JPH10153783A - Liquid crystal-oriented film, its manufacture, liquid crystal display device using the same and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a uniform and thin oriented film to be used in a liquid crystal display panel with a high efficiency without necessitating a rubbing treatment, by using a molecular absorption method, thereby forming the liquid crystal-oriented film, and a method for manufacturing the display panel using the same. SOLUTION: A positive resist containing a blended photosensing agent of a naphthoquinone diazido-system consisting essentially of a novolak resin as a resin inductive to energy beams (a photosensitive film, for example), is applied in a thickness of 0.1 to 0.2μm on the surface of a glass substrate 1, on which a transparent electrode is formed, and dried to form a photosensitive film. Next, the film is exposed with ultraviolet rays (365nm) by using a mask 3, and moisture in air is allowed to react with the resist at an exposure part 2 to form a -COOH radical. Then, CH3 (CH2 )18 SiCl3 is brought to dehydrochlorination reaction to form a chemical absorption monomolecular film 6 including carbon chains 8 of the monomolecular film to be a liquid crystal-oriented film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to an image display device using a liquid crystal and a method of manufacturing the same. More specifically, the present invention relates to a liquid crystal alignment film used for a flat display panel using a liquid crystal for displaying a television (TV) image, a computer image, and the like, a method for manufacturing the same, a liquid crystal display device using the same, and a method for manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, a color liquid crystal display panel has a liquid crystal alignment film formed by spin-coating a polyvinyl alcohol or polyimide solution with a spinner or the like between two substrates having opposed electrodes arranged in a matrix. A device in which a liquid crystal is sealed via a liquid crystal display is generally used.

For example, a thin-film transistor (TFT) array having pixel electrodes formed on a first glass substrate in advance, and a plurality of red-blue-green color filters are formed on a second glass substrate. After forming a film by applying a polyvinyl alcohol or polyimide solution to each electrode surface using a spinner, forming a film, then rubbing to form a liquid crystal alignment film, and via a spacer Liquid crystal (twisted nematic (TN), etc.) after bonding and assembling so as to face each other at an arbitrary gap
Is injected to form a panel structure, polarizing plates are installed on the front and back of the panel, and T
A device that operates an FT to display a color image has been proposed.

[0004]

However, in the conventional method of forming an alignment film, polyvinyl alcohol or polyimide is dissolved in an organic solvent, coated by a spin coating method or the like, and then rubbed with a felt cloth or the like. Because of the use of such a method, there is a major problem that the uniformity of the alignment film is poor in a surface step portion or a large area panel (for example, a 14-inch display). Further, rubbing causes defects in the TFTs, and dust generated by rubbing also causes display defects.

According to the present invention, there is provided a method of forming an alignment film used in a liquid crystal display panel with high efficiency, uniformity and thinness without the need for a conventional rubbing treatment. It is an object of the present invention to provide a method for manufacturing a display panel.

[0006]

In order to achieve the above object, the first liquid crystal alignment film of the present invention comprises a silane surfactant having a linear carbon chain and Si formed on a predetermined substrate surface. A film that is chemically adsorbed through an energy beam-sensitive resin film that generates a functional group containing active hydrogen by irradiated energy beam irradiation, and wherein the linear carbon chain is oriented in a specific direction. It is characterized by.

In the liquid crystal alignment film, it is preferable that a film made of a surfactant is fixed to the energy beam sensitive resin film via a conjugate bond on the substrate surface in a streak pattern. Thereby, a liquid crystal alignment film having excellent uniaxial alignment can be obtained.

In the liquid crystal alignment film, it is preferable that the fixed film of the surfactant is fixed to an energy beam-sensitive resin film via a film having a siloxane bond. Thereby, peeling resistance,
That is, the adhesiveness is advantageously improved.

In the liquid crystal alignment film, it is preferable that the silane-based surfactant is a chlorosilane-based surfactant containing a linear hydrocarbon group and a chlorosilyl group.
Examples of the silane-based surfactant include a chlorosilyl group (SiCl), an alkoxysilyl group (SiOA, A is an alkyl group) and an isocyanatesilyl group (SiNCO) at the molecular terminal.
In particular, when a chlorosilane-based surfactant is used, an alignment film covalently bonded to a substrate via a siloxane bond can be efficiently and easily formed.

In the liquid crystal alignment film, it is preferable that at least a part of the linear hydrocarbon group of the chlorosilane-based surfactant is substituted with a fluorine atom. As a result, the critical surface energy of the alignment film can be reduced, and the response performance of the liquid crystal can be improved, which is advantageous.

In the liquid crystal alignment film, it is preferable to use a mixture of a plurality of chlorosilane-based surfactants having different molecular lengths as a chlorosilane-based surfactant containing a linear hydrocarbon group and a chlorosilyl group. This makes it possible to form a film having an uneven surface at the molecular level, and to provide a liquid crystal alignment film capable of controlling the alignment angle (pretilt angle) of the liquid crystal at the molecular level.

The second liquid crystal alignment film of the present invention is a monomolecular film formed on the surface of a substrate on which a desired electrode is formed, and the molecules constituting the film have a desired inclination. Further, it is characterized in that it is fixed to one end of the substrate surface at one end in a specific direction.

In the liquid crystal alignment film, the desired inclination of the molecules is determined by immobilizing the molecules constituting the coating on the substrate by covalent bonds, washing the molecules with an organic solvent, and further raising the substrate in a desired direction. It is preferably formed by cutting.

In the liquid crystal alignment film, it is preferable that molecules constituting the film include a carbon chain or a siloxane bond chain. This is advantageous because the orientation of the coating can be improved.

Further, in the liquid crystal alignment film, it is preferable that a part of the carbon in the carbon chain has optical activity. This is more convenient for improving the orientation of the coating by light irradiation.

The liquid crystal alignment film preferably contains Si at both ends of molecules constituting the film.
This is advantageous because the coating can be firmly bonded to the substrate. Further, in the liquid crystal alignment film, it is preferable that molecules constituting the film are formed by mixing a plurality of types of chemisorbed molecules having different molecular lengths, and the fixed film is uneven at the molecular length level. This is convenient for controlling the tilt angle of the liquid crystal.

The third liquid crystal alignment film of the present invention is a monomolecular film formed on the surface of the substrate on which a desired electrode is formed, and the molecules constituting the film have carbon chains or siloxane bonding chains. Wherein at least a part of the carbon chain or the siloxane bond chain contains at least one functional group for controlling the surface energy of the coating. By preparing such a liquid crystal alignment film, it is possible to control the pretilt angle of the injected liquid crystal and control the liquid crystal in an arbitrary direction by controlling the critical surface energy of the alignment film without using the conventional rubbing. An alignment film having a function of enabling alignment can be provided.

In the liquid crystal alignment film, a plurality of types of silicon-based surfactants having different critical surface energies are mixed and used as molecules constituting the coating, and the fixed coating is controlled to have a desired critical surface energy value. It is preferred that This is convenient for controlling the pretilt angle of the liquid crystal.

In the liquid crystal alignment film, a carbon trifluoride group (-C
F ₃ ), methyl group (—CH ₃ ), vinyl group (—CH−CH)
_2), an allyl group (-CH = CH-), an acetylene group (carbon - triple bond of carbon), a phenyl group (-C ₆ H _5), an aryl group (-C ₆ H ₄ -), a halogen atom, an alkoxy A group (—OR; R represents an alkyl group;
Are preferred. ), Cyano group (-C
N), an amino group (—NH ₂ ), a hydroxyl group (—OH), a carbonyl group (＝ CO), an ester group (—COO—) and a carboxyl group (—COOH). preferable. This makes it possible to easily control the critical surface energy.

In the liquid crystal alignment film, it is preferable to include Si at the terminal of the molecule constituting the film. This makes it very easy to fix molecules to the substrate surface.

In the liquid crystal alignment film, it is preferable to control the critical surface energy of the coating to a desired value between 15 mN / m and 56 mN / m. This allows
The pretilt angle of the liquid crystal to be injected can be arbitrarily controlled within the range of 0 to 90 degrees.

Next, in the first method of manufacturing a liquid crystal alignment film of the present invention, active hydrogen is directly or indirectly applied via an arbitrary thin film to an predetermined substrate surface on which an electrode is formed by an energy beam. A step of applying and forming an energy beam-sensitive resin film for generating a functional group, a step of irradiating the surface of the resin film with an energy beam in an arbitrary pattern, and a step of forming the irradiated resin film into a linear carbon chain. And Si
After contacting with a chemisorption solution containing a silane-based surfactant having a group, the resin film is washed with a solvent that does not dissolve, thereby selectively irradiating the irradiated portion with a monomolecular film made of the surfactant. Is formed in one layer, and a linear carbon chain in the surfactant molecule is oriented and fixed.

In the above method, it is preferable that the energy beam is at least one selected from an electron beam, an X-ray, and light having a wavelength of 100 nm to 1 μm. It is particularly preferable to use ultraviolet rays.

In the above method, the chemical adsorption liquid may be
It is preferable to include a chlorosilane-based surfactant containing at least a linear carbon chain and a chlorosilyl group, and a solvent that does not damage the energy beam-sensitive resin film. This is advantageous because the underlying photosensitive thin film is not damaged.

In the above method, it is preferable that the energy beam is at least one light selected from ultraviolet light, visible light and infrared light, and the resin film sensitive to the energy beam is a photosensitive resin film. Thereby, the production of the liquid crystal alignment film becomes extremely easy.

In the above method, the photosensitive resin film is
It is preferable that the film is a polymer film or a monomer film containing at least one organic group selected from the groups represented by the formulas (1), (2) and (3). Use of these polymers is advantageous because ultraviolet light can be used as an energy beam.

Further, when a specific liquid crystal, for example, a nematic liquid crystal or a ferroelectric liquid crystal is combined and incorporated into a surfactant to be formed by adsorption, an alignment film having extremely excellent alignment controllability can be obtained.

In the above method, it is preferable to use a solvent containing a carbon fluoride group as the non-aqueous solvent. This is advantageous because the photosensitive base material is not damaged.

According to a second method for producing a liquid crystal alignment film of the present invention, the substrate on which the electrodes are formed is brought into contact with a chemical adsorption solution, and the surfactant molecules in the adsorption solution are chemically reacted with the substrate surface. A single molecule comprising a step of binding and fixing the activator molecule to the substrate surface at one end, and a step of washing the substrate with an organic solvent, further erecting the substrate in a desired direction, draining the liquid, and orienting the fixed molecule in the draining direction. This is a method for producing a film-like liquid crystal alignment film.

In the above-mentioned method, after the fixed molecules are oriented, they are further exposed to light polarized in a desired direction through a polarizing plate to specify the direction of the surfactant molecules in a state having a desired inclination. It is preferable to include a step of aligning in the direction of.

In the above method, it is preferable to use a silane-based surfactant containing a linear hydrocarbon group or a siloxane bonding chain and a chlorosilyl group, or an alkoxysilyl group or an isocyanatesilyl group. This makes it possible to efficiently produce a monomolecular liquid crystal alignment film.

In the above method, a silane-based surfactant containing a linear hydrocarbon group or a siloxane-bonded chain and a chlorosilyl group, an alkoxysilyl group or an isocyanatesilyl group may be used as a silane-based surfactant having different molecular lengths. It is preferable to use a mixture of activators. This is convenient for controlling the orientation angle of the molecules adsorbed and fixed, that is, the pretilt angle of the injected liquid crystal.

In the above method, it is preferable that some carbons of the hydrocarbon group have optical activity. Thereby, the orientation can be efficiently controlled at the time of re-alignment by light irradiation, which is convenient.

Further in the method is a hydrocarbon group or a terminal halogen atom or a methyl group of the siloxane bond chain (-CH _3), phenyl group (-C ₆ H _5), a cyano group (-CN), hydroxyl group (- OH), carboxyl group (-C
OOH), preferably it contains an amino group (-NH _2), or tri fluorocarbon group (-CF _3). Thereby, the surface energy of the coating can be controlled.

In the above method, the light used for exposure is 436 nm, 405 nm, 365 nm, 254 nm.
And at least one wavelength selected from 248 nm and 248 nm. The light used for exposure may be any light having a wavelength that is absorbed by the film, but the use of the light having the wavelength is convenient because most of the film absorbs the light.

In the above method, a silane-based surfactant containing a linear hydrocarbon group or a siloxane bonding chain and a chlorosilyl or isocyanatesilyl group is used as the surfactant, and water is not used as a washing organic solvent. It is preferable to use a non-aqueous organic solvent. The use of these is convenient for completely removing the unreacted surfactant. At this time, a photosensitive reactive group such as a vinyl group (> C = C <) or an acetylene bonding group (a carbon-carbon triple bonding group) is incorporated into the linear hydrocarbon group or the siloxane bonding chain, respectively, and at the time of photo-alignment. When the photosensitive group is photoreacted and crosslinked or polymerized, the heat resistance of the resulting monomolecular film can be improved.

In the above method, a solvent containing an alkyl group, a carbon fluoride group, a carbon chloride group or a siloxane group is preferably used as the non-aqueous organic solvent. When this is used, dehydration is extremely easy and efficiency is high.

In the above method, before the step of fixing the surfactant molecules at one end, a coating containing a large number of SiO groups is formed, and a monomolecular coating is formed through this coating. preferable. Thereby, a film with stable quality can be obtained.

According to a third method for producing a liquid crystal alignment film of the present invention, the substrate on which the electrode is formed is formed by bonding a carbon chain or a siloxane bonding chain to at least a part of the carbon chain or the siloxane bonding chain. Contact with a chemical adsorption solution prepared using a silane-based surfactant containing at least one functional group for controlling the surfactant molecule to chemically react the surfactant molecules in the adsorption solution with the substrate surface. Is fixed to the substrate surface at one end.

In the above method, a linear carbon chain or a siloxane bonding chain and a chlorosilyl group are used as surfactants.
Alternatively, a silane-based surfactant containing an alkoxysilyl group or an isocyanate silyl group is preferably used.

In the above method, it is preferable to use a mixture of a plurality of types of silicon-based surfactants having different critical surface energies. This allows
The critical surface energy of the coating can be more finely controlled.

In the above-mentioned method, 3 carbon atoms may be added to the terminal or main chain of the carbon chain or the siloxane bonding chain, or to the side chain.
Fluorocarbon group (-CF _3), a methyl group (-CH _3), a vinyl group (-CH = CH _2), allyl (-CH = CH
-), an acetylene group (carbon - triple bond of carbon), a phenyl group (-C ₆ H _5), an aryl group (-C ₆ H ₄ -), a halogen atom, an alkoxy group (-OR; with R is an alkyl group Represents, in particular, an alkyl group having 1 to 3 carbon atoms.), A cyano group (—CN), an amino group (—NH ₂ ),
It is preferable to incorporate at least one organic group selected from a hydroxyl group (—OH), a carbonyl group (＝ CO), an ester group (—COO—), and a carboxyl group (—COOH). This also allows fine control of the critical surface energy of the coating.

