JPH09244031A - Production of liquid crystal cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain any desired stable pretilt angle up to a specified angle by noncontact process by using a polymerizable liquid crystal monomers, irradiating the monomers with UV rays while applying a magnetic field and an electric field in specified directions to polymerize the monomers. SOLUTION: A mesogen layer 19 comprising a photopolymn. initiator and polymerizable liquid crystal monomers is formed on each principal planes of a pair of substrates 17, 22, and the layer 19 is maintained at specified temp. to maintain the liquid crystal state. Then, while a magnetic field in a desired direction is applied by using magnet poles 13, 14 and an electric field in another desired direction is applied by using a voltage applying terminal 22, the substrates are irradiated with UV rays from a UV lamp 16 to polymerize the polymerizable liquid crystal monomers to form polymer layers. The substrates 17, 22 are laminated with these polymer layers facing each other, and the space between the substrates is filled with a liquid crystal. The liquid crystal molecules can give a specified pretilt angle up to about 10 deg..

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method of manufacturing a liquid crystal cell in which liquid crystal molecules are aligned.

[0002]

2. Description of the Related Art Conventionally, an organic film having a thickness of several 100 nm, especially a polyimide film, is formed on a substrate by coating, and then rubbed with a high-speed fiber bundle. This is so-called rubbing processing. By doing so, for example, the main chain of the polyimide film is stretched in the movement direction of the fiber bundle. This is a so-called polyimide film orientation phenomenon. When the polyimide main chain and liquid crystal molecules come into contact with each other, the mutual interaction causes the liquid crystal molecules to be aligned. For this reason, this oriented polyimide film is referred to as an alignment film. This area is detailed in "Liquid Crystal-Basics" published by Baifukan, edited by Okano and Kobayashi.

[0003]

In the production of liquid crystal elements, only the rubbing method is applied. This rubbing method rubs the polyimide film at a high speed and inevitably accompanies more or less dust generation. For example, in the case of a liquid crystal display device, this is a display defect and should be avoided.

Further, in order to sufficiently perform the rubbing treatment on the polyimide film, it is necessary to rub considerably strongly.
This may cause local destructive scratches on the polyimide film, impairing the alignment uniformity of the liquid crystal molecules. In order to avoid this, rigorous control of this frictional state is required.

Further, during this rubbing, static electricity is generated between the polyimide film and the polyimide film. As a result, for example, in the case of an active matrix type liquid crystal display device, the thin film transistor may be destroyed.

In order to overcome these weak points, there is an attempt to cause the alignment phenomenon of the organic film on the substrate by some non-contact method. A typical attempt is an anisotropic polymerization method of a polyvinyl cinnamate film by polarized ultraviolet light. This has been successful in aligning liquid crystal molecules. However, such a non-contact method is in the research and development stage and has not been applied to the production site at all. One of the reasons for this is
The non-contact method has not succeeded in reproducibly expressing a pretilt of about 2 °.

On the other hand, in the conventional rubbing method, as a material for the alignment film, the structure of the polyimide main chain is devised, or an alkyl group or a fluoroalkyl group is bonded to the side chain to produce a reproducible pretilt. Have been successful.

Reproducible pretilt expression is an essential technique for stable alignment of liquid crystal molecules. In the current liquid crystal device, it is considered necessary to develop a pretilt of a predetermined angle up to about 10 °.

The present invention contemplates and succeeds in developing a stable pretilt of any angle up to about 10 ° in a non-contact process.

[0010]

In order to solve the above-mentioned problems, the present invention maintains a mesogenic layer formed on a pair of principal surfaces of a substrate and comprising a photopolymerization initiator and a polymerizable liquid crystalline monomer in a liquid crystal state. The substrate is kept at a predetermined temperature such that it is sagged, and then while applying a magnetic field in a desired direction alone, or applying a magnetic field in a desired direction and applying an electric field in another desired direction. At the same time, the substrate is simultaneously irradiated with ultraviolet rays to polymerize the monomers to form a polymer layer,
This is a method for producing a liquid crystal cell in which the polymer layers are opposed to each other while keeping a desired gap, the pair of substrates are bonded together, and liquid crystal is filled in the gap.

The above-mentioned irradiation of ultraviolet rays may be carried out by directly irradiating the mesogen layer, or by making the substrate a substrate through which ultraviolet rays can pass and irradiating ultraviolet rays through the substrate. Also,
In this manufacturing method, after the polymer layer is formed, the main surface of the substrate is washed with an organic solvent, the desired gap is maintained, the polymer layers are opposed to each other, and the pair of substrates are bonded to each other. To complete the liquid crystal cell, the desired result was obtained.

The present invention further includes the above-mentioned predetermined temperature at which the mesogen layer composed of the low-molecular liquid crystal, the photopolymerization initiator and the polymerizable liquid crystalline monomer formed on the pair of main surfaces of the substrate is kept in the liquid crystal state. While holding the substrate, then while applying a magnetic field in a desired direction alone, or while applying a magnetic field in a desired direction and an electric field in another desired direction, while simultaneously applying ultraviolet rays to the substrate To form a polymer layer by polymerizing the monomers, the main surface of the substrate is washed with an organic solvent, the desired gap is maintained, the polymer layers are opposed to each other, and the pair of substrates is A method for manufacturing a liquid crystal cell, which is obtained by laminating and filling the gap with liquid crystal, will be clarified.

The above-mentioned irradiation of ultraviolet rays may be carried out by directly irradiating the mesogen layer, or by forming the substrate as a substrate through which ultraviolet rays can pass and irradiating ultraviolet rays through the substrate. Also,
A volatile low-molecular liquid crystal is used.After forming the polymer layer, the low-molecular liquid crystal is volatilized, and the main surface of the substrate is lightly washed with an organic solvent to maintain a desired gap. Desirable results were obtained by laminating the pair of substrates with the molecular layers facing each other and filling the gap with a liquid crystal to complete the liquid crystal cell. The volatilization treatment refers to heat treatment or reduced pressure treatment.

In order to solve the above-mentioned problems, the present invention provides a mesogen layer composed of a UV absorber, a photopolymerization initiator and a polymerizable liquid crystalline monomer formed on a main surface of a substrate which can transmit a pair of UV rays. The substrate is kept at a predetermined temperature so as to be kept in a state, and then while applying a magnetic field in a desired direction alone, or applying a magnetic field in a desired direction and an electric field in another desired direction. Simultaneously applying two UV rays to the substrate main surface through the substrate at the same time to polymerize the monomers to form a polymer layer, and wash the substrate main surface with an organic solvent to maintain a desired gap. Then, a method for producing a liquid crystal cell in which the polymer layers are opposed to each other, the pair of substrates are bonded together, and liquid crystal is filled in the gaps will be clarified.

Further, according to the present invention, a mesogen layer composed of a low molecular weight liquid crystal, an ultraviolet absorber, a photopolymerization initiator and a polymerizable liquid crystalline monomer formed on a pair of ultraviolet ray transmitting substrate main surfaces is in a liquid crystal state. While maintaining the substrate at a predetermined temperature to be maintained, then while applying a magnetic field in a desired direction alone, or while applying a magnetic field in a desired direction, while two electric fields in another desired direction are applied. While applying, simultaneously irradiate the main surface of the substrate with ultraviolet rays through the substrate, polymerize the monomer to form a polymer layer, and wash the main surface of the substrate with an organic solvent, keeping a desired gap, A method for manufacturing a liquid crystal cell in which the polymer layers are opposed to each other, the pair of substrates are bonded to each other, and the gap is filled with liquid crystal is presented.

Throughout the present invention, ultraviolet rays are those having a wavelength effective for polymerization in a system comprising a photopolymerization initiator and a polymerizable liquid crystal monomer in the mesogen layer. Normal,
For ultraviolet rays, a discharge lamp for generating ultraviolet rays is suitable. In order to further improve the effect of the present application, it is desirable that the pseudo-parallel ultraviolet rays are linearly polarized in a desired direction.

The absorption coefficient of a predetermined ultraviolet ray of the ultraviolet absorber is
It is highly desirable that the photopolymerization initiator has an absorption coefficient of two or more orders of magnitude higher than the absorption coefficient of a predetermined ultraviolet ray. For example, as an ultraviolet absorber,

[0018]

[Chemical 6]

However, the present invention is not limited to this. In the present invention as a whole, it was effective to obtain a uniform and thin mesogen layer by using a flat plate whose main surface was covered with a coupler layer. Further, it was effective that the substrate for this purpose was a flat plate whose main surface was coated with a polar organic resin layer. For example, as the polymerizable liquid crystal monomer, at least

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image

Although any one of the above is included, the present invention is not limited to this.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The method of forming an alignment film for liquid crystal molecules by a non-contact method has advantages such that the possibility of dust generation is extremely small and the generation of static electricity which adversely affects the thin film transistor is extremely suppressed. However, the expression of pretilt up to about 10 ° was not successful. Here, first, some circumstances will be described.

