JP3486580B2 - Functional film and method for producing the same, liquid crystal display device using the same, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a functional film containing a silane compound as a film component and excellent in water repellency, durability and heat resistance and a method of manufacturing the same, and a liquid crystal display element using the functional film and a method of manufacturing the same. SOLUTION: A substrate layer solution containing a hydrolyzable compound represented by X-(SiOX2)n-SiX3 (wherein X is at least one compound selected from the group consisting of halogen, an alkoxy group and an isocyanate group and (n) is an integer of a 0 or more) is applied to the surface of a base material and dried at below 300 deg.C to form a substrate layer, a solution containing a silane compound is applied to the surface of the substrate layer to chemically adsorb silane compound molecules on the base material, and the coated base material is baked at 300 deg.C or higher to form a functional film. By this constitution, the water repellency, durability and heat resistance of the functional film comprising the silane compound used for the purpose of modifying the surface properties of the functional film can be enhanced.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a functional film formed on the surface of a base material for modifying the properties of the base material, a method for producing the same, and a liquid crystal display device using the same as a liquid crystal alignment film. The manufacturing method is related.

[0002]

2. Description of the Related Art Conventionally, means for modifying the properties of the surface of a base material to impart water repellency, antifouling property and a function of orienting liquid crystal to the surface of the base material has been used. As one of the methods, there is a method in which a solution in which a trichlorosilane-based compound, a silane coupling agent, or the like is dissolved is applied to the base material to chemically adsorb the coating component on the base material surface. According to this method, the solute molecules, which are coating film components, are strongly bound to the base material by chemical adsorption, so that a coating film having excellent durability can be formed. However, when the surface of the base material has a small amount of active hydrogen such as hydroxyl groups, a rough coating film having a low density of adsorbed molecules is formed. Such a coating cannot sufficiently achieve the purpose of surface modification.

Therefore, for a base material having a low active hydrogen density, a sol-gel solution containing SiO ₂ as a main component is applied in advance and baked to form a base layer having a high active hydrogen density on the surface of the base material. A method of binding and fixing a coating film to a base material via an underlayer by a method of applying a coating solution containing a coupling agent and the like is adopted. According to this method, the durability of the film can be increased as compared with the method of directly applying the coating solution to the substrate.
However, the functional film according to the related art produced by using this method is still not sufficient in terms of adhesion with the substrate, uniformity of the film, durability, etc., and further improvement is desired. ing.

By the way, SiO ₂ is mixed in advance with a solution containing a silane coupling agent, a trichlorosilane-based compound, etc., and the mixture is directly applied to the base material.
A method of simplifying the work of forming the underlayer and increasing the density of active hydrogen can also be considered. However, according to this method, a silane coupling agent, a trichlorosilane-based compound, or the like is segregated at the interface between the substrate and the functional film during the process of drying the solution, and the adhesive force between the substrate and the functional film cannot be increased.

Further, the durability of the functional film also depends on the durability of the underlayer, and an underlayer having a higher durability than the SiO ₂ film is desired for further improvement of the durability.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above, and has the following characteristics: coating uniformity and adhesion to a substrate,
An object is to provide a functional film capable of producing a functional film having excellent durability and a method for producing the functional film. Moreover, it aims at providing the liquid crystal display element which used this functional film as a liquid crystal aligning film, and its manufacturing method.

[0007]

In order to achieve the above object, the functional film of the present invention has the constitution described below.

(1) The functional film according to the first aspect of the present invention is a functional film formed on the surface of a substrate via an underlayer, wherein the underlayer is X- (SiOX ₂ ) _n- SiX
₃ (wherein X is at least one functional group selected from the group consisting of halogen, an alkoxy group and an isocyanate group, and n is an integer of 0 or more),
A thin film formed of a compound capable of being hydrolyzed, the thin film including a structural unit represented by the following structural formula (1), which is bonded and fixed on the substrate through a siloxane bond, and has the above-mentioned function. The functional film is a thin film in which a group of silane-based compound molecules having a —O—Si bonding group at a molecular end group is chemically adsorbed to the underlying layer by chemical bonding.

[0009]

[Chemical 9] (However, n is an integer of 0 or more.) According to the above configuration, as shown in the structural formula (1),
Since the constituent molecules of the underlayer are polymerized with each other and some of the constituent molecules are chemically bonded to the substrate, the underlayer strongly adhered to the substrate can be obtained. Furthermore, in this underlayer,
Since the silane compound molecules constituting the functional film are chemically adsorbed at a high density, it is possible to obtain a uniform and good-quality functional film having excellent durability.

(2) The functional film according to the second aspect of the present invention is a functional film formed on the surface of a substrate via an underlayer, wherein the underlayer is X '-(AlOX' ) _N- Al
A thin film formed of a compound capable of being hydrolyzed, which is represented by X ′ ₂ (wherein X ′ represents an alkoxy group, and n is an integer of 0 or more).
A thin film containing a structural unit represented by the following structural formula (2), which is bonded and fixed on the substrate through an l bond, and the functional film has an —O—Si bonding group at a molecular end group. A thin film in which a group of silane-based compound molecules is chemically adsorbed to the underlayer by chemical bonding.

[0011]

[Chemical 10] (However, n is an integer of 0 or more.) Since the underlayer includes the structural unit represented by the structural formula (2) and is bonded and fixed on the base material through the —O—Al bond. , Excellent in durability such as abrasion resistance and heat resistance. Therefore, according to the above configuration, by forming the functional film on the underlayer, it is possible to obtain a thin film having extremely excellent durability.

(3) The functional film according to the third aspect of the present invention is a functional film formed on the surface of a substrate through an underlayer, wherein the underlayer is X- (SiOX ₂ ). _n- SiX
₃ (wherein X is at least one functional group selected from the group consisting of halogen, an alkoxy group and an isocyanate group, and n is an integer of 0 or more),
A compound capable of being hydrolyzed, and X ′-(A
1OX ′) _n -AlX ′ ₂ (where X ′ represents an alkoxy group, and n is an integer of 0 or more), which is a thin film formed of a compound capable of being hydrolyzed, A thin film comprising a structural unit represented by the following structural formula (1) and structural formula (2), which is bonded and fixed on the base material through a siloxane bond and a —O—Al bond, and the functional film is It is a thin film in which a group of silane-based compound molecules having a —O—Si bond group at a molecular end group is chemically adsorbed to the underlayer by a chemical bond.