In the above method, after the step of binding and fixing the surfactant molecules to the surface of the substrate at one end, the substrate is washed with an organic solvent, the substrate is set up in a desired direction, and the liquid is drained. Preferably, a step of orienting the fixed molecules is performed. Thereby, the tilt direction of the injected liquid crystal can also be controlled.

In the above method, it is preferable that after performing the step of aligning the molecules, the molecules are further exposed through a polarizing film to reorient the aligned molecules in a desired direction. Thereby, the alignment performance can be further improved.

In the above method, a silane-based surfactant containing a linear carbon chain or a siloxane bonding chain and a chlorosilyl group or an isocyanatesilyl group is used as a surfactant, and a water-free non-aqueous surfactant is used as a washing organic solvent. It is preferable to use the organic solvent of Thus, a monomolecular liquid crystal alignment film having fewer defects can be provided.

At this time, if a solvent containing an alkyl group, a fluorocarbon group, a carbon chloride group or a siloxane group is used as the non-aqueous organic solvent, it is convenient to drain the liquid. Further, in the above method, before the step of fixing the surfactant molecules at one end, a step of forming a film containing a large number of SiO groups is performed, and a monomolecular film-like film is formed through the film. preferable. Thereby, a higher-density monomolecular liquid crystal alignment film can be provided.

Next, the first liquid crystal display device of the present invention is:
A liquid crystal display device in which a pair of substrates, an electrode on the surface thereof, and an alignment film on the surface are formed in this order, and a liquid crystal is sandwiched between the two opposing electrodes via the alignment film, At least one alignment film, a silane-based surfactant having a linear carbon chain is chemically adsorbed via an energy beam-sensitive coating that generates a functional group containing active hydrogen by energy beam irradiation, and The coating is characterized in that the straight carbon chains are oriented in a specific direction.

The second liquid crystal display device of the present invention is a monomolecular film made of a silane-based surfactant having a linear carbon chain or a siloxane bond, and the molecules constituting the film are formed of a monomolecular film. A coating having a desired inclination and aligned and fixed at one end to the substrate surface in a specific direction is provided on at least one of the substrate surfaces on which two facing electrodes are formed as an alignment film for liquid crystal. It is formed directly on the electrode side surface or indirectly via another coating, and has a configuration in which liquid crystal is sandwiched between the two opposed electrodes via the alignment film.

In the liquid crystal display device, it is preferable that the coating is formed as an alignment film on the surface of the substrate on which the two electrodes facing each other are formed. This is convenient for improving the alignment regulating force for the injected liquid crystal.

In the liquid crystal display device, it is preferable that the coating on the substrate surface includes a plurality of portions having different pattern-like orientation directions. Thereby, a liquid crystal display device with multi-domain alignment can be easily provided.

Further, in the liquid crystal display device, it is preferable to use an IPS method (an in-plane switch method or a lateral drive method) in which opposing electrodes are formed on one substrate surface. This is advantageous in that the viewing angle can be greatly improved.

A third liquid crystal display device according to the present invention includes a carbon chain or a siloxane bonding chain, and at least a part of the carbon chain or the siloxane bonding chain includes at least one functional group for controlling the surface energy of the coating. Is formed on the electrode side surface of at least one of the substrate surfaces on which two opposed electrodes are formed as an alignment film for liquid crystal, directly or indirectly via another film. And the liquid crystal is sandwiched between the two opposing electrodes via the alignment film. By manufacturing such a liquid crystal display device, the pretilt angle of the injected liquid crystal can be controlled and the liquid crystal can be moved in an arbitrary direction by controlling the critical surface energy of the alignment film without using the conventional rubbing. An aligned liquid crystal display device can be provided.

In the liquid crystal display device, a liquid crystal display device having a higher contrast can be provided by forming the coating as an alignment film on the surface of the substrate on which the two electrodes facing each other are formed.

In the liquid crystal display device, it is convenient to form a plurality of portions having different pattern orientation directions in the coating on the substrate surface, since the display viewing angle can be greatly improved.

Further, in the liquid crystal display device, the present invention can be effectively used for an in-plane switch (IPS) type display element in which opposing electrodes are formed on one substrate surface.

Next, the first method of manufacturing a liquid crystal display device according to the present invention will be described.
Coating and forming an energy beam-sensitive resin film for generating a functional group containing active hydrogen by an energy beam directly or indirectly through an arbitrary thin film on a first substrate having an electrode group of Irradiating the surface of the resin film with an energy beam in an arbitrary pattern, and contacting the irradiated substrate with the resin film with a chemisorption liquid containing a silane-based surfactant having a linear carbon chain and Si. Thereafter, by washing with a solvent that does not dissolve the resin film, one layer of a monomolecular film composed of the surfactant is selectively formed on the irradiated portion, and the alignment of the linear carbon chains is fixed. And a first substrate having the first electrode group and a second substrate having a second electrode or an electrode group.
The method includes a step of positioning and bonding and fixing a predetermined gap so that the electrodes face each other, and a step of injecting a predetermined liquid crystal between the first and second substrates.

A second method of manufacturing a liquid crystal display device according to the present invention is a method of manufacturing a liquid crystal display device, wherein a first substrate having a first electrode group placed in a matrix is formed directly or after forming an arbitrary thin film. A step of chemically reacting the surfactant molecules in the adsorbent with the substrate surface and bonding and fixing the surfactant molecules to the substrate surface at one end, and further erecting the substrate in a desired direction after washing with an organic solvent. A step of aligning the fixed molecules in a draining direction by performing liquid draining, and further exposing the surface of the surfactant molecule to a desired inclination by exposing to light polarized in a desired direction through a polarizing plate. Aligning in a specific direction in a state where the first electrode group
A substrate and a second substrate, or a second substrate having a second electrode or electrode group, positioning and bonding and fixing the electrode surface inside while maintaining a predetermined gap; and The method includes a step of injecting a predetermined liquid crystal between the second substrates.

In the above method, the step of aligning the direction of the bound surfactant molecules in a specific direction with a desired inclination by exposing to light polarized in a desired direction through a polarizing plate is performed. When the step of exposing the polarizing plate with a patterned mask is performed a plurality of times, a so-called multi-domain liquid crystal display is provided in which a plurality of portions having different patterned orientations are provided in an alignment film in the same plane. It is convenient in providing the device.

In a third method of manufacturing a liquid crystal display device according to the present invention, a first substrate having a first electrode group mounted in a matrix is formed directly or after forming an arbitrary thin film, and then a carbon chain is formed. Or contact with a chemisorption solution prepared using a silane-based surfactant containing a siloxane-bonded chain and at least a part of the carbon chain or the siloxane-bonded chain containing at least one functional group that controls the surface energy of the coating. A step of chemically reacting the surfactant molecules in the adsorbent with the substrate surface to bond and fix the surfactant molecules at one end to the substrate surface, and after washing with an organic solvent, further raising the substrate in a desired direction to form a liquid. Slicing and orienting the fixed molecules in a draining direction, and a first substrate and a second substrate having the first electrode group, or a second electrode having a second electrode or electrode group. A step of aligning and bonding the plate while keeping a predetermined gap with the electrode surface inside, and a step of injecting a predetermined liquid crystal between the first and second substrates. Things. According to this method, a liquid crystal display device can be manufactured efficiently.

In the above method, after the step of orienting the fixed molecule, the surface of the surfactant molecule has a desired inclination by further exposing through a polarizing plate with light polarized in a desired direction. It is preferable to perform a process of aligning in a specific direction in the state. Thus, a liquid crystal display device having excellent alignment characteristics can be realized.

Further, in the above method, a step of exposing the bonded surfactant molecules to a specific direction with a desired inclination by exposing to light having a desired direction through a polarizing plate. In the liquid crystal display device having a multi-domain orientation, a plurality of steps of overlapping and exposing a patterned mask on the polarizing plate are performed, and a plurality of portions having different patterned orientation directions are provided in an orientation film in the same plane. Can be provided.

[0062]

BEST MODE FOR CARRYING OUT THE INVENTION A first liquid crystal alignment film according to an embodiment of the present invention is formed on a predetermined substrate surface on which an electrode is formed.
Directly or indirectly through an arbitrary thin film, applying and forming an energy beam-sensitive resin film for generating a functional group containing active hydrogen by an energy beam; and forming an energy beam on the surface of the resin film in an arbitrary pattern. And contacting the irradiated resin film with a chemisorption solution containing a silane-based surfactant having a linear carbon chain and a Si group, followed by washing with a solvent that does not dissolve the resin film Thereby, a monomolecular film composed of the surfactant is selectively formed in one layer on the irradiated portion, and the linear carbon chain in the surfactant molecule is oriented and fixed to produce a monolayer. I do.

Further, the first liquid crystal display device according to one embodiment of the present invention is a method in which a thin film is directly or arbitrarily formed on a first substrate having a first electrode group mounted in a matrix. Indirectly through the step of applying and forming an energy beam-sensitive resin film that generates a functional group containing active hydrogen by an energy beam, and the step of irradiating the surface of the resin film with an energy beam in an arbitrary pattern; The irradiated substrate with a resin film is converted into a linear carbon chain and S
After contacting with a chemical adsorption solution containing a silane-based surfactant having i, the monomolecular film composed of the surfactant is selectively applied to the irradiated portion by washing with a solvent that does not dissolve the resin film. Forming a single layer and fixing the orientation of the linear carbon chain; and forming a first electrode group having the first electrode group.
Bonding and fixing a substrate and a second substrate having a second electrode or an electrode group while maintaining a predetermined gap so that the respective electrodes face each other; and bonding and fixing the first and second substrates. It is manufactured using a process of injecting a predetermined liquid crystal during the process.

The second liquid crystal alignment film according to one embodiment of the present invention comprises the steps of: bringing at least the substrate on which the electrodes are formed into contact with a chemical adsorption solution to cause a chemical reaction between the surfactant molecules in the adsorption solution and the substrate surface; And fixing the surfactant molecules to the substrate surface at one end, and after washing with an organic solvent, further raising the substrate in a desired direction to perform liquid drainage, and primary aligning the fixed molecules in the liquid drainage direction. And a step of exposing the surfactant molecules to a specific direction with a desired inclination by exposing to light polarized in a desired direction through a polarizing plate.

Further, the second liquid crystal display device according to one embodiment of the present invention comprises a method in which at least a first substrate having a first electrode group previously mounted in a matrix is directly or arbitrary thin film-formed. After the formation, a step of contacting the surfactant molecule in the adsorption solution with the chemical adsorption solution to chemically react the surfactant molecule with the substrate surface and bonding and fixing the surfactant molecule to the substrate surface at one end, and further desired after washing with an organic solvent The substrate is set up in the direction of drainage to perform liquid drainage, and the step of aligning the fixed molecules in the liquid drainage direction, and further exposing the surfactant molecules by light polarized in a desired direction through a polarizing plate. Aligning the direction to a specific direction with a desired inclination, and placing the first substrate having the first electrode group and the second substrate having the second electrode or the electrode group with the electrode surface inside. While maintaining the specified gap A step of bonding and fixing to Align, prepared in the step of injecting a predetermined liquid crystal between the first and second substrates.

A third liquid crystal alignment film according to an embodiment of the present invention includes a substrate on which an electrode is formed, at least including a carbon chain or a siloxane bond, and at least a part of the carbon or siloxane bond. The silane-based surfactant containing at least one functional group that controls the surface energy of the coating is brought into contact with a chemical adsorption solution prepared by using a silane-based surfactant to chemically react surfactant molecules in the adsorption solution with the substrate surface. It is manufactured using a process in which surfactant molecules are bonded and fixed to the substrate surface at one end.

In a third liquid crystal display device according to an embodiment of the present invention, a first substrate having a first electrode group mounted in a matrix is formed directly or in an arbitrary thin film. Then, a chemical compound prepared using a silane-based surfactant containing a carbon chain or a siloxane-bonded chain, wherein at least a part of the carbon chain or the siloxane-bonded chain contains at least one functional group that controls the surface energy of the film. A step of causing the surfactant molecules in the adsorbent to come into contact with the adsorbent to cause a chemical reaction with the substrate surface to bond and fix the surfactant molecules at one end to the substrate surface; Erecting the liquid and orienting the fixed molecules in a liquid draining direction; and providing a first substrate and a second substrate having the first electrode group, or a second electrode or an electrode group. A step of aligning and bonding the second substrate with the electrode surface inside while maintaining a predetermined gap, and a step of injecting a predetermined liquid crystal between the first and second substrates. Manufacturing.

[0068]

The present invention will be described more specifically with reference to the following examples. (Example 1) First, as shown in FIG. 1, on a surface of a glass substrate 1 on which a transparent electrode was formed, a novolak resin as a main component was used as an energy beam-sensitive resin (in this case, a photosensitive resin). A positive resist containing a naphthoquinonediazide-based photosensitizer containing a group represented by the formula (Formula 1) (for example, OFPR800 or OFPR5000 manufactured by Tokyo Ohka, or AZ1400 or AZ5200 manufactured by Shipley Co., Ltd., or a single molecule composed of a monomer containing a naphthoquinonediazide group) (A film may be used) to a thickness of 0.1 to 0.2 μm and dried to form a photosensitive film 2. Next, using a mask 3 having a desired pattern, ultraviolet rays (365 nm) are used at 100 mJ / c.
Exposure of about m ² was performed. Then, in the exposure unit 2 ',
The moisture in the air reacted with the resist, and the reaction represented by the following formula (Formula 4) proceeded.