First, with visible light or ultraviolet light, the wavelength is about 2000 angstroms even if the wavelength is short, which is about the same as the desired thickness of the liquid crystal alignment film. In order to develop the pretilt, even if these polarized lights are used and also oblique light is used to interact with some kind of resin film, for example, polymerization or the like, the pretilt probably does not appear. Here, in order to develop the pretilt, the resin main chain that constitutes the liquid crystal alignment film is not parallel to the substrate, but may be obliquely stacked on the substrate in accordance with the pretilt to be developed,
We believe that the sharpness of the tilt angle at the molecular level of the fine irregularities of the resin film that should become the liquid crystal alignment film is necessary. Of course, even if the side chain of the resin is in such a state, it is considered that the pretilt is equally expressed. From such discussions, it is considered that the wavelength needs to be about 100 Å or less in order to develop the pretilt angle by using polarized light or oblique light. This is the X-ray region, and there are certain difficulties in practice.

It is known that the magnetic field causes the low-molecular liquid crystal to be oriented due to the diamagnetism of the electron cloud in the ring portion of the liquid crystal molecule. Of course, it is also a well-known fact to orient with respect to an electric field due to induced polarization. Align a low-molecular liquid crystal with a pretilt by a magnetic field in one direction or an electric field in one direction, then leave only the liquid crystal molecules adsorbed on the substrate wall and wash away most of the low-molecular liquid crystal to form an alignment film. It is possible. As can be inferred from the results of the academic conference so far, when a liquid crystal cell is manufactured from this kind of alignment film, the filled liquid crystal molecules do not have a pretilt and are aligned parallel to the substrate wall in the vicinity of the substrate wall. That is, the liquid crystal molecules adsorbed on the substrate wall do not store the pretilt angle. That is, in order to store the pretilt, a more rigid structure corresponding to the desired pretilt is required on the substrate wall. This is one of the starting points of the present invention.

When an electric field or a magnetic field is applied to a liquid in which liquid crystal molecules are lost by diluting liquid crystal molecules in an excess solvent,
what will happen. At reasonable electric or magnetic field strengths, liquid crystal molecules did not align due to thermal motion. This is understood from the idea that the interaction between molecules in the liquid crystal state plays an essential role for this alignment effect.

Due to the above-mentioned more rigid structure, it is possible to stabilize the alignment memory by polymerizing the liquid crystal monomer.
There is one of the essence of the present invention. However, there is always a sacrifice that the memory of the orientation is partially lost due to the rearrangement of molecules during the polymerization.

After polymerization by ultraviolet irradiation, treatment with an organic solvent to elute the surface layer of the polymer was effective in minimizing alignment unevenness when a liquid crystal cell was prepared from this. .

Irradiating ultraviolet rays through the substrate seems to tend to increase the degree of polymerization only in the vicinity of the substrate wall, which also contributes to the reduction of alignment unevenness of the liquid crystal cell. At this time, the treatment with an organic solvent is preferable because the resulting alignment film can be made considerably thin and uniform. Such an effect was further enhanced by incorporating an ultraviolet absorbing dye. It should be noted that when the absorption coefficient of ultraviolet rays of this ultraviolet absorbing dye is larger than that of the photopolymerization initiator by two orders of magnitude or more, effective ultraviolet rays seem to be limited to the vicinity of the substrate wall. As a result, the thickness of the resulting alignment film for liquid crystal could be reduced considerably.

Further, a method of irradiating and polymerizing ultraviolet rays while applying a voltage in addition to a magnetic field is to promote the orientation of organic molecules in the mesogen layer and solidify the organic molecules by ultraviolet rays. That is, the voltage gives a potential corresponding to the state immediately before the movement of the organic molecule, and the magnetic field, of course, strictly controls the actual orientation direction of the organic molecule. This may save the required magnetic field strength.

A uniform thin film can be formed by applying a spinner to a mesogen layer by performing a coupler treatment on a glass substrate or the like. Further, it was easy to form a uniform thin film by coating a glass substrate or the like with a polar organic resin such as a polyimide resin, a polyparabanic acid resin, a polyacrylonitrile resin, a polyamide resin or the like, and forming a mesogen layer thereon.

(Embodiment 1) The state of the substrate in this embodiment is shown in FIG. 1 in the form of a structural cross-sectional view. In FIG. 1, 1
Is a substrate, 2 is a main surface of the substrate, 3 is a coupler layer, and 4 is a formed mesogen layer.

Corning product number 7059, a transparent electrode of indium oxide containing tin in a low alkali glass (hereinafter referred to as IT
Substrate 1 was prepared by depositing O).
On the main surface 2 of the substrate 1, at about 4000 RPM for 3 minutes,
A silane coupler, vinyltrimethoxysilane, product number KBM1003 manufactured by Shin-Etsu Silicone Co., Ltd. was applied by a spinner to form a coupler layer 3. Of course, the thickness of the coupler layer 3 is so thin that it cannot be accurately measured even by a Dectak step meter manufactured by Sloan Co., Ltd. Maybe 5
nm or less.

Next, 4-acrylic oil oil-4 ', which is a polymerizable liquid crystal monomer manufactured by Dainippon Ink and Chemicals, Inc.
-Butyl-cyclohexylcyclohexane (Chemical formula 7) and 4
Acrylic oil Oil-4'-propylcyclohexylbenzene (Chemical Formula 8), a mixture of 50% by weight, respectively, was obtained. This mixture exhibits a nematic liquid crystal phase at room temperature. About 1% by weight of benzophenone-based photopolymerization initiator, product number Irgacure-651, manufactured by Ciba Geigy Co., Ltd. was added to this to obtain a mesogen substance. This mesogenic substance was diluted about 20 times with acetone to obtain a diluted solution.

This diluted solution was first applied to a spinner for 1 minute,
At 400 RPM, about 2 minutes, 1000 RPM
The coating was performed on the coupler layer 4 at a rotation speed of PM and further at a rotation speed of 1500 RPM for about 1 minute. As it is, it is air-dried for a while, and the solvent acetone is volatilized.
A mesogen layer having a thickness of m was obtained. This mesogen layer showed a liquid crystal phase according to a polarization microscope observation.

Next, in the apparatus shown in the sectional view of the construction of FIG. 2, photopolymerization was carried out while aligning the polymerizable liquid crystalline monomer. In the figure, 5 and 6 are poles of an electromagnet, 7 is a corresponding magnetic field line, 8 is an ultraviolet lamp, 9 is the above-mentioned mesogen layer, and 10 is a substrate. For convenience, the substrate 1 and the coupler layer 3 in FIG. 1 are referred to as the substrate 10 in FIG.

The ultraviolet lamp 8 is P, manufactured by Philips
L10 was used. This radiates ultraviolet rays of 365 nm, and the distance from the substrate 10 is about 20 cm. The electromagnet is
It is manufactured by Harvey Wells Corporation.

First, the substrate 10 having a mesogen layer is tilted with respect to the magnetic line of force 7 so as to correspond to the desired pretilt or desired orientation direction of the liquid crystal molecules in the resulting liquid crystal cell, and between the poles 5 and 6 of the electromagnet. Install. In the case of this embodiment, the angle formed by the normal line of the substrate 10 and the magnetic line of force is about 65 °. Next, a magnetic field is applied so that the magnetic flux density is about 30 K gauss. In that state, the ultraviolet lamp 8 is turned on and the ultraviolet rays are irradiated for about 2 minutes. Ultraviolet light was applied directly to the mesogenic layer. Thus, a polymer layer, which is at least partially polymerized, is obtained.

Next, the organic solvent was washed by only soaking in acetone for a few minutes. As a result, the polymer layer remains on the substrate.

The substrate was subjected to in-plane optical retardation measurement with a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present.

According to a known method, the remaining polymer layers are made to face each other on such a pair of substrates, and a gap of about 10 is formed.
A micron-sized empty cell was manufactured. At this time, the bonding directions of the upper and lower substrates were such that the directions of the magnetic lines of force applied to the respective substrates during the processing of FIG. 1 were antiparallel. Nematic liquid crystal, ZLI-229 manufactured by Merck & Co., Inc.
3 was filled by a known method to obtain a liquid crystal cell.

In this way, 10 liquid crystal cells were obtained. When observed with a polarizing microscope, all the liquid crystal cells were expected, and the filled liquid crystal molecules were oriented in the direction of the magnetic lines of force applied to each substrate. It had a so-called uniform orientation.

The pretilt angle was determined by the magnetic field-capacitance method.
The measured pretilt value is in the range of 23.2 ° to 23.5 °, which is far smaller than the variation in pretilt corresponding to the conventional rubbing method. Rather, such a high tilt is considered to be impossible by the conventional rubbing method.

In order to optically examine the degree of alignment of the liquid crystal molecules, the transmitted light was observed under the crossed Nicols with the polarization axis of the polarizing plate on the incident side aligned with the long axis of the filled liquid crystal molecules. The black subduction is about 60 in all liquid crystal cells.
It was extremely good at 0: 1 or more. This level is the highest level that can be reached by the liquid crystal cell corresponding to the conventional rubbing method.

No dust is generated in all the steps of manufacturing the liquid crystal cell. This is at the extreme of the conventional rubbing method. In addition, when the charging of the substrate surface was evaluated with an electrostatic meter in all the steps, the maximum voltage value of the generated static electricity was one-hundredth or less of that in the conventional steps.

(Example 2) In substantially the same manner as in Example 1,
A liquid crystal cell was manufactured. However, in FIG.
The angle between the normal line and the magnetic force line was set to about 80 °. Moreover, the organic solvent washing was omitted.