[0013]

[Chemical 11] (However, n is an integer of 0 or more.) In the above structure, the underlayer is a thin film containing structural units different from each other, which are represented by the structural formulas (1) and (2). It has a dense structure in which the Al-based compounds and the Al-based compounds enter each other at the molecular level and are disturbed. Therefore, the functional film provided on the base material via the underlayer can be highly dense and excellent in durability. This is because if the underlayer has a high density, a large number of silane compound molecules are chemically adsorbed to the adsorption sites as a result of the high density of adsorption sites on the surface layer.

The following constituent elements can be further added to the functional film according to the first to third aspects.

That is, the silane compound molecule in the above (1) to (3) can be a trichlorosilane compound molecule. A trichlorosilane-based compound molecule directly binds (chemisorbs) to an OH group exposed in the underlayer by a covalent bond without causing a polymerization reaction of itself, so that the trichlorosilane-based compound molecule is chemically bonded at high density. It is possible to manufacture a functional film that can be adsorbed and is less likely to deteriorate surface modification effects such as water repellency and liquid crystal alignment.

The silane compound molecule preferably has a linear carbon chain. This is because when a linear carbon chain is provided, silane-based compound molecules are arranged in an orderly manner on the substrate and can be chemically adsorbed at a high density, and the surface modification effects such as water repellency and liquid crystal alignment are less likely to deteriorate. .

The linear carbon chain may have an alkyl group or a fluoroalkyl group. A film made of a silane compound having an alkyl group or a fluoroalkyl group is preferable in that it is excellent in water repellency and antifouling property, and a film having excellent water repellency prevents moisture from entering between the underlayer and the substrate. To prevent. Therefore, the durability is further improved. When it is used as a liquid crystal alignment film, it can be controlled to any alignment such as homogeneous alignment, pretilt alignment, homeotropic alignment.

The linear carbon chain may be provided with a photosensitive group.

Further, the photosensitive base portion in the linear carbon chain can be polymerized and fixed in a desired direction. This makes it possible to provide a functional film having improved durability, and when the functional film is used as a liquid crystal alignment film, it is possible to provide excellent alignment stability.

Further, the photosensitive group may be a cinnamoyl group represented by the following chemical formula (3).

[0021]

[Chemical 12] The photosensitive group may be a chalconeyl group represented by the following chemical formula (4).

[0022]

[Chemical 13] If a cinnamoyl group or a chalconeyl group is used as the photosensitive group, polymerization can be performed with a small irradiation amount of polarized ultraviolet light, and thus the tact time in the ultraviolet irradiation process can be shortened.

The functional film in the above (1) to (3) is
It can be a thin film having a monomolecular layer. In the case of a monolayer thin film, the same functional groups are arranged on the film surface side,
The function of the functional film exerted due to the functional group can be improved. For example, when the functional group is a CF ₃ group, more CF ₃ groups are exposed on the film surface side of the functional film than in a thin film that is not a monomolecular layer, so that water repellency can be improved.
Further, it can be a functional film having excellent alignment and can be suitably formed as a liquid crystal alignment film.

The aggregated group of the silane-based compound molecules forming the functional film in the above (1) to (3) can be oriented in a predetermined direction. With such a structure, it is possible to obtain a liquid crystal alignment film capable of aligning liquid crystal molecules in the vicinity in a desired direction.

The above-mentioned substrate can be made of any one selected from glass, stainless steel and aluminum oxide. This makes it possible to form a highly durable functional film on a substrate made of glass, stainless steel, or aluminum oxide. As the method for producing the functional film described above, the following modes (4) to (6) can be adopted. Here, (4) to (6) correspond to the above-described first to third aspects, respectively.

(4) In the method for producing a functional film of the present invention, which corresponds to the above-mentioned first aspect, X- (SiOX) is formed on the surface of the base material.
₂ ) Hydrolyzed represented by _n- SiX ₃ (wherein X is at least one functional group selected from the group consisting of halogen, an alkoxy group and an isocyanate group, and n is an integer of 0 or more). A base layer forming step of contacting a base layer solution containing a compound capable of forming a base layer by drying, and contacting a solution containing a silane compound to the surface of the base material on which the base layer is formed to form a silane compound. A thin film forming step of forming a thin film by chemically adsorbing the base material on the surface of the base material; and a baking step of baking the base material after the thin film forming step.

In the above method, in the step of forming the underlayer, only the underlayer is dried and not baked, but in this method, SiX ₃ existing near the surface of the underlayer reacts with moisture in the drying process. The density of active hydrogen as an adsorption site of the silane-based compound is increased while changing to one having an OH group, and since firing is not performed, active hydrogen is not lost due to the temperature during firing. When a solution containing a silane-based compound is brought into contact with such an underlayer, the silane-based compound molecules are chemically bonded (also referred to as chemisorption) to active hydrogen sites that are present at a high density, so that the silane-based compound molecules are densified at a high density. A thin film formed by chemisorption can be formed.

In the above method, the base material is baked at the final stage of the manufacturing process. By this baking, the constituent molecules of the underlayer are polymerized and solidified to bond to the base material more strongly, and Part of the chemical bond with the substrate. Therefore, the base layer can be strongly fixed to the base material.

From the above, according to the above-mentioned manufacturing method, it is possible to manufacture a high-quality functional film in which a thin film made of a silane-based compound is uniformly bonded and fixed to a substrate through an underlayer strongly fixed to the substrate. This functional film has excellent durability and the like.

The silane-based compound is R _p Si (O
-) _3-p (R is a substituent, P is an integer of 1 to 3) is bonded (chemisorbed) to the surface of the base material having the underlayer by a covalent bond.