[0069]

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Here, since the —COOH group generated by the exposure contains active hydrogen, it condenses with the —SiCl group (dehydrochlorination reaction).
I do. Therefore, as a silane-based surfactant containing a linear hydrocarbon group and Si (hereinafter, referred to as a chemisorbed compound),
Using CH ₃ (CH ₂ ) ₁₈ SiCl ₃ , a chemical adsorption solution was prepared by dissolving it in a non-aqueous solvent at a concentration of about 1% by weight. As a non-aqueous solvent, an Aflud (available from Asahi Glass, a fluorinated solvent) solution was used. Since this solvent is inactive with respect to the positive resist, the solvent does not damage the resist film even when contacted. The solution thus prepared was used as an adsorption solution, and the exposed substrate 4 was immersed in the adsorption solution for about 5 minutes in a dry atmosphere (at a relative humidity of 30% or less). Thereafter, the solution is taken out of the solution and washed with a fluorine-based non-aqueous solvent (for example, Fluorinert PF5080 (trade name of 3M)). Since this solvent is also inactive with respect to the positive resist, the resist film is damaged even if contacted. And the exposed portion of the substrate surface is-
Since a large number of COOH (carboxyl groups) 5 are contained (FIG. 2; FIG. 2 is an enlarged view of part A in FIG. 1), the SiCl groups of the substance containing a hydrocarbon group and a chlorosilyl group and the carboxyl groups are removed. Hydrochloric acid reaction occurs, selectively in the exposed area,
The bond of the following formula (Formula 5) was produced. The line width and the pitch were 0.3 μm.

[0071]

Embedded image

With the above processing, a film thickness of about 25 angstroms (2.5 nm) is obtained in a state where the chemically adsorbed monomolecular film 6 containing hydrocarbons is selectively chemically bonded via siloxane covalent bonds to the exposed portions. And the treated part became lipophilic. At this time, the linear carbon chains in the chemisorption film were oriented almost perpendicular to the substrate (FIG. 3, where FIG. 3 is an enlarged view of a portion A in FIG. 1). Further, the critical surface energy of the chemisorption film at this time was 20 mN / m.

Then, a liquid crystal cell having a 20 micron gap was assembled by using two substrates in this state and combining them so that the chemisorption films faced each other.
(4792; manufactured by Merck & Co.) was injected to confirm the alignment state. Then, it was confirmed that the injected liquid crystal molecules were aligned almost perpendicularly to the substrate along the chemisorbed molecules. That is, the monomolecular film exhibited a vertical alignment effect on the liquid crystal. At this time, the liquid crystal did not align and became random because the monomolecular film was not formed in the unexposed portion. That is, when the liquid crystal comes into contact with the substrate on which such an alignment film is formed, the liquid crystal molecules 7 partially enter the gaps between the long carbon chains 8 of the monomolecular adsorption film as shown in FIG. Was controlled. On the other hand, in a portion having no monomolecular film, that is, in a portion which was not exposed, such liquid crystal molecules 7 'were not aligned and aligned because there was no such alignment regulating force.

Here, instead of the above-mentioned surfactant which is a chemisorbed compound, plural kinds of silane-based surfactants mixed at a predetermined ratio (for example, two kinds of silane-based surfactants having different linear carbon chain lengths) are used. ) Is mixed and chemisorbed at the same time, voids at the molecular level are generated in the monomolecular film, and the liquid crystal molecules are aligned along the gap. Therefore, it has been confirmed that the orientation angle of the liquid crystal can be controlled by changing the composition. Was. That is, a portion of a long linear carbon chain is an arbitrary substituent and the other end is a silane-based surfactant having a trichlorosilyl group, and a portion of a short carbon chain is an arbitrary substituent and the other end is a trichlorosilyl group. It was also possible to change the orientation characteristics by mixing the silane-based surfactants in a predetermined ratio and forming an adsorption.

Further, a silane-based surfactant containing a polymerizable group having a liquid crystal molecule similar to the liquid crystal encapsulated in a part of the substituent (eg, a nematic liquid crystal part) and a silane having a short carbon chain and a polymerizable group. When the system surfactants were mixed at a predetermined ratio, adsorption was formed and polymerization was performed in the same manner as in the above method, an alignment film having particularly excellent alignment characteristics with respect to the specific liquid crystal to be sealed was obtained. In particular, when the liquid crystal-like molecules to be encapsulated are ferroelectric liquid crystals, if a silane-based surfactant having a ferroelectric liquid crystal part and a silane-based surfactant having a short carbon chain are adsorbed and formed at a predetermined ratio, the response will be improved. A monomolecular adsorption film-like alignment film with excellent speed was produced. As the ferroelectric liquid crystal, an azomethine-based, azoxy-based, or ester-based liquid crystal could be used.

As the material for chemical adsorption, if a group having a binding property to an —OH group (for example, chlorosilyl group, isocyanatesilyl group, alkoxysilyl group, etc.) is contained, the silane shown in Example 1 can be used. It is not limited to a surfactant.

For example, a silane surfactant CF _3- (C) containing F (fluorine) in a part of a linear hydrocarbon chain
_{H 2) m -C = C- (} CH 2) n -SiCl 3 (m: 0~8 integer.
n: an integer of about 10 to 25 is easiest to treat) or CF _3- (CF ₂ ) _p- (CH ₂ ) _m -C = C- (CH ₂ ) _n -SiCl
₃ (p: an integer of 0 to 7; m: an integer of 0 to 4; n: an integer of 1 to 1
Even when 8) and the like were used, a monomolecular adsorption film having an orientation effect could be produced. The critical surface energy of the chemically adsorbed film when CF _3- (CH ₂ ) _m -C = C- (CH ₂ ) _n -SiCl ₃ is used is 15 m
_{N / m, CF 3 - (} CF 2) p - (CH 2) m -C = C- (CH 2) n -S
The critical surface energy of the chemically adsorbed film when iCl ₃ was used was 8 mN / m. In particular, when F atoms were introduced, the surface energy of the alignment film could be reduced and the response characteristics of the liquid crystal could be improved. In addition, the critical surface energy of the portion (resin surface) where there is no chemical adsorption film (monomolecular film) was 25 mN / m.

In addition to the novolak resist containing naphthoquinonediazide, any resist (polymer film) or surfactant (monomer film) having a functional group capable of generating active hydrogen upon irradiation with various energy beams can be used. is there.

For example, a polymer or monomer of the following formula (Chemical Formula 6) containing the group of the above Formula (Chemical Formula 2), a polymer or monomer of the following Formula (Chemical Formula 7) containing the group of the above Formula (Chemical Formula 3) can be used. .

[0080]

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[0081]

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Here, the above-mentioned formula (Chemical Formula 2) reacts with a decarboxylation reaction by ultraviolet rays and further reacts with moisture in the air to form an amino group containing active hydrogen as shown below. Equation (Formula 8) proceeds.

[0083]

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On the other hand, the above formula (Chemical Formula 3) is decomposed by ultraviolet rays, and the following reaction formula (Chemical Formula 9) for generating the following sulfonic acid group containing active hydrogen proceeds.

[0085]

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Further, in the above embodiment, the hydrocarbon-based
CH as surfactant_Three(CH_Two)₁₈SiCl_ThreeUsing
However, in addition to the above, compounds of the following formulas can be used.
Was. CH_Three(CH_Two)_nSiCl_Three (N is an integer and preferably 7 to 24
Good. ) CH_Three(CH_Two)_pSi (CH_Three)_Two(CH_Two)_qSiCl
_Three(P and q are preferably integers of 0 to 10.) CH_ThreeCOO (CH_Two)_mSiCl_Three (M is an integer of 7 to 2
4 is preferred. In addition, instead of hydrocarbon surfactants, fluorocarbons
-Based surfactant, for example, CF_Three(CF_Two)₇(CH_Two)_TwoS
iCl_Three, CF_ThreeCH_TwoO (CH_Two)_FifteenSiCl_Three, CF
_Three(CH_Two)_TwoSi (CH_Three)_Two(CH_Two)_FifteenSiCl_Three, F
(CF_Two)_Four(CH_Two) _TwoSi (CH_Three)_Two(CH_Two)₉SiC
l_Three, F (CF_Two)₈(CH_Two)_TwoSi (CH_Three)_Two(CH_Two)
₉SiCl_Three, CF_ThreeCOO (CH_Two)_FifteenSiCl_Three, CF_Three
(CF_Two)_Five(CH_Two)_TwoSiCl_Three Etc. were available.

(Example 1-2) In Example 1, after the entire surface exposure, a linear hydrocarbon group containing one functional group for controlling the surface energy of the film and Si as a silane-based surfactant were added. CH ₃ (CH ₂ ) ₁₄ SiCl ₃ containing
The same experiment was conducted except that and NC (CH ₂ ) ₁₄ SiCl ₃ (used in a molar ratio of 1: 1) were used.

As a result, the state in which the chemically adsorbed monomolecular film formed by the reaction of the chlorosilane-based surfactant is selectively chemically bonded via a siloxane covalent bond to the hydroxyl group formed on the substrate surface by exposure. Was formed into a monomolecular film with a thickness of about 1.5 nm. At this time, the critical surface energy of the chemisorption film was about 27 mN / m.

Further, using two substrates in this state, a liquid crystal cell having a 20-micron gap was assembled so as to be antiparallel aligned by combining the chemical adsorption films to face each other, and a nematic liquid crystal (ZLI4792; manufactured by Merck) was injected. When the alignment state of the portion where the monomolecular film was formed was confirmed, the injected liquid crystal molecules were substantially aligned with the chemically adsorbed molecules at a pretilt angle of about 65 ° with respect to the substrate in a direction opposite to the direction pulled up from the cleaning solution. Was.

At this time, when the composition of CH ₃ (CH ₂ ) ₁₄ SiCl ₃ and NC (CH ₂ ) ₁₄ SiCl ₃ is changed from 1: 0 to 0: 1 (preferably from 10: 1 to 1:50), the critical The surface energy changed from 20 mN / m to 29 mN / m, and the pretilt angle could be controlled arbitrarily in the range of 90 ° to 40 °. Further, a surfactant containing fluorine as a chemisorption compound, for example, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ S
As iCl ₃ is added, the critical surface energy becomes 15 m
N / m.

(Example 2) First, a naphthoquinonediazide-based sensitizer containing a novolak resin as a main component and a group represented by the above formula (1) was formed on the surface of a glass substrate 21 on which a TFT array having pixel electrodes on the surface was formed. Positive resist 2
2, 0.1 (for example, AZ1400 manufactured by Shipley)
It was applied and dried to a thickness of 0.2 μm to form a film. At this time, the critical surface energy of the coating was 28 mN / m. Next, a photomask 2 that divides each pixel into two parts
3 (at this time, a polarizing plate or a diffraction grating may be superimposed on a mask for pixel division to improve the orientation of the adsorption film molecules) at 100 mJ / cm ² with light of 435 nm (see FIG. 5). Then, in the exposed portion 22 ', the moisture in the air reacted with the resist, and the reaction represented by the formula (Formula 4) proceeded. At this time, -CO generated by the exposure
Since the OH group 25 contains active hydrogen (FIG. 6, and FIG. 6 is a partially enlarged view of a portion B in FIG. 5), a dehydrochlorination reaction occurred with the SiCl group.

Therefore, a non-aqueous solvent mixed with a substance containing a hydrocarbon group and a chlorosilyl group, for example, CH ₃ (C
H ₂ ) ₁₃ SiCl ₃ was dissolved at a concentration of about 1% by weight in afluid (made by Asahi Glass, a fluorinated solvent) to prepare an adsorbent, and the exposed substrate was dried in a dry atmosphere (relative humidity 30% or less). 24 was immersed for about 5 minutes.

Thereafter, the substrate is taken out of the solution and washed with a fluorine-based solvent (for example, Fluorinert PF5080 (trade name of 3M)).
Since a large amount of OH (carboxyl group) is contained, the SiCl group of the substance containing a hydrocarbon group and a chlorosilyl group and the carboxyl group are subjected to a dehydrochlorination reaction, and selectively exposed to the exposed portion.
The bond represented by the following formula (Formula 10) is formed, and the chemical adsorption film 26 containing a hydrocarbon group is selectively chemically bonded to the exposed portion to about 15 angstroms (1.5 n).
m) (FIG. 7; FIG. 7 is a partially enlarged view of portion B in FIG. 5), and the treated portion became water and oil repellent.

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Further, after the entire unexposed portion is exposed (may be exposed using a mask) (FIG. 8), a second adsorption reagent, for example, CH ₃ (CH ₂ ) ₉ SiCl ₃ and CH ₃ SiC is used.
l ₃ and 1 at the molar ratio: was immersed for about 5 minutes adsorption solution prepared in the same concentration dissolved in 5. Thereafter, the solution is pulled up from the solution, and a fluorine-based solvent (eg, Fluorinert PF5080)
And washed with (3M trade name)), since the second time exposed portions of the substrate surface includes -COOH (carboxyl group) is a _{number, CH 3 (CH 2) 9} SiCl 3 and C
The SiCl group of H ₃ SiCl ₃ and the carboxyl group are subjected to a dehydrochlorination reaction to selectively cause a chemical adsorption film 27 containing a hydrocarbon group, which is selectively bonded to the exposed portion, to be selectively bonded to the exposed portion at about 10 angstroms. (1.0 nm) (FIG. 9). At this time, since the first chemically adsorbed portion no longer has an active group and a monomolecular film is formed, the second adsorption does not occur at all. Therefore, 1
A portion 27 having a different orientation from the first exposed and chemically adsorbed portion 26 in the pixel was formed. At the time of exposure, when a polarizing plate or a diffraction grating was overlaid on the mask and exposed, a monomolecular film in which the adsorbed molecules were aligned in a streak shape could be selectively formed. Further, the critical surface energy of the monomolecular film at this time was 20 mN / m.

Then, a liquid crystal cell having a 20 micron gap was assembled by using two substrates 28 and assembling them so that the chemisorption films faced each other.
I4792 (manufactured by Merck & Co.) was injected to check the alignment state. When the liquid crystal molecules injected in one pixel were aligned almost vertically and obliquely with respect to the substrate along the chemisorbed molecules. It can be confirmed that the multi-domain has the same. That is, in this case, since the pixel portion was divided into two, an alignment film in which the alignment domain of the liquid crystal was divided into two could be produced.

When the number of divisions is to be increased, the exposure and suction step using a mask may be repeated a desired number of times. (Example 3) In Example 1, after the exposure and before the step of chemically adsorbing a molecule containing a linear hydrocarbon group, an adsorption solution prepared by dissolving a compound containing a plurality of chlorosilyl groups was used. It was immersed in a dry atmosphere. Then, the chlorosilyl group of the compound containing a plurality of chlorosilyl groups and the hydroxyl group contained in the carboxyl group formed on the resist surface was subjected to a dehydrochlorination reaction. After that, when the chlorosilyl group was further reacted with water, the remaining chlorosilyl groups were changed to hydroxyl groups, and a chemically adsorbed film containing many hydroxyl groups was formed on the surface.