Optical in-plane measurement of retardation was confirmed for all the substrates treated in accordance with FIG. 2 with a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present. did.

Observation with a polarization microscope revealed that all the liquid crystal cells were expected, and the filled liquid crystal molecules were oriented in the direction of the lines of magnetic force applied to each substrate. It had a so-called uniform orientation.

The pretilt angle was determined by the magnetic field-capacitance method.
The measured pretilt value is in the range of 9.4 ° to 9.7 °, which is far smaller than the variation in pretilt corresponding to the conventional rubbing method.

In order to optically examine the degree of alignment of the liquid crystal molecules, the transmitted light was observed under the crossed Nicols and with the polarization axis of the incident side polarization plate aligned with the long axis of the filled liquid crystal molecules. The black subduction is about 70 in all liquid crystal cells.
It was extremely good at 0: 1 or more. This level is the highest level that can be reached by the liquid crystal cell corresponding to the conventional rubbing method.

(Example 3) Example 1 except for the following points
A liquid crystal cell was manufactured in substantially the same manner as.

However, the main surface 2 of the substrate 1 of FIG.
00 RPM, 3 minutes, Shin-Etsu Silicone Co.,
Apply silane coupler, γ-glycidoxypropyltriethoxysilane, product number KBE403 with a spinner,
The coupler layer 3 was formed. Of course, the thickness of the coupler layer 3 is so thin that it cannot be accurately measured even by a Dectak step meter manufactured by Sloan Co., Ltd. Probably 5 nm or less.

Next, the constituent material of the mesogen layer will be described.
Low-molecular liquid crystal obtained from Kanto Chemical Co., Inc., 4-n-propyl-4′-cyanophenylcyclohexane

[0056]

Embedded image

Was obtained. Also manufactured by Dainippon Ink Co., Ltd.
Polymerizable liquid crystalline monomer, 4-acrylic oil oil-4′-butyl-cyclohexylcyclohexane (Chemical formula 7), 33.3% by weight, and 4-acrylic oil oil
4'-propylcyclohexylbenzene (Chemical formula 8), 3
A mixture was obtained with 3.3% by weight and the balance being 4-acrylic oil -4'-heptyldibenzilidine.

Approximately 75% by weight of the low-molecular liquid crystal of (Chemical Formula 11),
A new mixture was prepared such that the mixture was about 25% by weight. It exhibits a nematic liquid crystal phase at room temperature. About 1% by weight of benzophenone-based photopolymerization initiator, product number Irgacure-651, manufactured by Ciba Geigy Co., Ltd. was added to this to obtain a mesogen substance. This mesogenic substance was diluted about 20 times with acetone to obtain a diluted solution.

In addition, in FIG. 2, the angle between the normal line of the substrate 10 and the magnetic force line was set to about 80 ° for processing. Thus, at least a partially polymerized polymer layer was obtained on the substrate.
After the treatment corresponding to FIG. 2, it was placed in a reduced pressure atmosphere using a rotary pump for about 1 hour. After that, in the same manner as in Example 1, the organic solvent was washed with ethanol for a dipping time of about 1 minute. At this time, a residual polymer layer was obtained on the substrate.

The in-plane optical retardation of the substrate after washing with the organic solvent was measured by a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present.

Observation of the completed liquid crystal cells with a polarization microscope showed that all the liquid crystal cells were expected, and the filled liquid crystal molecules were oriented in the direction of the lines of magnetic force applied to each substrate. It had a so-called uniform orientation.

The pretilt angle was determined by the magnetic field-capacitance method.
The measured pretilt value is in the range of 9.5 ° to 9.7 °, which is far smaller than the variation in pretilt corresponding to the conventional rubbing method.

In order to optically examine the degree of alignment of the liquid crystal molecules, the transmitted light was observed under the crossed Nicols and with the polarization axis of the incident side polarization plate aligned with the long axis of the filled liquid crystal molecules. The black subduction is about 75 in all liquid crystal cells.
It was extremely good at 0: 1 or more. This level is the highest level that can be reached by the liquid crystal cell corresponding to the conventional rubbing method.

(Embodiment 4) Except for the following points, Embodiment 1
A liquid crystal cell was manufactured in substantially the same manner as.

However, the main surface 2 of the substrate 1 of FIG.
00 RPM, 3 minutes, Shin-Etsu Silicone Co.,
Apply silane coupler, γ-glycidoxypropyltriethoxysilane, product number KBE403 with a spinner,
Heat treatment was performed at about 100 ° C. to form the coupler layer 3. Of course, the thickness of the coupler layer 3 is so thin that it cannot be accurately measured even by a Dectak step meter manufactured by Sloan Co., Ltd. Probably 5 nm or less.

Next, the constituent material of the mesogen layer will be described.
Two low molecular weight liquid crystal components, 4-n-, obtained from Merck & Co., Inc.
Pentanyl-4'-cyanobiphenyl

[0067]

Embedded image

59 mol%, 4-n-pentanyl-
4'-cyanobiphenyl

[0069]

Embedded image

A low molecular weight liquid crystal was prepared by mixing 41 mol%. Also, a polymerizing liquid crystal monomer manufactured by Dainippon Ink and Chemicals, Inc., 4-acrylic oil oil-4′-propylcyclohexylbenzene (Chemical formula 8), 50% by weight,
Acrylic Oil Oil-4'-Heptyldibenzilidine (Formula 9) A mixture was obtained with the balance.

Approximately 75% by weight of the low-molecular liquid crystal of (Chemical Formula 11),
A new mixture was prepared such that the mixture was about 25% by weight. It exhibits a nematic liquid crystal phase at room temperature. About 1% by weight of benzophenone-based photopolymerization initiator, product number Irgacure-651, manufactured by Ciba Geigy Co., Ltd. was added to this to obtain a mesogen substance. This mesogenic substance was diluted about 20 times with acetone to obtain a diluted solution.

Further, in FIG. 2, the angle between the normal line of the substrate 10 and the magnetic force line is set to about 80 °. After the treatment corresponding to FIG. 2, in the same manner as in Example 1, the organic solvent was washed with acetone for about 2 minutes for the immersion time.

The in-plane optical retardation of the substrate after washing with the organic solvent was measured by a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present.

Observation of the completed liquid crystal cells with a polarizing microscope showed that all the liquid crystal cells were expected, and the filled liquid crystal molecules were oriented in the direction of the lines of magnetic force applied to each substrate. It had a so-called uniform orientation.

The pretilt angle was determined by the magnetic field-capacitance method.
The measured pretilt value is in the range of 9.3 ° to 9.5 °, which is far smaller than the variation in pretilt corresponding to the conventional rubbing method.

In order to optically examine the degree of alignment of the liquid crystal molecules, the transmitted light was observed under the crossed Nicols and with the polarization axis of the incident side polarization plate aligned with the long axis of the filled liquid crystal molecules. The black subduction is about 70 in all liquid crystal cells.
It was extremely good at 0: 1 or more. This level is the highest level that can be reached by the liquid crystal cell corresponding to the conventional rubbing method.

(Embodiment 5) The condition of the substrate in this embodiment is shown in FIG. 1 in the form of a structural sectional view, in this case, 3 is a polar organic resin layer.

Corning product number 7059, a transparent electrode of indium oxide containing tin in a low alkali glass (hereinafter referred to as IT
Substrate 1 was prepared by depositing O).
About 2% by weight of normal methylpyrrolidone (NMP) in which polyacrylonitrile (PAN) is dissolved in about 3% by weight on the main surface 2 of the substrate 1.
A polar organic resin layer 3 was formed by coating with a spinner under conditions of 000 RPM and 3 minutes. After this, about 100 ℃, 3
Heat treated for hours. Of course, the thickness of the organic resin layer 3 is so thin that it cannot be accurately measured even by a Dectak step meter manufactured by Sloan Co., Ltd. Probably about 10 nm.

Next, 4-acrylic oil oil-4 ', which is a polymerizable liquid crystal monomer manufactured by Dainippon Ink and Chemicals, Inc.
-Propyl-cyclohexylbenzene (Chemical formula 8), 40 wt%, 4-acrylic oil oil-4'-heptyldibenzilidine (Chemical formula 9), 40 wt%, 4-acrylic oil oil-4'-cyanobiphenyl ( 10), 2
0% by weight of the mixture was obtained. This mixture exhibits a nematic liquid crystal phase at room temperature. About 1% by weight of benzophenone-based photopolymerization initiator, product number Irgacure-651, manufactured by Ciba Geigy Co., Ltd. was added to this to obtain a mesogen substance. This mesogenic substance was diluted about 20 times with acetone to obtain a diluted solution.

The diluted solution was first applied to the spinner for 1 minute,
At 400 RPM, about 2 minutes, 1000 RPM
The coating was performed on the coupler layer 4 at a rotation speed of PM and further at a rotation speed of 1500 RPM for about 1 minute. As it is, air-dry for a while to evaporate acetone as a solvent, about 200n
A mesogen layer having a thickness of m was obtained. This mesogen layer showed a liquid crystal phase according to a polarization microscope observation.