(5) In the method for producing a functional film according to the present invention, which corresponds to the second aspect, X '-(AlO
X ') _n -AlX' ₂ ( _where X'represents an alkoxy group, and n is an integer of 0 or more), and a base layer solution containing a hydrolyzable compound represented by
An underlayer forming step of drying and forming an underlayer, and a film-forming solution containing a silane-based compound are brought into contact with the surface of the base material on which the underlayer is formed to chemically adsorb silane-based compound molecules on the surface of the base material. A film forming step of forming a film by the above,
And a baking step of baking the base material after the film forming step.

The underlying layer forming step in the above method is characterized in that the underlying layer is dried only and not baked. With this configuration, Al-X 'existing near the surface of the underlayer reacts with moisture to change to one having an Al-OH group during the drying process, and active hydrogen as an adsorption site of the silane-based compound molecule is converted. While the density is increased, since the firing is not performed, active hydrogen is not lost depending on the temperature at the time of firing.
When a solution containing a silane-based compound is brought into contact with such an underlayer, the silane-based compound molecules chemically bond (also referred to as chemisorption) to active hydrogen sites that are present at high density. Therefore,
It is possible to form a thin film in which silane compound molecules are chemically adsorbed at high density and uniformly.

Further, in the above method, the base material is baked at the final stage of the manufacturing process. By this baking, the constituent molecules of the underlayer are polymerized and solidified to bond more strongly to the base material. Some of the molecules chemically bond with the substrate. Therefore, the base layer can be strongly fixed to the base material.

Further, the durability of the functional film, such as abrasion resistance and heat resistance, is greatly affected by the abrasion resistance and heat resistance of the underlayer, but X '-(AlOX') _n -AlX. Since the underlayer made of the compound represented by ' ₂ is superior in durability to the SiO ₂ single layer (main body of the functional film), the above-mentioned configuration provides the functional film having excellent durability. That is, according to the above structure, the silane compound molecules can be bonded and fixed to the base material at high density and uniformly through the underlying layer strongly adhered to the base material. Then, the functional film thus formed has extremely excellent durability and the like.

The silane compound is R _p Si (O
−) _3-p (R is a substituent, p is an integer of 1 to 3) is bonded (chemisorption) to the surface of the base material having the underlayer by a covalent bond.

(6) In the method for producing a functional film of the present invention, which corresponds to the third aspect, the X- (SiOX) is formed on the surface of the base material.
₂ ) _n- SiX ₃ (wherein X is at least one functional group selected from the group consisting of a halogen, an alkoxy group and an isocyanate group, and n is an integer of 0 or more) Possible compounds and X'-
(AlOX ′) _n —AlX ′ ₂ (where X ′ is an alkoxy group and n is an integer of 0 or more) and a hydrolyzable compound represented by the underlayer containing a binary mixture. A base layer forming step of contacting a solution and drying to form a base layer, and a film forming solution containing a silane compound on the surface of the base material on which the base layer is formed are contacted to form a base material containing silane compound molecules. A film forming step of forming a film by chemical adsorption on the surface, and a baking step of baking the substrate after the film forming step are provided.

In this method, X- (S
iOX _{2) n} -SiX ₃ and _{X '- (AlOX') n} -Al
Which comprises using a two-component underlying layer solution containing the X _'2. In other respects, it is a method for producing a functional film in the same manner as in the case of claim 1. With this structure, A existing in the vicinity of the surface of the underlayer during the drying process
l-X 'and Si-X respectively react with moisture to form Al-
It is changed to a compound having an OH group or a Si—OH group, and the density of active hydrogen as an adsorption site for silane-based compound molecules is increased. Also, in this configuration, as in the case of claim 1, since the firing is not performed, active hydrogen is not lost due to the temperature at the time of firing.

Further, in this constitution, the compound [X- (Si
OX _{2) n} -SiX _3] and the compound [X '- (AlOX') _n
-AlX ' ₂ ] and a two-component underlayer solution with
In the case of the two-component system composed of the above Si-based and Al-based compounds, the compounds having different structures enter each other at the molecular level and are disturbed, so that an underlayer having a dense structure is formed as compared with the case of using each independently. To do. This underlayer has a high density of hydroxyl groups in the surface layer due to its high density, so that more film forming molecules are chemically adsorbed. Therefore, a more dense functional film is formed, and as a result, deterioration of water repellency due to thermal energy is reduced. In the method for manufacturing a functional film according to the first to third aspects, the constituent elements described below can be further added.

That is, Si and A of the binary mixture
The molar ratio Si / Al of 1 can be 1 or more. That is, the molar ratio of Si to Al of the underlayer formed by using a two-component underlayer solution composed of a Si-based compound and an Al-based compound Si /
When Al is 1 or more, an underlayer of SiO ₂ alone or Al ₂
An underlayer that is superior in wear resistance and heat resistance to an underlayer containing only O ₃ and is also superior in wear resistance and heat resistance than a two-component underlayer having a molar ratio Si / Al of less than 1 is formed. it can. And, as described above, the durability of the functional film largely depends on the durability and the like of the underlayer. Therefore, according to this configuration,
A functional film having excellent wear resistance and heat resistance can be manufactured.

Further, the above-mentioned X- (SiOX ₂ ) _n -SiX ₃
The compound represented by can be an alkoxysilane. The alkoxysilane has the advantage that it is easy to control the reaction with water and the polymerization reaction by temperature and does not produce harmful products such as hydrochloric acid when reacting with water, and thus is easy to handle. Therefore, with the above configuration, it is possible to form a good quality underlayer having good manufacturing workability and many chemical adsorption sites. In addition, the base layer can be firmly fixed to the base material by firing performed in the final stage of the production, and as a result, a functional film excellent in water repellency and durability can be produced.

The drying in the underlayer forming step is characterized in that the solvent contained in the underlayer solution is evaporated.
The drying in the base layer forming step can be performed at a temperature lower than 300 ° C. When the underlayer is dried at a temperature of less than 300 ° C., Al-X ′ exposed on the surface of the underlayer,
Alternatively, Si-X can be appropriately reacted with water to form Al-OH or Si-OH, while the hydroxyl group (OH) is not lost by an unnecessary decomposition reaction. Therefore, with this structure, the active hydrogen density on the surface of the base material is significantly increased, and as a result, silane compound molecules can be chemically adsorbed at high density in the thin film forming step.

