JPH103072A - Liquid crystal display element and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal display element with which the occurrence of circular arc-shaped specks around an encapsulating port in a liquid crystal panel is prevented and a manufacturing method of the element. SOLUTION: Liquid crystals 54 are oriented while inclined at a pre-tilt angle of 0.5 to 15 deg. in the liquid crystal display element in which the liquid crystals 54 and macromolecules 52 are oriented and dispersed each other between an oriented films 14, 24. Or the surface energy of the oriented films 14, 24 is kept within the range of 2.0 to 5.0×10<-2> J.m<-2> . Otherwise, a mixed material having a liquid crystal property which is a mixture of liquid crystal compositions and macromolecular precursor body is encapsulated within an empty panel at (a liquid crystal isotropic phase transition temp. of the mixed material having the liquid crystal property of -60 deg.) to (a liquid crystal isotropic phase transition temp. of the mixed material having the liquid crystal property of +20 deg.), and thereafter, the polymers are deposited to separate the liquid crystal 54 from the polymers 52. Or the mixed material having the liquid crystal property is encapsulated, and thereafter, is heat-treated at (a liquid crystal isotropic phase transition temp. of the mixed material having the liquid crystal property of -40 deg.) to (a liquid crystal isotropic phase transition temp. of the mixed material having the liquid crystal property of +30 deg.), and thereafter, the liquid crystal 54 is separated from the polymer 52.

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 and a method of manufacturing the same, and more particularly, to a polymer dispersed liquid crystal display device using a polymer dispersed liquid crystal and a method of manufacturing the same.

[0002]

2. Description of the Related Art In recent years, as information devices have become smaller and lighter,
The display mounted on it is also required to save power. A liquid crystal display element of the TN mode is used for a small display capacitance device, and a liquid crystal display device of an FTN mode is used for a medium display capacitance device as a reflective display. Further, applications for combining an information input device such as a tablet on a reflective display are also expanding, and a reflective liquid crystal display element is required to have good brightness and visibility.

[0003] However, T using a conventional polarizing plate
Since the liquid crystal display elements of the N type and the FTN type have low light use efficiency, they become dark when they are of a reflective type, and further, when combined with an information input device such as a tablet, the display becomes very dark, which is problematic.

On the other hand, recently, a bright reflective display using no polarizing plate is being developed. For example,
A liquid crystal display device (such as Japanese Patent Publication No. 58-501631) that uses a polymer-dispersed liquid crystal in which a liquid crystal and a polymer are dispersed to control transparency so that light is applied when an electric field is applied and light scattering when no electric field is applied. A liquid crystal display element which is controlled so as to be transparent or absorb light without application of an electric field (EPO 488116A2, JP-A-4-2276).
84, JP-A-5-119302).

[0005] Such a polymer-dispersed liquid crystal display device using a polymer-dispersed liquid crystal does not use a polarizing plate, so that a bright display, particularly a bright reflective display, can be manufactured.

[0006]

FIG. 3 is a plan view for explaining a polymer-dispersed liquid crystal display device using such a polymer-dispersed liquid crystal and a method of manufacturing the same.

An empty panel 70 is formed by fixing the side wall member 30 around the two glass substrates 10 and 20, and the empty panel 7 is formed by the glass substrates 10 and 20 and the side wall member 30.
A liquid crystal enclosing space 80 is defined in 0. Side wall member 3
A sealing port 40 is provided at 0 so as to communicate with a liquid crystal sealing space 80.

When manufacturing the polymer-dispersed liquid crystal display element 100, the liquid crystal, a monomer as a polymer precursor, a chiral agent, and a dye are prepared in a vacuum vessel while the inside of the liquid crystal enclosure space 80 is evacuated. In the liquid crystal mixed material mixed with
The empty panel 70 is immersed so that the value is set to 0, and then the inside of the vacuum container is returned to the atmospheric pressure.

Thereafter, the liquid crystal and the polymer are phase-separated by irradiating ultraviolet rays to polymerize the monomer to precipitate the polymer, and the liquid crystal and the polymer are interposed between the two glass substrates 10 and 20. The polymer-dispersed liquid crystal display device 100 in which the oriented polymer-dispersed liquid crystal is sandwiched is obtained.

However, the polymer-dispersed liquid crystal display element 100 manufactured as described above has a problem that an arc-shaped spot 60 is generated around the sealing opening 40.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a liquid crystal display element in which arc-shaped spots are prevented from being generated around a sealing opening for sealing a liquid crystal material in a panel of the liquid crystal display element, and a method of manufacturing the same. is there.

[0012]

According to the present invention, a first substrate, a second substrate opposed to the first substrate, and a first main surface of the first substrate are provided. The first formed on
Electrode, a second electrode formed on a second main surface of the second substrate, a first alignment film formed on the first electrode, and a second electrode formed on the second electrode. The formed second alignment film is provided between the periphery of the first substrate and the periphery of the second substrate so as to be fixed to the periphery of the first substrate and the periphery of the second substrate. A side wall member, a liquid crystal enclosing space formed by being surrounded by the first alignment film, the second alignment film, and the side wall member, and a side wall member formed in communication with the liquid crystal enclosing space. A liquid crystal display comprising: a sealing port; and a polymer dispersed liquid crystal in which liquid crystal and a polymer are aligned and dispersed in the liquid crystal sealing space between the first alignment film and the second alignment film. In the device, the liquid crystal is pretilted by 0.5 to 15 degrees with respect to the first main surface and the second main surface. The liquid crystal display element characterized by inclined to to align is provided.

As described above, the liquid crystal is oriented at a pretilt angle of 0.5 to 15 degrees with respect to the first main surface and the second main surface so as to form an arc around the sealing opening. The occurrence of spots is prevented.

The pretilt angle is preferably 1
To 10 degrees.

Preferably, the first and second alignment films are made of one material selected from the group consisting of an inorganic vapor-deposited film, polyimide, polyamide, and polyvinyl alcohol. Can be easily obtained.