For example, if SiCl ₄ is used as a silyl compound containing a plurality of chloro groups and dissolved in Fluorinert FC40 (trade name of 3M) to prepare an adsorbent, and the exposed substrate is immersed, the exposed resist 32 ′ is exposed. Since a -COOH group is formed in the portion, a dehydrochlorination reaction occurs on the surface, and the following formula (Chem. 11) and / or (Chem. 12)
Was formed, and the chlorosilane molecules were fixed in a pattern on the substrate surface via the -SiO- bond.

[0099]

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[0100]

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Thereafter, when the substrate was washed with a non-aqueous solvent such as Fluorinert FX3252 (trade name of 3M), SiCl ₄ molecules that had not reacted with the resist were removed, and when they were further reacted with water, the surface represented by the following formula (Formula 13) A siloxane monomolecular adsorption film 33 represented by (Formula 14) was obtained (FIG. 10).

[0102]

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[0103]

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At this time, if the step of washing with a non-aqueous solvent such as Fluorinert FX3252 (trade name of 3M) was omitted, a polysiloxane chemically adsorbed film was formed.
In addition, the siloxane monomolecular film 33 formed at this time was completely bonded to the resist through the chemical bond of -SiO-, and thus did not peel off at all. Furthermore, the obtained monomolecular film has many SiOH bonds on the surface. About 2-3 times the number of original -COOH groups was produced.
The treated part in this state had extremely high hydrophilicity. Therefore, in this state, when the same chemical adsorption step of a substance containing a hydrocarbon group as in Example 1 is performed, the same part as that in FIG. Approximately 25 angstroms (2.5 nm) with siloxane covalently bonded through a siloxane monolayer
It was formed with a film thickness of. At this time, since the number of adsorption sites (OH groups in this case) on the surface of the base material was about 2 to 3 times as large as that of Example 1, the adsorbed molecular density could be larger than that of Example 1. Also, the processing unit became lipophilic. The molecules in the chemically adsorbed film at this time had different densities, but were oriented almost perpendicular to the substrate as in FIG.

Then, a liquid crystal cell having a 20 micron gap was assembled by using two substrates in this state and combining them so that the chemical adsorption films faced each other.
When the alignment state was confirmed by injecting 4792 (manufactured by Merck & Co.), it was confirmed that the injected liquid crystal molecules were aligned almost perpendicularly to the substrate along the chemisorbed molecules. That is, this monomolecular film also exhibited a vertical alignment effect on the liquid crystal. At this time, the liquid crystal was not aligned in the portion not exposed.

[0106] As silyl compound containing a plurality of chloro groups, in addition to the SiCl _4, for example, Cl @ - (SiC
l ₂ O) ₂ -SiCl ₃ , or SiHCl ₃ , SiH ₂ Cl
_{2, further, Cl- (SiCl 2 O) n} -SiCl 3 (n is an integer) is available.

(Embodiment 4) Next, a manufacturing process for actually manufacturing a liquid crystal display device using the liquid crystal alignment film will be described with reference to FIG.

First, a photosensitive solution (for example, a novolak positive resist such as AZ1400) prepared by previously diluting a resin containing an energy beam sensitive group represented by the above formula (Formula 1) to 5% by weight in ethyl cellosolve acetate may be used. 11), as shown in FIG. 11, on a first substrate 43 having a first electrode group 41 placed in a matrix and a transistor group 42 for driving this electrode, and a first electrode group. Each of the two electrodes on the second substrate 46 having the color filter group 44 and the second electrode 45 placed so as to face each other is applied using a spin coating method, and the photosensitive material is applied in the same manner as in Example 1. A resin film (a novolak-based positive resist film) was formed. Then, after heating at 100 ° C. for 10 minutes to remove the solvent to a certain extent, 1000 fibers / m 2
The electrode pattern and the grating were set parallel to each other using a diffraction grating (a polarizing plate may be used) as a mask, and an ultra-high pressure mercury lamp of 500 W from the vertical direction was used.
Light with a wavelength of 5 nm (g-line) (28 mJ / c after passing through the mask)
m ² ) was irradiated for 5 seconds to react the naphthoquinonediazide in the photosensitive novolak-based positive resist, and a —COOH group was generated in the exposed portion in proportion to the exposure amount. Thus, when a chemical adsorption process was performed in the same manner as in Example 1, a liquid crystal alignment film 47 in which linear hydrocarbon groups were aligned along the electrode pattern could be produced. Next, the first and second substrates 4
3 and 46 are aligned so as to face each other,
8 and an adhesive 49 were used to fix them with a gap of about 5 microns. Thereafter, the TN liquid crystal 50 is placed on the first and second substrates.
Was injected, and the display element was completed by combining the polarizing plates 51 and 52.

In such a device, an image can be displayed in the direction of arrow A by driving each transistor using a video signal while irradiating the backlight 53 to the entire surface. (Example 5) Glass substrate 6 having a transparent electrode formed on the surface
1 (containing many hydroxyl groups on the surface) is prepared and thoroughly washed and degreased in advance. Then, silane-based surfactant comprising a linear hydrocarbon group and Si as a carbon chain (hereinafter, referred to as chemisorption _{compound), CN (CH 2) 1} 4 SiCl 3 and CH ₃ SiC
l ₃ (used in a molar ratio of 1:10),
A chemisorption solution was prepared by dissolving in a non-aqueous solvent at a concentration of% by weight. Well-dehydrated hexadecane was used as the non-aqueous solvent. The solution thus prepared was used as an adsorption solution 62, and the substrate 61 was immersed (may be coated) in the adsorption solution 62 for about 50 minutes in a dry atmosphere (relative humidity 30% or less) ( (FIG. 12). Thereafter, the substrate was pulled up from the liquid, washed with n-hexane 63, which is a well-dehydrated non-aqueous solvent, and then the substrate was pulled up from the cleaning liquid while standing in a desired direction, drained, and exposed to air containing moisture. (FIG. 13). Arrow 65 is the pulling direction.
In the above series of steps, a dehydrochlorination reaction occurred between the SiCl group of the chlorosilane-based surfactant and the hydroxyl group on the substrate surface, and a bond represented by the following formulas (Formulas 15 and 16) was generated.
Further, it reacts with the moisture in the air to obtain the formula (Formula 17 and 18)
A bond was generated.

[0110]

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[0111]

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[0112]

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[0113]

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By the above treatment, the chemically adsorbed monomolecular film 64 formed by the reaction of the chlorosilane-based surfactant is chemically bonded to the portion of the substrate surface containing the hydroxyl group through the covalent bond of siloxane. It was formed into a monomolecular film with a thickness of 1 nm. At this time, CN in the chemically adsorbed film
The (CH ₂ ) ₁₄ Si— straight-chain carbon chain was almost oriented at a tilt angle of about 20 ° in a direction opposite to the direction 65 pulled up from the cleaning solution (FIG. 14). That is, the direction of the molecules immobilized by adsorption was substantially primary. Here, the tilt angle is controlled from 0 ° by changing the composition of CN (CH ₂ ) ₁₄ SiCl ₃ and CH ₃ SiCl ₃ from 1: 0 to 0: 1 (preferably 10: 1 to 1:50). Arbitrary control was possible in the range of 90 °. At this time, if it is desired to selectively form a film, the adsorbing liquid 6 is applied to the substrate surface 61 in a desired pattern using a printing machine.
2 may be printed. Alternatively, after the substrate surface is selectively covered with a resist in advance, the resist may be removed after performing a chemical adsorption step. In this case, since the chemically adsorbed film does not peel off with an organic solvent, a resist that can be dissolved and removed with an organic solvent is used.

(Example 6) Using the substrate obtained in Example 5, a polarizing plate (HNP'B) 66 (manufactured by Polaroid) was applied to the substrate so that the polarization direction was substantially perpendicular to the pulling direction. 365n of super high pressure mercury lamp
m (i-line) light 67 was irradiated at 100 mJ / cm ² . At this time, in order to align the orientation directions of the adsorbed molecules in one direction, it is necessary to shift the orientation slightly, preferably several degrees or more, instead of completely intersecting at 90 ° (maximum, parallel to the draining direction). The polarization direction may be adjusted so as to be as follows). If they completely cross at 90 °, individual molecules may be oriented in two directions (FIG. 15). In FIG. 15, an arrow 73 indicates the polarization direction.

Thereafter, when the orientation direction of the linear carbon chain in the chemisorption monomolecular film 64 'was examined, the tilt angle did not change, but the orientation direction 68 changed in a direction almost perpendicular to the pulling direction. The variation was also improved from that at the time of primary orientation (FIGS. 16 and 17). In the figure, 69 represents a transparent electrode.

Here, when it is desired to selectively change the orientation direction, a step of overlapping a desired mask on a polarizing plate and exposing the same is performed a plurality of times, so that it is extremely easy to form a monomolecular film having a different orientation in a pattern. Was prepared.

In this example, a hydrocarbon-based n-hexane containing an alkyl group was used as a water-free solvent for washing. However, any other solvent that does not contain water and dissolves a surfactant can be used. Anything can be used. For example, in addition to this, a solvent containing a fluorocarbon group, a carbon chloride group, or a siloxane group, for example, Freon 113, chloroform, hexamethyldisiloxane, or the like could be used.

(Example 7) In Example 5, as a silane-based surfactant, a linear hydrocarbon group incorporating one functional group for controlling the surface energy of the film at the terminal and Si
And _{CH 3 (CH 2) 14 SiCl} 3 containing NC (CH _{2) 14} S
The same experiment was performed except that iCl ₃ (mixed at a molar ratio of 1: 1) was used.

As a result, the chemically adsorbed monomolecular film formed by the reaction of the chlorosilane-based surfactant is selectively bonded to the portion of the substrate surface where the hydroxyl group has been formed, selectively through a siloxane covalent bond. It was formed into a monomolecular film with a thickness of 0.5 nm. At this time, the critical surface energy of the chemisorption film was about 27 mN / m.

Further, using two substrates in this state, a liquid crystal cell having a gap of 20 μm was assembled by combining the chemical adsorption films so as to face each other, and anti-parallel alignment was performed, and a nematic liquid crystal (ZLI4792, manufactured by Merck) was injected. When the alignment state of the portion where the monomolecular film was formed was confirmed, the injected liquid crystal molecules were substantially aligned with the chemically adsorbed molecules at a pretilt angle of about 65 ° with respect to the substrate in a direction opposite to the direction pulled up from the cleaning solution. Was.

At this time, when the composition of CH ₃ (CH ₂ ) ₁₄ SiCl ₃ and NC (CH ₂ ) ₁₄ SiCl ₃ is changed from 1: 0 to 0: 1 (preferably 10: 1 to 1:50), the critical The surface energy changed from 20 mN / m to 29 mN / m, and the pretilt angle could be controlled arbitrarily in the range of 90 ° to 40 °. Further, a surfactant containing fluorine as a chemisorption compound, for example, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ S
As iCl ₃ is added, the critical surface energy becomes 15 m
N / m.

(Example 8) In Example 5, before the step of chemically adsorbing a surfactant molecule containing a carbon chain or a siloxane bond chain, the adsorption prepared by dissolving a compound containing a plurality of chlorosilyl groups. A solution was made and immersed in a dry atmosphere. Then, the chlorosilyl group of the compound containing a plurality of hydroxyl groups and chlorosilyl groups contained in the substrate surface was subjected to a dehydrochlorination reaction. After that, when the chlorosilyl group was further reacted with water, the remaining chlorosilyl groups were changed to hydroxyl groups, and a chemically adsorbed film containing many hydroxyl groups was formed on the surface.

For example, if SiCl ₄ is used as a silyl compound containing a plurality of chloro groups and dissolved in n-octane to prepare an adsorbent, and the substrate is immersed in a dry atmosphere, the surface contains —OH groups. Therefore, a dehydrochlorination reaction occurred at the interface, and the following formulas (Formula 19) and / or (Formula 20) were formed, and the chlorosilane molecule 71 was fixed to the substrate surface via a -SiO- bond.

[0125]

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[0126]

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Thereafter, when the substrate is washed with a non-aqueous solvent such as chloroform, excess SiCl ₄ not reacting with the substrate is obtained.
The molecules are removed (FIG. 18). Further, when taken out into the air and reacted with water, a siloxane monomolecular adsorption film 72 containing a large number of SiO bonds represented by the following formulas (Formula 21) and / or (Formula 22) on the surface was obtained (FIG. 19).

[0128]

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[0129]

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At this time, if the step of washing with a non-aqueous solvent such as chloroform was omitted, a polysiloxane chemically adsorbed film was formed. Since the siloxane monomolecular film 72 formed at this time is completely bonded to the substrate via the chemical bond of -SiO-, it does not peel off at all. Moreover, the obtained monomolecular film has many SiOH bonds on the surface. About 2-3 times the number of original -OH groups was produced. The treated part in this state had extremely high hydrophilicity.
Then, in this state, when the chemical adsorption step is performed using the same surfactant as in Example 5, the chemically adsorbed monomolecular film containing the carbon chain formed by the reaction of the same surfactant as in FIG. The film was formed with a thickness of about 1 nm in a state where the siloxane was chemically bonded through a molecular film through a covalent bond. At this time,
The number of adsorption sites (OH groups in this case) on the surface of the base material before the surfactant is adsorbed is about 2 to 3 times as large as in Example 5, so that the adsorbed molecular density is higher than in Example 5. It was big. Also, the processing unit became lipophilic. Although the molecular density in the chemisorption film at this time was different, it was oriented in the direction opposite to the pulling direction, that is, in the liquid draining direction.

Next, using the substrate in this state, a polarizing plate is superposed on the substrate so that the polarization direction is oriented in a direction substantially perpendicular to the pulling direction, and a KrF excimer laser of 248 nm is used.
Of 80 mJ / cm ^{2 was} applied. Thereafter, when the orientation direction of the linear carbon chain in the chemisorption monomolecular film was examined, the tilt angle was slightly large at 25 °, but the orientation direction changed to a direction almost perpendicular to the pulling direction, and furthermore, the alignment variation was observed. Had also been improved.

Thus, a liquid crystal cell having a 20-micron gap was assembled by using two substrates in this state and combining them so that the chemisorption films faced each other so as to perform antiparallel alignment, and a nematic liquid crystal (ZLI4792; manufactured by Merck) was used.
Was injected to confirm the alignment state, it was confirmed that the injected liquid crystal molecules were aligned at about 25 ° with respect to the substrate along the chemisorbed molecules.

[0133] As silyl compound containing a plurality of chloro groups, in addition to the SiCl _4, for example, Cl @ - (Si
Cl ₂ O) ₂ -SiCl ₃ or SiHCl _3, SiH _2,
Cl ₂ , and further, Cl- (SiCl ₂ O) _n -SiCl
₃ (n is an integer) were available.

