684 (manufactured by Nippon Kayaku Co., Ltd.)
And liquid crystal material ZLI-4792 (made by Merck) S-8
4 g of a mixture containing 11% (Merck) 0.3%,
Irgacure184, a photocurable catalyst (manufactured by Ciba Geigy)
A cell prepared in the same manner as in Example 7 is injected with a uniform mixture of 0.12 g.

Next, using a high-pressure mercury lamp capable of obtaining parallel rays, the resin was cured by continuously irradiating with ultraviolet rays for 5 minutes at an irradiation intensity of 45 mW / cm ² while covering the photomask shown in FIG.

When the cell manufactured as described above was observed with a polarization microscope, as shown in FIG.
It was observed that a large number of circular liquid crystal regions d were formed in the portion corresponding to. Polarizing plates were attached to both sides of the cell so that the planes of polarization were orthogonal to each other. Table 7 shows the electro-optical characteristics of the manufactured cell.

Comparing Concrete Example 7, Concrete Example 8 and Concrete Example 9 on the basis of Tables 7 and 6, in Concrete Example 8 of the liquid crystal region shown in FIG. Is almost as good as that of Example 7 in which it is radially surrounded, but the contrast is slightly inferior. Since the specific example 9 has the structure of the liquid crystal region as shown in FIG. 23, the inversion phenomenon in the halftone occurs and the contrast is lowered.

[0199] In the embodiment 7-9, is performed with ultraviolet irradiation at a high pressure mercury lamp under ^{15mW / cm 2 ~45mW / cm 2} , UV irradiation conditions, the liquid crystal - although not limited particularly depends resin mixture composition , 60 mW / cm ² (365n) in order to sufficiently grow the liquid crystal region and to suppress damage to the liquid crystal material by ultraviolet rays.
m) or less is preferable.

In the above-mentioned Concrete Example 7, irradiation is performed for 1 second to 30
The reason why pulse irradiation is performed in the second non-irradiation cycle is as follows.

That is, when the mixture of liquid crystal and photocurable resin is cured by light having an irradiation intensity distribution, the photocurable resin in the irradiated region first reacts to form a nucleus of the polymer wall. After that, since the concentration of the photocurable resin is lowered in the irradiation part, a concentration gradient of the photocurable resin is formed, and the unreacted photocurable resin in the weak illuminance region gathers in the irradiation region along the concentration gradient. The polymer is polymerized to form a polymer wall. At this time, if the polymerization rate is fast, the photopolymerization reaction occurs in the weak irradiation area due to the light leaking from the irradiation area before the photocurable resin in the weak illumination area reaches the irradiation area due to mass transfer. A plurality of liquid crystal regions are also generated in the irradiation region. If these liquid crystal regions are extremely small (20 μm or less), a scattering phenomenon occurs at the boundary between the polymer and the liquid crystal, which lowers the contrast, which is not preferable. Therefore, by slowing down the polymerization reaction,
The photocurable resin in the weak illuminance region can reach the irradiation region by mass transfer, and the phase separation between the liquid crystal region and the polymer wall can be clarified. This means that each picture element of the liquid crystal display device can be almost covered with the liquid crystal region, and the contrast can be improved.

As a method of clarifying the phase separation, light irradiation in a pulsed manner is performed to allow sufficient mass transfer of the photocurable resin in the non-irradiated state, so that a small liquid crystal region is included in the weak illuminance region. It is also possible to use a method of forming a liquid crystal region without forming. As the pulse irradiation pattern, it is preferable to perform pulse irradiation for a time of 5 seconds or less at which the resin material is not sufficiently cured at intervals of 30 seconds or more.
In the case of this pulse irradiation, it is also possible to make the liquid crystal domains random alignment instead of omnidirectional alignment by adjusting the resin material and the irradiation conditions.

[Embodiment 10] In Embodiment 10, the photopolymerization reaction is suppressed, and the phase separation between the liquid crystal molecule and the polymer material is clarified.
In addition, it is a case where the liquid crystal region is formed in a shape matching the weak illuminance region of the photomask. In order to suppress the photopolymerization reaction, it is preferable to add a photoreaction inhibitor.

Glass substrate (flint glass: 1.1 mm thick)
ITO (a mixture of indium oxide and tin oxide,
(500 angstrom) was used as it was, two substrates were combined, and a cell was constructed by keeping the cell thickness with a spacer of 5 μm (Micropearl: manufactured by Sekisui Fine Chemical Co., Ltd.). A photomask 43 that resembles a square pixel having a pitch of 250 μm and a light-shielding portion of 200 μm shown in FIG. 14 is placed on the fabricated cell, and 0.85 g of isobornyl methacrylate and R684 are placed in the cell.
(Nippon Kayaku Co., Ltd.) 0.1 g, styrene 0.05 g as a photopolymerization inhibitor, and liquid crystal material ZLI-4792
0.3% of S-811 (Merck) on (Merck)
A mixture of 4 g of the added mixture and 0.02 g of the photocurable catalyst Irgacure651 (manufactured by Ciba Geigy) is homogeneously mixed and then injected.

After that, 15 mw / cm ² (356 n under a high pressure mercury lamp capable of obtaining parallel rays from the dot pattern side)
(measured with m), the resin was cured by continuous irradiation with ultraviolet rays for 5 minutes.

Observation of the generated cells with a polarization microscope revealed that they had the same regularity as the dot pattern (same regularity as the picture elements).
Then, it was confirmed that a liquid crystal region was formed in each dot in the liquid crystal region, and the liquid crystal region was uniformly aligned with the same size, and that the liquid crystal domains in the liquid crystal region were omnidirectionally aligned.
A pair of polarizing plates was attached to the cell thus prepared to form a liquid crystal display device.

Table 8 shows the electro-optical characteristics of the manufactured cell.

[0208]

[Table 8]

The contrast was measured by combining a cell and a polarizing plate in a normally white state and using a liquid crystal evaluation device LC.
-6000 (Otsuka Electronics Co., Ltd.) using a light transmittance in the light transmittance T _o and the saturation voltage application when a voltage OFF using a lens from the vertical converging angle 24 ° of the cell T _sut. The ratio T _o / T _sut . In Table 8, ∘ indicates a state where the inversion phenomenon hardly occurs, X indicates a state where the inversion phenomenon is easily observed, and Δ indicates a state where the inversion phenomenon is barely observed.

In Comparative Example 11, a cell was produced in the same manner as in Example 10, and the same liquid crystal, photocurable resin, and photoinitiator mixture as in Example 10 was injected into the produced cell, without covering with a photomask. Then, photocuring was performed under the same conditions as in Example 10. Polarizing plates were attached to the prepared cell so that the polarizing directions of the polarizing plates were orthogonal to each other, and a device in which a conventional polymer dispersed liquid crystal display device was sandwiched between the polarizing plates was manufactured. In Comparative Example 12, polyimide (SE150: manufactured by Nissan Kagaku Co., Ltd.) was applied on the same substrate as in Example 10 by spin coating, and rubbed in one direction with a nylon cloth. The two substrates that have been subjected to the above processing are combined so that the rubbing directions are orthogonal to each other.
A cell was constructed by keeping the cell thickness with a spacer (micropearl: manufactured by Sekisui Fine Chemical Co., Ltd.) of μm. A liquid crystal material ZLI-4792 (manufactured by Merck), to which 0.3 of S-811 (manufactured by Merck) was added, was injected into the prepared cell. Furthermore, a conventional TN display device was manufactured by adhering the polarizing plate to the cell in which the liquid crystal material was injected according to the polarization method of the polarizing plate in the direction along the alignment direction.

As can be seen from Table 8, this specific example 10
Is comparable to the conventionally used TN cell (Comparative Example 12) in terms of electro-optical characteristics, and in particular, when the viewing angle seen in the TN cell in the halftone is changed, no reversal phenomenon is observed and 40% from the vertical direction. The contrast observed from the direction is almost unchanged. In addition, compared with the polymer dispersion type liquid crystal display device (Comparative Example 11) which has been conventionally studied, the contrast is high because of less scattering in the picture element.

Further, in comparison with the case of the specific example 8 in which the liquid crystal region shown in FIG. 25 was obtained, the specific example 10 using the photopolymerization inhibitor was compared with the specific example 10 using no photopolymerization inhibitor.
In FIG. 26, a liquid crystal region as shown in FIG. 26 (a) (b) (c) or (d) is obtained, and the contrast is excellent.

The above-mentioned photopolymerization inhibitor is a compound that reduces the polymerization reaction rate when added to the resin composition used, and specifically, has a lower reactivity than the above acrylates and methacrylates. Polymerizable compound,
Specifically, styrene having a so-called Q value of 0.8 or more, which indicates the resonance stability of a monomer in radical polymerization (Q =
1), parachlorostyrene (Q = 1.03), α-methylstyrene (Q = 0.98), butadiene (Q = 2.3)
9) etc. As the Q value of the monomer increases, the generated radicals are stabilized by the resonance effect, and as a result, the radical polymerization reaction rate decreases. In the present invention, when the polymerization reaction is slow, the phase separation rate of the liquid crystal and the polymer material is slow. This is preferable because the generated liquid crystal region becomes large and the liquid crystal region becomes almost the same size as the light-shielding portion of the photomask to improve the contrast. In addition, radical scavengers such as p-quinone derivatives (for example, p-quinone, p-chloroquinone, p-methylquinone),
2,2-diphenyl-1picrylhydrazyl (DPP
H), aromatic nitro compounds and nitroso compounds (eg, nitrobenzene, nitrotoluene, aniline, nitrosodimethylaniline, etc.) are preferred.