The firing step is characterized by polymerizing and solidifying the constituent molecules in the underlayer. The firing in the firing step can be performed at a temperature of 300 ° C. or higher. When the firing temperature is 300 ° C. or higher, the polymerization reaction of unreacted molecules contained in the underlayer is sufficiently promoted. Therefore, according to the above configuration, the hardness of the underlayer can be increased and the underlayer can be strongly adhered to the base material. As a result,
A functional film having excellent adhesiveness and durability can be formed.

As the silane compound for forming a film,
A trichlorosilane-based compound can be used. Since the trichlorosilane-based compound has high reactivity with the OH group, when it is brought into contact with the substrate in an anhydrous atmosphere, it is chemically bonded only to the OH group on the surface of the underlayer. Therefore, when forming a film, it is not necessary to use an acid, an alkali, water or the like, so that the polymerization reaction of the trichlorosilane compound itself does not occur. That is, when the film-forming component is a trichlorosilane-based compound, the functional group that should be bonded to the OH group on the surface of the underlayer is not lost by the polymerization reaction, so that the film-forming substance is present at a high density. It surely binds to the OH group on the surface of the underlayer. As a result, a functional film excellent in water repellency and durability can be manufactured.

As the silane compound for forming a film,
A silane compound having an alkyl group or a fluoroalkyl group can be used. A coating film composed of an alkyl group or a fluoroalkyl group-based silane compound is preferable in that it is excellent in water repellency and antifouling property, and when it is a coating film having excellent water repellency, water penetrates between the underlayer and the substrate. Prevent. Therefore, the durability is further improved.

A non-aqueous solvent can be used as the solvent for the film forming solution. With the above configuration using a non-aqueous solvent, the trichlorosilane-based compound is not hydrolyzed by the solvent and loses reactivity, so that the silane-based compound is efficiently chemically adsorbed on the hydrophilic group portion of the underlayer surface. .
Therefore, it is possible to form a functional film that is firmly bonded to the underlayer.

Further, the non-aqueous solvent may be silicone. Silicone has less moisture,
It is difficult to absorb moisture and acts as a solvate with the chlorosilane compound to prevent the chlorosilane compound from coming into direct contact with water. Therefore, when the solution is composed of a chlorosilane compound and silicone, the chlorosilane compound is attached to the hydrophilic group (OH group) portion of the underlayer while preventing the adverse effect of water in the ambient atmosphere when contacting the underlayer. It can be chemisorbed.

In the film forming step, the film forming solution is preferably brought into contact with the surface of the substrate in an atmosphere having a relative humidity of 35% or less. With the above configuration in which the solution containing the trichlorosilane compound is brought into contact with the atmosphere in which the relative humidity is kept at 35% or less, the adverse effect of water in the atmosphere (reaction between water and the trichlorosilane compound) can be substantially suppressed.

After the firing step, a washing step for removing unadsorbed silane compound molecules can be performed. This makes it possible to form a uniform monomolecular film made of the chemically adsorbed silane-based compound on the substrate and realize a functional film having uniform orientation.

A non-aqueous solvent can be used as a cleaning agent in the above cleaning step. Thereby, the unreacted silane-based compound can be removed without reacting with water.

Further, chloroform can be used as the non-aqueous solvent. Chloroform is preferred because it has a low boiling point and is excellent in drying property after washing.

Further, N-methyl-2pyrrolidinone can be used as the non-aqueous solvent. N-methyl-
2 Pyrrolidinone is excellent in removability, for example, when a chlorosilane compound is used as a silane-based compound, it dissolves a chlorosilane polymer produced by the reaction between the chlorosilane and water in the thin film forming step or the firing step. Further, the liquid crystal display element of the present invention has the configuration described below.

(7) A liquid crystal display element according to a fourth aspect of the present invention is provided with an electrode and a liquid crystal alignment film, respectively, and a liquid crystal layer having a liquid crystal layer provided between a pair of substrates arranged to face each other. In the display element, the liquid crystal alignment film is formed on the surface of the electrode via an underlayer, and the underlayer is X-
(SiOX ₂ ) _n -SiX ₃ (wherein X is at least one functional group selected from the group consisting of halogen, an alkoxy group and an isocyanate group, and n is an integer of 0 or more), water A thin film formed of a compound capable of being decomposed, the thin film comprising a structural unit represented by the following structural formula (1), which is bonded and fixed on the base material through a siloxane bond, The film is an alignment film in which a group of silane-based compound molecules having a —O—Si bond group at a molecular end group is chemically adsorbed to the underlayer by a chemical bond.

[0053]

[Chemical 14] (However, n is an integer of 0 or more.) According to the above configuration, the silane compound molecules are bonded and fixed to the substrate at high density and uniformly through the underlying layer strongly fixed to the substrate. There is. By providing the liquid crystal alignment film on the substrate in this manner, the durability and the like can be improved.

With the above structure, an ultra-thin liquid crystal alignment film can be provided, and a liquid crystal display device having excellent electro-optical characteristics can be realized.

(8) A liquid crystal display element according to a fifth aspect of the present invention is provided with an electrode and a liquid crystal alignment film, and a liquid crystal layer having a liquid crystal layer provided between a pair of substrates arranged to face each other. In the display element, the liquid crystal alignment film is formed on the surface of the electrode via an underlayer, and the underlayer is X′-
(AlOX ′) _n —AlX ′ ₂ (wherein X ′ represents an alkoxy group and n is an integer of 0 or more),
A thin film formed of a compound capable of being hydrolyzed, the thin film including a structural unit represented by the following structural formula (2), which is bonded and fixed on the base material through an —O—Al bond. The liquid crystal alignment film has a molecular end group of -OS.
An alignment film in which a group of silane-based compound molecules having an i-bonding group is chemically adsorbed to the underlayer by chemical bonding.