Next, in the apparatus shown in the sectional view of the construction of FIG. 3, photopolymerization was carried out while aligning the polymerizable liquid crystalline monomer. In FIG. 3, 11 and 12 are electromagnet poles, and 13
Is a corresponding magnetic field line, 14 is an ultraviolet lamp, 15 is the above-mentioned mesogen layer, and 16 is a substrate. For convenience, FIG.
The substrate 1 and the polar organic resin layer 3 of FIG.
And The electromagnet and the ultraviolet lamp used are the same as in Example 1.

First, the substrate 16 having the mesogen layer is tilted with respect to the magnetic force lines 13 in accordance with the desired pretilt and the desired orientation direction of the liquid crystal molecules in the resulting liquid crystal cell, and the poles 11 and 12 of the electromagnets are tilted. Install. In the case of this embodiment, the angle formed by the normal line of the substrate 16 and the magnetic line of force is about 83 °. Next, so that the magnetic flux density is about 35 K gauss,
Apply a magnetic field. In this state, the ultraviolet lamp 14 is turned on and the ultraviolet rays are irradiated for about 3 minutes. UV rays on the substrate 16
The mesogen layer 15 is irradiated from the back side of the substrate through the substrate. Thus, a polymer layer, which was at least partially polymerized, was obtained.

Next, the organic solvent was washed by only soaking in acetone for a few minutes. As a result, the polymer layer was uniformly present on the substrate.

The in-plane optical retardation of this substrate was measured with a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present.

By a known method, such a pair of substrates was used to fabricate an empty cell having a gap of about 10 μm so that the polymer layers face each other. At this time, the bonding directions of the upper and lower substrates were such that the directions of the magnetic lines of force applied to the respective substrates during the processing of FIG. 1 were antiparallel. A liquid crystal cell was obtained by filling this empty cell with a nematic liquid crystal, ZLI-2293 manufactured by Merck Ltd. by a known method.

In this way, 10 liquid crystal cells were obtained. When observed with a polarizing microscope, all the liquid crystal cells were expected, and the filled liquid crystal molecules were oriented in the direction of the magnetic lines of force applied to each substrate. It had a so-called uniform orientation.

The pretilt angle was determined by the magnetic field-capacitance method.
The measured pretilt value is in the range of 6.5 ° to 6.8 °, which is far smaller than the variation in pretilt corresponding to the conventional rubbing method.

In order to optically examine the degree of alignment of the liquid crystal molecules, the transmitted light was observed under the crossed Nicols and with the polarization axis of the incident-side polarizing plate aligned with the long axis of the filled liquid crystal molecules. The black subduction is about 60 in all liquid crystal cells.
It was extremely good at 0: 1 or more. This level is the highest level that can be reached by the liquid crystal cell corresponding to the conventional rubbing method.

No dust is generated in all the steps of manufacturing the liquid crystal cell. This is at the extreme of the conventional rubbing method. In addition, when the charging of the substrate surface was evaluated with an electrostatic meter in all the steps, the maximum voltage value of the generated static electricity was one-hundredth or less of that in the conventional steps.

Example 6 A liquid crystal cell was manufactured in substantially the same manner as in Example 5 except for the following points.

The state of the substrate in this embodiment is as shown in FIG. 1 in the form of a sectional view of the structure, and in this case, 3 is a polar organic resin layer.

Corning product number 7059, indium oxide transparent electrode containing tin in low alkali glass (hereinafter referred to as IT
Substrate 1 was prepared by depositing O).
Approximately 2% by weight of Aldrich Chemical Company, m-cresol in which nylon 6/6 was dissolved, was applied to the main surface 2 of the substrate 1 with a spinner at about 3000 RPM for 3 minutes to form a polar organic resin. Layer 3 was formed. after this,
Heat treatment was performed at about 100 ° C. for 3 hours. Of course, the thickness of the organic resin layer 3 is so thin that it cannot be accurately measured even by a Dectak step meter manufactured by Sloan Co., Ltd. Maybe 10n
m.

Next, the constituent material of the mesogen layer will be described.
Two low molecular weight liquid crystal components, 4-n-, obtained from Merck & Co., Inc.
Pentanyl-4′-cyanobiphenyl (Chemical Formula 12), 59
A low-molecular liquid crystal was prepared by mixing 41% by mol of 4-n-pentanyl-4′-cyanobiphenyl (Chemical Formula 13) with 41% by mol. Also, 4-acrylic oil oil-4'-propylcyclohexylbenzene (Chemical formula 8), which is a polymerizable liquid crystal monomer manufactured by Dainippon Ink and Chemicals, Inc., 50% by weight, and 4
Acrylic Oil Oil-4'-Heptyldibenzilidine (Formula 9) A mixture was obtained with the balance.

Approximately 75% by weight of the low-molecular liquid crystal of (Chemical Formula 11),
A new mixture was prepared such that the mixture was about 25% by weight. It exhibits a nematic liquid crystal phase at room temperature. About 1% by weight of benzophenone-based photopolymerization initiator, product number Irgacure-651, manufactured by Ciba Geigy Co., Ltd. was added to this to obtain a mesogen substance. This mesogenic substance was diluted about 20 times with acetone to obtain a diluted solution.

Further, in FIG. 3, the angle between the normal line of the substrate 16 and the magnetic force line is set to about 85 °. After the treatment corresponding to FIG. 3, in the same manner as in Example 5, the organic solvent was washed with acetone for about 2 minutes for the immersion time.

When the substrate after washing with the organic solvent was subjected to in-plane optical retardation measurement with a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., it was confirmed that retardation was present.

Observation of the completed liquid crystal cells with a polarization microscope showed that all the liquid crystal cells were expected, and the filled liquid crystal molecules were oriented in the direction of the lines of magnetic force applied to each substrate. It had a so-called uniform orientation.

The pretilt angle was determined by the magnetic field-capacitance method.
The measured pretilt value is in the range of 5 ° ± 0.1 °, which is far smaller than the variation in pretilt corresponding to the conventional rubbing method.

In order to optically examine the degree of alignment of the liquid crystal molecules, the transmitted light was observed under the crossed Nicols and with the polarization axis of the incident side polarizing plate aligned with the long axis of the filled liquid crystal molecules. The black subduction is about 70 in all liquid crystal cells.
It was extremely good at 0: 1 or more. This level is the highest level that can be reached by the liquid crystal cell corresponding to the conventional rubbing method.

Example 7 A liquid crystal cell was manufactured in substantially the same manner as in Example 5 except for the following points.

The state of the substrate in this embodiment is as shown in FIG. 1 in the form of a sectional view of the structure, and in this case, 3 is a polar organic resin layer.

Corning product number 7059, a transparent electrode of indium oxide containing tin in a low alkali glass (hereinafter referred to as IT
Substrate 1 was prepared by depositing O).
The main surface 2 of the substrate 1 has about 2% by weight of Nitrogen Petrochemical Co., Ltd.
Normal methylpyrrolidone in which polyamic acid was dissolved was applied by a spinner at about 3000 RPM for 3 minutes to form a polar organic resin layer 3. After this, about 2
It heat-processed at 00 degreeC for 1 hour. Of course, the thickness of the organic resin layer 3 is so thin that it cannot be accurately measured even by a Dectak step meter manufactured by Sloan Co., Ltd. Probably about 50 nm.

Next, the constituent material of the mesogen layer will be described.
Dainippon Ink Co., Ltd., a polymerizable liquid crystal monomer,
4-acrylic oil oil-4'-butyl-cyclohexylcyclohexane (chemical formula 7) and 4-acrylic oil oil-4'-propylcyclohexylbenzene (chemical formula 8)
50% by weight of each mixture was obtained. This mixture exhibits a nematic liquid crystal phase at room temperature. To this, Ciba
Approximately 1% by weight of benzophenone-based photopolymerization initiator, product number Irgacure-651 manufactured by Geigy Corporation, and an ultraviolet absorber obtained from Aldrich Chemical Company, 4- (1-sulfonyl-2-hexyl)- 4'-
About 1% by weight of (1-oxa-6-hexanor) -transstilbene (Chemical Formula 6) was added to obtain a mesogenic substance. This mesogenic substance was diluted about 20 times with acetone to obtain a diluted solution.

Further, in FIG. 3, the angle formed by the normal line of the substrate 16 and the magnetic force line is set to about 85 °. After the treatment corresponding to FIG. 3, the organic solvent was washed with acetone for about 5 minutes in the immersion time in the same manner as in Example 5.

The substrate after the cleaning with the organic solvent was subjected to in-plane optical retardation measurement by a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present.

When the completed liquid crystal cells were observed with a polarization microscope, all the liquid crystal cells were expected, and the filled liquid crystal molecules were oriented in the direction of the magnetic lines of force applied to each substrate. It had a so-called uniform orientation.

The pretilt angle was determined by the magnetic field-capacitance method.
The measured pretilt value is in the range of 5 ° ± 0.1 °, which is far smaller than the variation in pretilt corresponding to the conventional rubbing method.

In order to optically examine the degree of alignment of the liquid crystal molecules, the transmitted light was observed under the crossed Nicols and with the polarization axis of the incident-side polarizing plate aligned with the long axis of the filled liquid crystal molecules. The black subduction is about 70 in all liquid crystal cells.
It was extremely good at 0: 1 or more. This level is the highest level that can be reached by the liquid crystal cell corresponding to the conventional rubbing method.