Further, according to the present invention, a first substrate, a second substrate provided opposite to the first substrate, and a first substrate formed on a first main surface of the first substrate are provided. A first electrode,
A second electrode formed on a second main surface of the second substrate; a first alignment film formed on the first electrode; and a second alignment film formed on the second electrode. And the first alignment film and the first alignment film.
A side wall member fixed to the periphery of the first substrate and the periphery of the second substrate and provided between the periphery of the first substrate and the periphery of the second substrate; A liquid crystal enclosing space formed by being surrounded by a second alignment film and the side wall member; an encapsulation opening formed in the side wall member in communication with the liquid crystal enclosing space; A liquid crystal display device comprising a polymer dispersed liquid crystal in which liquid crystal and a polymer are aligned and dispersed in the liquid crystal sealed space between the first alignment film and the second alignment film. The surface energy of the alignment film of 2.0 to 5.0 ×
A liquid crystal display device characterized by being within the range of 10-2J · m-2 is provided.

As described above, the surface energy of the first alignment film and the second alignment film is set to 2.0 to 5.0 × 1.
By setting it within the range of 0-2J · m-2, the occurrence of arc-shaped spots around the sealing port is prevented.

The surface energy of the first alignment film and the second alignment film is preferably in the range of 2.5 to 3.5 × 10 −2 J · m −2.

Preferably, the first and second alignment films are made of one substance selected from the group consisting of an inorganic vapor-deposited film, polyimide, polyamide, and polyvinyl alcohol. 0 × 10-2J ・ m
A surface energy in the range of -2 is easily obtained.

The polymer-dispersed liquid crystal in the liquid crystal display device of the present invention is preferably formed by precipitating a polymer from a liquid crystalline mixed material obtained by mixing a polymer or a polymer precursor and a liquid crystal composition, thereby obtaining a highly liquid crystal. This is a polymer-dispersed liquid crystal formed by phase separation of molecules.

The present invention works particularly effectively when the polymer-dispersed liquid crystal contains a chiral agent. When a chiral agent is included, a phenomenon in which an arc-shaped spot is generated around the sealing port is remarkably observed as compared with a case where the chiral agent is not included. The occurrence of such arc-shaped spots is effectively prevented.

The present invention works particularly effectively when the polymer-dispersed liquid crystal contains a dye. When a pigment is contained, arc-shaped spots are particularly likely to appear near the sealing port as compared to the case where the pigment is not contained. However, by adopting the configuration of the present invention, such arc-shaped spots are generated. Is effectively prevented.

Further, according to the present invention, a first substrate, a second substrate provided to face the first substrate, and a first substrate formed on a first main surface of the first substrate are provided. A first electrode,
A second electrode formed on a second main surface of the second substrate, and a first alignment film formed on the first electrode, the film being an inorganic vapor-deposited film, polyimide, polyamide, or polyvinyl alcohol. A first alignment film made of one substance selected from the group consisting of: and a second alignment film formed on the second electrode, wherein the first alignment film is made of an inorganic vapor-deposited film, polyimide, polyamide, or polyvinyl alcohol. A second alignment film made of one substance selected from a group, and a periphery of the first substrate and a periphery of the second substrate fixedly attached to the periphery of the second substrate; A side wall member provided between the side wall member, the first alignment film, the second alignment film, and a liquid crystal sealed space formed by being surrounded by the side wall member; and a communication with the liquid crystal sealed space. And the sealing port formed in the side wall member. A step of enclosing a liquid crystalline mixed material of a polymer or a polymer precursor and a liquid crystal composition from the sealing opening in the liquid crystal enclosing space of the obtained panel, and depositing a polymer from the liquid crystalline mixed material, Phase-separating the liquid crystal and the polymer, and aligning the liquid crystal with a pretilt angle of 0.5 to 15 degrees with respect to the first main surface and the second main surface; And a method for manufacturing a liquid crystal display element, characterized by having:

When a polymer-dispersed liquid crystal display element is manufactured by this manufacturing method, a liquid crystal display element in which arc-shaped spots are not observed around the sealing opening can be obtained.

Further, according to the present invention, a first substrate, a second substrate provided opposite to the first substrate, and a first substrate formed on a first main surface of the first substrate are provided. A first electrode,
A second electrode formed on a second main surface of the second substrate, and a first alignment film formed on the first electrode, the film being an inorganic vapor-deposited film, polyimide, polyamide, or polyvinyl alcohol. A first alignment film made of one substance selected from the group consisting of: and a second alignment film formed on the second electrode, wherein the first alignment film is made of an inorganic vapor-deposited film, polyimide, polyamide, or polyvinyl alcohol. A second alignment film made of one substance selected from a group, and a periphery of the first substrate and a periphery of the second substrate fixedly attached to the periphery of the second substrate; A side wall member provided between the side wall member, the first alignment film, the second alignment film, and a liquid crystal sealed space formed by being surrounded by the side wall member; and a communication with the liquid crystal sealed space. And the sealing port formed in the side wall member. A step of enclosing a liquid crystalline mixed material of a polymer or a polymer precursor and a liquid crystal composition from the sealing opening in the liquid crystal enclosing space of the obtained panel, and depositing a polymer from the liquid crystalline mixed material, Phase-separating the liquid crystal and the polymer, and aligning the liquid crystal at a pretilt angle of 1 to 10 degrees with respect to the first main surface and the second main surface. A method for manufacturing a liquid crystal display device is provided.

According to this manufacturing method, it is possible to particularly effectively prevent the occurrence of arc-shaped spots around the sealing port.