[0056]

[Chemical 15] (However, n is an integer of 0 or more.) According to the above structure, the underlying layer is formed by being fixed to the substrate by polymerizing and solidifying the constituent molecules of each other and further strongly bonding and fixing to the substrate. Therefore, it can be made to have excellent wear resistance and heat resistance. As a result, the liquid crystal alignment film formed on the underlayer can have excellent wear resistance and heat resistance.

Further, in a conventional liquid crystal display device having an alignment film made of, for example, a polyimide resin, when an electric field is applied to the liquid crystal layer, charges are accumulated by spontaneous polarization in the alignment film. As a result, the image sticking phenomenon was visually recognized. However, since the liquid crystal alignment film according to the present invention has a structure in which a group of silane-based compound molecules is chemically adsorbed to the underlayer as in the above structure, it can be an ultrathin film.
As a result, the charge accumulated by spontaneous polarization is extremely smaller than that of the conventional alignment film described above, so that the occurrence of image sticking can be reduced, and a liquid crystal display element having excellent electro-optical characteristics can be realized.

(9) A liquid crystal display element according to a sixth aspect of the present invention is provided with an electrode and a liquid crystal alignment film, respectively, and a liquid crystal layer having a liquid crystal layer provided between a pair of substrates arranged facing each other. In the display element, the liquid crystal alignment film is formed on the surface of the electrode via an underlayer, and the underlayer is X-
(SiOX ₂ ) _n -SiX ₃ (wherein X is at least one functional group selected from the group consisting of halogen, an alkoxy group and an isocyanate group, and n is an integer of 0 or more), water compound capable of decomposing, and _{X '- (AlOX') n} -AlX '(. 2 but, X' represents an alkoxy group, n represents an integer of 0 or more) is expressed by, be hydrolyzed A structural unit represented by the following structural formulas (1) and (2), which is a thin film formed of a compound capable of being bonded and fixed on the base material through a siloxane bond and a —O—Al bond. The liquid crystal alignment film is a thin film containing
It is a thin film in which a group of silane-based compound molecules having an O—Si bond group is chemically adsorbed to the underlayer by a chemical bond.

[0059]

[Chemical 16] (However, n is an integer of 0 or more.) With the above configuration, it is possible to reduce the occurrence of image sticking and realize a liquid crystal alignment film having excellent electro-optical characteristics.

Here, in the liquid crystal display element according to the fourth to sixth aspects, the following constituent elements can be added.

The aggregated group of silane-based compound molecules constituting the liquid crystal alignment film can be aligned in a predetermined direction or in a plurality of directions so as to form a pattern.

The silane compound molecule has a linear carbon chain having a photosensitive group, and the photosensitive group can be polymerized and fixed in a desired direction.

The liquid crystal layer may be pretilt aligned. In addition, the liquid crystal layer can have a homogeneous alignment. Further, the liquid crystal layer can have homeotropic alignment.

The liquid crystal display element may be an in-plane switching type liquid crystal display element in which the opposing electrodes are formed on the surface of one substrate. As a result, it is possible to provide a liquid crystal display element which is excellent in electro-optical characteristics with less image sticking in the in-plane switching mode.

As a method of manufacturing the above-mentioned liquid crystal display device, the following modes (10) to (12) can be adopted. Here, (10) to (12) are manufacturing methods corresponding to the above fourth to sixth aspects.

(10) Liquid crystal table corresponding to the fourth mode
The manufacturing method of the display element is such that at least one of the liquid
Provided between a pair of substrates having a crystal orientation film and the above substrates.
A liquid crystal layer having a predetermined alignment structure by the liquid crystal alignment film.
To a method of manufacturing a liquid crystal display device having a liquid crystal layer having a structure
Then, on the substrate, X- (SiOX₂)_n-SiX ₃
(However, X is a halogen, an alkoxy group or isocyanate.
At least one functional group selected from the group consisting of
And n is an integer of 0 or more. ), Water
Contact underlayer solution containing compounds that can be decomposed
And a base layer forming step of drying to form a base layer,
Includes a silane compound on the surface of the substrate on which the underlayer is formed
The solution is contacted and the silane compound molecules are chemically
Thin film forming process that forms liquid crystal alignment film by adsorption
And a baking step of baking the substrate, and the liquid crystal alignment film
And an alignment treatment step of aligning.

(11) In the method of manufacturing a liquid crystal display element according to the fifth aspect, a pair of substrates having a liquid crystal alignment film inside at least one of them and a liquid crystal layer provided between the substrates are provided. In the method for manufacturing a liquid crystal display device including a liquid crystal layer having a predetermined alignment structure with the liquid crystal alignment film, X ′-(AlOX ′) _n -Al is formed on the substrate.
A base layer solution containing a compound capable of being hydrolyzed represented by X ′ ₂ (wherein X ′ represents an alkoxy group and n is an integer of 0 or more), and dried to form the base layer. And a step of forming a base layer, and contacting a solution containing a silane-based compound to the surface of the substrate on which the base layer is formed,
A thin film forming step of forming a liquid crystal alignment film by chemically adsorbing silane-based compound molecules on the surface of the substrate, a baking step of baking the substrate, and an alignment treatment step of aligning the liquid crystal alignment film.

(12) Liquid crystal table corresponding to the sixth aspect
The manufacturing method of the display element is such that at least one of the liquid
Provided between a pair of substrates having a crystal orientation film and the above substrates.
A liquid crystal layer having a predetermined alignment structure by the liquid crystal alignment film.
To a method of manufacturing a liquid crystal display device having a liquid crystal layer having a structure
Then, on the substrate, X- (SiOX₂)_n-SiX ₃
(However, X is a halogen, an alkoxy group or isocyanate.
At least one functional group selected from the group consisting of
And n is an integer of 0 or more. ), Water
A compound that can be decomposed and X '-(AlO
X ')_n-AlX '₂(However, X'is an alkoxy group, n
Is an integer of 0 or more. ) Hydrolyzed product
Substrate containing a binary mixture of a compound capable of forming
Underlayer type in which the layer solution is contacted and dried to form the underlayer
And a silane-based coating on the substrate surface on which the underlayer is formed.
Contact the solution containing the compound, and
A liquid crystal alignment film is formed by chemical adsorption on the plate surface.
A thin film forming step and a baking step of baking the substrate
And an alignment treatment step of aligning the liquid crystal alignment film.
It

In the method of manufacturing the liquid crystal display element according to the fourth to sixth aspects, the following constituent elements can be further added.