Example 8 A liquid crystal cell was manufactured in substantially the same manner as in Example 5 except for the following points.

The condition of the substrate in this embodiment is as shown in FIG. 1 in the form of a sectional view of the structure, and in this case, 3 is a coupler layer.

Corning product number 7059, a transparent electrode of indium oxide containing tin in a low alkali glass (hereinafter referred to as IT
Substrate 1 was prepared by depositing O).
Substrate 1 However, on the main surface 2 of the substrate 1 of FIG.
Under the condition of 0 RPM and 3 minutes, Shin-Etsu Silicone Co., Ltd., silane coupler, γ-glycidoxypropyltriethoxysilane, product number KBE403 is applied with a spinner and heat-treated at about 100 ° C. to form a coupler layer 3. did.
Of course, the thickness of the coupler layer 3 is so thin that it cannot be accurately measured even by a Dectak step meter manufactured by Sloan Co., Ltd. Probably 5 nm or less.

Next, the constituent material of the mesogen layer will be described.
4-n-propyl-4'-cyanophenylcyclohexane (Chemical formula 11), a low-molecular liquid crystal obtained from Kanto Chemical Co., Inc.
Was obtained.

Also, 4-acrylic oil oil-4'-butyl-cyclohexylcyclohexane (Chemical formula 7), which is a polymerizable liquid crystal monomer manufactured by Dainippon Ink and Chemicals, Inc., 33.
3% by weight, 4-acrylic oil oil-4'-propylcyclohexylbenzene (Chemical formula 8), 33.3% by weight
And a mixture of 4-acrylic oil oil-4′-heptyldibenzilidine (formula 9), the balance being obtained.

Approximately 70% by weight of the low-molecular liquid crystal of (Chemical Formula 11),
A new mixture was prepared such that the mixture was about 30% by weight. It exhibits a nematic liquid crystal phase at room temperature. About 1% by weight of benzophenone photopolymerization initiator, product number Irgacure-651, manufactured by Ciba Geigy Co.,
UV absorber, 4- (1-sulfonyl-2-hexyl)-, obtained from Aldrich Chemical Company
About 1.5% by weight of 4 '-(1-oxa-6-hexanor) -transstilbene (Chemical formula 6) was added to obtain a mesogen substance. This mesogenic substance was diluted about 20 times with acetone to obtain a diluted solution.

Further, in FIG. 3, the angle between the normal line of the substrate 16 and the magnetic force line is set to about 75 °. After the treatment corresponding to FIG. 3, the organic solvent was washed with acetone for about 5 minutes in the immersion time in the same manner as in Example 5.

With respect to the substrate after washing with the organic solvent, an in-plane optical retardation measurement was carried out with a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present.

Observation of the completed liquid crystal cells with a polarization microscope showed that all the liquid crystal cells were expected, and the filled liquid crystal molecules were oriented in the direction of the lines of magnetic force applied to each substrate. It had a so-called uniform orientation.

The pretilt angle was determined by the magnetic field-capacitance method.
The measured pretilt value is in the range of 13.6 ° to 13.8 °, which is far smaller than the variation in pretilt corresponding to the conventional rubbing method.

In order to optically examine the degree of alignment of the liquid crystal molecules, the transmitted light was observed under the crossed Nicols and with the polarization axis of the incident side polarizing plate aligned with the long axis of the filled liquid crystal molecules. Black subduction is about 64 in all liquid crystal cells
It was extremely good at 0: 1 or more. This level is the highest level that can be reached by the liquid crystal cell corresponding to the conventional rubbing method.

Example 9 A liquid crystal cell was manufactured in substantially the same manner as in Example 8 except for the following points.

The condition of the substrate in this embodiment will be described. The coupler layer or the polar organic resin layer 3 in FIG. 1 is omitted. That is, in FIG. 1, a mesogen layer is directly laminated on a substrate made of Corning, product number 7059, indium oxide transparent electrode containing tin (hereinafter referred to as ITO) deposited on low alkali glass.

Prior to the formation of the mesogen layer, the substrate is thoroughly washed, dried at about 120 ° C., and then the formation of the mesogen layer is completed in a short time.

The same evaluation as in Example 8 was performed on the processed substrate and the liquid crystal cell corresponding to FIG. 3, and good results were obtained.

(Embodiment 10) The state of the substrate in this embodiment is shown in FIG. 1 in the form of a sectional view of the structure. In the figure, 1
Is a substrate, 2 is a main surface of the substrate, 3 is a coupler layer, and 4 is a formed mesogen layer.

Corning product number 7059, a transparent electrode of indium oxide containing tin in a low alkali glass (hereinafter referred to as IT
Substrate 1 was prepared by depositing O).
On the main surface 2 of the substrate 1, at about 4000 RPM for 3 minutes,
A silane coupler, vinyltrimethoxysilane, product number KBM1003 manufactured by Shin-Etsu Silicone Co., Ltd. was applied by a spinner to form a coupler layer 3. Of course, the thickness of the coupler layer 3 is so thin that it cannot be accurately measured even by a Dectak step meter manufactured by Sloan Co., Ltd. Maybe 5
nm or less.

Next, 4-acrylic oil oil-4 ', which is a polymerizable liquid crystal monomer manufactured by Dainippon Ink and Chemicals, Inc.
-Butyl-cyclohexylcyclohexane (Chemical formula 7) and 4
Acrylic oil Oil-4'-propylcyclohexylbenzene (Chemical Formula 8), a mixture of 50% by weight, respectively, was obtained. This mixture exhibits a nematic liquid crystal phase at room temperature. About 1% by weight of benzophenone-based photopolymerization initiator, product number Irgacure-651, manufactured by Ciba Geigy Co., Ltd. was added to this to obtain a mesogen substance. This mesogenic substance was diluted about 20 times with acetone to obtain a diluted solution.

This diluted solution was first applied to the spinner for 1 minute,
At 400 RPM, about 2 minutes, 1000 RPM
The coating was performed on the coupler layer 4 at a rotation speed of PM and further at a rotation speed of 1500 RPM for about 1 minute. As it is, it is air-dried for a while, and the solvent acetone is volatilized.
A mesogen layer having a thickness of m was obtained. This mesogen layer showed a liquid crystal phase according to a polarization microscope observation.

Next, in the apparatus shown in the sectional view of the structure of FIG. 4, photopolymerization was carried out while aligning the polymerizable liquid crystal monomer. In the figure, 17 and 18 are electromagnet poles, and 19
Is a corresponding magnetic field line, 20 is an ultraviolet lamp, 21 is a quartz glass substrate, 22 is an ITO electrode layer, 23 is a mesogen layer, 24 is an ITO electrode layer, 25 is a substrate, and 26 is IT.
It is a voltage application terminal for applying a voltage to the O electrode layers 22 and 24. Although not shown clearly in the figure, I
An air, gas, or vacuum gap of about several tens of microns is provided between the TO electrode layer 22 and the mesogen layer 23. This was done by dispersing glass spacers for liquid crystals as spacers. For convenience, the substrate 1 (see FIG. 1) and the coupler layer 3 are referred to as the substrate 25 in FIG.
And The electromagnet and the ultraviolet lamp used are the same as in Example 1.

In this example, about 30 spacers were used.
Dispersed glass fibers of micron diameter.

First, the substrate 25 having the mesogen layer is tilted with respect to the magnetic force lines 19 in accordance with the desired pretilt and desired orientation direction of the liquid crystal molecules in the resulting liquid crystal cell, and is placed between the poles 17 and 18 of the electromagnet. Install. In the case of this embodiment, the angle formed by the normal line of the substrate 25 and the magnetic force line 19 is set to about 65 °. Next, a magnetic field is applied to the voltage application terminal 26 while applying a DC voltage of 2 V so that the magnetic flux density is about 25 K gauss. The magnetic field strength may be rather low. In that state, the ultraviolet lamp 20 is turned on, and ultraviolet rays are irradiated for about 4 minutes. Ultraviolet rays were applied to the mesogen layer through the quartz glass substrate 21 side. After this processing, IT
The quartz glass substrate 21 with the O electrode layer 22 was separated.
The obtained product has a polymer layer which is treated and at least partially polymerized on the substrate 25 having the ITO electrode layer 24.

Next, the organic solvent was washed by only immersing it in acetone for several minutes. of course,
The glass fibers adhering to the substrate 35 were washed away at this stage. As a result, a uniform polymer layer remained on the substrate.

The in-plane optical retardation of this substrate was measured with a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present.

According to a known method, such an empty cell in which the polymer layers were opposed to each other on the pair of substrates and the gap was set to about 10 μm was manufactured. At this time, the bonding directions of the upper and lower substrates were such that the directions of the magnetic lines of force applied to the respective substrates during the processing of FIG. 1 were antiparallel. A liquid crystal cell was obtained by filling this empty cell with a nematic liquid crystal, ZLI-2293 manufactured by Merck Ltd. by a known method.

In this way, 10 liquid crystal cells were obtained. Observation with a polarization microscope revealed that the filled liquid crystal molecules were aligned in the direction of the lines of magnetic force applied to each substrate, as expected in all liquid crystal cells. It had a so-called uniform orientation.