The addition amount of these photopolymerization inhibitors varies depending on the effect and is not particularly limited in the present invention. However, a mixture of a photocurable resin material, a photoinitiator and a photopolymerization inhibitor is mixed with a photo differential thermal balance (optical DSC). : Seiko Denshi Co., Ltd. PDC121), irradiation intensity 100 mW / cm ² (365 nm), 25
When measured with a photoinitiator Irugacure 651 0.3% addition system at ℃, the addition amount at which the peak value is 20 seconds or more is preferable. In 20 seconds or less, the liquid crystal region does not grow sufficiently, the polymer wall is partially formed in the weak illuminance region of the photomask,
This leads to a decrease in contrast.

The liquid crystal is an organic mixture which exhibits a liquid crystal state near room temperature, and includes nematic liquid crystal (including dual frequency driving liquid crystal and liquid crystal with Δε <0) and cholesteric liquid crystal (especially, selective reflection for visible light). Liquid crystals having characteristics), or smectic liquid crystals, ferroelectric liquid crystals, and discotic liquid crystals. These liquid crystals may be mixed, and in particular, nematic liquid crystals, cholesteric liquid crystals, or nematic liquid crystals to which a chiral agent is added are preferable in view of characteristics such as hysteresis, uniformity, and coloring due to dΔn (phase difference). A chiral agent having a helical pitch of 10 μm or more is preferably added. Further, a liquid crystal having excellent chemical reaction resistance is preferable because it is accompanied by a photopolymerization reaction during processing. Specifically, it is a liquid crystal having a functional group such as a fluorine atom in the compound. In particular,
ZL1-4801-000, ZLI-4801-00
1, ZLI-4792 (manufactured by Merck & Co., Inc.) and the like.

In combining these liquid crystal materials and polymer materials, when a polymer dispersion type liquid crystal element was prepared by a conventional photopolymerization phase separation method, the prepared liquid crystal droplet diameter was the same as that of the photomask used in the present invention. It is preferable to make it larger than the dot diameter, and conversely, even if it is small, it can be used by weakening the UV intensity or suppressing the addition amount of the photoinitiator.

The mixing ratio of the liquid crystal material and the resin material is preferably such that the weight ratio of the liquid crystal material to the resin material is 60:40 to 95: 5. If the amount of resin material is more than 60:40, the area that changes with respect to the voltage decreases and contrast cannot be obtained.
If the amount of the resin material is less than 95: 5, it becomes difficult to sufficiently prepare the polymer wall, and the T _NI point of the mixture of the liquid crystal and the resin material becomes high, which makes it difficult to perform vacuum injection.

The addition amount of the photoinitiator is preferably 3 to 0.01% by weight with respect to the liquid crystal and the resin mixture, and when it is 3% by weight or more, the polymerization rate is too fast to increase the liquid crystal droplet diameter. Cannot be achieved, and the electrical holding ratio required for driving the TFT is reduced. Also,
If it is 0.01% by weight or less, the polymerization reaction does not sufficiently occur and the polymer wall cannot be produced.

[Specific Example 11] This specific example 11 is specific example 1.
Using the same substrate and material as 0, only Photomax is shown in Fig. 1.
5 has a circular light-transmitting hole 44b having a diameter of 5 μm at the center of the light-shielding portion 44a, and a mask 44 having light-transmitting slits 44c having broken lines toward the four corners of the light-shielding portion 44a. A liquid crystal display device surrounded by polymer walls was prepared in the same manner as in Example 8.

When the manufactured cell was observed with a polarization microscope, as shown in FIG. 27, an island-shaped polymer region i was provided in the center of the liquid crystal region d having regularity, and the liquid crystal domain g was in a radial shape. A liquid crystal region d was observed. The contrast of the fabricated cell measured from the vertical direction is 29
The contrast measured from the 45 ° direction was between 25 and 21 regardless of the direction. In the conventional TN cell, an inversion phenomenon was observed in the normal viewing angle direction, and the display quality was remarkably reduced. In the present invention, a conventionally used display element (TN, STN, ECB, ferroelectric liquid crystal element, etc.) sandwiched between two polarizing plates and having a high contrast and a steep driving voltage is used as a liquid crystal in a polymer. It can be manufactured by a pseudo-solidified liquid crystal device including a material. The fabricated cells are simple matrix drive, TFT, MI
It can be driven by a driving method such as active driving of M or the like, and is not particularly limited in the present invention.

[Specific Example 12] A method of manufacturing a liquid crystal display device according to the specific example 12 will be specifically described below. First, on a glass substrate (flint glass: 1.1 mm thick), a substrate having ITO (a mixture of indium oxide and tin oxide) having a thickness of 500 angstrom was attached,
Polyimide (SE150: manufactured by Nissan Kagaku) was applied by a spin coating method to form an alignment film.

Between the two substrates that have been subjected to the above processing, 5 μm
The spacer was inserted, and the gap between both substrates was kept constant to produce a cell.

On the fabricated cell, a circular light transmitting hole 44b having a diameter of 25 μm is formed in the central portion of the light shielding portion 44a shown in FIG.
The photomask 44 having the above is arranged. The cell contains 0.9 g of isobornyl methacrylate and R-68.
4 (manufactured by Nippon Kayaku Co., Ltd.) and liquid crystal material ZLI
-4792 (Merck) S-811 (Merck)
Is a photocurable catalyst and 4 g of a mixture containing 0.3% of
A mixture of 0.02 g of Irgacure 184 (manufactured by Ciba Geigy) and a uniform mixture is poured.

Next, using a high-pressure mercury lamp capable of producing parallel rays, ultraviolet rays were continuously irradiated for 5 minutes at an irradiation intensity of 15 mW / cm ² to cure the resin.

When the manufactured cell was observed with a polarization microscope, as shown in FIG. 27, a liquid crystal having an island-shaped polymer region i in the center of a liquid crystal region d having regularity and a liquid crystal domain g having a radial shape. Area d was observed. The contrast of the fabricated cell measured from the vertical direction is 28,
The contrast measured from the 45 ° direction was between 25 and 21 measured from any direction. In the conventional TN cell, an inversion phenomenon was observed in the normal viewing angle direction, and the display quality was remarkably reduced.

Therefore, as described in the twelfth example and the eleventh example, when irradiation is performed using a photomask having a light-shielding hole in the center of the light-shielding portion, omnidirectionality is obtained in the liquid crystal region. By aligning the liquid crystal molecules, suppressing the viewing angle dependence in the halftone, and making the liquid crystal region cover most of the picture elements, it is possible to suppress the decrease in contrast due to scattering, and It can be applied to liquid crystal display devices that require a large screen and low viewing angle dependency, and its application range is extremely high. The scope of application is LCD TVs and video camera display devices (LCD view cams: Sharp Corporation).
Glasses type liquid crystal display device for virtual reality,
It covers liquid crystal displays for vehicles. In addition, when the area of the weak irradiation region such as the light shielding portion of the photomask is very large, a plurality of light transmitting holes may be provided. One of them
It may or may not be present in the central portion of the weakly illuminated area. The point is that almost all of the weakly illuminated region becomes a liquid crystal region, and the liquid crystal molecules can be made to be radial.

Further, the technique of the third embodiment can be applied to the case where two or more liquid crystal regions are provided in one picture element, and an application example thereof is shown in FIG. In FIG. 17, b is a light-shielding portion of a pixel or a photomask, c is an opening portion of the photomask, d is a liquid crystal region, and e is a liquid crystal molecule.

In addition, in the third embodiment as well, the details of the second embodiment (light regulating means such as a photomask) to (others) will be described.
The same applies to each item of.

(Embodiment 4) In this Embodiment 4, in addition to the liquid crystal region as in Embodiment 3, as shown in FIG. 28A, a plurality of liquid crystal molecules j included in the liquid crystal region d are used. Is helically oriented around a helix axis k that is substantially perpendicular to the substrate surface. In this case, as the liquid crystal material, a nematic liquid crystal, a liquid crystal material obtained by adding a cholesteric liquid crystal, a chiral agent, or the like can be used. Specific examples of chiral agents include S-811, R-811, and CE12.
Chiral agents such as can be used.

For example, when a nematic liquid crystal (particularly, a liquid crystal having a spiral pitch) is used, its characteristics change depending on the spiral pitch.

When the spiral pitch is larger than 100 μm, it is observed with a polarization microscope as shown in FIGS. 29 (a) and 29 (b).
As shown in FIG. 5, the liquid crystal region d is parallel to the substrate and the alignment plane of the liquid crystal is almost untwisted and is in a state close to homogeneous alignment. In this case, when the cell is placed under the crossed Nicols, the light ray is transmitted only by the effect of the birefringence of the liquid crystal,
Its permeation amount is small. Also, the difference in the refractive index at the interface between the polymer wall and the liquid crystal region d becomes clear when the voltage is turned off, and when the cell is observed from a position at an angle from the vertical direction of the cell, the interface between the polymer wall and the liquid crystal region d is observed. Appears, and the display becomes rough.

When the helical pitch is between 100 μm and 15 μm, as shown in FIGS. 28 (a), (b) and (c), the liquid crystal molecules are parallel to the substrate, but the twisted alignment state (T
It was found by observation with a polarization microscope that the orientation was close to that of the N cell. In this case, when the cell is placed under the crossed Nicols, the twisting molecule exerts the optical property and the light transmission amount increases. Furthermore, at the interface between the liquid crystal and the polymer, the liquid crystal molecules are aligned horizontally with the substrate but randomly aligned in the plane, so when the cell is observed from a position at an angle from the vertical direction of the cell, The interface between the molecular wall and the liquid crystal region becomes difficult to see, the roughness is eliminated, and the display quality is improved.

When the spiral pitch is 15 μm or less, the spiral axis of the liquid crystal molecules falls from the vertical plane of the cell as shown in FIGS. Was confirmed by the occurrence of. In such an alignment state in which the spiral lays down, some of the liquid crystal molecules stand vertically to the cell, and the light transmittance decreases.