That is, after the firing step, a washing step for removing unadsorbed silane compound molecules can be performed.

Further, after the cleaning step, a liquid draining alignment step is performed in which the cleaning agent is drained in a desired liquid draining direction to align the silane compound molecules constituting the liquid crystal alignment film in the liquid draining direction. It can be carried out. This makes it possible to orient the silane-based compound molecules constituting the liquid crystal alignment film in the liquid draining direction. Therefore, when performing the alignment treatment after the liquid draining alignment step, for example, in the photo-alignment method, the irradiation amount of ultraviolet rays is adjusted. The treatment conditions of the alignment treatment can be relaxed by reducing the number of treatments or reducing the number of treatments in the rubbing treatment method.

Further, the above-mentioned alignment treatment step may be a rubbing alignment step of aligning the silane compound molecules in the liquid crystal alignment film in a desired direction by rubbing treatment. Thereby, the rubbing condition is relaxed, and the liquid crystal alignment film in which the silane compound molecules are aligned in a desired direction can be manufactured without scraping the film by the rubbing method.

When the liquid crystal alignment film is composed of a group of silane-based compound molecules having a photosensitive group, the alignment treatment step includes irradiating the surface of the substrate on which the liquid crystal alignment film is formed with polarized light to generate silane. By performing a cross-linking reaction between the system compound molecules, it is possible to obtain a polarization alignment step of imparting an alignment regulating force capable of aligning the liquid crystal molecules in a specific direction. The liquid-removing orientation process or the rubbing orientation process for orienting the film having the chemically adsorbed photosensitive group facilitates anisotropic photoreaction of the photosensitive group in a desired direction. It is possible to reduce the irradiation dose of polarized ultraviolet light. Further, it is possible to perform the alignment treatment without performing the rubbing treatment that causes the generation of static electricity, and it is possible to provide a liquid crystal display element having excellent electro-optical characteristics such as suppressing the occurrence of image sticking.

Further, the light intensity of the polarized light irradiated in the above-mentioned polarization alignment step can be 1 J / cm ² or more at a wavelength of 365 nm. Thereby, the alignment structure of the liquid crystal layer can be made to be a homogeneous alignment, and can be suitably applied to an in-plane switching mode liquid crystal display element or the like.

In addition, in the solution containing the silane compound,
A silane compound having a fluoroalkyl group of 5 mol% or less can be mixed. As a result, the alignment structure in the liquid crystal layer can be homeotropically aligned.

[0076]

BEST MODE FOR CARRYING OUT THE INVENTION In the method for producing a functional film of the present invention, (1) X- (SiOX ₂ ) _n -SiX ₃ (where X is
Is at least one functional group selected from the group consisting of halogen, an alkoxy group and an isocyanate group, and n
Is an integer of 0 or more. (2) X '-(AlOX') _n-
AlX ' ₂ (where X'is an alkoxy group and n is an integer of 0 or more) and is capable of being hydrolyzed (hereinafter referred to as an underlayer forming substance), or (3) X-
(SiOX _{2) n} -SiX ₃ (where, X is at least one functional group selected from the group consisting of halogen, alkoxy group and isocyanate group, n represents an integer of 0 or more.) Hydrolysis represented by And a hydrolyzable compound represented by X ′-(AlOX ′) _n —AlX ′ ₂ (where X ′ is an alkoxy group and n is an integer of 0 or more). The underlayer solution prepared by using the mixture is applied to the surface of a glass substrate, for example, and the solvent is dried to form an underlayer on the glass substrate.

Then, a solution containing a silane-based compound is applied onto this underlayer, and the solvent is dried. As a result, the molecules of the silane compound are chemically adsorbed on the surface of the underlayer,
Then, the glass base material is fired to firmly fix the underlayer to the substrate.

According to this production method, the silane compound molecules can be strongly and uniformly bound to the underlayer, and the underlayer can be strongly adhered to the base material by firing at the final stage of production. Therefore, it is possible to manufacture a functional film which is firmly and uniformly bonded and fixed to the glass substrate as a whole. Such a functional film suitably functions as a surface-modified film for a long period of time.
On the other hand, according to the conventional manufacturing method in which the base layer is baked, the hydroxyl groups on the surface of the base layer are lost depending on the temperature during the baking, and thus the adsorption site (OH group) of the silane compound cannot be sufficiently secured. Therefore, the functional film produced by the conventional method has a higher adhesiveness than the functional film produced by the method of the present invention.
The uniformity and durability will be poor.

Here, in the above-mentioned production method of the present invention,
Drying at the time of forming the underlayer is preferably performed at a temperature of less than 300 ° C, preferably 50 ° C to 200 ° C, more preferably 80 ° C.
It is preferable to carry out at a temperature of from 150 ° C to 150 ° C. When the drying temperature is 300 ° C. or higher, X ′-(AlOX ′) _n − which is a component of the underlayer.
AlX ' ₂ is polymerized or X'-(AlOX ') _n -A
This is because lX ' ₂ and X- (SiOX ₂ ) _n- SiX ₃ are polymerized and active hydrogen on the surface of the underlayer is lost. Considering both the drying efficiency and the polymerization of the underlayer forming substance, 5
A temperature of 0 ° C to 200 ° C is preferable, and a more preferable drying temperature is 80 ° C to 150 ° C. 80 ℃ ~ 1
At a temperature of 50 ° C, Al-X 'on the surface of the underlayer, or Al-X' in the two-component system and Si-X react appropriately with moisture to increase active hydrogen on the surface of the underlayer, while It does not cause disassembly.