The pretilt angle was determined by the magnetic field-capacitance method.
The measured pretilt value is in the range of 23.7 ° to 23.8 °, which is far smaller than the variation in pretilt corresponding to the conventional rubbing method. Rather, such a high tilt is considered to be impossible by the conventional rubbing method.

In order to optically examine the degree of alignment of the liquid crystal molecules, the transmitted light was observed under the crossed Nicols and with the polarization axis of the incident side polarization plate aligned with the long axis of the filled liquid crystal molecules. The black subduction is about 44 for all liquid crystal cells.
It was extremely good at 0: 1 or more. Light leakage due to scratches in the polymer layer due to the glass spacers described above slightly lowers the level, which is the highest level that can be reached by a liquid crystal cell corresponding to the conventional rubbing method.

Example 11 A liquid crystal cell was manufactured in substantially the same manner as in Example 10. However, in FIG. 4, the angle formed by the normal line of the substrate 25 and the magnetic force line was set to about 80 °. Moreover, the organic solvent washing was omitted.

Optical in-plane retardation measurement was carried out on all the substrates treated in accordance with FIG. 4 with a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present. did.

Observation with a polarization microscope revealed that the filled liquid crystal molecules were oriented in the direction of the lines of magnetic force applied to each substrate, as expected in all liquid crystal cells. It had a so-called uniform orientation.

The pretilt angle was determined by the magnetic field-capacitance method.
The measured pretilt value is in the range of 9.2 ° to 9.5 °, which is far smaller than the variation in pretilt corresponding to the conventional rubbing method.

In order to optically examine the degree of alignment of the liquid crystal molecules, the transmitted light was observed under the crossed Nicols and with the polarization axis of the incident-side polarizing plate aligned with the long axis of the filled liquid crystal molecules. The black subduction is about 41 for all liquid crystal cells.
It was extremely good at 0: 1 or more. This level is the highest level that can be reached by the liquid crystal cell corresponding to the conventional rubbing method.

(Embodiment 12) The state of the substrate in this embodiment is as shown in FIG. 1 in the form of a structural cross-sectional view, and in this case, 3 is a polar organic resin layer.

Corning product number 7059, a transparent electrode of indium oxide containing tin in a low alkali glass (hereinafter referred to as IT
Substrate 1 was prepared by depositing O).
About 2% by weight of normal methylpyrrolidone (NMP) in which polyacrylonitrile (PAN) is dissolved in about 3% by weight on the main surface 2 of the substrate 1.
A polar organic resin layer 3 was formed by coating with a spinner under conditions of 000 RPM and 3 minutes. After this, about 100 ℃, 3
Heat treated for hours. Of course, the thickness of the organic resin layer 3 is so thin that it cannot be accurately measured even by a Dectak step meter manufactured by Sloan Co., Ltd. Probably about 10 nm.

Next, 4-acrylic oil oil-4 ', which is a polymerizable liquid crystalline monomer manufactured by Dainippon Ink and Chemicals, Inc.
-Propyl-cyclohexylbenzene (Chemical formula 8), 40 wt%, 4-acrylic oil oil-4'-heptyldibenzilidine (Chemical formula 9), 40 wt%, 4-acrylic oil oil-4'-cyanobiphenyl ( 10), 2
0% by weight of the mixture was obtained. This mixture exhibits a nematic liquid crystal phase at room temperature. About 1% by weight of benzophenone-based photopolymerization initiator, product number Irgacure-651, manufactured by Ciba Geigy Co., Ltd. was added to this to obtain a mesogen substance. This mesogenic substance was diluted about 20 times with acetone to obtain a diluted solution.

[0145] This diluted solution was first applied to the spinner for 1 minute,
At 400 RPM, about 2 minutes, 1000 RPM
The coating was performed on the coupler layer 4 at a rotation speed of PM and further at a rotation speed of 1500 RPM for about 1 minute. As it is, air-dry for a while to evaporate acetone as a solvent, about 200n
A mesogen layer having a thickness of m was obtained. This mesogen layer showed a liquid crystal phase according to a polarization microscope observation.

Next, in the apparatus shown in the sectional view of the construction shown in FIG. 5, photopolymerization was carried out while aligning the polymerizable liquid crystal monomer. In the figure, 27 and 28 are poles of an electromagnet, 29 is a corresponding magnetic field line, 30 is an ultraviolet lamp, 31 is a quartz glass substrate, 32 is an ITO electrode layer, 33
Is a mesogen layer, 34 is an ITO electrode layer, 35 is a substrate, 3
Reference numeral 6 is a voltage application terminal for applying a voltage to the ITO electrode layers 32 and 34. Although not clearly shown in the figure, an air, gas, or vacuum gap of about several tens of microns is provided between the ITO electrode layer 32 and the mesogen layer 33. This was done by dispersing glass spacers for liquid crystals as spacers. For convenience, the substrate 1 and the coupler layer 3 in FIG. 1 are referred to as a substrate 35 in FIG. The electromagnet and the ultraviolet lamp used are the same as in Example 1.

In this example, about 30 spacers were used as spacers.
Dispersed glass fibers of micron diameter.

First, the substrate 35 having a mesogen layer is tilted with respect to the magnetic force line 29 so as to correspond to the desired pretilt and the desired orientation direction of the liquid crystal molecules in the resulting liquid crystal cell, and between the poles 27 and 28 of the electromagnet. Install. In the case of this embodiment, the angle formed by the normal line of the substrate 35 and the magnetic force line 29 is about 83 °. Next, a magnetic field is applied to the voltage application terminal 36 while applying a DC voltage of 2 V so that the magnetic flux density is about 25 K gauss. The magnetic field strength may be rather low. In this state, the ultraviolet lamp 30 is turned on and the ultraviolet rays are irradiated for about 4 minutes. Ultraviolet rays were applied to the mesogen layer 33 from the back surface of the substrate 35 through the back surface. After this treatment, ITO
The quartz glass substrate 31 with the electrode layer 32 was separated. The obtained product has a polymer layer which is treated and at least partially polymerized on the substrate 35 having the ITO electrode layer 34.

Next, the organic solvent was washed by only immersing it in acetone for several minutes. of course,
The glass fibers adhering to the substrate 35 were washed away at this stage. As a result, a uniform polymer layer remained on the substrate.

The in-plane optical retardation of this substrate was measured with a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., and it was confirmed that retardation was present.

A known method was used to fabricate an empty cell in which the polymer layers were opposed to each other on a pair of substrates and the gap was set to about 10 microns. At this time, the bonding directions of the upper and lower substrates were such that the directions of the magnetic lines of force applied to the respective substrates during the processing of FIG. 5 were anti-parallel. A liquid crystal cell was obtained by filling this empty cell with a nematic liquid crystal, ZLI-2293 manufactured by Merck Ltd. by a known method.

In this way, 10 liquid crystal cells were obtained. When observed with a polarizing microscope, all the liquid crystal cells were expected, and the filled liquid crystal molecules were oriented in the direction of the magnetic lines of force applied to each substrate. It had a so-called uniform orientation.

The pretilt angle was determined by the magnetic field-capacitance method.
The measured pretilt value is in the range of 6.7 ° to 6.8 °, which is far smaller than the variation in pretilt corresponding to the conventional rubbing method. Rather, such a high tilt is considered to be impossible by the conventional rubbing method.

In order to optically examine the degree of alignment of the liquid crystal molecules, the transmitted light was observed under the crossed Nicols and with the polarization axis of the incident side polarizing plate aligned with the long axis of the filled liquid crystal molecules. The black subduction is about 48 for all liquid crystal cells.
It was extremely good at 0: 1 or more. Light leakage due to scratches in the polymer layer due to the glass spacers described above slightly lowers the level, which is the highest level that can be reached by a liquid crystal cell corresponding to the conventional rubbing method.

(Example 13) Example 12 was carried out except the following points.
A liquid crystal cell was manufactured in substantially the same manner as.

The state of the substrate in this example is as shown in FIG. 1 in the form of a structural cross-sectional view, and in this case, 3 is a polar organic resin layer.

Corning product number 7059, a transparent electrode of indium oxide containing tin in a low alkali glass (hereinafter referred to as IT
Substrate 1 was prepared by depositing O).
Approximately 2% by weight of Aldrich Chemical Company, m-cresol in which nylon 6/6 was dissolved, was applied to the main surface 2 of the substrate 1 with a spinner at about 3000 RPM for 3 minutes to form a polar organic resin. Layer 3 was formed. after this,
Heat treatment was performed at about 100 ° C. for 3 hours. Of course, the thickness of the organic resin layer 3 is so thin that it cannot be accurately measured even by a Dectak step meter manufactured by Sloan Co., Ltd. Maybe 10n
m.

Next, the constituent material of the mesogen layer will be described.
Two low molecular weight liquid crystal components, 4-n-, obtained from Merck & Co., Inc.
Pentanyl-4′-cyanobiphenyl (Chemical Formula 12), 59
A low-molecular liquid crystal was prepared by mixing 41% by mol of 4-n-pentanyl-4′-cyanobiphenyl (Chemical Formula 13) with 41% by mol. Also, 4-acrylic oil oil-4'-propylcyclohexylbenzene (Chemical formula 8), which is a polymerizable liquid crystal monomer manufactured by Dainippon Ink and Chemicals, Inc., 50% by weight, and 4
Acrylic Oil Oil-4'-Heptyldibenzilidine (Formula 9) A mixture was obtained with the balance.