Therefore, the spiral pitch is 15 in the fourth embodiment.
It is preferably not less than 100 μm and not more than 100 μm. More preferably, considering the light transmittance and roughness, the thickness is preferably 25 μm or more and 75 μm or less.

[Specific Examples 13, 14, 15, 16] ITO
Transparent electrode substrate 2 with (indium tin oxide)
A cell was produced by laminating the sheets so that the cell thickness was 5.5 μm. In the prepared cell, R-6840.1 g, styrene 0.05 g, and isobornyl methacrylate 0.8.
5 g and liquid crystal material ZLI-4792 {S-8110 0%
(Comparative Example 13), 0.3% (Specific Example 13), 0.6
% (Specific example 14), 0.9% (specific example 15), 1.
2% (specific example 16), the same 1.5% (comparative example 14) additive} 4g, and the mixture which mixed the photoinitiator Irugacure651 0.02g were inject | poured. The mixture is brought to a uniform mixed state at 40 ° C., and a photomask in which the light-shielding portions are squares of 200 μm square and the distance between the light-shielding portions is 50 μm is arranged in a grid pattern, and 14 mW / cm under a high-pressure mercury lamp from the photomask side.
^{In step 2} , (1 second irradiation + 29 seconds non-irradiation) × 20 cycles of irradiation, followed by continuous irradiation for 5 minutes, removing the mask, and continuous irradiation for 5 minutes.

Polarizing plates were attached to the upper and lower sides of the cell so as to be orthogonal to each other. Table 9 shows the electro-optical characteristics of the manufactured element. The drive voltage (V _th ) represents the voltage when the change in the transmittance is 10%, and T _o is the light transmittance when no voltage is applied with 100% of the two polarizing plates having the same polarization plane. Indicated. The helical pitch of the liquid crystal material was measured using a wedge cell.

[0237]

[Table 9]

As can be seen from Table 9, when the spiral pitch of the liquid crystal material is between 100 and 15 μm, the light transmittance is improved and bright display is possible. More preferably 75
Is about 25 μm. Furthermore, the driving voltage tends to decrease due to the addition of the chiral agent.

(Embodiment 5) The present embodiment 5 is a case where it is possible to improve the transmittance and the contrast in a liquid crystal display device in which liquid crystal domains are aligned radially or randomly. Hereinafter, description will be given based on a specific example according to the fifth embodiment.

[Specific Examples 17, 18, 19, 20] Two substrates having ITO (mixture of indium oxide and tin oxide, 500 angstrom) as transparent electrodes on a glass substrate (1.1 mm thick) were separated by 6 μm spacers. The cell was constructed by maintaining the cell thickness. A photomask shown in FIG. 31 was arranged on the prepared cell so that the pixel portion was shielded from light, and further R-684 (Nippon Kayaku Co., Ltd.) 0.1 g and styrene 0.05 g were placed in the cell. , Isobornyl methacrylate 0.85 g, 4 g of a fluorine- and chlorine-based liquid crystal material (added 0.5% of S-811) shown in Table 10, and a photoinitiator Irugacure651 0.0025.
A mixture was prepared by mixing g and g.

[0241]

[Table 10]

[0242] The mixture was injected in a uniform state, and thereafter, 20 cycles of irradiation (1 second irradiation, 30 seconds non-irradiation) were performed at 10 mW / cm ² under a high pressure mercury lamp capable of obtaining parallel rays from the photomask side. Then 10
The resin was cured by irradiating it for 10 minutes, removing the mask for 10 minutes, and irradiating it with ultraviolet rays. Two polarizing plates orthogonal to each other were attached to the front and back of the produced cell to produce a liquid crystal display device surrounded by polymer walls.

Table 11 shows the results of measurement of the light transmittance T ₀ at the time of voltage OFF, which is the electro-optical characteristic of the fabricated cell, with 100% when two polarizing plates are aligned in the same direction. .

[0244]

[Table 11]

The viewing angle characteristics of the cells of these specific examples 17 to 20 were good without any inversion phenomenon.

[Specific Examples 21 and 22] By using the same substrate material as in Specific Example 17 and changing the spacer between cells, the cell thickness is 3.5 μm (Comparative Example 15) and 7.2 μ.
m (Specific Example 21), 9.1 μm (Specific Example 22), 12.
Each cell was prepared so as to have a thickness of 0 μm (Comparative Example 16).

A mixture similar to that in Example 17 was injected into the manufactured cell, and a photomask was covered in the same manner as in Example 17, and UV irradiation was performed. Observation of the generated cells with a polarization microscope revealed that in Examples 21 and 22, a liquid crystal region having a shape substantially conforming to the photomask was formed. In Comparative Example 15, however, the cell gap was too small, and thus the liquid crystal material and photocuring were performed. Since the resin or the like is not sufficiently moved, a polymer wall is formed inside the light shielding portion, and the light transmittance when the voltage is OFF is low.

Table 12 is a table showing the electro-optical characteristics of the manufactured cells.

[0249]

[Table 12]

As can be understood from Table 12 and Table 11 described above, the viewing angle characteristics of the cells of these Examples 21 and 22 were good without any inversion phenomenon. The product Δn · d of the liquid crystal material Δn and the thickness d of the liquid crystal layer greatly affects the display characteristics of the liquid crystal display element, in particular, the light transmittance T ₀ when the voltage is OFF. It shows a high transmittance when it is between 1.1 μm. Furthermore, the cell thickness is Δn
Although the value of d is changed, if the cell thickness is 3 μm or less, the mass transfer of the liquid crystal material or the photocurable resin does not sufficiently occur, and innumerable liquid crystal regions are generated in the light shielding portion, which lowers the contrast. On the other hand, when the thickness is 10 μm or more, a portion where the polymer material is not sufficiently adhered is generated between the upper and lower substrates, and the controllability of the shape of the liquid crystal region is reduced. Therefore, as a preferable range, the product of the thickness (d) of the liquid crystal layer and the refractive index anisotropy (Δn) of the liquid crystal material is in the range of 0.4 to 1.1 μm, and the cell thickness is 3 to 10 μm. is there.

(Embodiment 6) This embodiment 6 describes an example of a photomask suitable for manufacturing a liquid crystal display device in which liquid crystal domains are aligned radially or randomly.

A cell was prepared in the same manner as in Example 17, the same mixture as in Example 17 was used, and a photomask shown in FIG. When the manufactured cell was observed with a polarization microscope, a liquid crystal region as shown in FIG. 33 was formed. In the liquid crystal region d, the inner liquid crystal d1 and the outer liquid crystal part d2 are divided by the polymer part between them, and a polymer island i is formed in the substantially central part of the inner liquid crystal part d1. ing.

FIG. 34 shows the viewing angle characteristics of this liquid crystal display element. In the same figure (a) and (b), the applied voltage-transmittance curve of a cell in which polarizing plates are laminated so that the polarization planes are orthogonal to each other on both sides of the produced cell is shown. When measured from the vertical direction of the cell as shown in d),
(B) is the case measured from an angle of 40 ° from the vertical direction of the cell. (C) shows the curves when measured from the direction rotated by 90 ° in the cell plane from (b). As can be seen from the figure, even if the viewing angle is changed, the amount of change in the applied voltage-transmittance curve is small, and the viewing angle characteristics are excellent. Especially, the floating of the transmittance at the time of voltage saturation,
That is, there is almost no case where the transmittance exceeds 0.

When a photomask having an irradiation portion (closed curve, partially cut closed curve) having substantially the same shape as the outer shape is used inside each light shielding portion as in this embodiment, the distance between the outer circumference and the inner curve is Then, the liquid crystal domains are arranged in a radial pattern,
Greatly improves the viewing angle characteristics. The outer peripheral shape and the shape of the inner curve need not be similar shapes. For example, when the outer circumference is rectangular, the same effect can be obtained even if the inner curve is circular, hexagonal, or square. When a hexagon is used as in the present embodiment, it is preferable because it can cover the entire flat surface, and can easily radiate the liquid crystal region close to a circle.

(Embodiment 7) Embodiment 7 is a case where the viewing angle dependency is further improved.

The viewing angle characteristics of the non-scattering type liquid crystal display element are dramatically improved in the halftone as compared with the conventional liquid crystal display element, but since the liquid crystal molecules are inclined with respect to the vertical direction of the cell. The refractive index from the vertical direction and the refractive index from the oblique direction are slightly changed, and the apparent contrast is also slightly changed due to the phenomenon. In order to correct the phenomenon, as shown in FIG. 18, a disc-shaped refractive index anisotropic film 62 having a refractive index anisotropy is laminated between one polarizing plate (not shown) and the substrate 61. You can adapt the way you do. As a result, the refractive indexes in the vertical direction (m direction) and the oblique direction (n direction) are almost the same, and the viewing angle dependence of contrast can be extremely reduced. This is a general method for canceling birefringence, which has been already disclosed in Japanese Patent Laid-Open No. 2-400795.

The refractive index anisotropic film 62 is, for example, a biaxially stretched film of polyvinyl alcohol (PVA) or the like, has no refractive index anisotropy in the film plane, and has an in-plane refractive index in the vertical direction. It is formed so as to have a larger refractive index.

(Embodiment 8) In this embodiment 8, a polymer wall is covered with a light-shielding mask such as a black mask to improve the light-shielding property.

FIG. 19 is a sectional view showing a liquid crystal display element according to this embodiment. This liquid crystal display device includes two transparent substrates 31 and 35 arranged opposite to each other, and a polymer wall 37 provided so as to reach the inner surfaces of both substrates 31 and 35.
And the liquid crystal region 38 surrounded by the wall 37 and the substrates 3
Polarizing plates 39a, 3 provided on the outer sides of 1, 35, respectively.
9b and a backlight 40 provided on the outside of one (lower) substrate 31.