On the other hand, the firing in the firing step performed in the final stage of production is preferably carried out at a temperature of 300 ° C. or higher, preferably 300 ° C. to 500 ° C., more preferably 400 ° C.
It is preferable to carry out at a temperature of 500 ° C. When the temperature is lower than 300 ° C, X '-(AlOX') _n -A which is a component of the underlayer.
lX ' ₂ polymerization reaction or X'-(AlOX ') _n -A
Since the polymerization reaction between 1X ' ₂ and X- (SiOX ₂ ) _n- SiX ₃ does not proceed sufficiently, it becomes an underlayer having a low hardness, and the bonding force with the base material is weak. On the other hand, if the firing temperature is 500 ° C. or higher, the base layer forming substance and the silane compound that is a thin film component may be decomposed. Therefore, in terms of both firing efficiency and decomposition, it is preferable to perform firing at a temperature of 400 ° C to 500 ° C.

The solution containing the silane compound means a solution in which the silane compound is dissolved in a solvent, but a part of the silane compound may be in an undissolved state. A typical example of such a solution is a supersaturated solution.

In the above manufacturing method of the present invention, X- (Si
Examples of the compound represented by OX ₂ ) _n -SiX ₃ (wherein X is at least one functional group selected from the group consisting of halogen, an alkoxy group and an isocyanate group, and n is an integer of 0 or more): The compound represented by the following general formula is mentioned.

As described above, the reaction with water and the polymerization reaction are easily controlled by the temperature, and since no harmful product such as hydrochloric acid is generated when reacting with water, it is easy to handle, so that the following compound Of these, alkoxysilane is particularly preferable. (1) SiX ₄ (corresponding to n = 0) (2) SiX ₃ —O—SiX ₃ (corresponding to n = 1) Further specific compounds include (3) Si (OC ₂ H ₅ ) ₄ (4) _{Si (OCH 3) 3 -O-} Si (OCH 3) 3 (5) Si (OC 2 H 5) 3 -O-Si (OCH 3) 3 (6) Si (OC 2 H 5) 3 -O-Si _{(OC 2 H 5) 3 (} 7) Si (NCO) 4 (8) Si (NCO) 3 -O-Si (NCO) 3 (9) SiCl 4 (10) SiCl 3 -O-SiCl 3 (11) Si in _{(OCH 3) 3 -O-Si} (OC 2 H 5) 3 the present invention production process, X '- (AlOX') n
Examples of the compound represented by —AlX ′ ₂ (wherein X ′ is an alkoxy group and n is an integer of 0 or more) include compounds represented by the following general formula. (12) AlX ′ ₃ (corresponding to n = 0) (13) AlX ′ ₂ —AlX ′ ₂ (corresponding to n = 1) Further specific compounds include (14) Al (OC ₂ H ₅ ) ₃ (15 _{) Al (OCH 3) 2 -O} -Al (OCH 3) 2 (16) Al (OCH 3) 2 -O-Al (OC 2 H 5) 2 On the other hand, as the silane compound which can be used in the present invention, The following compounds can be illustrated. _{(17) SiY p Cl 3-} p (18) CH 3 (CH 2) s O (CH 2) t SiY q Cl 3-q (19) CH 3 (CH 2) u -Si (CH 3) 2 (CH ₂ ) _{v
-SiY q Cl 3-q (20} ) CF 3 COO (CH 2) w SiY q Cl 3-q (21) CH 3 - (CH 2) r SiY q Cl 3-q where, p is an integer of 0 to 3 , Q is an integer of 0 to 2, r is 1 to
An integer of 25, s is an integer of 0 to 12, t is an integer of 1 to 20, u is an integer of 0 to 12, v is an integer of 1 to 20, and w is 1.
Indicates an integer of -25. Y is hydrogen, an alkyl group,
It is an alkoxyl group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.

Specific examples of the trichlorosilane compound include the compounds shown in the following (22)-(34). (22) CH ₃ CH ₂ O (CH ₂ ) ₁₅ SiCl ₃ (23) CH ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ S
iCl ₃ (24) CH ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ S
_{iCl 3 (25) CH 3 COO} (CH 2) 15 SiCl 3 (26) CF 3 (CF 2) 7 - (CH 2) 2 -SiCl 3 (27) CF 3 (CF 2) 5 - (CH 2) 2 _{-SiCl 3 (28) CF 3 (} CF 2) 7 -C 6 H 4 -SiCl 3 (29) CF 3 (CH 2) 9 SiCl 3 (30) CH 3 (CH 2) 9 OSiCl 3 (31) CH 3 (CH ₂ ) ₉ Si (CH ₃ ) ₂ (CH ₂ ) ₁₀ S
_{iCl 3 (32) C 6 H} 5 -CH = CH-CO-O- (CH 2) 6 -
_{O-SiCl 3 (33) C} 6 H 5 -CO-CH = CH-C 6 H 4 -O- (C
_{H 2) 6 -O-SiCl 3} (34) C 6 H 5 -CH = CH-CO-C 6 H 4 -O- (C
H ₂ ) ₆ —O—SiCl ₃ Here, the compound (32) has a cinnamoyl group as a photosensitive group, and the compounds (33) and (34) also have a chalconel group as a photosensitive group. The photosensitive base can be polymerized by irradiating with.