Further, according to the present invention, a first substrate, a second substrate provided to face the first substrate, and a first substrate formed on a first main surface of the first substrate are provided. A first electrode,
A second electrode formed on a second main surface of the second substrate; and a first alignment film formed on the first electrode, the second alignment film having a surface energy of 2.0 to 5.0. × 10-2J ・ m
-2, and a second alignment film formed on the second electrode and having a surface energy of 2.0.
A second alignment film within a range of from about 5.0 × 10 −2 J · m −2 to a circumference of the first substrate and a circumference of the second substrate fixed to the circumference of the second substrate. A side wall member provided between the periphery of the second substrate, a liquid crystal enclosing space formed by being surrounded by the first alignment film, the second alignment film, and the side wall member; A liquid crystal mixed material of a polymer or a polymer precursor and a liquid crystal composition is sealed from the sealing hole into the liquid crystal sealing space of the panel having a sealing hole formed in the side wall member in communication with the sealing space. And then separating a polymer from the liquid crystalline mixed material to phase separate the liquid crystal and the polymer, thereby providing a method of manufacturing a liquid crystal display device.

If a polymer-dispersed liquid crystal display device is manufactured by this manufacturing method, a liquid crystal display device in which arc-shaped spots are not observed around the sealing opening can be obtained.

The surface energy of the first alignment film and the second alignment film is preferably 2.5 to 3.
It is within the range of 5 × 10−2 J · m−2.

The first and second alignment films are preferably made of one substance selected from the group consisting of an inorganic vapor-deposited film, polyimide, polyamide, and polyvinyl alcohol. 0 × 10-2J ・ m
A surface energy in the range of -2 is easily obtained.

Further, according to the present invention, a first substrate, a second substrate provided to face the first substrate, and a first substrate formed on a first main surface of the first substrate are provided. A first electrode,
A second electrode formed on a second main surface of the second substrate; a first alignment film formed on the first electrode; and a second alignment film formed on the second electrode. And the first alignment film and the first alignment film.
A side wall member fixed to the periphery of the first substrate and the periphery of the second substrate and provided between the periphery of the first substrate and the periphery of the second substrate; A liquid crystal enclosing space formed by being surrounded by a second alignment film and the side wall member, and an enclosing port formed in the side wall member in communication with the liquid crystal enclosing space are provided in the liquid crystal enclosing space of the panel. The liquid crystal mixed material of the polymer precursor and the liquid crystal composition is supplied from the sealing opening to (liquid crystal isotropic phase transition temperature of the liquid crystal mixed material −60 ° C.) to (liquid crystal isotropic phase of the liquid crystal mixed material). (Transition temperature + 20 ° C.), and then a step of precipitating a polymer from the liquid crystalline mixed material to phase-separate the liquid crystal and the polymer. A method for manufacturing a device is provided.

According to the study of the present inventors, the cause of the occurrence of arc-shaped spots around the sealing hole is that impurities inevitably contained in the liquid crystalline mixed material are surrounded by the sealing liquid at the time of sealing the liquid crystal. This is because it is adsorbed on the surface. Accordingly, as described above, the liquid crystal isotropic phase transition temperature of the liquid crystal mixed material −60 ° C. to the liquid crystal isotropic phase transition temperature of the liquid crystal mixed material + 20 ° C. In the range, if the liquid crystalline mixed material of the polymer precursor and the liquid crystal composition is sealed from the sealing opening, impurities of the liquid crystal mixing material are prevented from adsorbing around the sealing opening, and as a result, Even when a polymer is precipitated from the ionic mixed material and the liquid crystal and the polymer are phase-separated to form a polymer-dispersed liquid crystal, the occurrence of arc-shaped spots around the sealing opening is prevented.

The encapsulation of the liquid crystalline mixed material is performed in the range of (liquid crystal isotropic phase transition temperature of the liquid crystalline mixed material−60 ° C.) to (liquid crystal isotropic phase transition temperature of the liquid crystalline mixed material + 20 ° C.). It is preferably performed, but more preferably in the range of (liquid crystal isotropic phase transition temperature of the liquid crystalline mixed material −50 ° C.) to (liquid crystal isotropic phase transition temperature of the liquid crystalline mixed material + 10 ° C.). . When the temperature is lower than (the liquid crystal isotropic phase transition temperature of the liquid crystalline mixed material −60 ° C.), diffusion of impurities is insufficient and it is difficult to prevent the occurrence of arc-shaped spots around the sealing port. If the temperature exceeds (the liquid crystal isotropic phase transition temperature of the liquid crystalline mixed material + 20 ° C), the polymerization of the polymer precursor due to heat and the thermal decomposition of the liquid crystal material, the sealant, etc. occur, and the reliability decreases.

Further, according to the present invention, a first substrate, a second substrate provided to face the first substrate, and a first substrate formed on a first main surface of the first substrate are provided. A first electrode,
A second electrode formed on a second main surface of the second substrate; a first alignment film formed on the first electrode; and a second alignment film formed on the second electrode. And the first alignment film and the first alignment film.
A side wall member fixed to the periphery of the first substrate and the periphery of the second substrate and provided between the periphery of the first substrate and the periphery of the second substrate; A liquid crystal enclosing space formed by being surrounded by a second alignment film and the side wall member, and an enclosing port formed in the side wall member in communication with the liquid crystal enclosing space are provided in the liquid crystal enclosing space of the panel. Enclosing a liquid crystalline mixed material of a polymer precursor and a liquid crystal composition from the enclosing opening, heating the panel in which the liquid crystalline mixed material is encapsulated, and thereafter, the liquid crystalline mixed material A phase separation between the liquid crystal and the polymer by precipitating a polymer from the liquid crystal, to provide a method for manufacturing a liquid crystal display device.

As described above, the cause of the occurrence of arc-shaped spots around the sealing opening is that impurities inevitably contained in the liquid crystalline mixed material are adsorbed around the sealing opening when the liquid crystal is sealed. However, as described above, by heating the panel in which the liquid crystal mixed material is sealed, impurities adsorbed around the sealing opening are diffused, and as a result, the liquid crystal mixed material is thereafter Even when a polymer is precipitated from the polymer and the liquid crystal and the polymer are phase-separated to form a polymer-dispersed liquid crystal, the occurrence of arc-shaped spots around the sealing opening is prevented.