Substrate 3 located on the side of the backlight 40
The liquid crystal display device 1 has, on the liquid crystal region 38 side thereof, picture element electrodes 32 formed in a matrix and scanning lines and signal lines (both not shown) provided between adjacent picture element electrodes 32. Further, on the substrate 31 on which the pixel electrodes 32, the scanning lines and the signal lines are formed, a flat film for flattening, a light shielding mask 3
3 and the alignment film 34a are formed in this order. The light-shielding mask 33 is formed on the wall 37 reaching the inner surface of the substrate 31.
The portion is arranged so as to cover 50% or more of the area of the wall 37 portion. The other substrate 35 has its liquid crystal region 38.
A counter electrode 36 formed on the side facing the pixel electrode 32.
And an alignment film 34b formed so as to cover the counter electrode 36.

In the picture element, the light-shielding mask 33 is provided on the wall 3
In the case of covering 100% or more of the area of the seven portions, the portion not covered by the light shielding mask 33 corresponds. Conversely, 100
When it is less than%, it corresponds to the size of the pixel electrode 32.

The liquid crystal display device having such a structure is manufactured as follows.

First, the substrate 31 on which the pixel electrodes 32, the scanning lines, the signal lines, the flat film, the light shielding mask 33 and the alignment film 34a are formed, and the substrate 35 on which the counter electrode 36 and the alignment film 34b are formed are prepared. Or make it.

Next, the two substrates 31 and 35 are disposed so as to face each other, and a mixture containing at least a photo-curable polymer material and a liquid crystal material prepared in advance is injected between the two substrates 31 and 35. Prior to this implantation, the alignment films 34a and 34b are rubbed. Subsequently, on the outer side of the substrate 35 on the opposite side of the substrate 31 having the light shielding mask 33, light shielding portions smaller than the size of the picture element are arranged in a matrix, and the outer side of each light shielding portion is a light transmitting portion. The above photomask is provided, and the mixture is irradiated with light from the light transmitting portion of the photomask. The light transmitting part of the photomask is
The position and size are set so that the light-shielding mask 33 covers 50% or more of the area of the wall 37.

The area where the light shielding mask 33 covers the wall 37 portion reaching the inner surface of the substrate 31 may be 50% or more. However, when it exceeds 300%, the area covering the peripheral portion of the pixel electrode 32 increases. As a result, the brightness is lowered, so that it is preferable to set it to 50% or more and 300% or less. Furthermore, 80%
As described above, it is desirable to set it to 150% or less. In the case of covering with the light-shielding mask 33 in this way, even if one liquid crystal region is formed across two picture elements or is formed between adjacent picture elements, even if the adjacent picture elements are adjacent to each other. Since the light-shielding mask 33 shields light between the areas, there is an advantage that light transmission from that portion can be suppressed and a reduction in contrast can be prevented.

As for the position where the light-shielding mask 33 is installed, in this embodiment, the backlight 4 is located from the liquid crystal region 38.
Although it is provided on the 0 side, it may be provided on the opposite side. However, when it is provided closer to the backlight 40 than the liquid crystal region 38, light can be blocked before the light is scattered by the polymer wall 37, and the light blocking property can be further improved. Furthermore, on the wall 37 portion reaching the inner surface of the substrate 31,
It is preferable to be closer.

The material of the light-shielding mask 33 is 50.
Anything that can block visible light at a percentage
Applicable materials include, for example, metals such as aluminum, tantalum and molybdenum, and organic materials such as colored paints, which are used as thin films.

A specific example of the eighth embodiment will be described below.

[Specific Example 23] On a PET film having a thickness of 0.25 mm, electrode wires made of ITO having a thickness of 500 angstrom (the number of wires is 20, the width of the electrode wire is 200).
Two substrates having a size of 50 μm and a distance between the electrode lines of 50 μm) were used.

Next, on one set of substrates having such a structure,
Polyimide (SE150: manufactured by Nissan Kagaku Co., Ltd.) was applied by a spin coating method to form an alignment film, and the alignment film was rubbed with a nylon cloth.

Next, the two rubbing-treated substrates were combined so that the electrode lines were orthogonal to each other, and a spacer of 6 μm was interposed between the two substrates to maintain the cell thickness to form a cell. .

Next, as shown in FIG. 20, for example, one side of the light shielding portion 41a in the shape of a square is 50 μm, the center distance between adjacent light shielding portions 41a is 60 μm, and the width of the light transmitting portion 41b is 10 μm. The manufactured photomask 41 is placed on the produced cell. Then, between the two substrates, 0.1 g of trimethylolpropane trimethacrylate,
0.9 g of 2-ethylhexyl acrylate and 0.3 g of CN (cholesteric nonanate) added to liquid crystal material ZLI-3700-000 (Merck) 4 g
And 0.03 g of a photocurable catalyst Irgacure 184 (manufactured by Ciba Geigy) are uniformly mixed, and a mixture is injected.

Thereafter, the mixture is cured by irradiating it with ultraviolet rays for 2 minutes from the photomask side. At this time, the cell was placed at a position of 10 mW / cm ² under a high-pressure mercury lamp capable of obtaining a parallel light beam and cured.

Finally, a polarizing plate was attached to the cured cell by aligning the polarization direction with the direction along the alignment direction of the alignment film to prepare a polymer dispersed TN liquid crystal display device. The liquid crystal display element thus manufactured is hereinafter referred to as cell A.

Further, another cell was prepared as follows. First, a cell was prepared in the same manner as before until the polarizing plates were laminated. Next, as shown in FIG. 21, a light-shielding mask 42 made of molybdenum, in which the light-transmitting portion of the photomask was the light-shielding portion 42a, was attached to the outside of this cell. This attachment was performed so that the light-shielding portion 42a of the light-shielding mask 42 overlaps the light-transmitting portion of the photomask on the substrate on the backlight side.

Next, a polarizing plate was attached to the cell thus obtained by aligning the polarization direction with the alignment direction of the alignment film to fabricate a polymer dispersed TN liquid crystal display device. The liquid crystal display element manufactured in this manner is hereinafter referred to as cell B.

Table 13 shows the contrast characteristics of the produced cell A and cell B together with those of Comparative Examples 17 and 18 by the conventional method. In Comparative Example 17, a cell was prepared in the same manner as in Concrete Example 23 using ITO-containing glass (ITO-500 Å flint glass manufactured by Nippon Sheet Glass) instead of the substrate of Concrete Example 23. Furthermore, a liquid crystal material similar to that of Example 23 was injected into this cell, and the polarization direction of the polarizing plate was aligned with the prepared cell in the direction of the alignment direction, and the polarizing plate was bonded to the cell to manufacture a conventional TN display element. did. On the other hand, the comparative example 18 is a specific example 23.
A TN-type cell was prepared in the same manner as in Example 2, and the same mixture of liquid crystal and photocurable resin as in Example 23 was used. After the mixture was injected into the cell, the cell was not covered with a photomask, and the specific example 2 was obtained.
UV irradiation was performed in the same manner as in Example 3 to prepare a polymer dispersion type display device.

[0278]

[Table 13]

As can be seen from Table 13, Example 23 (cell A) of the present invention was used in Comparative Example 17 which was conventionally used.
In comparison with Comparative Example 17, the specific example 23 (cell B) in which a light-shielding mask is installed shows almost the same contrast as the comparative example 17. It should be noted that in both the specific example 23 (cell A) and the specific example 23 (cell B), good contrast that is not comparable to the comparative example 18 was obtained.

Therefore, by using the method of Example 8, a film substrate can be used, and
Compared with the polymer-dispersed liquid crystal display element that has been studied conventionally, since there is almost no scattering within the picture element, it is possible to increase the contrast. The cell A and the cell B were separated, the cell was peeled off in liquid nitrogen, and the horizontal section of the polymer wall after rinsing the liquid crystal material with acetone was observed by SEM. As a result, the same regularity as that of the light-shielding portion of the photomask, That is, it was confirmed that liquid crystal regions having the same regularity as the picture elements and the same size and uniform alignment were formed.

Note that, also in the above-described eighth embodiment, the description of the second embodiment has been made (light regulating means such as a photomask).
Of course, the contents from (1) to (others) can be similarly applied.

[0282]

As described in detail above, in the case of the present invention, since the position and size of the liquid crystal region can be controlled by the light distribution forming means such as a photomask, the droplet-shaped liquid crystal region has a uniform diameter. In addition, it is possible to provide a scattering type liquid crystal display element having a sharp threshold characteristic and excellent contrast, and a method for manufacturing the same, which can be arranged regularly in the direction along the surface of the substrate. Further, it is possible to provide a non-scattering type liquid crystal display device in which the size of the liquid crystal region is adjusted with respect to the picture element to form the liquid crystal region, and a manufacturing method thereof.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a liquid crystal display element according to a first embodiment.

2A is a cross-sectional view showing a state before irradiating light to the liquid crystal display element of the first embodiment, and FIG. 2B is a cross-sectional view showing a state after light irradiation.

FIG. 3 is a diagram showing a boundary portion between a polymer wall cured by light irradiation and a liquid crystal in the first embodiment.

FIG. 4 is an example of a photomask usable in the present invention,
FIG. 6 is a plan view showing a case where one liquid crystal region is assigned to one pixel electrode.

FIG. 5 is a plan view showing an example of another photomask usable in the present invention and showing a case where one liquid crystal region is assigned to two pixel electrodes.

FIG. 6 is a cross-sectional view showing a case where the size of the liquid crystal region is made larger than that in the case of FIG. 2B and brought closer to the pixel electrode.

FIG. 7 is a plan view illustrating a method of inserting a mixture into a cell by vacuum injection.