(Embodiment 9) Next, a manufacturing process for actually manufacturing a liquid crystal display device using the liquid crystal alignment film will be described with reference to FIG.

First, as shown in FIG. 20, a first electrode group 81 placed in a matrix and a first substrate 83 having a transistor group 82 for driving the electrodes, and a first electrode group 81 On a second substrate 86 having a color filter group 84 and a second electrode 85 placed so as to face each other, a chemical adsorption liquid is applied using a spin coating method, respectively.
A chemically adsorbed film was formed in the same manner as in Example 5. Then, using a polarizing plate HNP'B (manufactured by Polaroid), the electrode pattern and the polarization direction were set parallel to each other, and an ultrahigh-pressure mercury lamp of 500 W from the vertical direction was used to emit light having a wavelength of 365 nm (i-line). 3.6 mJ / cm ² · s) after passing through the polarizing plate
Irradiated for 0 seconds. Then, similarly to the fifth embodiment, the liquid crystal alignment film 8 in which the linear hydrocarbon groups are realigned along the electrode pattern.
7 was produced. Next, the first and second substrates 83, 8
6 so that the electrodes face each other,
8 and an adhesive 89 were used to fix the gap of about 5 microns. Thereafter, the TN liquid crystal 90 is placed on the first and second substrates.
Was injected, and the display device was completed by combining the polarizing plates 91 and 92.

In such a device, an image can be displayed in the direction of arrow A by driving each transistor using a video signal while illuminating the entire surface of the backlight 93. (Embodiment 10) In the light reorienting step in Embodiment 9, if the step of overlapping and exposing a pattern-like mask for dividing each pixel into four in a checkered manner on the polarizing plate is performed twice, the same pixel can be obtained. Four portions having different orientation directions could be provided in a pattern. When the substrate on which the alignment film was formed was used, the viewing angle of the liquid crystal display device could be greatly improved.

Example 11 As a chemisorbed compound, C
H ₃ (CH ₂ ) ₁₈ SiCl ₃ and CH ₃ (CH ₂ ) ₃ SiCl ₃
(Used in a molar ratio of 1: 1) was dissolved in a non-aqueous solvent at a concentration of about 1% by weight to prepare a chemisorption solution. At this time, well-dehydrated hexadecane was used as the non-aqueous solvent. The solution thus prepared was used as an adsorption solution, and the substrate on which the electrodes were formed was dried in a dry atmosphere (30% or less relative humidity) in the same manner as in Example 5.
It was immersed for about an hour. Thereafter, the substrate is pulled up from the liquid, washed with n-hexane, which is a non-aqueous solvent not containing water that has been well dehydrated, and then pulled up from the cleaning liquid as in FIG. Exposure to moist air.

Thereafter, in order to examine the state of the primary orientation, F
Analysis was performed using TIR. The results are shown in FIGS.
You. 21 and 22, the lifting direction
Absorption spectrum measured in the direction perpendicular to (FIG. 21)
And absorption spectrum measured in the direction parallel to the lifting direction
The absorption pattern differs from that of the torr (FIG. 22). FIG.
In 1, CH_Two 2930c caused by asymmetric stretching vibration of
m^-1Absorption intensity of CH_Two28 due to the symmetric stretching vibration of
57cm^-1Is twice the absorption intensity of
Is CH_Two 2929cm caused by asymmetric stretching vibration of^-1
Absorption intensity of CH _Two 2859 due to symmetric stretching vibration of
cm^-1Is about 1.7 times the absorption intensity. Ma
2930cm^-1Red shift of the absorption peak of
857cm^-1Is blue-shifted. This
It means that the hydrocarbon chains of the molecules fixed
Parallel to the direction, that is, oriented in the draining direction.
Is shown.

Further, using two substrates in this state, a liquid crystal cell having a 20-micron gap was assembled by combining the chemical adsorption films so as to face each other, and anti-parallel alignment was performed, and a nematic liquid crystal (ZLI4792; manufactured by Merck) was injected. When the alignment state was confirmed using a polarizing plate, the injected liquid crystal molecules were aligned in the liquid draining direction, that is, the direction opposite to the direction pulled up from the cleaning liquid. Furthermore, the cell is sandwiched between two polarizing plates combined in crossed Nicols,
When the light transmittance was measured when the electrode was applied with 20 volts and when the voltage was not applied, that is, on and off, a contrast of 358 was obtained. This indicates that a practical level of alignment performance can be obtained only by the pulling alignment step.

In the above Examples 6, 8, 9 and 10, the light used for exposure is i-line of an ultra-high pressure mercury lamp.
24 obtained by 65 nm light or KrF excimer laser
Although the light of 8 nm is used, it is also possible to use light of 436 nm, 405 nm, and 254 nm according to the degree of light absorption of the film material. In particular, light of 248 nm or 254 nm is easily absorbed by most substances, and thus has high alignment efficiency.

As a silane-based surfactant containing a linear hydrocarbon group or a siloxane bonding chain and a chlorosilyl group, or an alkoxysilyl group or an isocyanatesilyl group, a cyano group at the molecular end and a chlorosilyl group at the other end. Shown below is an example in which a mixed chlorosilane-based surfactant containing a methyl group and a chlorosilyl group was used in combination with two chlorosilane-based surfactants having different molecular lengths. However, the present invention is not limited to these, and a halogen atom or a methyl group (-
CH ₃ ), phenyl group (—C ₆ H ₅ ), cyano group (—C
N) or a chlorosilane-based surfactant containing a carbon trifluoride group (—CF ₃ ) or a chlorosilane-based surfactant in which some of the carbon atoms in the hydrocarbon groups in the molecule have optical activity (particularly in this case) Could be efficiently oriented).

Ha (CH ₂ ) _n SiCl ₃ (Ha represents a halogen atom such as chlorine, bromine, iodine, fluorine, etc.)
n is an integer and preferably 1 to 24. A chlorosilane-based surfactant represented by ()) can also be used. Further, the following compounds can be used. (1) CH ₃ (CH ₂ ) _n SiCl ₃ (n is an integer of 0 to 2)
4 is preferred. (2) CH ₃ (CH ₂ ) _p Si (CH ₃ ) ₂ (CH ₂ ) _q Si
Cl ₃ (p and q are preferably integers of 0 to 10.) (3) CH ₃ COO (CH ₂ ) _m SiCl ₃ (m is an integer of 7
To 24 are preferable. _{) (4) C 6 H 5} (CH 2) n SiCl 3 (n is an integer from 0 to 2
4 is preferred. (5) CN (CH ₂ ) _n SiCl ₃ (n is an integer of 0 to 24)
Is preferred. _{) (6) Cl 3 Si (} CH 2) n SiCl 3 (n is 3 to an integer
24 is preferred. (7) Cl ₃ Si (CH ₂ ) ₂ (CF ₂ ) _n (CH ₂ ) ₂ Si
Cl ₃ (n is preferably an integer of 1 to 10.) (8) Br (CH ₂ ) ₈ SiCl ₃ (9) CH ₃ (CH ₂ ) ₁₇ SiCl ₃ (10) CH ₃ (CH ₂ ) ₅ Si (CH) ₃ ) ₂ (CH ₂ ) ₈ Si
_{Cl 3 (11) CH 3 COO} (CH 2) 14 SiCl 3 (12) C 6 H 5 (CH 2) 8 SiCl 3 (13) CN (CH 2) 14 SiCl 3 (14) Cl 3 Si (CH 2) _{8 SiCl 3 (15) Cl 3} Si (CH 2) 2 (CF 2) 4 (CH 2) 2 Si
Cl ₃ (16) Cl ₃ Si (CH ₂ ) ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ Si
_{Cl 3 (17) CF 3 CF} 3 (CF 2) 7 (CH 2) 2 SiCl 3 (18) CF 3 CF 3 CH 2 O (CH 2) 15 Si (CH 3) 2 C
l (19) CF ₃ CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ )
₁₅ SiCl ₃ (20) F (CCF ₃ (CF ₂ ) ₄ (CH ₂ ) ₂ Si (CH ₃ )
_{2 (CH 2) 9 SiCl 3} (21) F (CF 2) 8 (CH 2) 2 Si (CH 3) 2 (C
_{H 2) 9 SiCl 3 (22} ) CF 3 COO (CH 2) 15 SiCH 3 Cl 2 (23) CF 3 (CF 2) 5 (CH 2) 2 SiCl 3 (24) CH 3 CH 2 CHC * H 3 CH ₂ OCO (CH ₂ ) ₁₀ S
iCl ₃ (25) CH ₃ CH ₂ CHC ^* H ₃ CH ₂ OCOC ₆ H ₄ OCOC ₆ H ₄ O (CH ₂ ) ₅ SiCl _{3 In the} above chemical formula, C ^* represents optically active carbon.

The following compounds containing a siloxane bond chain and a chlorosilyl group, or an alkoxysilyl group or an isocyanatesilyl group could be used. (Also in this case,
A highly oriented film was obtained. _{) (26) ClSi (CH 3} ) 2 OSi (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 Cl (27) Cl 3 SiOSi (CH 3) 2 OSi (CH 3) 2 OSi (CH 3 ) ₂ OSi (CH ₃ ) ₂ OSi
In addition to Cl ₃ and chlorosilane-based surfactants, the following silane-based surfactants containing an alkoxysilyl group or an isocyanatesilyl group could be used. (28) Ha (CH ₂ ) _n Si (OCH ₃ ) ₃ (Ha is chlorine,
Represents a halogen atom such as bromine, element, fluorine, etc., and n is preferably an integer of 1 to 24. (29) CH ₃ (CH ₂ ) _n Si (NCO) ₃ (n is an integer of 0
To 24 are preferable. ) (30) CH ₃ (CH ₂ ) _p Si (CH ₃ ) ₂ (CH ₂ ) _q Si
(OCH ₃ ) ₃ (p and q are preferably integers from 0 to 10.) (31) HOOC (CH ₂ ) _m Si (OCH ₃ ) ₃ (m is an integer of 7
To 24 are preferable. _{) (32) H 2 N (} CH 2) m Si (OCH 3) 3 (m is 7-24 in integer _{preferred.) (33) C 6 H} 5 (CH 2) n Si (NCO) 3 (n is (34) CN (CH ₂ ) _n Si (OC ₂ H ₅ ) ₃ (n is preferably an integer from 0 to 24) (Example 12) A transparent electrode is formed on the surface. A prepared glass substrate 101 (containing a large number of hydroxyl groups on the surface) is prepared and thoroughly cleaned and degreased in advance. Next, a silane-based surfactant containing a linear hydrocarbon group incorporating one functional group for controlling the surface energy of the film at the terminal and Si (hereinafter, also referred to as a chemisorbed compound), CH ₃ (CH ₂ ) ₁₄ SiCl ₃ and NC
Using (CH ₂ ) ₁₄ SiCl ₃ (mixed at a molar ratio of 1: 1), the solution was dissolved in a non-aqueous solvent at a concentration of about 1% by weight to prepare a chemisorption solution. Well-dehydrated hexadecane was used as the non-aqueous solvent. The solution thus prepared is referred to as an adsorption solution 102, and the adsorption solution 102
The substrate 101 was immersed (may be applied) for about one hour in a dry atmosphere (relative humidity 30% or less) (FIG. 23). Thereafter, the substrate is pulled up from the liquid, washed with n-hexane 103 which is a non-aqueous solvent not containing water which has been well dehydrated, and then pulled up from the cleaning liquid in a state where the substrate is set in a desired direction. (Figure 2)
4). In the above series of steps, a dehydrochlorination reaction occurred between the SiCl group of the chlorosilane-based surfactant and the hydroxyl group on the substrate surface, and a bond represented by the following formulas (Formulas 23 and 24) was generated. Further, the reaction with the moisture in the air produced the bond of the formula (Formulas 25 and 26).

[0144]

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[0145]

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[0146]

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[0147]

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By the above treatment, the chemically adsorbed monomolecular film 104 formed by the reaction of the chlorosilane-based surfactant is chemically bonded to a portion of the substrate surface containing a hydroxyl group through a siloxane covalent bond. It was formed into a monomolecular film with a thickness of 1.5 nm. At this time, the critical surface energy of the chemisorption film was about 27 mN / m.

Further, a liquid crystal cell having a 20 micron gap was assembled by using two substrates in this state and combining them so that the chemical adsorption films faced each other, and anti-parallel alignment was performed, and a nematic liquid crystal (ZLI4792; manufactured by Merck) was injected. When the alignment state was confirmed, the injected liquid crystal molecules were substantially aligned along the chemically adsorbed molecules at a pretilt angle of about 65 ° with respect to the substrate in the direction opposite to the direction 105 pulled up from the cleaning liquid (FIG. 25). .

At this time, when the composition of CH ₃ (CH ₂ ) ₁₄ SiCl ₃ and NC (CH ₂ ) ₁₄ SiCl ₃ is changed from 1: 0 to 0: 1 (preferably 10: 1 to 1:50), the critical The surface energy changed from 20 mN / m to 29 mN / m, and the pretilt angle could be controlled arbitrarily in the range of 90 ° to 40 °. Further, a surfactant containing fluorine as a chemisorption compound, for example, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ S
As iCl ₃ is added, the critical surface energy becomes 15 m
N / m.

When it is desired to selectively form a film,
A method of printing the adsorption liquid 102 on the substrate surface 101 in a desired pattern using a printing machine was available. Alternatively, a method in which the substrate surface is selectively covered with a resist in advance and then the resist is removed after performing a chemical adsorption step. However, in this case, the chemically adsorbed film is never peeled off with an organic solvent, so a resist that can be dissolved and removed with an organic solvent is used.

As described above, in this embodiment, the obtained films have different critical surface energies and a carbon chain length of −
A silane-based surfactant having the same length as (CH ₂ ) _14- was used, but the length of the carbon chain length was different (for example,-(CH ₂ ) _n
-; N is an integer in the range of 1 to 30) When a surfactant was used in combination, the alignment regulating force was further increased.

Next, using two types of substrates in this state, a polarizing plate (HNP'B) 106 (manufactured by Polaroid) is set on the substrate so that the polarization direction 113 is oriented in a direction substantially perpendicular to the pulling direction 105. Then, light 107 of 365 nm (i-line) from a 500 W ultra-high pressure mercury lamp (3.
6 mW / cm ² ) and 50 mJ.