The heat treatment of the panel in which the liquid crystal mixed material is sealed is performed at a temperature ranging from (liquid crystal isotropic phase transition temperature of the liquid crystal mixed material−40) ° C. to (the isotropic phase transition temperature of the liquid crystal mixed material + 40). C) It is preferred to be carried out in the range of ° C. (Liquid crystal isotropic phase transition temperature of the liquid crystal mixed material-4
0) When the temperature is lower than 0 ° C., the diffusion of impurities is not sufficient, and it is not enough to prevent the occurrence of arc-shaped spots around the sealing opening, and spots may remain. (The isotropic phase transition of the liquid crystalline mixed material) If the temperature exceeds (40 ° C.) ° C., thermal decomposition of the liquid crystal and polymerization of the polymer precursor due to heat occur, and spots are easily generated on the entire panel.

Further, even if the polymer is precipitated from the liquid crystalline mixed material and the liquid crystal and the polymer are phase-separated and then heat-treated, the impurities adsorbed around the sealing hole can hardly diffuse any more. However, it is not possible to prevent the occurrence of arc-shaped spots around the sealing port, and it is not possible to eliminate it.

In the present invention, the step of precipitating the polymer from the liquid crystalline mixed material and phase-separating the liquid crystal and the polymer is preferably performed by irradiating the liquid crystalline mixed material with ultraviolet rays to form the polymer precursor. This is a step of curing and precipitating the polymer to phase-separate the liquid crystal and the polymer.

Further, the production method of the present invention works particularly effectively when the liquid crystalline mixed material contains a chiral agent or contains a dye.

Further, in the manufacturing method of the present invention, the step of enclosing a liquid crystal mixed material of a polymer or a polymer precursor and a liquid crystal composition from the enclosing opening into the liquid crystal enclosing space of the panel includes the step of It is used particularly preferably in the case where the enclosed space is previously evacuated, and then the step of enclosing the liquid crystalline mixed material under atmospheric pressure in the evacuated liquid crystal enclosed space is particularly effective. .

[0041]

Next, embodiments of the present invention will be described.

(First Embodiment) FIG. 1 is a plan view for explaining a first embodiment of the present invention, and FIG. 2 is a sectional view taken along line XX of FIG.

First, referring to FIG. 1, in the liquid crystal display device 100 of the present embodiment, two glass substrates 10 and 2
An empty panel 70 is formed by fixing the side wall member 30 around the periphery of the reference numeral 0, and a liquid crystal sealing space 80 is defined in the empty panel 70 by the glass substrates 10 and 20 and the side wall member 30. A sealing port 40 is provided in the side wall member 30 so as to communicate with the liquid crystal sealing space 80.

Next, referring to FIG. 2, a patterned ITO electrode 12 is formed on the upper glass substrate 10 after forming about 1500 Å of ITO (Indium Tin Oxide) by sputtering. On the lower glass substrate 20, after forming chromium by sputtering to about 2000 angstroms, a patterned reflective electrode 22 is formed. Alignment films 14 and 24 are formed on both glass substrates 10 and 20, respectively. The two glass substrates 10 and 20 have a gap of 5 μm.
At m, the periphery of the substrate is bonded by the side wall member 30.

In this embodiment, polyimide SP-7 is used.
40 (manufactured by Toray Industries, Inc.) was used as a liquid crystal alignment film, and provided on the glass substrates 10 and 20, respectively.
Rubbing treatment was performed under the conditions of rpm, indentation length of 0.2 mm, and speed of 2 cm / sec. The rubbing direction was set to 270 ° of liquid crystal right twist.

Next, a mixture of a liquid crystal and a polymer precursor to be sealed between the substrates 10 and 20 will be described.
TL-202 (Merck) and MJ9278 as liquid crystal
6 (manufactured by Merck) in a ratio of 7: 3 (hereinafter, this mixed liquid crystal is referred to as liquid crystal A), and 0.5% by weight of R1011 (manufactured by Merck) as a chiral component. M361, SI512 and M137 as sex dyes
(All manufactured by Mitsui Higashi Atsushi Dye Co., Ltd.)
A mixture of 0.9% by weight, 0.2% by weight and 0.2% by weight was used as a liquid crystal mixture. The liquid crystal isotropic phase transition temperature of this liquid crystal mixture was 83 degrees. As a polymer precursor, biphenyl methacrylate was used in an amount of 5% by weight based on the liquid crystal mixture. After the above was mixed by heating to form a liquid crystal mixed material in a liquid crystal state, the liquid crystal mixed material was vacuum-sealed in the empty panel described above.

The vacuum encapsulation of the liquid crystal mixed material is performed by immersing the empty panel 70 in the vacuum container with the liquid crystal encapsulating space 80 evacuated and the sealing port 40 down in the liquid crystal mixed material. By returning the inside of the vacuum vessel to atmospheric pressure,
This was performed by sealing the liquid crystal mixed material into the liquid crystal sealing space 80 from the sealing port 40. In the sealed state, no spots were observed around the sealing port 40, and the spots were uniform.

The liquid crystal mixed material sealed in the empty panel 70 took a right-handed 270 degree alignment from the rubbing axis of the upper substrate 10 to the rubbing axis of the lower substrate 20. Thereafter, while maintaining the panel 70 at 50 ° C., ultraviolet light of 5 mW / cm 2 (wavelength 350 nm) is irradiated for 7 minutes to polymerize the polymer, thereby precipitating the polymer from the liquid crystal mixed material, thereby forming the liquid crystal 54. The polymer 52 was phase-separated to complete the liquid crystal display device 100 of this example. The liquid crystal 54 is in an alignment state before the irradiation of ultraviolet rays, that is, the upper substrate 1
0 right rubbing axis to rubbing axis of lower substrate 20
It shows an alignment state of 70 degrees, and the polymer 52 and the liquid crystal 54
A structure in which the glass substrates 10 and 20 were oriented and dispersed with each other was adopted. Even in this state, no spots were observed around the sealing port 40, and the spots were uniform.