8 is a side view (cross-sectional view) of FIG.

FIG. 9 is a front view showing the injector.

FIG. 10 is a cross-sectional view showing an example of a liquid crystal display device with an alignment film to which the present invention can be applied, where (a) shows a case where the size of the liquid crystal region is slightly smaller than the pixel electrode, and (b). Shows the case where the size of the liquid crystal region is increased and brought close to the pixel electrode.

11A is a diagram showing an alignment state of liquid crystal molecules when a voltage is not applied in a conventional ECB mode liquid crystal display element, and FIG. 11B is a diagram showing an alignment state of liquid crystal molecules when a voltage is applied. Is.

12A is a diagram showing an alignment state of liquid crystal molecules when a voltage is not applied in an ECB mode liquid crystal display device to which the present invention is applied, and FIG. 12B is a alignment state of liquid crystal molecules when a voltage is applied. FIG.

13 is a diagram showing a boundary portion between a polymer wall and liquid crystal in the liquid crystal display element of Comparative Example 6. FIG.

FIG. 14 is a plan view showing another example of a photomask used in the present invention.

FIG. 15 is a plan view showing another example of a photomask used in the present invention.

FIG. 16 is a plan view showing still another example of a photomask used in the present invention.

FIG. 17 is a diagram showing a case where a plurality of liquid crystal regions are formed in one picture element according to the present invention.

FIG. 18 is a diagram showing a configuration of the liquid crystal display element of the present invention when the viewing angle dependency is further improved.

FIG. 19 is a sectional view showing a liquid crystal display element according to still another embodiment of the present invention.

20 is a front view showing a photomask used for manufacturing the liquid crystal display element of FIG.

21 is a front view showing a light-shielding mask provided in the liquid crystal display element of FIG.

FIG. 22 is a diagram showing a liquid crystal region in a scattering mode.

FIG. 23 is a diagram showing a non-scattering mode liquid crystal region obtained when the photopolymerization rate is high.

FIG. 24 is a diagram showing a liquid crystal region in a non-scattering mode obtained when the photopolymerization rate is slow.

25 is a diagram showing a liquid crystal region in a non-scattering mode obtained when the photopolymerization rate is higher than that in FIG. 24 and is slower than that in FIG. 23.

FIG. 26 is a diagram showing a liquid crystal region in a non-scattering mode, which is obtained when the photopolymerization rate is slower.

FIG. 27 is a diagram showing a liquid crystal region in a non-scattering mode obtained when a light transmitting hole is provided in the central portion of the light shielding portion of the photomask.

28 is a liquid crystal region of the liquid crystal display element according to Example 4, showing a case where the spiral pitch is 15 μm or more and 100 μm or less, and FIG. 28 (a) is a front view (cross-sectional view) of the liquid crystal region, ) Is its plan view, (c) is (a) I, II, I
FIG. 4 is a plan view of each of II and IV layers.

FIG. 29 shows a case where the spiral pitch is larger than 100 μm, (a) is a front view (cross-sectional view) of a liquid crystal region,
(B) is its plan view, (c) is (a) I, II, III, IV.
3 is a plan view of each of the layers. FIG.

FIG. 30 shows a case where the spiral pitch is smaller than 15 μm, (a) is a front view (cross-sectional view) of the liquid crystal region, and (b) is a diagram.
Is a plan view thereof.

FIG. 31 is a plan view showing an example of a photomask used in Example 5.

FIG. 32 is a plan view showing an example of a photomask used in Example 6.

FIG. 33 is a plan view showing a liquid crystal region obtained by using the photomask of FIG. 32.

FIG. 34 is a diagram showing viewing angle characteristics of the liquid crystal display element of Example 6.

[Explanation of symbols]

 1 Active Matrix Substrate 2 Picture Element Electrode 3 Counter Substrate 4 Counter Electrode 5 Mixture 6 Glass Plate 7 Photomask 8 Wall 8a Alignment Film 9 Liquid Crystal Region 9a Picture Element 10 Ultraviolet Light 11 Picture Element Electrode 12 Glass Substrate 13 Glass Substrate 14 Photomask 15 Counter Electrode 16 liquid crystal region 17 wall 31 substrate 32 picture element electrode 33 light-shielding mask 34a alignment film 34b alignment film 35 substrate 36 counter electrode 37 wall 38 liquid crystal region 39a polarizing plate 39b polarizing plate 40 backlight

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 9, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction content]

Further, a uniform mixture of a photo-curable polymer material and a liquid crystal material is dropped or applied on one of two opposing substrates, the two substrates are bonded together, and then the polymer material is cured. You may allow it.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0074

[Correction method] Change

[Correction content]

By limiting in this way, the distance a in the direction along the substrate surface from one liquid crystal region to the adjacent liquid crystal region is within the pixel size in the same direction, and the average value b of the distances is On the other hand, 3b / 2>a> b / 2
The liquid crystal regions having the regularity have a regularity of 80% or more of the whole. That is, the regularity of the liquid crystal region is increased.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0082

[Correction method] Change

[Correction content]

The selection of the polymer material is important because it is a substance that is mixed with the liquid crystal material to form a mixture and finally becomes a wall that supports the two substrates and the liquid crystal region. The polymer material that can be used in this embodiment corresponds to a photo-curable monomer, and may be another polymer substance or the like. Examples of the photocurable monomer include acrylic acid and acrylic acid ester having a C3 or longer long-chain alkyl group or an aromatic ring. Furthermore, isobutyl acrylate, stearyl acrylate, lauryl acrylate, isoamyl acrylate, n-butyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, 2-ethylhexyl acrylate, n-stearyl methacrylate, cyclohexyl methacrylate,
There are benzyl methacrylate and 2-phenoxyethyl methacrylate.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0083

[Correction method] Change

[Correction content]

Further, in order to increase the physical strength of the polymer, a polyfunctional compound having two or more functional groups, for example, bisphenol A dimethacrylate, bisphenol A diacrylate, 1,4-butanediol dimethacrylate, 1, 6
-Hexanediol dimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, etc. can also be used.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0084

[Correction method] Change

[Correction content]

Further, usable compounds include compounds obtained by halogenating, especially chlorinating or fluorinating, the above-mentioned monomers.
There is a thing . Examples of such a material include 2, 2,
3,4,4,4-hexafluorobutyl methacrylate,
2,2,3,4,4,4-hexachlorobutyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, perfluorooctylethyl methacrylate, perchloro Examples include octylethyl methacrylate, perfluorooctylethyl acrylate, and perchlorooctylethyl acrylate.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0099

[Correction method] Change

[Correction content]

As described above, according to the first embodiment,
A polymer-dispersed liquid crystal display device in which liquid crystal regions having a uniform diameter are regularly arranged along the surface of a substrate can be manufactured with a good yield in a small number of steps.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0102

[Correction method] Change

[Correction content]

A method of manufacturing the liquid crystal display element according to the second embodiment will be described with reference to FIG. First, as shown in FIG. 2A, a substrate 1 and a counter substrate 3 are opposed to each other, and a liquid crystal material and a mixture 5 composed of a photocurable polymer raw material are placed between the two opposed substrates 1 and 3. Encapsulate. The upper substrate 1 shown in the figure is transparent, and a pixel electrode 2 is formed on the inner surface side thereof. A counter electrode 4 is formed on the entire inner surface of one counter substrate 3.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0103

[Correction method] Change

[Correction content]

Next, the glass plate 6 having the photomask 7 formed thereon is placed on the substrate 1, and the photomask 7 is placed.
Ultraviolet (UV) light 10 is irradiated from the side toward the mixture 5. As a result, as shown in FIG. 2B, a wall 8 made of a polymer resin and a liquid crystal region 9 surrounded by the wall 8 are formed. In this formation, the polymerization rate is high in the portion having high UV intensity and the polymer is rapidly deposited, and coexisting liquid crystal molecules are extruded to the portion having low light intensity. As a result, the liquid crystal region 9 is formed in the portion having low UV intensity. To do. The liquid crystal region 9 is
The portion close to the substrates 1 and 3 has a parallel portion parallel to the surfaces of the substrates 1 and 3.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0106

[Correction method] Change

[Correction content]

Further, since the wall 8 is formed so as to reach both the substrates 1 and 3, both the substrates 1 and 3 are firmly held by the wall 8 and the shock resistance is improved. Furthermore, it is possible to suppress the lower side of the gap between the substrates 1 and 3 by the weight of the liquid crystal be used liquid crystal display device in an upright state substrates 1 and 3 are wider than the gap between the upper side. This is particularly effective when a film-shaped substrate is used as the substrate.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0107

[Correction method] Change

[Correction content]

The shape of the liquid crystal region actually formed in Example 2 was as follows: the liquid crystal display element was peeled into two pieces, the liquid crystal molecules were removed with a solvent, and the polymer matrix consisting of the remaining walls 8 was SEM (scanning electron). It can be observed and confirmed with a microscope. Since there is a portion where the structure is destroyed during the preparation of the SEM observation sample, it is preferable to select the 20 liquid crystal regions having the most regularity in the sample and observe the polymer matrix.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0108

[Correction method] Change

[Correction content]

In FIG . 3, the wall 8 and the liquid crystal region 9 are phase-separated.
It is a figure obtained by observing the existing state with a microscope.
It As can be seen from this figure, a photomask is used to block the light.
A polymer wall 8 is formed in the illuminated area.
On the other hand, on the other hand,
It was confirmed that the wall 8 was formed. However, this wall
8 may have a small liquid crystal region formed therein.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0109

[Correction method] Change

[Correction content]

The configuration of each part applied to this embodiment will be described below.
A modified example will be described. (Light control means such as photomask) Results of examination by the present inventors
According to the report, the high illuminance area and the low illuminance area that form uneven illuminance
And the size of the weak illuminance area is 30% or less of the area of the pixel.
If you use the size below, the generated liquid crystal area will also be
It was found that the size was 30% or less of the area of the element.
In this case, a liquid crystal region and a polymer wall are included in one pixel.
Since there are many interfaces in the
This is not practical because the reduction in strike becomes large. Therefore, the picture
At least one liquid crystal region included in the pixel is the area of the pixel
The size is limited to 30% or more.