At this time, in order to align the orientation directions of the adsorbed molecules in one direction, it is necessary to shift the orientation slightly, preferably several degrees or more, instead of completely intersecting at 90 °. In this case, the polarization direction 1 is set to be at most parallel to the draining direction.
13 may be combined. If they completely cross at 90 °, individual molecules may be oriented in two directions (FIG. 26). Thereafter, when the orientation direction of the linear carbon chain in the chemisorption monomolecular film 104 ′ was examined, the critical surface energy and the tilt angle did not change, but the orientation direction 108 changed almost parallel to the polarization direction 113, and The orientation variation was also improved from that at the time of the primary orientation (FIGS. 27 to 28).
In the figure, 109 represents a transparent electrode.

Here, when it is desired to selectively change the orientation direction, a step of superposing a desired mask on a polarizing plate and exposing the same is performed a plurality of times, thereby making it very easy to form a monomolecular film having a different orientation in a pattern. Was prepared.

In the present embodiment, a hydrocarbon-based n-hexane containing an alkyl group was used as a water-free solvent for washing. However, any other solvent that does not contain water and dissolves a surfactant can be used. Any solvent can be used. For example, in addition to this, a solvent containing a fluorocarbon group, a carbon chloride group, or a siloxane group, for example, Freon 113, chloroform, hexamethyldisiloxane, or the like could be used.

(Example 13) [0157] In Example 12, prior to the step of chemically adsorbing a surfactant molecule containing a carbon chain or a siloxane bond chain, the adsorption prepared by dissolving a compound containing a plurality of chlorosilyl groups. A solution was made and immersed in a dry atmosphere. Then, the chlorosilyl group of the compound containing a plurality of hydroxyl groups and chlorosilyl groups contained in the substrate surface was subjected to a dehydrochlorination reaction. After that, when the chlorosilyl group was further reacted with water, the remaining chlorosilyl groups were changed to hydroxyl groups, and a chemically adsorbed film containing many hydroxyl groups was formed on the surface.

For example, if SiCl ₄ is used as a silyl compound containing a plurality of chloro groups and dissolved in n-octane to prepare an adsorbent, and the substrate is immersed in a dry atmosphere, the surface contains —OH groups. Therefore, a dehydrochlorination reaction occurs at the interface, and the following formulas (Formula 27) and / or (Formula 28) are formed, and the chlorosilane molecule 111 is fixed to the substrate surface via a -SiO- bond.

[0159]

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[0160]

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Thereafter, when the substrate is washed with a non-aqueous solvent such as chloroform, excess SiCl ₄ not reacting with the substrate is obtained.
The molecules are removed (FIG. 29). Further, when taken out into the air and reacted with water, a siloxane monomolecular adsorption film 112 containing a large number of SiO bonds represented by the following formulas (Formula 29) and / or (Formula 30) on the surface was obtained (FIG. 30).

[0162]

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[0163]

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In this case, if the step of washing with a non-aqueous solvent such as chloroform was omitted, a polysiloxane chemically adsorbed film was formed. Since the siloxane monomolecular film 112 formed at this time is completely bonded to the substrate via a chemical bond of —SiO—, it does not peel off. Also,
The obtained monomolecular film has many SiOH bonds on the surface.
About 2-3 times the number of original -OH groups was produced. The treated part in this state had extremely high hydrophilicity. Therefore, in this state, when the chemical adsorption step is performed using the same surfactant as in Example 12, the chemically adsorbed monomolecular film containing the carbon chain formed by the reaction of the same surfactant as in FIG. The film was formed to have a thickness of about 1.5 nm in a state of being chemically bonded by siloxane covalent bonds via the molecular film 112. At this time, the adsorption site (OH group in this case) on the surface of the base material before the surfactant was adsorbed was about 2 to 3 compared to Example 12.
Since the number was twice as large, the density of adsorbed molecules could be increased as compared with the case of Example 12. Also, the processing unit became lipophilic. Although the molecular density in the chemisorption film at this time was different, it was oriented in the direction opposite to the pulling direction, that is, in the liquid draining direction.

Next, using the substrate in this state, a polarizing plate is superposed on the substrate so that the polarization direction is oriented in a direction substantially perpendicular to the pulling direction, and a KrF excimer laser of 248 nm is used.
Was irradiated at 80 mJ. After that, when the orientation direction of the linear carbon chain in the chemisorption monomolecular film was examined, the tilt angle was 8
Although it was slightly larger at 7 °, the orientation direction changed to a direction almost perpendicular to the pulling-up direction, and the orientation variation was also improved. The critical surface energy at this time was 28 mN / m.

Therefore, a liquid crystal cell having a 20-micron gap was assembled by using two substrates in this state and combining them so that the chemisorption films faced each other so as to perform anti-parallel alignment, and a nematic liquid crystal (ZLI4792; manufactured by Merck) was used.
Was injected, and the alignment state was confirmed. It was confirmed that the injected liquid crystal molecules were aligned with the substrate at a pretilt angle of about 46 ° along the chemisorbed molecules.

[0167] As silyl compound containing a plurality of chloro groups, in addition to the SiCl _4, for example, Cl @ - (Si
Cl ₂ O) ₂ -SiCl ₃ or SiHCl _3, SiH _2,
Cl ₂ , and further, Cl- (SiCl ₂ O) _n -SiCl
₃ (n is an integer) were available.

(Example 14) In Example 12, CH ₃ (CH ₂ ) ₁₄ SiCl ₃ and NC (C
Instead of H ₃ ) ₂ (CH ₂ ) ₁₄ SiCl ₃ , ClSi (C
_{H 3) 2 OSi (CH 3} ) 2 OSi (CH 3) 2 OSi (CH
_{3) 2} Cl and CH ₃ and _{(CH 2) 14 SiCl 3 1} : 0~0:
When used as a mixture between 1, the critical surface energy could be controlled in the range of 35 mN / m to 21 mN / m depending on the mixing ratio. Further, when a liquid crystal was injected as in the case of assembling the cell, the pretilt angle could be controlled in the range of 5 to 90 degrees.

Incidentally, ClSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ containing a linear siloxane bonding chain
OSi (CH ₃ ) ₂ Cl and C containing linear hydrocarbon chains
When a film is prepared by mixing H ₃ (CH ₂ ) ₁₄ SiCl ₃ at a desired ratio, a chemical adsorption containing molecules represented by the following formulas (Formula 31) and (Formula 32) on the surface according to the mixture ratio is obtained. A monolayer was obtained.

[0170]

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[0171]

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(Example 15) In Example 12, CH ₃ (CH ₂ ) ₁₄ SiCl ₃ and NC (C
Instead of H ₃ ) ₂ (CH ₂ ) ₁₄ SiCl ₃ , HOOC (C
H ₂ ) ₁₆ Si (OCH ₃ ) ₃ and Br (CH ₂ ) ₈ Si (OC
The H _{3) 3} 1: 0~0: used by mixing among 1, and refluxed for 2 hours at 100 ° C. during chemisorption. In this case, the critical surface energy is from 56 mN / m to 31 m depending on the mixing ratio.
Control was possible in the range of N / m. Further, when the same liquid crystal was injected after the cell was assembled, the pretilt angle could be controlled in the range of 0 to 28 degrees.

(Example 16) In Example 12, CH ₃ (CH ₂ ) ₁₄ SiCl ₃ and NC (C
H ₃ ) ₂ (CH ₂ ) ₁₄ Instead of SiCl ₃ , CH ₃ CH ₂ C
^* HCH ₃ CH ₂ OCO (CH ₂ ) ₁₀ SiCl ₃ (however,
C ^* is an asymmetric carbon) and _{CH 3 SiCl 3 1: 0~1:} 2
A similar alignment film was prepared using a mixture between 0. In this case, the critical surface energy is 36 mN depending on the mixing ratio.
/ M to 41 mN / m. Further, when the same liquid crystal was injected after the cell was assembled, the pretilt angle could be controlled in the range of 3 degrees to 0.1 degrees.

(Embodiment 17) Next, a manufacturing process in the case of actually manufacturing a liquid crystal display device using the above liquid crystal alignment film will be described with reference to FIG.

First, as shown in FIG. 31, a first substrate 123 having a first electrode group 121 mounted in a matrix and a transistor group 122 driving the electrodes.
A second filter having a color filter group 124 and a second electrode 125 mounted on the upper electrode and opposed to the first electrode group;
According to the same procedure as in Example 16, the prepared chemisorption liquid was applied onto the substrate 126 of No. 16 to produce a chemisorption monomolecular film having a critical surface energy of 36 mN / m.

Thereafter, a polarizing plate HNP'B (manufactured by Polaroid) was set so that the polarization direction was parallel to the electrode pattern, and the wavelength of 365 nm (i-line) was measured using a 500 W ultra-high pressure mercury lamp from the vertical direction. (3.6 mJ / cm ² after passing through the polarizing plate) for 20 seconds. As a result, a liquid crystal alignment film 127 having a critical surface energy of 37 mN / m in which linear hydrocarbon groups were realigned along the electrode pattern as in Example 16 was produced. Next, the first and second
The substrates 123 and 126 were aligned so that the electrodes faced each other, and fixed with a spacer 128 and an adhesive 129 with a gap of about 5 μm. Then, after injecting the TN liquid crystal 130 into the first and second substrates, the polarizing plate 13 is formed.
The display element was completed by combining Nos. 1 and 132. At this time, the pretilt angle of the injected liquid crystal was 3 degrees.

[0177] Such a device includes a backlight 133.
By driving each transistor using a video signal while illuminating the entire surface, an image could be displayed in the direction of arrow A.

(Embodiment 18) In the light reorienting step in Embodiment 17, if the step of overlapping and exposing a pattern-like mask for dividing each pixel into four in a checkered manner on the polarizing plate is performed twice, the same result can be obtained. Four portions having different alignment directions could be provided in a pattern in the pixel. When the substrate on which the alignment film was formed was used, the viewing angle of the liquid crystal display device could be greatly improved.

In Examples 12 to 18 described above, the light used for exposure was 365 nm, which is the i-line of an extra-high pressure mercury lamp.
Or 248 nm light obtained with a KrF excimer laser was used, but depending on the degree of light absorption of the film material, 436 nm was used.
nm, 405 nm, and 254 nm can also be used. In particular, light of 248 nm or 254 nm is easily absorbed by most substances, and thus has high alignment efficiency.

As a silane-based surfactant containing a linear hydrocarbon group or a siloxane bond chain and a chlorosilyl group, or an alkoxysilyl group or an isocyanatesilyl group, a cyano group at the molecular end and a chlorosilyl group at the other end. A mixture of chlorosilane-based surfactants containing chlorosilane-based surfactants and chlorosilane-based surfactants containing methyl and chlorosilyl groups was used, that is, films having different surface energies 2
Examples in which various kinds of chlorosilane-based surfactants are used in combination are shown. However, the present invention is not limited to these, and various surfactants having different surface energies are combined to form alignment films having different surface energies. Could be produced. For example, at the terminal of a hydrocarbon group as shown below, 3
Fluorocarbon group (-CF _3), a methyl group (-CH _3), a vinyl group (-CH = CH _2), allyl (-CH = CH
-), an acetylene group (carbon - triple bond of carbon), a phenyl group (-C ₆ H _5), an aryl group (-C ₆ H ₄ -), a halogen atom, an alkoxy group (-OR; with R is an alkyl group Represents, in particular, an alkyl group having 1 to 3 carbon atoms.), A cyano group (—CN), an amino group (—NH ₂ ),
Chlorosilanes substituted with at least one organic group selected from a hydroxyl group (-OH), a carbonyl group (= CO), an ester group (-COO-) and a carboxyl group (-COOH), or an optically active hydrocarbon group Surfactant could be used.

Incidentally, Ha (CH ₂ ) _n SiCl ₃ (Ha represents a halogen atom such as chlorine, bromine, iodine, fluorine, etc.)
n is an integer and preferably 1 to 24. A chlorosilane-based surfactant represented by ()) can also be used. Further, compounds represented by the following general formula can also be used. (1) CH ₃ (CH ₂ ) _n SiCl ₃ (n is preferably an integer from 0 to 24) (2) CH ₃ (CH ₂ ) _p Si (CH ₃ ) ₂ (CH ₂ ) _q SiCl ₃ (p, q is an integer 0
To 10 are preferred. _{) (3) CH 3 COO (} CH 2) m SiCl 3 (m is 7-24 in integer _{preferred.) (4) C 6 H} 5 (CH 2) n SiCl 3 (n is 0-24 preferably an integer (5) CN (CH ₂ ) _n SiCl ₃ (n is an integer of preferably 0 to 24) (6) Cl ₃ Si (CH ₂ ) _n SiCl ₃ (n is an integer of 3 to 24 is preferable) (7) Cl ₃ Si (CH ₂ ) ₂ (CF ₂ ) _n (CH ₂ ) ₂ SiCl ₃ (n is an integer of 1 to 1
0 is preferred. In addition to the chlorosilane-based surfactants, the following silane-based surfactants containing an alkoxysilyl group or an isocyanatesilyl group could be used. (8) Ha (CH ₂ ) _n Si (OCH ₃ ) ₃ (Ha is chlorine, bromine, iodine,
Represents a halogen atom such as fluorine, and n is preferably an integer of 1 to 24. (9) CH ₃ (CH ₂ ) _n Si (NCO) ₃ (n is preferably an integer of 0 to 24) (10) CH ₃ (CH ₂ ) _p Si (CH ₃ ) ₂ (CH ₂ ) _q Si (OCH ₃ ) ₃ (p and q are preferably integers of 0 to 10.) (11) HOOC (CH ₂ ) _m Si (OCH ₃ ) ₃ (m is an integer of 7 to 24)
Is preferred. _{) (12) H 2 N (} CH 2) m Si (OCH 3) 3 (m is 7-24 in integer _{preferred.) (13) C 6 H} 5 (CH 2) n Si (NCO) 3 (n is (14) CN (CH ₂ ) _n Si (OC ₂ H ₅ ) ₃ (n is preferably an integer from 0 to 24) More specifically, the following compounds can also be used. (1) Br (CH ₂ ) ₈ SiCl ₃ (2) CH ₂ = CH (CH ₂ ) ₁₇ SiCl ₃ (3) CH ₃ (CH ₂ ) ₈ -CO- (CH ₂ ) ₁₀ SiCl ₃ (4) CH ₃ (CH ₂ ) ₅ -COO- (CH ₂ ) ₁₀ SiCl ₃ (5) CH ₃ (CH ₂ ) ₈ -Si (CH ₃ ) _2- (CH ₂ ) ₁₀ SiCl ₃ (6) CH ₃ (CH ₂ ) ₁₇ SiCl ₃ (7) CH ₃ (CH ₂ ) ₅ Si (CH ₃ ) ₂ (CH ₂ ) ₈ SiCl ₃ (8) CH ₃ COO (CH ₂ ) ₁₄ SiCl ₃ (9) C ₆ H ₅ (CH ₂ ) ₈ SiCl ₃ (10) CN (CH ₂ ) ₁₄ SiCl ₃ (11) Cl ₃ Si (CH ₂ ) ₈ SiCl ₃ (12) Cl ₃ Si (CH ₂ ) ₂ (CF ₂ ) ₄ (CH ₂ ) ₂ SiCl ₃ ( 13) Cl ₃ Si (CH ₂ ) ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ SiCl ₃ (14) CF ₃ CF ₂ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ (15) (CF ₃ ) ₂ CHO (CH ₂ ) ₁₅ Si (CH ₃ ) ₂ Cl (16) CF ₃ CF ₂ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ SiCl ₃ (17) CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ SiCl ₃ (18) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ SiCl ₃ (19) CF ₃ COO ( CH ₂ ) ₁₅ SiCH ₃ Cl ₂ (20) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ SiCl ₃ (21) CH ₃ CH ₂ CHC ^* H ₃ CH ₂ OCO (CH ₂ ) ₁₀ SiCl ₃ (C ^* is shows the asymmetric carbon of the optically _{active.) (22) CH 3 CH} 2 CHC * H 3 CH 2 OCOC 6 H 4 OCOC 6 H 4 O (CH 2) 5 SiCl 3 (23) the following formula (formula 3 Compounds represented by)

[0182]

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(24) Compound represented by the following formula (Formula 34)

[0184]

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The following compounds containing a siloxane bonding chain and a chlorosilyl group, or an alkoxysilane group or an isocyanatesilane group could be used. Also in this case, a highly oriented film was obtained. _{(25) ClSi (CH 3)} 2 OSi (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 Cl (26) Cl 3 SiOSi (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) ₂ OSi (CH ₃ ) ₂ OSiC
l ₃

[0186]

As described above, the first liquid crystal alignment film of the present invention has an effect that a highly efficient, uniform and thin alignment film can be formed in a desired pattern without requiring rubbing.