The electro-optical characteristics of the liquid crystal display device 100 obtained in this example showed a threshold characteristic, and a normally black characteristic in which the reflectance was increased by applying a voltage was obtained. That is, when the voltage is off, a black display is obtained due to the absorption of the dichroic dye, and when a sufficient voltage is applied, the liquid crystal 54 is oriented in the direction of the electric field. As a result, a discontinuous point of the refractive index was generated in the medium, so that the medium was in a light scattering state. At this time, since the dichroic dye was also oriented in the direction of the electric field, the absorption was very small, and a white display was obtained.

Next, the pretilt angle of the liquid crystal A was measured by a crystal rotation method.
It was 2.6 degrees.

In the liquid crystal display element 100 of this embodiment, no arc-shaped spot 60 is observed around the enclosing port 40 even when the liquid crystal display element 100 is turned on and when the liquid crystal display element 100 is turned off. No arcuate spots 60 were observed around it.

(Second Embodiment) In this embodiment, S
iO was obliquely vapor-deposited at an angle of 75 degrees from the normal direction of the glass substrate for 1 minute to form alignment films 14 and 24 on glass substrates 10 and 20 without rubbing. The other points are the same as those of the first embodiment.
0 was produced.

Also in the liquid crystal display element 100 of this embodiment, the liquid crystal mixed material is supplied from the sealing port 40 to the liquid crystal sealing space 80.
In the state where the inside was sealed in a vacuum, no spots were observed around the sealing opening 40 and the inside was uniform. The liquid crystal 54 and the polymer 5
2 after the phase separation from the upper substrate 10.
From the rubbing axis to the rubbing axis of the lower substrate 20
The polymer 52 and the liquid crystal 54 were aligned and dispersed between the glass substrates 10 and 20, indicating a 0 degree alignment state. Even in this state, no spots were observed around the sealing port 40, and the spots were uniform. And the liquid crystal display element 1
The electro-optical characteristics of No. 00 exhibited threshold characteristics, and a normally black characteristic in which the reflectance increased with the application of a voltage was obtained.

Next, the pretilt angle of the liquid crystal A was measured by a crystal rotation method.
It was 5.3 degrees.

In the liquid crystal display element 100 of the present embodiment, no arc-shaped spot 60 is observed around the enclosing port 40 even when the liquid crystal display element 100 is turned on and when the liquid crystal display element 100 is turned off. No arcuate spots 60 were observed around it.

(First Comparative Example) In this comparative example, polyvinyl alcohol and denka vinyl (Electrochemical Co., Ltd.)
Is used as a liquid crystal alignment film, and the glass substrates 10, 2
The rubbing treatment is then performed using a flocking cloth having a hair length of 2 mm and a hair density of 100 hairs / cm 2 at 50 rpm, a pushing length of 0.1 mm, and a speed of 10 cm / sec. 24. Other points are the first
The liquid crystal display element 100 was produced in the same manner as in the example.

In the liquid crystal display element 100 of this comparative example, the liquid crystal mixed material is supplied from the sealing port 40 to the liquid crystal sealing space 80.
In the state where the inside was sealed in a vacuum, no spots were observed around the sealing opening 40 and the inside was uniform. The liquid crystal 54 and the polymer 5
2 after the phase separation from the upper substrate 10.
From the rubbing axis to the rubbing axis of the lower substrate 20
The polymer 52 and the liquid crystal 54 were aligned and dispersed between the glass substrates 10 and 20, indicating a 0 degree alignment state. In this state, arc-shaped spots were observed around the sealing port 40. More specifically, a slightly cloudy arc-shaped region was observed because the degree of scattering in the vicinity of the sealing port was slightly larger than in other portions. Then, the electro-optical characteristics of the liquid crystal display element 100 showed a threshold characteristic, and a normally black characteristic in which the reflectance (scattering degree) increased by applying a voltage was obtained.

Next, the pretilt angle of the liquid crystal A was measured by the crystal rotation method.
0.3 degrees.

In the liquid crystal display element 100 of this comparative example, an arc-shaped spot 60 is observed around the enclosing opening 40 when the liquid crystal display device 100 is turned on and off. , An arc-shaped spot 60 was observed.

(Third Embodiment) In this embodiment, polyvinyl alcohol and denka vinyl (Electrochemical Co., Ltd.)
Is used as a liquid crystal alignment film, and the glass substrates 10, 2
The rubbing treatment is then performed on a flocked cloth having a bristle length of 2 mm and a hair density of 500 hairs / cm 2 at 200 rpm, a pushing length of 0.1 mm, and a speed of 5 cm / sec. 24. Other points are the first
The liquid crystal display element 100 was produced in the same manner as in the example.

Also in the liquid crystal display element 100 of this embodiment, the liquid crystal mixed material is supplied from the filling port 40 to the liquid crystal filling space 80.
In the state where the inside was sealed in a vacuum, no spots were observed around the sealing opening 40 and the inside was uniform. The liquid crystal 54 and the polymer 5
2 after the phase separation from the upper substrate 10.
From the rubbing axis to the rubbing axis of the lower substrate 20
The polymer 52 and the liquid crystal 54 were aligned and dispersed between the glass substrates 10 and 20, indicating a 0 degree alignment state. Even in this state, no spots were observed around the sealing port 40, and the spots were uniform. And the liquid crystal display element 1
The electro-optical characteristics of No. 00 exhibited threshold characteristics, and a normally black characteristic in which the reflectance increased with the application of a voltage was obtained.

Next, in order to measure the surface energies of the alignment films 14 and 24, the surface energies were measured from the contact angles of the alignment films with pure water and CH 2 I 2. Cm2.

In the liquid crystal display element 100 of the present embodiment, no arc-shaped spot 60 is observed around the enclosing port 40 even when the liquid crystal display element 100 is turned on and when the liquid crystal display element 100 is turned off. No arcuate spots 60 were observed around it.

(Fourth Embodiment) In this embodiment, polyimide and AL-3402 (manufactured by Nippon Synthetic Rubber Co., Ltd.) are used as liquid crystal alignment films and provided on glass substrates 10 and 20, respectively. 200 rpm with a flocking cloth having a hair length of 2 mm and a hair density of 200 hairs / cm 2, and a pressing length of 0.
A rubbing treatment was performed under the conditions of 2 mm and a speed of 10 cm / sec to form alignment films 14 and 24. In other respects, the liquid crystal display element 100 was manufactured in the same manner as in the third example.