[Procedure Amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0118

[Correction method] Change

[Correction content]

(Method of Injecting Mixture Between Substrates) In the present embodiment, a method of putting a mixture of a liquid crystal material and a photocurable polymer resin between the substrates is a conventional general method. After the two substrates are bonded together, the mixture may be injected between the two substrates. Alternatively, before the two substrates are bonded together, the mixture is dropped or applied on one substrate, and in that state, UV light is irradiated to cure the polymer resin, and then the two substrates are bonded. You may adopt the method. The latter method has an advantage that a spacer or the like for controlling the thickness of the liquid crystal layer can be eliminated.

[Procedure Amendment 14]

[Document name to be amended] Statement

[Name of item to be corrected] 0122

[Correction method] Change

[Correction content]

The polymer material that can be used in this embodiment corresponds to a photo-curable monomer, and other polymerizable polymer substances may be used. As the photocurable monomer,
For example, there are acrylic acid and acrylate having a long-chain alkyl group of C3 or more or an aromatic ring. Furthermore, 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 There is phenoxyethyl methacrylate.

[Procedure Amendment 15]

[Document name to be amended] Statement

[Name of item to be corrected] 0123

[Correction method] Change

[Correction content]

Further, in order to enhance the physical strength of the polymer, a polyfunctional compound having two or more functional groups such as bisphenol A dimethacrylate, bisphenol A diacrylate, 1,4-butanediol dimethacrylate and 1,6
-Hexanediol dimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, etc. can also be used.

[Procedure Amendment 16]

[Document name to be amended] Statement

[Correction target item name] 0124

[Correction method] Change

[Correction content]

Further, as a usable compound , a compound obtained by halogenating, especially chlorinating or fluorinating, the above-mentioned monomer is used.
There is a thing . Examples of such a material include 2, 2,
3,4,4,4-hexafluorobutyl methacrylate,
2,2,3,4,4,4-hexachlorobutyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, perfluorooctylethyl methacrylate, perchloro Examples include octylethyl methacrylate, perfluorooctylethyl acrylate, and perchlorooctylethyl acrylate.

[Procedure Amendment 17]

[Document name to be amended] Statement

[Correction target item name] 0129

[Correction method] Change

[Correction content]

These liquid crystal materials may be a mixture of two or more liquid crystals, and nematic liquid crystal or cholesteric liquid crystal or nematic liquid crystal to which a chiral agent is added is preferable in view of characteristics. Furthermore, since a photopolymerization reaction accompanies the production of the liquid crystal region, it is preferable that the liquid crystal material has excellent chemical reactivity resistance that does not cause modification during the polymerization reaction,
For example, a liquid crystal having an inert substituent such as a fluorine atom in the compound is suitable. Although not particularly limited to those having such properties, ZLI-4801-000 and ZLI-commercially available from Merck & Co., Inc.
4801-001, ZLI-4792, etc. are mentioned.

[Procedure 18]

[Document name to be amended] Statement

[Name of item to be corrected] 0159

[Correction method] Change

[Correction content]

SmC ^* ← 25 ° C. → SmA ← 31 ° C. → Ch ← 35 ° C. → Iso Next, a light-shielding photomask was set in the same manner as in Example 3.
While the liquid crystal-polymer precursor mixture was in the nematic phase or the isotropic liquid phase, ultraviolet irradiation was performed from the photomask side for 2 minutes at an irradiation intensity of 10 mW / cm ² using a high pressure mercury lamp capable of obtaining parallel rays. This irradiation photocured the liquid crystal-polymer precursor mixture and caused phase separation of the mixture of liquid crystal and polymer.

[Procedure Amendment 19]

[Document name to be amended] Statement

[Correction target item name] 0175

[Correction method] Change

[Correction content]

SmC ^* ← 25 ° C. → SmA ← 31 ° C. → Ch ← 35 ° C. → Iso Next, a light-shielding photomask is arranged in the same manner as in Example 5, and ultraviolet rays are irradiated from the side of the photomask under the same conditions as in Example 5. Then, the liquid crystal-polymer precursor mixture was cured to cause phase separation between the liquid crystal and the polymer composition.

[Procedure amendment 20]

[Document name to be amended] Statement

[Name of item to be corrected] 0182

[Correction method] Change

[Correction content]

As shown in FIG. 14, a photomask 43 was placed on the produced cell, which is likened to square picture elements having a pitch of 250 μm. 43a is a light shielding part. In the cell, 0.9 g of isobornyl methacrylate and 2
0.1 g of Noh acrylate R-684 (manufactured by Nippon Kayaku Co., Ltd.) and 0.3% of S-811 (manufactured by Merck) as a chiral agent in liquid crystal material ZLI-4792 (manufactured by Merck). 4 g of the added mixture and Ir which is a photocurable catalyst
A mixture of 0.02 g of gacure184 (manufactured by Ciba Geigy) and a uniform mixture is poured.

[Procedure correction 21]

[Document name to be amended] Statement

[Correction target item name] 0189

[Correction method] Change

[Correction content]

In Comparative Example 9, a cell was prepared in the same manner as in Concrete Example 7, and the same liquid crystal material (S-8 as in Concrete Example 7 was used in the prepared cell.
11: 0.3% added) was injected, and the polarization direction of the polarizing plate was aligned in the direction along the alignment direction of the prepared cell, and the polarizing plate was bonded to the cell to manufacture a conventional TN display element. Comparative Example 1
0 is the same as in Example 7 except that a cell was prepared in the same manner as described above, and the same liquid crystal, photocurable resin, and photoinitiator mixture as in Example 7 was injected into the prepared cell, and the cell was not covered with a photomask. Photocuring was performed under the conditions of. Polarizing plates were attached to the prepared cell so that the polarizing directions of the polarizing plates were orthogonal to each other, and a device in which a conventional polymer dispersed liquid crystal display device was sandwiched between the polarizing plates was manufactured.

[Procedure correction 22]

[Document name to be amended] Statement

[Correction target item name] 0191

[Correction method] Change

[Correction content]

[Specific Example 8] 0.9 g of isobornyl methacrylate and R-684 which is a bifunctional acrylate.
(Nippon Kayaku Co., Ltd.) 0.1 g and liquid crystal material ZLI-
4792 (manufactured by Merck) as a chiral agent S-811
(Merck) 0.3% added mixture 4g, and photocurable catalyst Irgacure184 (Ciba Geigy) 0.0
A cell prepared in the same manner as in Example 7 is injected with a mixture of 2 g and the mixture.

[Procedure amendment 23]

[Document name to be amended] Statement

[Name of item to be corrected] 0195

[Correction method] Change

[Correction content]

[Specific Example 9] 0.9 g of isobornyl methacrylate and R-684 which is a bifunctional acrylate.
(Nippon Kayaku Co., Ltd.) 0.1 g and liquid crystal material ZLI-
4792 (manufactured by Merck) as a chiral agent S-811
(Merck) 0.3% added mixture 4g, and a photocurable catalyst Irgacure184 (Ciba Geigy) 0.1
A cell prepared in the same manner as in Example 7 is injected with a mixture of 2 g and the mixture.

[Procedure correction 24]

[Document name to be amended] Statement

[Correction target item name] 0204

[Correction method] Change

[Correction content]

Glass substrate (flint glass: 1.1 mm thick)
ITO (a mixture of indium oxide and tin oxide,
(500 angstrom) was used as it was, two substrates were combined, and a cell was constructed by keeping the cell thickness with a spacer of 5 μm (Micropearl: manufactured by Sekisui Fine Chemical Co., Ltd.). A photomask 43 that resembles a square pixel having a pitch of 250 μm and a light-shielding portion of 200 μm shown in FIG. 14 is placed on the prepared cell, and 0.85 g of isobornyl methacrylate and bifunctional are added in the cell.
Acrylate of R684 (manufactured by Nippon Kayaku Co., Ltd.)
0.1 g and 0.05 g of styrene which is a photopolymerization inhibitor
And, Kaila to the liquid crystal material ZLI-4792 (manufactured by Merck & Co., Inc.)
A mixture of 4 g of a mixture containing 0.3% of S-811 (manufactured by Merck) as a luster agent and 0.02 g of a photocurable catalyst Irgacure651 (manufactured by Ciba-Geigy) is uniformly mixed and then injected.

[Procedure correction 25]

[Document name to be amended] Statement

[Correction target item name] 0210

[Correction method] Change

[Correction content]

In Comparative Example 11, a cell was produced in the same manner as in Example 10, and the same liquid crystal, photocurable resin, and photoinitiator mixture as in Example 10 was injected into the produced cell, without covering with a photomask. Then, photocuring was performed under the same conditions as in Example 10. Polarizing plates were attached to the prepared cell so that the polarizing directions of the polarizing plates were orthogonal to each other, and a device in which a conventional polymer dispersed liquid crystal display device was sandwiched between the polarizing plates was manufactured. In Comparative Example 12, polyimide (SE150: manufactured by Nissan Kagaku Co., Ltd.) was applied on the same substrate as in Example 10 by spin coating, and rubbed in one direction with a nylon cloth. The two substrates that have been subjected to the above processing are combined so that the rubbing directions are orthogonal to each other.
A cell was constructed by keeping the cell thickness with a spacer (micropearl: manufactured by Sekisui Fine Chemical Co., Ltd.) of μm. Liquid crystal material ZLI-4792 (manufactured by Merck) was added to the prepared cell as a chiral agent S-811 (manufactured by Merck).
Was added at a rate of 0.3 % by weight . Further, the polarization direction of the polarizing plate is adjusted in the direction along the alignment direction to the cell in which the liquid crystal material is injected, and the polarizing plate is bonded to the conventional T
An N display element was produced.