About 75% by weight of the low-molecular liquid crystal of (Chemical Formula 11),
A new mixture was prepared such that the mixture was about 25% by weight. It exhibits a nematic liquid crystal phase at room temperature. About 1% by weight of benzophenone-based photopolymerization initiator, product number Irgacure-651, manufactured by Ciba Geigy Co., Ltd. was added to this to obtain a mesogen substance. This mesogenic substance was diluted about 20 times with acetone to obtain a diluted solution.

Further, in FIG. 5, the angle between the normal line of the substrate 35 and the magnetic force line is set to about 85 °. After the treatment corresponding to FIG. 5, the organic solvent was washed with acetone for about 2 minutes in the immersion time in the same manner as in Example 5.

When the substrate after washing with the organic solvent was subjected to in-plane optical retardation measurement with a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., it was confirmed that retardation was present.

Observation of the completed liquid crystal cells with a polarizing microscope showed that all the liquid crystal cells were expected, and the filled liquid crystal molecules were oriented in the direction of the magnetic lines of force applied to each substrate. It had a so-called uniform orientation.

The pretilt angle was determined by the magnetic field-capacitance method.
The measured pretilt value is in the range of 5 ° ± 0.1 °, which is far smaller than the variation in pretilt corresponding to the conventional rubbing method.

In order to optically examine the degree of alignment of the liquid crystal molecules, the transmitted light was observed under the crossed Nicols and with the polarization axis of the incident side polarizing plate aligned with the long axis of the filled liquid crystal molecules. The black subduction is about 50 in all liquid crystal cells.
It was extremely good at 0: 1 or more. This level is the highest level that can be reached by the liquid crystal cell corresponding to the conventional rubbing method.

(Example 14) Example 12 was carried out except the following points.
A liquid crystal cell was manufactured in substantially the same manner as.

The state of the substrate in this example is as shown in FIG. 1 in the form of a sectional view of the structure, and in this case, 3 is a polar organic resin layer.

Corning product number 7059, a transparent electrode of indium oxide containing tin in a low alkali glass (hereinafter referred to as IT
Substrate 1 was prepared by depositing O).
The main surface 2 of the substrate 1 has about 2% by weight of Nitrogen Petrochemical Co., Ltd.
Normal methylpyrrolidone in which polyamic acid was dissolved was applied by a spinner at about 3000 RPM for 3 minutes to form a polar organic resin layer 3. After this, about 2
It heat-processed at 00 degreeC for 1 hour. Of course, the thickness of the organic resin layer 3 is so thin that it cannot be accurately measured even by a Dectak step meter manufactured by Sloan Co., Ltd. Probably about 50 nm.

Next, the constituent material of the mesogen layer will be described.
Dainippon Ink Co., Ltd., a polymerizable liquid crystal monomer,
4-acrylic oil oil-4'-butyl-cyclohexylcyclohexane (chemical formula 7) and 4-acrylic oil oil-4'-propylcyclohexylbenzene (chemical formula 8)
50% by weight of each mixture was obtained. This mixture exhibits a nematic liquid crystal phase at room temperature. To this, Ciba
Approximately 1% by weight of benzophenone-based photopolymerization initiator, product number Irgacure-651 manufactured by Geigy Corporation, and an ultraviolet absorber obtained from Aldrich Chemical Company, 4- (1-sulfonyl-2-hexyl)- 4'-
About 1% by weight of (1-oxa-6-hexanor) -transstilbene (Chemical Formula 6) was added to obtain a mesogenic substance. This mesogenic substance was diluted about 20 times with acetone to obtain a diluted solution.

Further, in FIG. 5, the angle formed by the normal line of the substrate 35 and the magnetic force line is set to about 85 °. After the treatment corresponding to FIG. 5, the organic solvent was washed with acetone for about 5 minutes in the immersion time in the same manner as in Example 5.

When the substrate after washing with the organic solvent was subjected to in-plane optical retardation measurement with a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., it was confirmed that retardation was present.

Observation of the completed liquid crystal cells with a polarization microscope showed that all the liquid crystal cells were expected, and the filled liquid crystal molecules were oriented in the direction of the lines of magnetic force applied to each substrate. It had a so-called uniform orientation.

The pretilt angle was determined by the magnetic field-capacitance method.
The measured pretilt value is in the range of 5 ° ± 0.1 °, which is far smaller than the variation in pretilt corresponding to the conventional rubbing method.

In order to optically examine the degree of alignment of the liquid crystal molecules, the transmitted light was observed under the crossed Nicols and with the polarization axis of the incident side polarizing plate aligned with the long axis of the filled liquid crystal molecules. The black subduction is about 50 in all liquid crystal cells.
It was extremely good at 0: 1 or more. This level is the highest level that can be reached by the liquid crystal cell corresponding to the conventional rubbing method.

(Example 15) Example 12 was applied except the following points.
A liquid crystal cell was manufactured in substantially the same manner as.

The state of the substrate in this embodiment is as shown in FIG. 1 in the form of a sectional view of the structure, and in this case, 3 is a coupler layer.

A Corning product number 7059, a transparent electrode of indium oxide containing tin in a low alkali glass (hereinafter referred to as IT
Substrate 1 was prepared by depositing O).
However, the main surface 2 of the substrate 1 (FIG. 1) has about 40
00 RPM, 3 minutes, Shin-Etsu Silicone Co.,
Apply silane coupler, γ-glycidoxypropyltriethoxysilane, product number KBE403 with a spinner,
Heat treatment was performed at about 100 ° C. to form the coupler layer 3. Of course, the thickness of the coupler layer 3 is so thin that it cannot be accurately measured even by a Dectak step meter manufactured by Sloan Co., Ltd. Probably 5 nm or less.

Next, the constituent material of the mesogen layer will be described.
4-n-propyl-4'-cyanophenylcyclohexane (Chemical formula 11), a low-molecular liquid crystal obtained from Kanto Chemical Co., Inc.
Was obtained.

Further, 4-acrylic oil oil-4'-butyl-cyclohexylcyclohexane (Chemical formula 7), which is a polymerizable liquid crystal monomer manufactured by Dainippon Ink and Chemicals, Inc., 33.
3% by weight, 4-acrylic oil oil-4'-propylcyclohexylbenzene (Chemical formula 8), 33.3% by weight
And a mixture of 4-acrylic oil oil-4′-heptyldibenzilidine (formula 9), the balance being obtained.

Approximately 70% by weight of the low molecular weight liquid crystal of (Chemical Formula 11),
A new mixture was prepared such that the mixture was about 30% by weight. It exhibits a nematic liquid crystal phase at room temperature. About 1% by weight of benzophenone photopolymerization initiator, product number Irgacure-651, manufactured by Ciba Geigy Co.,
UV absorber, 4- (1-sulfonyl-2-hexyl)-, obtained from Aldrich Chemical Company
About 1.5% by weight of 4 '-(1-oxa-6-hexanor) -transstilbene (Chemical formula 6) was added to obtain a mesogen substance. This mesogenic substance was diluted about 20 times with acetone to obtain a diluted solution.

Further, in FIG. 5, the angle formed by the normal line of the substrate 35 and the magnetic force line is set to about 75 °. After the treatment corresponding to FIG. 5, the organic solvent was washed with acetone for about 5 minutes in the immersion time in the same manner as in Example 5.

When the substrate after washing with the organic solvent was subjected to in-plane optical retardation measurement with a micro birefringence meter manufactured by Oak Manufacturing Co., Ltd., it was confirmed that retardation was present.

Observation of the completed liquid crystal cells with a polarization microscope revealed that all the liquid crystal cells were expected, and the filled liquid crystal molecules were oriented in the direction of the magnetic lines of force applied to each substrate. It had a so-called uniform orientation.

The pretilt angle was determined by the magnetic field-capacitance method.
The measured pretilt value is in the range of 13.9 ° to 14.0 °, which is far smaller than the variation in pretilt corresponding to the conventional rubbing method.

In order to optically examine the degree of alignment of the liquid crystal molecules, the transmitted light was observed under the crossed Nicols and with the polarization axis of the incident side polarization plate aligned with the long axis of the filled liquid crystal molecules. Black subduction is about 53 in all liquid crystal cells
It was extremely good at 0: 1 or more. This level is the highest level that can be reached by the liquid crystal cell corresponding to the conventional rubbing method.

(Example 16) Example 12 is described except for the following points.
A liquid crystal cell was manufactured in substantially the same manner as.

The state of the substrate in this embodiment will be described. The coupler layer or the polar organic resin layer 3 in FIG. 1 is omitted. That is, in FIG. 1, a mesogen layer is directly laminated on a substrate made of Corning, product number 7059, indium oxide transparent electrode containing tin (hereinafter referred to as ITO) deposited on low alkali glass.

Prior to the formation of the mesogen layer, the substrate is thoroughly washed and dried at about 120 ° C., and then the mesogen layer is formed in a short time.