In the production of the liquid crystal alignment film, a silane surfactant was applied to the electrode surface in a monomolecular film form along the exposure pattern.
By using the above-described process using the layer chemical adsorption method a plurality of times, a multi-domain liquid crystal alignment film in which the alignment of individual pixels is divided into a plurality of types, which has been difficult with conventional rubbing, can be produced very easily. effective.

Further, by using such a liquid crystal alignment film, there is no chance of occurrence of a defect which has occurred in the conventional rubbing step, and the yield is high, the cost is very low, the reliability is high, and a wide viewing angle display is achieved. There is an effect that a possible liquid crystal display device can be provided.

Note that the alignment film formed by adsorption can incorporate a specific liquid crystal, for example, a nematic liquid crystal or a ferroelectric liquid crystal, and thus has extremely good alignment controllability. As described above, the second liquid crystal alignment film of the present invention can control the pretilt angle of the liquid crystal and can align the liquid crystal in any direction without using the conventional rubbing. This has the effect that it can be provided uniformly and thinly.

Further, the method for producing a liquid crystal alignment film of the present invention provides an alignment film having extremely excellent adhesion strength in which molecules constituting a coating film are aligned in a specific direction and fixed to one end of a substrate surface at one end. It has the effect that it can be provided efficiently.

In the production of a liquid crystal alignment film, if a process of exposing a polarizing plate with a patterned mask is performed a plurality of times, a plurality of portions having different patterned orientations in the alignment film in the same plane are formed. This is advantageous in that a multi-domain liquid crystal display device in which the alignment of individual pixels is divided into a plurality of types, which is difficult with conventional rubbing, can be manufactured very easily.

Furthermore, by using such a liquid crystal alignment film, there is no chance of occurrence of a defect which has occurred in the conventional rubbing step, and the yield is high, the cost is very low, the reliability is high, and a wide viewing angle display is achieved. There is an effect that a possible liquid crystal display device can be provided.

The alignment film formed by adsorption can incorporate a specific liquid crystal, such as a nematic liquid crystal or a ferroelectric liquid crystal, so that the alignment controllability can be extremely improved.
As described above, the third liquid crystal alignment film of the present invention is:
Even without using conventional rubbing, it is possible to control the critical surface energy of the alignment film, control the pretilt angle of the injected liquid crystal, and efficiently provide an alignment film having a function of aligning the liquid crystal in an arbitrary direction. There is an effect that can be provided.

In the production of the liquid crystal alignment film, if the process of exposing the polarizing plate with a patterned mask is performed a plurality of times, a plurality of portions in the alignment film in the same plane that differ only in the patterned alignment direction are formed. This makes it possible to efficiently and rationally manufacture a multi-domain liquid crystal display device in which the orientation of individual pixels is divided into a plurality of types, which has been difficult with conventional rubbing.

Further, by using such a liquid crystal alignment film, there is no chance of occurrence of a defect which has occurred in the conventional rubbing step, a desired tilt angle can be obtained, and the yield is high, the cost is extremely low, and the reliability is low. And a liquid crystal display device capable of displaying a wide viewing angle.

Since the alignment film formed by adsorption can incorporate a liquid crystal having a specific surface energy, such as a nematic liquid crystal or a ferroelectric liquid crystal, not only the control of the alignment direction and the tilt angle but also the alignment control force. Can be efficiently and rationally produced.

[Brief description of the drawings]

FIG. 1 is a conceptual cross-sectional view for explaining an exposure step for producing a liquid crystal alignment film in Example 1 of the present invention.

FIG. 2 is a conceptual diagram in which a portion A in FIG. 1 is enlarged to a molecular level, and illustrates a -CO formed on a substrate surface by exposure.
Shows the OH group part.

FIG. 3 is a conceptual diagram in which a portion A in FIG. 1 is enlarged to a molecular level, and shows a lipophilic surface portion on which a chemically adsorbed film is formed.

FIG. 4 is a conceptual cross-sectional view illustrating a liquid crystal alignment state in a liquid crystal cell manufactured using the liquid crystal alignment film manufactured in Example 1 of the present invention.

FIG. 5 is a conceptual cross-sectional view for explaining an exposure step for producing a liquid crystal alignment film in Example 2 of the present invention.

FIG. 6 is a conceptual diagram in which a portion B in FIG. 5 is enlarged to a molecular level, and shows -CO formed on a substrate surface by exposure.
Shows the OH group part.

FIG. 7 is a conceptual diagram in which the portion B in FIG. 5 is enlarged to the molecular level, and shows a lipophilic surface portion on which a chemically adsorbed film is formed.

FIG. 8 is a view for explaining a step of newly generating a carboxyl group by the second exposure in Example 3 of the present invention.

FIG. 9 is a conceptual cross-sectional view of a liquid crystal alignment film used to explain a state in which two types of chemically adsorbed films having different alignments are formed in Example 3.

FIG. 10 is a conceptual sectional view enlarged to a molecular level for explaining a state in which a siloxane monomolecular film is formed in Example 4 of the present invention.

FIG. 11 is a conceptual cross-sectional view for explaining the manufacture of a liquid crystal display device in Embodiment 4 of the present invention.

FIG. 12 is a conceptual cross-sectional view illustrating a chemical adsorption step used for producing a monomolecular liquid crystal alignment film in Example 5 of the present invention.

FIG. 13 is a conceptual cross-sectional view for explaining a cleaning step for producing a monomolecular liquid crystal alignment film.

FIG. 14 is a conceptual diagram in which a cross section is enlarged to a molecular level in order to explain a molecular alignment state in a monomolecular liquid crystal alignment film after solvent washing.

FIG. 15 is a conceptual diagram of an exposure step used to reorient molecules adsorbed by light exposure in Example 6 of the present invention.

FIG. 16 is a conceptual diagram for explaining a molecular alignment state in a monomolecular liquid crystal alignment film after photo alignment.

FIG. 17 is a conceptual diagram in which a cross section is enlarged to a molecular level in order to explain a molecular alignment state of a chemically adsorbed monomolecular film after photoalignment.

FIG. 18 is a conceptual cross-sectional view enlarged to a molecular level to explain a state in which a chlorosilane monomolecular film is formed (before reaction with moisture in the air) in Example 8 of the present invention.

FIG. 19 is a conceptual sectional view enlarged to a molecular level for explaining a state in which a siloxane monomolecular film is formed in Example 8 of the present invention.

FIG. 20 is a conceptual cross-sectional view for explaining manufacturing of a liquid crystal display device in Example 9 of the present invention.

FIG. 21 shows an FTIR absorption spectrum measured in a direction perpendicular to the pulling direction in Example 11 of the present invention.

FIG. 22 shows an FTIR absorption spectrum measured in a direction parallel to the pulling-up direction in Example 11 of the present invention.

FIG. 23 is a conceptual cross-sectional view for explaining a chemical adsorption step used for producing a monomolecular liquid crystal alignment film in Example 12 of the present invention.

FIG. 24 is a conceptual cross-sectional view for explaining a cleaning step of manufacturing a monomolecular liquid crystal alignment film.

FIG. 25 is a conceptual diagram in which a cross section is enlarged to a molecular level in order to explain a molecular alignment state in a monomolecular liquid crystal alignment film after solvent washing.

FIG. 26 is a conceptual diagram of an exposure step used to reorient molecules adsorbed by light exposure.

FIG. 27 is a conceptual diagram for explaining a molecular alignment state in a monomolecular liquid crystal alignment film after optical alignment.

FIG. 28 is a conceptual diagram in which a cross section is enlarged to a molecular level in order to explain a molecular alignment state of a chemisorption monomolecular film after photo-alignment.

FIG. 29 shows a state in which a chlorosilane monomolecular film is formed in Example 13 of the present invention (before reaction with moisture in the air).
FIG. 2 is a conceptual cross-sectional view enlarged to a molecular level in order to explain FIG.

FIG. 30 is a conceptual sectional view enlarged to a molecular level to explain a state in which a siloxane monomolecular film is formed in Example 13 of the present invention.

FIG. 31 is a conceptual sectional view for explaining the production of a liquid crystal display device in Example 14 of the present invention.

[Explanation of symbols]

 1,21 Substrate on which electrodes are formed 2,2 ', 22,22', 32 'Resist 3,23 Mask 4,24 Substrate with exposed resist 5,25 Carboxyl group 6,26,27 Lipophilic chemisorption Monomolecular film 7, 7 'Liquid crystal molecule 8 Carbon chain of monomolecular film 28 Substrate on which multi-domain alignment film is formed 33 Hydrophilic monomolecular film 41 First electrode group 42 Transistor group 43 First substrate 44 Color filter Group 45 Second electrode 46 Second substrate 47 Liquid crystal alignment film 48 Spacer 49 Adhesive 50 Liquid crystal 51, 52 Polarizing plate 53 Backlight 61 Substrate 62 Chemical adsorption liquid 63 Nonaqueous solvent for cleaning 64 Primary chemically adsorbed Monomolecular film 64 ′ Reoriented chemisorption monomolecular film 65 Pulling direction from cleaning solution 66 Polarizing film 67 Irradiation light 68 Reorientation direction 69 Transparent electrode 71 Chlorosilane molecule 72 Siloxane monomolecular film 73 Polarization direction 81 First electrode group 82 Transistor group 83 First substrate 84 Color filter group 85 Second electrode 86 Second substrate 87 Liquid crystal alignment film 88 Spacer 89 Adhesive 90 Liquid crystal Reference Signs 91, 92 Polarizing plate 93 Backlight 101 Substrate 102 Chemical adsorption liquid 103 Nonaqueous solvent for cleaning 104 Primary chemically adsorbed monomolecular film 104 'Reoriented chemical adsorption monomolecular film 105 Pulling up direction from cleaning liquid 106 Polarized light Film 107 Irradiation light 108 Reorientation direction 109 Transparent electrode 111 Chlorosilane molecule 112 Siloxane monomolecular film 113 Polarization direction 121 First electrode group 122 Transistor group 123 First substrate 124 Color filter group 125 Second electrode 126 Second substrate 127 Liquid crystal alignment film 28 spacer 129 adhesive 130 LCD 131 polarizer 133 Backlight

Claims (57)