[Procedure Amendment 26]

[Document name to be amended] Statement

[Correction target item name] 0214

[Correction method] Change

[Correction content]

The addition amount of these photopolymerization inhibitors varies depending on the effect and is not particularly limited in the present invention. However, a mixture of a photocurable resin material, a photoinitiator and a photopolymerization inhibitor is mixed with a photo differential thermal balance (optical DSC). : Seiko Denshi Co., Ltd. PDC121), irradiation intensity 100 mW / cm ² (365 nm), 25
° C., mixed with a photoinitiator Irugacure651 0.3% addition system
When the heat of photopolymerization reaction of the product is measured, the amount added is preferably such that the peak value is 20 seconds or more. In 20 seconds or less, the liquid crystal region does not grow sufficiently, the polymer wall is partially formed in the weak illuminance region of the photomask, and the contrast is lowered.

[Procedure Amendment 27]

[Document name to be amended] Statement

[Correction target item name] 0215

[Correction method] Change

[Correction content]

The liquid crystal is an organic mixture which exhibits a liquid crystal state near room temperature, and includes nematic liquid crystal (including dual frequency driving liquid crystal and liquid crystal with Δε <0) and cholesteric liquid crystal (especially, selective reflection for visible light). Liquid crystals having characteristics), or smectic liquid crystals, ferroelectric liquid crystals, and discotic liquid crystals. These liquid crystals may be mixed, and in particular, nematic liquid crystals, cholesteric liquid crystals, or nematic liquid crystals to which a chiral agent is added are preferable in view of characteristics, such as hysteresis, uniformity, dΔn ( retardation liquid crystal ).
It is preferable that a chiral agent having a spiral pitch of 10 μm or more is added in view of the problem of coloration due to (1 ). Further, a liquid crystal having excellent chemical reaction resistance is preferable because it is accompanied by a photopolymerization reaction during processing. Specifically, it is a liquid crystal having a functional group such as a fluorine atom in the compound.
Specifically, ZL I -4801-000, ZLI-48
01-001, ZLI-4792 (manufactured by Merck & Co., Inc.) and the like.

[Procedure correction 28]

[Document name to be amended] Statement

[Name of item to be corrected] 0223

[Correction method] Change

[Correction content]

On the fabricated cell, a circular light transmitting hole 44b having a diameter of 25 μm is formed in the central portion of the light shielding portion 44a shown in FIG.
The photomask 44 having the above is arranged. In the cell, 0.9 g of isobornyl methacrylate and bifunctional
R-684 which is an acrylate (manufactured by Nippon Kayaku Co., Ltd.)
0.1 g and liquid crystal material ZLI-4792 (Merck)
S-811 (Merck) as a chiral agent is added to 0.3
% Mixture added with 4%, and Irgacure which is a photocurable catalyst
A mixture of 0.02 g of 184 (manufactured by Ciba Geigy) and a uniform mixture is poured.

[Procedure correction 29]

[Document name to be amended] Statement

[Correction target item name] 0235

[Correction method] Change

[Correction content]

[Specific Examples 13, 14, 15, 16] ITO
Transparent electrode substrate 2 with (indium tin oxide)
A cell was produced by laminating the sheets so that the cell thickness was 5.5 μm. Into the prepared cell, 0.1 g of bifunctional acrylate R-684, 0.05 g of styrene, 0.85 g of isobornyl methacrylate, and liquid crystal material ZLI
-4792 {S-8110% (Comparative Example 13), the same as 0.
3% (Specific Example 13), 0.6% (Specific Example 14), 0.9% (Specific Example 15), 1.2% (Specific Example 16),
Same as 1.5% (Comparative Example 14) additive} 4 g, and photoinitiator Ir
A mixture of 0.02 g of gacure 651 was injected. To 40 ° C. comprising the mixture homogeneous mixed state, a square of the light shielding portion is 200μm square, covered with a photomask between the light-shielding portions are arranged in square shape with 50 [mu] m, a high pressure mercury lamp under 14 mW / cm ² from the photomask side, ( Irradiation was performed for 1 second + 29 seconds non-irradiation) × 20 cycles, followed by continuous irradiation for 5 minutes, and then continuous irradiation for 5 minutes with the mask removed.

[Procedure amendment 30]

[Document name to be amended] Statement

[Correction target item name] 0239

[Correction method] Change

[Correction content]

(Embodiment 5) The present embodiment 5 is a case where a liquid crystal display device in which liquid crystal domains are aligned radially or randomly is capable of improving the transmittance and the contrast. Hereinafter, description will be given based on a specific example according to the fifth embodiment.

[Procedure correction 31]

[Document name to be amended] Statement

[Correction target item name] 0240

[Correction method] Change

[Correction content]

[Specific Examples 17, 18, 19, 20] Two substrates having ITO (mixture of indium oxide and tin oxide, 500 angstrom) as transparent electrodes on a glass substrate (1.1 mm thick) were separated by 6 μm spacers. The cell was constructed by maintaining the cell thickness. The photomask shown in FIG. 31 is placed on the fabricated cell so that the pixel portion is shielded from light, and further, a bifunctional acrylic resin is placed in the cell.
With a rate of R-684 (Nippon Kayaku Co., Ltd.) 0.1 g,
0.05 g of styrene, 0.85 g of isobornyl methacrylate, and fluorine- and chlorine-based liquid crystal materials shown in Table 10 (adding 0.5% of S-811 as a chiral agent ) 4
g and 0.0025 g of the photoinitiator Irgacure 651 were mixed to prepare a mixture.

[Procedure correction 32]

[Document name to be amended] Statement

[Correction target item name] 0241

[Correction method] Change

[Correction content]

[0241]

[Table 10]

[Procedure amendment 33]

[Document name to be amended] Statement

[Correction target item name] 0253

[Correction method] Change

[Correction content]

FIG. 34 shows the viewing angle characteristics of this liquid crystal display element. In the same figure (a) and (b), the applied voltage-transmittance curve of the cell which attached the polarizing plate on both surfaces of the produced cell so that a polarizing plane may mutually orthogonally cross is shown, (a) shows the same figure. When measured from the vertical direction of the cell as shown in (d),
(B) is the case measured from an angle of 40 ° from the vertical direction of the cell. (C) shows the curves when measured from the direction rotated by 90 ° in the cell plane from (b). As can be seen from the figure, even if the viewing angle is changed, the amount of change in the applied voltage-transmittance curve is small, and the viewing angle characteristics are excellent. Especially, the floating of the transmittance at the time of voltage saturation,
That is, there is almost no case where the transmittance exceeds 0.

[Procedure amendment 34]

[Document name to be amended] Statement

[Correction target item name] 0260

[Correction method] Change

[Correction content]

Substrate 3 located on the side of the backlight 40
1 has a pixel electrode 32 on the liquid crystal region 38 side.
Further, on the substrate 31 on which the pixel electrodes 32 are formed, a flat film for flattening, a light shielding mask 33, and an alignment film 34.
a is formed in this order. This light-shielding mask 33 is
The portion of the wall 37 reaching the inner surface of the substrate 31 is referred to as the wall 3
It is arranged so as to cover 50% or more of the area of 7 parts.
The other substrate 35 has a counter electrode 36 formed on the liquid crystal region 38 side so as to face the picture element electrode 32, and an alignment film 34 b formed so as to cover the counter electrode 36.

[Procedure amendment 35]

[Document name to be amended] Statement

[Correction target item name] 0261

[Correction method] Change

[Correction content]

In the picture element, the light-shielding mask 33 is provided on the wall 3
In the case of covering 100% or more of the area of the seven portions, the portion not covered by the light shielding mask 33 corresponds. Conversely, 100
If less than% , the weight of the pixel electrode 32 and the counter electrode 36
Corresponds to the size of the rounded part .

[Procedure correction 36]

[Document name to be amended] Statement

[Correction target item name] 0263

[Correction method] Change

[Correction content]

First, the substrate 31 on which the pixel electrodes 32, the flat film, the light-shielding mask 33 and the alignment film 34a are formed, and the substrate 35 on which the counter electrode 36 and the alignment film 34b are formed are prepared or prepared. .

[Procedure amendment 37]

[Document name to be amended] Statement

[Correction target item name] 0272

[Correction method] Change

[Correction content]

Next, as shown in FIG. 20, one side of the light shielding portion 41a in the shape of, for example, a square is 200 μm, the center distance between adjacent light shielding portions 41a is 250 μm, and the light transmitting portion 41 is formed.
An Al photomask 41 having a width b of 50 μm is placed on the fabricated cell. Then, between the two substrates, trimethylolpropane trimethacrylate 0.1
g, 0.9 g of 2-ethylhexyl acrylate, CN in liquid crystal material ZLI-3700-000 (Merck)
4 g of 0.3 g of (cholesteric nonanate) added and 0.03 g of photocurable catalyst Irgacure 184 (manufactured by Ciba Geigy) are uniformly mixed, and a mixture is injected.