The same evaluation as in Example 12 was carried out on the processed substrate corresponding to FIG. 5 and the liquid crystal cell, and good results were obtained.

[0189]

Industrial Applicability As described above, although mainly related to the alignment method of liquid crystal molecules, this technique is largely related to the production of highly oriented films, which is considered to lead to new functional films. Is of great value.

[Brief description of drawings]

FIG. 1 is a structural cross-sectional view for explaining an embodiment of the present invention.

FIG. 2 is a configuration cross-sectional view for explaining an embodiment of the present invention.

FIG. 3 is a configuration cross-sectional view for explaining an embodiment of the present invention.

FIG. 4 is a sectional view of a configuration for explaining an embodiment of the present invention.

FIG. 5 is a sectional view of a configuration for explaining an embodiment of the present invention.

[Explanation of symbols]

 1 Substrate 2 Substrate Main Surface 3 Coupler Layer 4 Mesogen Layer 5,6 Electromagnet Pole 7 Magnetic Field Line 8 UV Lamp 9 Mesogen Layer 10 Substrate 11, 12 Electromagnet Pole 13 Magnetic Field Line 14 Ultraviolet Lamp 15 Mesogen Layer 16 Substrate 17,18 Electromagnetic Pole 19 Magnetic Lines 20 Ultraviolet Lamp 21 Quartz Glass Substrate 22 ITO Electrode Layer 23 Mesogen Layer 24 ITO Electrode Layer 25 Substrate 26 Voltage Application Terminal 27, 28 Electromagnet Pole 29 Magnetic Line 30 Ultraviolet Lamp 31 Quartz Glass Substrate 32 ITO Electrode Layer 33 Mesogen Layer 34 ITO Electrode layer 35 Substrate 36 Voltage application terminal

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location // C08F 20/12 MLY 7824-4J C08F 20/12 MLY 20/34 MMQ 7824-4J 20/34 MMQ

Claims (18)

[Claims] 1. The substrate is kept at a predetermined temperature such that a mesogen layer formed of a photopolymerization initiator and a polymerizable liquid crystalline monomer formed on a pair of principal surfaces of the substrate is kept in a liquid crystal state, and a desired direction is maintained. While applying a magnetic field, the substrate is simultaneously irradiated with ultraviolet rays to polymerize the monomers to form a polymer layer, and a desired gap is maintained, and the polymer layers are opposed to each other.
A method for manufacturing a liquid crystal cell, which comprises laminating the pair of substrates and filling a liquid crystal in the gap. 2. The substrate is kept at a predetermined temperature such that a mesogen layer formed of a photopolymerization initiator and a polymerizable liquid crystalline monomer formed on a pair of principal surfaces of the substrate is kept in a liquid crystal state, and a desired direction is maintained. While applying a magnetic field and an electric field in another desired direction, at the same time, irradiating the substrate with ultraviolet rays to polymerize the monomers to form a polymer layer and maintain a desired gap. A method for producing a liquid crystal cell, comprising polymer layers facing each other, bonding the pair of substrates to each other, and filling the gap with liquid crystal. 3. The method for producing a liquid crystal cell according to claim 1, wherein the substrate is a substrate through which ultraviolet rays can pass, and the ultraviolet rays are radiated through the substrate. 4. After the polymer layer is formed, the principal surface of the substrate is washed with an organic solvent, the desired gap is maintained, the polymer layers are opposed to each other, and the pair of substrates are bonded to each other. The method for producing a liquid crystal cell according to claim 1, wherein the liquid crystal cell is filled with. 5. The substrate is kept at a predetermined temperature such that a mesogen layer composed of a low-molecular liquid crystal, a photopolymerization initiator and a polymerizable liquid crystalline monomer formed on a pair of substrate main surfaces is kept in a liquid crystal state, While applying a magnetic field in a desired direction, at the same time, the substrate is irradiated with ultraviolet rays to polymerize the monomers to form a polymer layer, and the main surface of the substrate is washed with an organic solvent to maintain a desired gap. A method for manufacturing a liquid crystal cell, characterized in that the polymer layers are opposed to each other, the pair of substrates are bonded to each other, and a liquid crystal is filled in the gap. 6. The substrate is kept at a predetermined temperature such that a mesogen layer composed of a low-molecular liquid crystal, a photopolymerization initiator and a polymerizable liquid crystalline monomer formed on a pair of main surfaces of the substrate is kept in a liquid crystal state, While applying a magnetic field in a desired direction and an electric field in another desired direction, at the same time, the substrate is irradiated with ultraviolet rays to polymerize the monomers to form a polymer layer, and the substrate main surface Is washed with an organic solvent, a desired gap is maintained, the polymer layers are opposed to each other, the pair of substrates are bonded together, and liquid crystal is filled into the gap. 7. The method for producing a liquid crystal cell according to claim 5, wherein the substrate is a substrate through which ultraviolet rays can pass, and the ultraviolet rays are irradiated through the substrate. 8. After forming the polymer layer, the low-molecular liquid crystal is subjected to volatilization treatment, the main surface of the substrate is washed with an organic solvent, and the polymer layers are opposed to each other with a desired gap maintained, and the pair of the 7. The method for manufacturing a liquid crystal cell according to claim 5, wherein substrates are bonded together and liquid crystal is filled in the gaps. 9. A predetermined temperature at which a mesogen layer composed of an ultraviolet absorber, a photopolymerization initiator and a polymerizable liquid crystalline monomer formed on a pair of ultraviolet ray transmitting substrate main surfaces is kept in a liquid crystal state. While holding the substrate and applying a magnetic field in a desired direction, at the same time irradiating the main surface of the substrate with ultraviolet rays through the substrate to polymerize the monomer to form a polymer layer, and the main surface of the substrate is an organic solvent. A method for producing a liquid crystal cell, which comprises: washing with a liquid crystal, maintaining a desired gap between the polymer layers, adhering the pair of substrates to each other, and filling the gap with liquid crystal. 10. A predetermined temperature at which a mesogen layer composed of a UV absorber, a photopolymerization initiator and a polymerizable liquid crystalline monomer formed on a pair of main surfaces of a substrate capable of transmitting ultraviolet rays is kept in a liquid crystal state. While holding the substrate, applying a magnetic field in a desired direction and an electric field in another desired direction, at the same time, irradiating ultraviolet rays to the main surface of the substrate through the substrate to polymerize the monomer and increase the intensity. A molecular layer is formed, the main surface of the substrate is washed with an organic solvent, the desired gap is maintained, the polymer layers are opposed to each other, the pair of substrates are bonded together, and the gap is filled with liquid crystal. A method for manufacturing a characteristic liquid crystal cell. 11. A mesogen layer composed of a low-molecular liquid crystal, an ultraviolet absorber, a photopolymerization initiator, and a polymerizable liquid crystalline monomer formed on a pair of ultraviolet ray transmitting substrate main surfaces is kept in a liquid crystal state. While maintaining the substrate at a predetermined temperature, applying a magnetic field in a desired direction, at the same time, irradiating the main surface of the substrate with ultraviolet rays through the substrate to polymerize the monomers to form a polymer layer. Clean the surface with an organic solvent,
A method for producing a liquid crystal cell, characterized in that the polymer layers are opposed to each other with a desired gap maintained, the pair of substrates are bonded together, and liquid crystal is filled into the gap. 12. A mesogen layer composed of a low-molecular liquid crystal, an ultraviolet absorber, a photopolymerization initiator, and a polymerizable liquid crystalline monomer formed on a pair of ultraviolet ray transmitting substrate main surfaces is kept in a liquid crystal state. While maintaining the substrate at a predetermined temperature, applying a magnetic field in a desired direction and an electric field in another desired direction, at the same time irradiating ultraviolet rays through the substrate to the main surface of the substrate to polymerize the monomer. Then, the polymer layer is formed, the main surface of the substrate is washed with an organic solvent, the desired gap is maintained, the polymer layers are opposed to each other, the pair of substrates are bonded, and the gap is filled with liquid crystal. A method for manufacturing a liquid crystal cell, comprising: 13. The ultraviolet ray is a substantially parallel ultraviolet ray of linearly polarized light in a desired direction.
13. The method for producing a liquid crystal cell according to any one of 6, 9, 10, 11 and 12. 14. The extinction coefficient of a predetermined ultraviolet ray of an ultraviolet absorber is larger than that of a predetermined ultraviolet ray of a photopolymerization initiator by at least two digits, according to any one of claims 9, 10, 11 and 12. A method for producing the described liquid crystal cell. 15. The ultraviolet absorber comprises: 13. The method for manufacturing a liquid crystal cell according to claim 9, 10, 11, or 12. 16. The substrate according to claim 1, wherein the substrate is a flat plate whose main surface is covered with a coupler layer.
13. The method for producing a liquid crystal cell according to any one of 6, 9, 10, 11 and 12. 17. A substrate comprising a flat plate whose main surface is coated with a polar organic resin layer.
13. The method for producing a liquid crystal cell according to any one of 5, 6, 9, 10, 11 and 12. 18. The polymerizable liquid crystal monomer is at least Embedded image Embedded image Embedded image 2. Any one of claims 1 to 3 is included.
13. The method for producing a liquid crystal cell according to any one of 2, 5, 6, 9, 10, 11 or 12.