[Claims] An energy beam-sensitive resin film in which a silane-based surfactant having a linear carbon chain and Si forms a functional group containing active hydrogen upon irradiation of an energy beam formed on a predetermined substrate surface. A liquid crystal alignment film, which is a film that is chemisorbed through a film and in which the linear carbon chain is oriented in a specific direction. 2. The liquid crystal alignment film according to claim 1, wherein the film made of the surfactant is fixed to the energy beam-sensitive resin film via a conjugate bond on the surface of the substrate in a streak pattern. 3. The liquid crystal alignment film according to claim 2, wherein the film made of the fixed surfactant is fixed to an energy beam-sensitive resin film via a film having a siloxane bond. 4. The liquid crystal alignment film according to claim 1, wherein the silane-based surfactant is a chlorosilane-based surfactant containing a linear hydrocarbon group and a chlorosilyl group. 5. The liquid crystal alignment film according to claim 4, wherein a part of the hydrogen of the linear hydrocarbon group of the chlorosilane-based surfactant is substituted with at least a fluorine atom. 6. The liquid crystal according to claim 4, wherein a mixture of a plurality of chlorosilane-based surfactants having different molecular lengths is used as the chlorosilane-based surfactant containing a linear hydrocarbon group and a chlorosilyl group. Alignment film. 7. A monomolecular film-like film formed on a substrate surface on which a desired electrode is formed, wherein the molecules constituting the film have a desired inclination and are oriented in a specific direction. A liquid crystal alignment film characterized by being fixedly bonded at one end to a substrate surface. 8. The desired inclination of a molecule is formed by immobilizing a molecule constituting a film on a substrate by a covalent bond, washing the molecule with an organic solvent, and further standing the substrate in a desired direction to form a liquid. The liquid crystal alignment film according to claim 7, which is: 9. The liquid crystal alignment film according to claim 7, wherein the molecules constituting the coating include a carbon chain or a siloxane bond chain. 10. The liquid crystal alignment film according to claim 9, wherein a part of carbon in the carbon chain has optical activity. 11. The liquid crystal alignment film according to claim 7, wherein Si is contained at both ends of molecules constituting the film. 12. The film according to claim 7, wherein the molecules constituting the film are formed by mixing a plurality of types of chemisorbed molecules having different molecular lengths, and the fixed film is uneven at the molecular length level.
12. The liquid crystal alignment film according to any of 11. 13. A monomolecular film formed on the surface of a substrate on which a desired electrode is formed, wherein the molecules constituting the film include a carbon chain or a siloxane bond, and A liquid crystal alignment film, characterized in that at least a part thereof contains at least one functional group for controlling the surface energy of the film. 14. A method in which a plurality of types of silane-based surfactants having different critical surface energies are mixed and used as molecules constituting the coating, and the fixed coating is controlled so as to exhibit a desired critical surface energy value. Item 14. A liquid crystal alignment film according to item 13. 15. The functional group for controlling surface energy,
3 fluorocarbon group (-CF _3), a methyl group (-CH _3), a vinyl group (-CH = CH _2), allyl (-CH = CH
-), an acetylene group (carbon - triple bond of carbon), a phenyl group (-C ₆ H _5), an aryl group (-C ₆ H ₄ -), a halogen atom, an alkoxy group (-OR; with R is an alkyl group represented), a cyano group (-CN), amino group (-NH _2), a hydroxyl group (-OH), a carbonyl group (= CO), at least a selected from an ester group (-COO-) and a carboxyl group (-COOH) The liquid crystal alignment film according to claim 13 or 14, which is one organic group. 16. The liquid crystal alignment film according to claim 13, wherein the terminal of the molecule constituting the film contains Si. 17. The film has a critical surface energy of 15 mN.
The liquid crystal alignment film according to any one of claims 13 to 16, wherein the liquid crystal alignment film is controlled to a desired value between / m and 56 mN / m. 18. The method according to claim 18, wherein the surface of the predetermined substrate on which the electrodes are formed is
Directly or indirectly through an arbitrary thin film, applying and forming an energy beam-sensitive resin film for generating a functional group containing active hydrogen by an energy beam; and forming an energy beam on the surface of the resin film in an arbitrary pattern. And contacting the irradiated resin film with a chemisorption solution containing a silane-based surfactant having a linear carbon chain and a Si group, followed by washing with a solvent that does not dissolve the resin film A liquid crystal alignment comprising a step of selectively forming one layer of a monomolecular film made of the surfactant in the irradiated portion and fixing a linear carbon chain in the surfactant molecule. Manufacturing method of membrane. 19. The method for manufacturing a liquid crystal alignment film according to claim 18, wherein the energy beam is at least one selected from an electron beam, an X-ray, and light having a wavelength of 100 nm to 1 μm. 20. The liquid crystal alignment according to claim 19, wherein the chemical adsorption liquid contains a chlorosilane-based surfactant containing at least a linear carbon chain and a chlorosilyl group, and a solvent that does not damage the energy beam-sensitive resin film. Manufacturing method of membrane. 21. The liquid crystal alignment film according to claim 19, wherein the energy beam is at least one light selected from ultraviolet light, visible light and infrared light, and the energy beam-sensitive resin film is a photosensitive resin film. Production method. 22. A photosensitive resin film represented by the following formula (Formula 1)
22. The method for producing a liquid crystal alignment film according to claim 21, wherein the method is a polymer film or a monomer film containing at least one organic group selected from a group represented by the following formulas. Embedded image Embedded image Embedded image 23. The method for producing a liquid crystal alignment film according to claim 18, wherein a solvent containing a carbon fluoride group is used as the non-aqueous solvent. 24. A step of bringing a substrate on which electrodes are formed into contact with a chemical adsorption solution to cause a chemical reaction between surfactant molecules in the adsorption solution and the substrate surface to bond and fix the surfactant molecules to the substrate surface at one end. A method of producing a monomolecular liquid crystal alignment film, comprising the steps of: washing the substrate with an organic solvent; further erecting the substrate in a desired direction; and draining the liquid; and aligning the fixed molecules in the draining direction. 25. After aligning the molecules, the molecules are further exposed to light polarized in a desired direction through a polarizing plate to align the direction of the surfactant molecules in a specific direction with a desired inclination. The method for producing a monomolecular liquid crystal alignment film according to claim 24, comprising a step. 26. The method according to claim 24, wherein a silane-based surfactant containing a linear hydrocarbon group or a siloxane bond chain and a chlorosilyl group, or an alkoxysilyl group or an isocyanatesilyl group is used as the surfactant. A method for producing a monomolecular liquid crystal alignment film. 27. A mixture of a plurality of silane-based surfactants having different molecular lengths as a silane-based surfactant containing a linear hydrocarbon group or a siloxane-bonded chain and a chlorosilyl group, an alkoxysilyl group or an isocyanatesilyl group. The method for producing a monomolecular liquid crystal alignment film according to claim 26, which is used as a liquid crystal alignment film. 28. The method for producing a monomolecular liquid crystal alignment film according to claim 26, wherein a part of carbons of the hydrocarbon group has optical activity. 29. hydrocarbon group or terminal halogen atom or a methyl group of the siloxane bond chain (-CH _3), phenyl group (-C ₆ H _5), a cyano group (-CN), hydroxyl group (-
OH), carboxyl group (-COOH), amino group (-
NH _2), or the method of manufacturing a monomolecular film-like liquid crystal alignment film according to any one of claims 26 to 28 which contains birds fluorocarbon group (-CF _3). 30. Light used for exposure is 436 nm, 40
The method for producing a monomolecular liquid crystal alignment film according to claim 25, wherein the light is at least one wavelength selected from 5 nm, 365 nm, 254 nm, and 248 nm. 31. A silane-based surfactant containing a linear hydrocarbon group or a siloxane bonding chain and a chlorosilyl group or an isocyanatesilyl group is used as the surfactant.
31. The method for producing a monomolecular liquid crystal alignment film according to claim 26, wherein a non-aqueous organic solvent containing no water is used as the washing organic solvent. 32. The method for producing a monomolecular liquid crystal alignment film according to claim 31, wherein a solvent containing an alkyl group, a carbon fluoride group, a carbon chloride group or a siloxane group is used as the non-aqueous organic solvent. 33. The method according to claim 24, wherein a film containing a large number of SiO groups is formed before the step of fixing the surfactant molecules at one end, and a monomolecular film is formed through the film. A method for producing a monomolecular liquid crystal alignment film according to any one of the above. 34. A silane wherein a substrate on which an electrode is formed includes a carbon chain or a siloxane bonding chain, and at least a part of the carbon chain or the siloxane bonding chain includes at least one functional group for controlling the surface energy of the coating. Contacting the surface of the substrate with a chemically adsorbed liquid prepared using a surfactant to chemically react the surfactant molecules in the adsorbed liquid with the surface of the substrate. A method for producing a monomolecular liquid crystal alignment film, characterized in that: 35. The monomolecular film according to claim 34, wherein a silane-based surfactant containing a linear carbon chain or a siloxane bond chain and a chlorosilyl group, an alkoxysilyl group or an isocyanatesilyl group is used as the surfactant. Method for producing liquid crystal alignment film. 36. The method for producing a monomolecular liquid crystal alignment film according to claim 34, wherein a mixture of a plurality of silicon-based surfactants having different critical surface energies is used as the surfactant. 37. A carbon trifluoride group (—CF ₃ ), a methyl group (—CH ₃ ), a vinyl group (—CH ＝ CH ₂ ), an allyl group (— CH = CH-), an acetylene group (carbon - triple bond of carbon), a phenyl group (-C ₆ H _5), an aryl group (-C ₆
H ₄ —), a halogen atom, an alkoxy group (—OR; R represents an alkyl group), a cyano group (—CN), an amino group (—NH ₂ ), a hydroxyl group (—OH), a carbonyl group (＝ C
The method for producing a monomolecular liquid crystal alignment film according to any one of claims 34 to 36, wherein the method is at least one organic group selected from O), an ester group (-COO-), and a carboxyl group (-COOH). 38. After the step of binding and fixing the surfactant molecules to the substrate surface at one end, the substrate is washed with an organic solvent, and further, the substrate is set up in a desired direction and drained. The method for producing a monomolecular liquid crystal alignment film according to any one of claims 34 to 37, wherein the molecules are aligned. 39. The method for producing a monomolecular liquid crystal alignment film according to claim 38, wherein after the molecules are aligned, the molecules are further exposed through a polarizing film to reorient the aligned molecules in a desired direction. Method. 40. A silane-based surfactant containing a linear carbon chain or a siloxane bond chain and a chlorosilyl group or an isocyanate silane group as a surfactant, and a non-aqueous organic solvent containing no water as a washing organic solvent. The method for producing a monomolecular liquid crystal alignment film according to claim 38 or 39, wherein the method is used. 41. The method for producing a monomolecular liquid crystal alignment film according to claim 40, wherein a solvent containing an alkyl group, a carbon fluoride group, a carbon chloride group or a siloxane group is used as the non-aqueous organic solvent. 42. A step of forming a film containing a large number of SiO groups before the step of fixing the surfactant molecules at one end, and forming a monomolecular film through this film. 42. The method for producing a monomolecular liquid crystal alignment film according to any one of items 41 to 41. 43. A liquid crystal display device in which a pair of substrates, an electrode on the surface thereof, and an alignment film on the surface are formed in this order, and a liquid crystal is sandwiched between the two opposing electrodes via the alignment film. The at least one alignment film is formed by forming a silane-based surfactant having a linear carbon chain through an energy beam-sensitive film that generates a functional group containing active hydrogen by energy beam irradiation. A liquid crystal display device, wherein the film is adsorbed and the linear carbon chain is oriented in a specific direction. 44. A monomolecular film formed of a silane-based surfactant having a linear carbon chain or a siloxane-bonded chain, wherein the molecules constituting the film have a desired inclination and a specific direction. The coating fixed and fixed at one end to the substrate surface in the same direction as the alignment film for liquid crystal is directly or another coating on the electrode side surface of at least one of the substrate surfaces on which the two facing electrodes are formed. A liquid crystal display device in which a liquid crystal is interposed between the two opposing electrodes via the alignment film. 45. The liquid crystal display device according to claim 44, wherein the coating is formed as an alignment film on the surface of the substrate on which the two electrodes facing each other are formed. 46. The liquid crystal display device according to claim 44, wherein the coating on the surface of the substrate includes a plurality of portions having a pattern orientation different from each other. 47. The liquid crystal display device according to claim 44, wherein the opposing electrode is formed on the surface of one of the substrates. 48. A coating comprising a molecule comprising a carbon chain or a siloxane bonding chain, wherein at least a part of the carbon chain or the siloxane bonding chain contains at least one functional group that controls the surface energy of the coating, A liquid crystal alignment film is formed directly or indirectly via another coating on at least one of the substrate surfaces on which two opposed electrodes are formed as an alignment film for liquid crystal, and the liquid crystal is formed on the two opposed electrodes. A liquid crystal display device, wherein the liquid crystal display device is interposed between the liquid crystal display device and the liquid crystal display device. 49. The liquid crystal display device according to claim 48, wherein each of the coatings is formed as an alignment film on the surface of the substrate on which the two electrodes facing each other are formed. 50. The liquid crystal display device according to claim 48, wherein the film on the surface of the substrate includes a plurality of portions having different pattern-like orientation directions. 51. The liquid crystal display device according to claim 48, wherein the opposing electrodes are formed on one substrate surface. 52. A functional group containing active hydrogen is generated by an energy beam directly or indirectly through an arbitrary thin film on a first substrate having a first electrode group mounted in a matrix in advance. Applying an energy beam sensitive resin film to the substrate, irradiating the surface of the resin film with an energy beam in an arbitrary pattern, and applying a linear carbon chain and S
After contacting with a chemical adsorption solution containing a silane-based surfactant having i, the monomolecular film composed of the surfactant is selectively applied to the irradiated portion by washing with a solvent that does not dissolve the resin film. Forming a single layer and fixing the orientation of the linear carbon chain; and forming a first electrode group having the first electrode group.
Bonding and fixing a substrate and a second substrate having a second electrode or an electrode group while maintaining a predetermined gap so that the respective electrodes face each other; and bonding and fixing the first and second substrates. And a step of injecting a predetermined liquid crystal between them. 53. A first substrate having a first electrode group previously placed in a matrix form, directly or after forming an arbitrary thin film, is brought into contact with a chemical adsorption solution to cause the surfactant molecules in the adsorption solution to contact with the chemical adsorption solution. A step of chemically reacting with the substrate surface to bond and fix the surfactant molecule to the substrate surface at one end; and further, after washing with an organic solvent, the substrate is erected in a desired direction, drained, and the liquid is fixed in the draining direction. Aligning the molecules, and further aligning the surfactant molecules in a specific direction with a desired inclination by exposing to light polarized in a desired direction through a polarizing plate; and The first substrate having one electrode group and the second substrate, or the second substrate having the second electrode or the electrode group, are aligned and fixed while maintaining a predetermined gap with the electrode surface inside. The process of
A method for manufacturing a liquid crystal display device, comprising a step of injecting a predetermined liquid crystal between the first and second substrates. 54. A step of exposing the bonded surfactant molecules to a specific direction with a desired inclination by exposing to light with light polarized in a desired direction through a polarizing plate. 54. The method for manufacturing a liquid crystal display device according to claim 53, wherein the step of exposing a pattern-shaped mask on the plate is performed a plurality of times, and a plurality of portions having different pattern-shaped alignment directions are provided in the alignment film in the same plane. . 55. A method of forming a first substrate having a first electrode group mounted in a matrix form directly or after forming an arbitrary thin film, comprising a carbon chain or a siloxane-bonded chain; A surfactant is prepared by using a silane-based surfactant containing at least a functional group that controls the surface energy of the coating on at least a part of the chain. And chemically fixing the surfactant molecules at one end to the substrate surface, and after washing with an organic solvent, further erecting the substrate in a desired direction and draining the liquid to remove the fixed molecules in the draining direction. Orienting the first substrate and the second substrate having the first electrode group, or the second substrate having the second electrode or the electrode group, by keeping a predetermined gap with the electrode surface inside. A method of manufacturing a liquid crystal display device, comprising the steps of: aligning and fixing while positioning; and injecting a predetermined liquid crystal between the first and second substrates. 56. After the step of orienting the fixed molecule, the surface of the surfactant molecule is specified in a state having a desired inclination by further exposing through a polarizing plate with light polarized in a desired direction. The method for manufacturing a liquid crystal display device according to claim 55, wherein a step of aligning the liquid crystal display device is performed. 57. A step of exposing with light polarized in a desired direction through a polarizing plate to align the direction of the bound surfactant molecules in a specific direction with a desired inclination, 57. The method for manufacturing a liquid crystal display device according to claim 56, wherein a step of exposing a pattern-shaped mask on the plate is performed a plurality of times, and a plurality of portions having different pattern-shaped alignment directions are provided in the alignment film in the same plane. .