Also in the liquid crystal display element 100 of this embodiment, the liquid crystal mixed material is supplied from the filling port 40 to the liquid crystal filling space 80.
In the state where the inside was sealed in a vacuum, no spots were observed around the sealing opening 40 and the inside was uniform. The liquid crystal 54 and the polymer 5
2 after the phase separation from the upper substrate 10.
From the rubbing axis to the rubbing axis of the lower substrate 20
The polymer 52 and the liquid crystal 54 were aligned and dispersed between the glass substrates 10 and 20, indicating a 0 degree alignment state. Even in this state, no spots were observed around the sealing port 40, and the spots were uniform. And the liquid crystal display element 1
The electro-optical characteristics of No. 00 exhibited threshold characteristics, and a normally black characteristic in which the reflectance increased with the application of a voltage was obtained.

Next, in order to measure the surface energies of the alignment films 14 and 24, the surface energies were measured from the contact angles of the alignment films with pure water and CH 2 I 2. Cm2.

In the liquid crystal display element 100 of this embodiment, no arc-shaped spot 60 is observed around the enclosing port 40 even when the liquid crystal display element 100 is turned on and when the liquid crystal display element 100 is turned off. No arcuate spots 60 were observed around it.

(Fifth Embodiment) In this embodiment, polyvinyl alcohol and denkavinyl (Electrochemical Co., Ltd.)
Is used as a liquid crystal alignment film, and the glass substrates 10, 2
The rubbing treatment is then performed using a flocking cloth having a hair length of 2 mm and a hair density of 100 hairs / cm 2 at 50 rpm, a pushing length of 0.1 mm, and a speed of 10 cm / sec. 24. Other points are the first
An empty panel 70 was produced in the same manner as in the Example.

Next, a liquid crystal mixed material was prepared in the same manner as in the first embodiment, and this liquid crystal mixed material was vacuum-sealed in the empty panel 70 in the same manner as in the first embodiment. In the sealed state, when the area around the opening 40 was sandwiched between polarizing plates in a crossed Nicols state and observed, spots were observed in the vicinity of the opening as differences in transmittance.

The liquid crystalline mixed material sealed in the empty panel 70 took a right-handed 270 degree alignment from the rubbing axis of the upper substrate 10 to the rubbing axis of the lower substrate 20. Thereafter, the panel 70 in which the liquid crystal mixed material was sealed was heat-treated at 60 ° C. for 24 hours. After this heat treatment, even if the surroundings of the sealing port 40 are sandwiched between polarizing plates in a crossed Nicols state and observed,
No spots could be confirmed as a difference in transmittance.

Then, while keeping the panel 70 at 50 ° C., an ultraviolet ray of 5 mW / cm 2 (wavelength 350 nm) was irradiated
By irradiating the liquid crystal for one minute to polymerize the polymer, thereby precipitating the polymer from the liquid crystal mixed material.
And the polymer 52 were phase-separated to complete the liquid crystal display device 100 of this example. The liquid crystal 54 is aligned with the lower substrate 2 from the rubbing axis of the upper substrate 10 before the ultraviolet irradiation.
The polymer 52 and the liquid crystal 54 were aligned and dispersed between the glass substrates 10 and 20 in a 270 degree right-twisted alignment state with a rubbing axis of 0. Even in this state, no spots were observed around the sealing port 40, and the spots were uniform.

The electro-optical characteristics of the liquid crystal display device 100 obtained in this example showed a threshold characteristic, and a normally black characteristic in which the reflectance was increased by applying a voltage was obtained.

In the liquid crystal display element 100 of this embodiment, no arc-shaped spot 60 is observed around the enclosing opening 40 even when the liquid crystal display device 100 is turned on and when the liquid crystal display device 100 is turned off. No arcuate spots 60 were observed around it.

(Sixth Embodiment) In this embodiment, polyimide and AL-3402 (manufactured by Nippon Synthetic Rubber Co., Ltd.) are used as liquid crystal alignment films and provided on glass substrates 10 and 20, respectively. 200 rpm with a flocking cloth having a hair length of 5 mm and a hair density of 400 hairs / cm 2, and a pressing length of 0.
A rubbing treatment was performed under the conditions of 2 mm and a speed of 10 cm / sec to form alignment films 14 and 24. Otherwise, an empty panel 70 was manufactured in the same manner as in the first embodiment.

Next, a liquid crystal mixed material was prepared in the same manner as in the first embodiment, and then this liquid crystal mixed material was vacuum-sealed in the empty panel 70. The present embodiment is different from the first embodiment in that the temperature at the time of vacuum sealing is set to 45 ° C., but the other points are the same as in the first embodiment.
In the sealed state, no spots were observed around the sealing port 40, and the spots were uniform.

The liquid crystalline mixed material sealed in the empty panel 70 has a right-handed 270 degree alignment from the rubbing axis of the upper substrate 10 to the rubbing axis of the lower substrate 20. Thereafter, while maintaining the panel 70 at 50 ° C., ultraviolet light of 5 mW / cm 2 (wavelength 350 nm) is irradiated for 7 minutes to polymerize the polymer, thereby precipitating the polymer from the liquid crystal mixed material, thereby forming the liquid crystal 54. The polymer 52 was phase-separated to complete the liquid crystal display device 100 of this example. The liquid crystal 54 is in an alignment state before the irradiation of ultraviolet rays, that is, the upper substrate 1
0 right rubbing axis to rubbing axis of lower substrate 20
It shows an alignment state of 70 degrees, and the polymer 52 and the liquid crystal 54
A structure in which the glass substrates 10 and 20 were oriented and dispersed with each other was adopted. Even in this state, no spots were observed around the sealing port 40, and the spots were uniform.