[Procedure amendment 38]

[Document name to be amended] Statement

[Correction target item name] Explanation of code

[Correction method] Change

[Correction content]

[Explanation of symbols] 1 substrate 2 picture element electrode 3 counter substrate 4 counter electrode 5 mixture 6 glass plate 7 photomask 8 wall 8a alignment film 9 liquid crystal region 9a picture element 10 ultraviolet light 11 picture element electrode 12 glass substrate 13 glass substrate 14 photomask 15 counter electrode 16 liquid crystal region 17 wall 31 substrate 32 picture element electrode 33 light-shielding mask 34a alignment film 34b alignment film 35 substrate 36 counter electrode 37 wall 38 liquid crystal region 39a polarization plate 39b polarization plate 40 backlight

[Procedure amendment 39]

[Document name to be corrected] Drawing

[Name of item to be corrected] Fig. 19

[Correction method] Change

[Correction content]

FIG. 19

[Procedure amendment 40]

[Document name to be corrected] Drawing

[Correction target item name] Fig. 28

[Correction method] Change

[Correction content]

FIG. 28

[Procedure Amendment 41]

[Document name to be corrected] Drawing

[Name of item to be corrected] Fig. 29

[Correction method] Change

[Correction content]

FIG. 29

 ─────────────────────────────────────────────────── ─── Continuation of the front page (31) Priority claim number Japanese Patent Application No. 5-30996 (32) Priority date Hei 5 (1993) February 19 (33) Priority claim country Japan (JP) (72) Inventor Toshiyuki Hirai 22-22 Nagaike-cho, Abeno-ku, Osaka-shi, Osaka Prefecture (72) Inventor Noriaki Onishi, 22-22 Nagaike-cho, Nagano-cho, Abeno-ku, Osaka-shi, Osaka (72) Inventor Tokihiko Shinomiya Osaka Prefecture 22-22 Nagaike-cho, Abeno-ku, Osaka-shi, Ltd.Sharp Co., Ltd. 22-22 Nagaikecho, Ward Within SHARP Co., Ltd. (72) Inventor Masahiko Kondo 22-22 22 Nagaikecho, Abeno-ku, Osaka City, Osaka Prefecture Within SHARP Co., Ltd.

Claims (31)

[Claims] 1. A polymer-dispersed liquid crystal display device in which picture elements are arranged in a matrix and is a scattering type, wherein at least one of two substrates each having an electrode is transparent. Two substrates are arranged so as to face each other with the electrode side facing inward, and between the two substrates facing each other, a wall made of a polymer reaching both substrates and a liquid crystal region surrounded and confined by the walls are formed. The liquid crystal layer is sandwiched, and the distance a from one liquid crystal region to the adjacent liquid crystal region in the direction along the substrate surface is within the pixel size in that direction, and
A liquid crystal display device having regularity in which the distance between liquid crystal regions satisfying 3b / 2>a> b / 2 with respect to the average value b of the distance is 80% or more of the whole. 2. A method for producing a polymer-dispersed liquid crystal display element in which picture elements are arranged in a matrix and is a scattering type, at least one of which is transparent and has a pair of electrodes serving as picture elements. A mixture of a photo-curable polymer material and a liquid crystal material is injected between both substrates, which are opposed to each other, and at least one portion of the mixture is centered on the picture element in one picture element. 90 for the maximum illuminance within a circle that is 10 times the area of the picture element
A method for manufacturing a liquid crystal display device, which irradiates light with a light intensity distribution of not more than%. 3. The liquid crystal display according to claim 2, wherein a transparent mask side of the pair of substrates is covered with a photomask having a regular pattern, and the mixture injected between the substrates is irradiated with light from the photomask side. Device manufacturing method. 4. Inside one of the pair of substrates,
3. The method for manufacturing a liquid crystal display element according to claim 2, wherein a photomask having a regular pattern is provided, and the mixture injected between both substrates is irradiated with light from the photomask side. 5. The photomask according to claim 3, wherein the regular pattern is formed continuously or independently, and the regular pattern covers at least 30% or more of the area of each picture element. 4. The method for manufacturing a liquid crystal display element according to 4. 6. The photomask has its regular pattern formed continuously or independently, and the minimum repeating unit portion of the pattern has a size that can be accommodated within a circle having a diameter of 1 μm or more and 50 μm or less, and 5. The method for manufacturing a liquid crystal display device according to claim 3, wherein the distance from the center of the unit portion to the center of the closest unit portion is 1 μm or more and 50 μm or less. 7. A liquid crystal display element in which picture elements are arranged in a matrix, wherein at least one of two substrates each having an electrode is transparent, and the two substrates are arranged facing each other with the electrode side facing inward. The display medium sandwiched between two opposing substrates is composed of a polymer-based wall and a liquid crystal-based liquid crystal region, and the wall is formed by reaching both substrates. A liquid crystal display element having a parallel portion in which a region is surrounded by the wall and which is close to both substrates and whose approaching portions are parallel to the substrates. 8. The liquid crystal display element according to claim 7, wherein the liquid crystal region is provided for one or more picture elements. 9. The liquid crystal display element according to claim 8, wherein at least one liquid crystal region included in the picture element has a size of 30% or more of the area of the picture element. 10. The liquid crystal display element according to claim 7, wherein two or more of the liquid crystal regions are included in one pixel in whole or in part. 11. The picture element has a long side dimension of 200 μm.
The liquid crystal display element according to claim 10, wherein the liquid crystal display element has a length of m or more. 12. The liquid crystal region has a plurality of liquid crystal domains, and the alignment direction of each liquid crystal domain or liquid crystal molecule is concentric along a polymer wall on a plane substantially parallel to the substrate surface. 7. The liquid crystal display device according to 7, 8 or 10. 13. The liquid crystal region is formed by enclosing an inner liquid crystal domain located in a central portion, a polymer region surrounding the outer side of the inner liquid crystal domain, and an outer region of the polymer region. 11. The liquid crystal according to claim 7, 8 or 10, comprising a plurality of outer liquid crystal domains separated by disclination, and the directions of the respective outer liquid crystal domains are radial on a plane substantially parallel to the substrate surface. Display element. 14. The liquid crystal region comprises a plurality of liquid crystal domains separated by disclination, and the liquid crystal domains are oriented in different directions on a plane substantially parallel to the substrate surface. 8. The liquid crystal display element according to 8 or 10. 15. The liquid crystal region is formed by surrounding a polymer region located in a central portion and the outside of the polymer region,
11. The liquid crystal display device according to claim 7, comprising a plurality of liquid crystal domains separated by disclination, and the directions of the liquid crystal domains being radial on a plane substantially parallel to the substrate surface. 16. The liquid crystal display element according to claim 7, wherein a plurality of liquid crystal molecules included in the liquid crystal region are spirally aligned around a spiral axis substantially perpendicular to the surface of the substrate. . 17. The liquid crystal display device according to claim 16, wherein a plurality of liquid crystal molecules included in the liquid crystal region are provided with a spiral pitch of 15 μm or more and 100 μm or less. 18. The product of the thickness between both parallel portions of the liquid crystal region and the refractive index anisotropy is 0.4 μm or more and 1.1 μm or less, and the separation distance between both substrates is 3 μm or more and 10 or more.
The liquid crystal display element according to claim 7, which has a thickness of not more than μm. 19. The light shielding mask is provided on one side of the substrate, and the light shielding mask is configured to cover a wall portion reaching the substrate at least 50% or more of an area of the wall portion. 5. The liquid crystal display device according to any one of 1. 20. The liquid crystal display device according to claim 7, wherein an alignment film is formed on each of the electrodes provided on the two substrates. 21. The liquid crystal display element according to claim 20, wherein the alignment film is uniaxially aligned by an alignment treatment. 22. The liquid crystal display element according to claim 7, wherein a polarizing plate is provided on the outside of at least one of the two substrates. 23. A method of manufacturing a polymer-dispersed liquid crystal display device in which picture elements are arranged in a matrix, comprising: a mixture containing at least a photocurable polymer material and a liquid crystal material; A step of injecting between the substrates, irradiating the mixture with light by reducing the light intensity in the liquid crystal region forming part, and reaching the both substrates, a wall mainly composed of a polymer and surrounded by the walls, And, it has a parallel part which is close to both substrates and has the approaching part parallel to the substrates.
A method of manufacturing a liquid crystal display element, comprising: forming a display medium composed of a liquid crystal region mainly containing liquid crystal between both substrates. 24. The mixture portion for reducing the light intensity and irradiating with light is a range extending over one or more picture elements, and a liquid crystal region is provided for one or more picture elements.
A method for manufacturing a liquid crystal display device according to item 1. 25. A pixel size of 3 with respect to the mixture
24. A portion corresponding to an area of 0% or more is irradiated with light by reducing the light intensity, and at least one liquid crystal region included in the pixel has a size of 30% or more of the area of the pixel. Liquid crystal display device manufacturing method. 26. A photomask having a plurality of light-shielding portions for forming a liquid crystal region, wherein each light-shielding portion is provided with one or more light-transmitting portions including a substantially central portion of the light-shielding portion, 24. The method for manufacturing a liquid crystal display device according to claim 23, wherein the mixture is irradiated with light from the photomask side to radially form each liquid crystal domain existing in the liquid crystal region. 27. A photomask having a light-transmitting hole in a central portion of a light-shielding portion for forming a liquid crystal region and having a light-transmitting slit radially provided from the light-transmitting hole in the light-shielding portion is used. The method for manufacturing a liquid crystal display element according to claim 26. 28. The liquid crystal display element according to claim 23, wherein light intensity is reduced in a liquid crystal region forming portion of the mixture, and light is irradiated to the mixture by alternately providing a light irradiation period and a light non-irradiation period. Production method. 29. The method for producing a liquid crystal display device according to claim 23, wherein the mixture contains a compound having a photopolymerization inhibiting effect. 30. The step of injecting the mixture between two substrates is performed by attaching the mixture to one substrate and then bonding the two substrates together. 7. A method for manufacturing a liquid crystal display device according to item 1. 31. The liquid crystal display element according to claim 23, 24, 25 or 28, wherein the means for reducing the light intensity is a photomask, and the photomask is formed on one liquid crystal layer side of the two substrates. Production method.