The electro-optical characteristics of the liquid crystal display device 100 obtained in this example showed a threshold characteristic, and a normally black characteristic in which the reflectance was increased by applying a voltage was obtained.

In the liquid crystal display element 100 of the present embodiment, no arc-shaped spot 60 is observed around the enclosing port 40 even when the liquid crystal display element 100 is turned on and off, and even when the halftone display is performed, No arcuate spots 60 were observed around it.

[0079]

According to the present invention, a uniform display, particularly a uniform halftone display, can be achieved without causing arc-shaped spots around the sealing opening, and a liquid crystal display device having excellent display characteristics can be obtained. Can be

[Brief description of the drawings]

FIG. 1 is a plan view for explaining an embodiment of the present invention.

FIG. 2 is a sectional view taken along line XX of FIG.

FIG. 3 is a plan view illustrating a conventional polymer-dispersed liquid crystal display device.

[Explanation of symbols]

 10, 20: glass substrate 12: ITO electrode 14, 24: alignment film 22: reflective electrode 30: side wall member 40: sealing hole 50: polymer dispersed liquid crystal 52: polymer 54: liquid crystal 60: arc-shaped spot 70 ... ( Empty) Panel 80: Liquid crystal sealed space 100: Liquid crystal display element

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Shuhei Yamada 3-3-5 Yamato, Suwa City, Nagano Prefecture Inside Seiko Epson Corporation (72) Inventor Eiji Iizaka 3-5-5 Yamato, Suwa City, Nagano Prefecture Seiko Epson (72) Inventor Eiji Chino 3-3-5 Yamato, Suwa City, Nagano Prefecture Seiko Epson Corporation

Claims (20)

[Claims] A first substrate, a second substrate provided to face the first substrate, and a first electrode formed on a first main surface of the first substrate. A second electrode formed on a second main surface of the second substrate, a first alignment film formed on the first electrode, and a second electrode formed on the second electrode. A second alignment film, and a side wall member fixed between the periphery of the first substrate and the periphery of the second substrate and provided between the periphery of the first substrate and the periphery of the second substrate When,
A liquid crystal enclosing space formed by being surrounded by the first alignment film, the second alignment film, and the side wall member; an encapsulation opening formed in the side wall member in communication with the liquid crystal enclosing space;
A liquid crystal display device comprising: a polymer-dispersed liquid crystal in which liquid crystal and a polymer are aligned and dispersed in the liquid crystal-enclosed space between the first alignment film and the second alignment film. A liquid crystal display device characterized in that liquid crystal is oriented with a pretilt angle of 0.5 to 15 degrees with respect to the first main surface and the second main surface. 2. The method according to claim 1, wherein the liquid crystal is provided on the first main surface and the second main surface.
2. The liquid crystal display device according to claim 1, wherein the liquid crystal display device is oriented at a pretilt angle of 1 to 10 degrees with respect to the main surface of the liquid crystal display. 3. A first substrate, a second substrate provided opposite to the first substrate, and a first electrode formed on a first main surface of the first substrate. A second electrode formed on a second main surface of the second substrate, a first alignment film formed on the first electrode, and a second electrode formed on the second electrode. A second alignment film, and a side wall member fixed between the periphery of the first substrate and the periphery of the second substrate and provided between the periphery of the first substrate and the periphery of the second substrate When,
A liquid crystal enclosing space formed by being surrounded by the first alignment film, the second alignment film, and the side wall member; an encapsulation opening formed in the side wall member in communication with the liquid crystal enclosing space;
A liquid crystal display device comprising: a polymer-dispersed liquid crystal in which liquid crystal and a polymer are aligned and dispersed in the liquid crystal-enclosed space between the first alignment film and the second alignment film. A liquid crystal display device, wherein the surface energy of the first alignment film and the second alignment film is in the range of 2.0 to 5.0 × 10 −2 J · m −2. 4. The surface energy of said first alignment film and said second alignment film is 2.5 to 3.5 × 10 −2 J · m.
The liquid crystal display device according to claim 3, wherein the value is within the range of -2. 5. The method according to claim 1, wherein the first and second alignment films are made of one substance selected from the group consisting of an inorganic vapor-deposited film, polyimide, polyamide, and polyvinyl alcohol. The liquid crystal display device according to any one of the above. 6. The polymer-dispersed liquid crystal is formed by precipitating a polymer from a liquid crystalline mixed material obtained by mixing a polymer or a polymer precursor and a liquid crystal composition, and phase-separating the liquid crystal and the polymer. 6. The liquid crystal display device according to claim 1, wherein the liquid crystal display device is a polymer dispersed liquid crystal. 7. The liquid crystal display device according to claim 1, wherein said polymer-dispersed liquid crystal contains a chiral agent. 8. The liquid crystal display device according to claim 1, wherein the polymer-dispersed liquid crystal contains a dye. 9. A first substrate, a second substrate provided opposite to the first substrate, and a first electrode formed on a first main surface of the first substrate. A second electrode formed on a second main surface of the second substrate, and a first alignment film formed on the first electrode, the film including an inorganic vapor-deposited film, polyimide, polyamide, and polyvinyl. A first alignment film made of one substance selected from the group consisting of alcohol, and a second alignment film formed on the second electrode, wherein the first alignment film is made of an inorganic vapor-deposited film, polyimide, polyamide, or polyvinyl alcohol. A second alignment film made of one substance selected from the group consisting of: a first alignment substrate and a second substrate; and a second alignment film fixed to the first substrate and the second substrate. A side wall member provided between the first alignment film and the periphery of the substrate; 2, a liquid crystal enclosing space formed by being surrounded by the alignment film and the side wall member, and an enclosing port formed in the side wall member in communication with the liquid crystal enclosing space, in the liquid crystal enclosing space of the panel. Enclosing a liquid crystalline mixed material of a polymer or a polymer precursor and a liquid crystal composition from the sealing opening; and depositing a polymer from the liquid crystalline mixed material to phase-separate the liquid crystal and the polymer. Liquid crystal display element comprising: aligning the liquid crystal at a pretilt angle of 0.5 to 15 degrees with respect to the first main surface and the second main surface. Manufacturing method. 10. A first substrate, a second substrate provided to face the first substrate, and a first electrode formed on a first main surface of the first substrate. , The second of the second substrate
A second electrode formed on the main surface of the first electrode, and a first alignment film formed on the first electrode, the one being selected from the group consisting of an inorganic vapor-deposited film, polyimide, polyamide, and polyvinyl alcohol. A first alignment film made of a substance,
A second alignment film formed on the second electrode, the second alignment film being made of one substance selected from the group consisting of an inorganic vapor-deposited film, polyimide, polyamide, and polyvinyl alcohol; The periphery of one substrate and the second
A side wall member fixed to the periphery of the first substrate and provided between the periphery of the first substrate and the periphery of the second substrate, the first alignment film, the second alignment film, and the side wall A liquid crystal enclosing space formed by being surrounded by members, and an enclosing opening formed in the side wall member in communication with the liquid crystal enclosing space, the polymer or Enclosing a liquid crystalline mixed material of a polymer precursor and a liquid crystal composition; depositing a polymer from the liquid crystalline mixed material to phase-separate the liquid crystal and the polymer; And a step of inclining at a pretilt angle of 1 to 10 degrees with respect to the main surface and the second main surface. 11. A first substrate, a second substrate provided facing the first substrate, and a first electrode formed on a first main surface of the first substrate. , The second of the second substrate
And a first alignment film formed on the first electrode and having a surface energy of 2.0 to 5.0 × 10 −2 J · m −2. The first in the range
And a second alignment film formed on the second electrode and having a surface energy of 2.0 to 5.0 × 10 −
A second alignment film in a range of 2 J · m−2, and a periphery of the first substrate and a periphery of the second substrate, which are fixed to the periphery of the first substrate and the periphery of the second substrate; A liquid crystal enclosing space formed by being surrounded by the first alignment film, the second alignment film, and the side wall member; and Enclosing a liquid crystal mixed material of a polymer or a polymer precursor and a liquid crystal composition from the encapsulation port into the liquid crystal encapsulation space of a panel having an encapsulation port formed in a side wall member; A method of precipitating a polymer from a liquid crystalline mixed material to phase-separate the liquid crystal and the polymer. 12. The surface energy of the first alignment film and the second alignment film is 2.5 to 3.5 × 10 −2 J ·.
The method for manufacturing a liquid crystal display device according to claim 11, wherein the value is in the range of m-2. 13. The method according to claim 11, wherein the first and second alignment films are made of one substance selected from the group consisting of an inorganic vapor-deposited film, polyimide, polyamide, and polyvinyl alcohol. Method for manufacturing a liquid crystal display element. 14. A first substrate, a second substrate provided to face the first substrate, and a first electrode formed on a first main surface of the first substrate. , The second of the second substrate
A second electrode formed on the main surface of the first electrode, a first alignment film formed on the first electrode, a second alignment film formed on the second electrode, A sidewall member fixed to the periphery of the first substrate and the periphery of the second substrate and provided between the periphery of the first substrate and the periphery of the second substrate; and the first alignment film. The liquid crystal sealing space of a panel including a liquid crystal sealing space formed by being surrounded by the second alignment film and the side wall member, and a sealing port formed in the side wall member in communication with the liquid crystal sealing space. Into the liquid crystal mixed material of the polymer precursor and the liquid crystal composition from the sealing port,
(Liquid crystal isotropic phase transition temperature of the liquid crystalline mixed material −60 ° C.)
To (liquid crystal isotropic phase transition temperature of the liquid crystalline mixed material + 20)
C)), and thereafter, a step of precipitating a polymer from the liquid crystalline mixed material to phase-separate the liquid crystal and the polymer. Method. 15. A first substrate, a second substrate provided opposite to the first substrate, and a first electrode formed on a first main surface of the first substrate. , The second of the second substrate
A second electrode formed on the main surface of the first electrode, a first alignment film formed on the first electrode, a second alignment film formed on the second electrode, A sidewall member fixed to the periphery of the first substrate and the periphery of the second substrate and provided between the periphery of the first substrate and the periphery of the second substrate; and the first alignment film. The liquid crystal sealing space of a panel including a liquid crystal sealing space formed by being surrounded by the second alignment film and the side wall member, and a sealing port formed in the side wall member in communication with the liquid crystal sealing space. Enclosing a liquid crystalline mixed material of a polymer precursor and a liquid crystal composition from the sealing opening; heat-treating the panel in which the liquid crystalline mixed material is encapsulated; Depositing a polymer from a material and phase separating the liquid crystal and the polymer, Method of manufacturing a liquid crystal display element characterized by having. 16. The heat treatment of the panel in which the liquid crystalline mixed material is encapsulated is performed at a temperature ranging from (liquid crystal isotropic phase transition temperature of the liquid crystalline mixed material −40 ° C.) to (liquid crystalline isotropic liquid crystal isotropic). The method according to claim 15, wherein the step is performed within a range of (phase transition temperature + 30 ° C). 17. The step of precipitating a polymer from the liquid crystalline mixed material and phase-separating the liquid crystal and the polymer comprises irradiating the liquid crystalline mixed material with ultraviolet light to cure the polymer precursor. A step of depositing a polymer to separate the liquid crystal and the polymer by phase.
7. The method for manufacturing a liquid crystal display device according to any one of 6. 18. The method according to claim 9, wherein the liquid crystalline mixed material contains a chiral agent. 19. The method of manufacturing a liquid crystal display device according to claim 9, wherein said liquid crystalline mixed material contains a dye. 20. A step of enclosing a liquid crystalline mixed material of a polymer or a polymer precursor and a liquid crystal composition from the enclosing opening into the liquid crystal enclosing space of the panel, wherein the liquid crystal enclosing space is previously evacuated. 20. The liquid crystal display element according to claim 9, wherein a step of sealing the liquid crystal mixed material under atmospheric pressure in the evacuated liquid crystal sealing space is performed. Production method.