Further, in place of the above chlorosilane compound, an isocyanate silane compound represented by the following general formulas (35) to (39) in which a chlorosilyl group is placed on an isocyanate group can be used. _{(35) SiY p (NCO)} 4-p (36) CH 3 - (CH 2) r SiY q (NCO) 3-q (37) CH 3 (CH 2) s O (CH 2) t SiY q (NC
_{O) 3-q (38)} CH 3 (CH 2) u -Si (CH 3) 2 (CH 2) v
_{-SiY q (NCO) 3-q} (39) CF 3 COO (CH 2) v SiY q (NCO) 3-q where, p, q, r, s , t, u, v, w and x are the Is the same as. Specific examples of the isocyanate-based silane compound include the compounds shown in (40) to (47) below. (40) CH ₃ CH ₂ O (CH ₂ ) ₁₅ Si (NCO) ₃ (41) CH ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ S
_{i (NCO) 3 (42)} CH 3 (CH 2) 6 Si (CH 3) 2 (CH 2) 9 S
_{i (NCO) 3 (43)} CH 3 COO (CH 2) 15 Si (NCO) 3 (44) CH 3 (CH 2) 9 Si (OC 2 H 5) 3 (45) CF 3 (CF 2) 7 - (CH _{2) 2} -Si (NC
_{O) 3 (46) CF 3} (CF 2) 5 - (CH 2) 2 -Si (NC
_{O) 3 (47) CF 3} (CF 2) 7 -C 6 H 4 -Si (NCO) 3 Furthermore, in the present invention, the general formula _{SiY k (OA) 4-k} ( where, Y is similar to the above, A Is an alkyl group, k is 0, 1, 2
Alternatively, it is possible to use an alkoxy silane compound represented by 3). Among _{these, CF 3 - (CF 2)} n -
(R) _l -SiY _p (OA) _3-p (n is an integer of 1 or more, preferably an integer of 1 to 22, R is an alkyl group, a vinyl group,
An alkenyl silane compound represented by an ethynyl group, an aryl group, a substituent containing a silicon or oxygen atom, 1 is 0 or 1, and Y, A and p are the same as the above) is excellent in enhancing antifouling property. There is. However, the alkoxy-based silane compound that can be used in the present invention is not limited to the above, and other than this, for example, the general formula CH ₃ — (CH ₂ ) _r —
SiY _q (OA) _3-q and _{CH 3 - (CH 2) s} -O-
_{(CH 2) t -SiY q (} OA) 3-q, CH 3 - (CH 2) u
_{-Si (CH 3) 2 - (} CH 2) v -SiY q (OA) 3-q,
_{CF 3 COO- (CH 2) v} -SiY q (OA) 3-q ( where, p, q, r, s , t, u, v, w, Y and A are
The same as the above) can be used. Specific examples of the alkoxy silane compound are shown below (47).
-(71) can be mentioned. _{(47) CH 3 CH 2 O} (CH 2) 15 Si (OCH 3) 3 (48) CF 3 CH 2 O (CH 2) 15 Si (OCH 3) 3 (49) CH 3 (CH 2) 2 Si ( CH ₃ ) ₂ (CH ₂ ) ₁₅ S
_{i (OCH 3) 3 (50} ) CH 3 (CH 2) 6 Si (CH 3) 2 (CH 2) 9 S
_{i (OCH 3) 3 (51} ) CH 3 (CH 2) 9 Si (NCO) 3 (52) CH 3 COO (CH 2) 15 Si (OCH 3) 3 (53) CF 3 (CF 2) 5 (CH _{2) 2 Si (OCH 3)} 3 (54) CF 3 (CF 2) 7 -C 6 H 4 -Si (OCH 3) 3 (55) CH 3 CH 2 O (CH 2) 15 Si (OC 2 H 5 ) ₃ (56) CH ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ S
i (OC ₂ H ₅ ) ₃ (57) CH ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ S
i (OC ₂ H ₅ ) ₃ (58) CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ S
_{i (OC 2 H 5) 3} (59) CH 3 COO (CH 2) 15 Si (OC 2 H 5) 3 (60) CF 3 COO (CH 2) 15 Si (OC 2 H 5) 3 (61) CF _{3 COO (CH 2) 15 Si} (OCH 3) 3 (62) CF 3 (CF 2) 9 (CH 2) 2 Si (OC 2 H 5) 3 (63) CF 3 (CF 2) 7 (CH 2) ₂ Si (OC ₂ H ₅ ) ₃ (64) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ (65) CF ₃ (CF ₂ ) ₇ C ₆ H ₄ Si (OC _{2 H 5) 3 (66) CF} 3 (CF 2) 9 (CH 2) 2 Si (OCH 3) 3 (67) CF 3 (CF 2) 5 (CH 2) 2 Si (OCH 3) 3 (68) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCH ₃ (OC _{2
H 5) 2 (69) CF} 3 (CF 2) 7 (CH 2) 2 SiCH 3 (OCH
₃ ) ₂ (70) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ O
_{C 2 H 5 (71) CF} 3 (CF 2) 7 (CH 2) 2 Si (CH 3) 2 O
CH _{3 In} addition, when the compounds (20)-(71) exemplified as the isocyanate-based or alkoxy-based silane compounds are used, hydrochloric acid is not generated during the chemical bonding, which has the advantage that the device is not damaged and the work is easy. .

Here, a process for forming a thin film on the surface of a substrate using a silane compound will be described, and a solvent and a substrate as elements for carrying out the present invention will be described. (CF _{2) 7} - CF ₃ as a silane compound -
(CH ₂₎ a reaction in the case of the ₂ -SiCl ₃ is brought into contact with the glass substrate (glass plate), shown in the following chemical reaction formula. It is assumed that a base layer has already been formed on this glass substrate.

[0087]

[Chemical 17] The first reaction step (dehydrochlorination reaction) shown in the above chemical reaction formula is a reaction generally called a chemisorption reaction, and when a silane compound solution is brought into contact with a substrate having an OH group, the dehydrochlorination reaction occurs. Occurs, one end of the silane compound molecule is chemically bonded to the OH group portion on the surface of the base material. Since this reaction is a reaction between the SiCl group and the OH group of the silane compound,
If the silane compound solution contains a large amount of water, the reaction with the base material is hindered. Therefore, in order to allow the reaction to proceed smoothly, it is preferable to use a non-aqueous solvent that does not contain active hydrogen such as an OH group, and it is preferable to perform the reaction in an atmosphere of low humidity. The humidity conditions will be described in detail in the experimental section below.

Examples of the silane compound solvent that can be preferably used in the present invention include water-free hydrocarbon-based solvents, fluorocarbon-based solvents, silicone-based solvents, and the like, which can be used as petroleum-based solvents. Examples thereof include petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, kerosene, ligroin, dimethyl myricone, phenyl silicone, alkyl-modified silicone, polyester silicone and the like. Further, as the fluorocarbon solvent, a fluorocarbon solvent or Fluorinate (3M
Company products), Aflude (Asahi Glass product), etc. can be used. One of these solvents may be used alone, or two or more compatible solvents may be used in combination.

In addition, the requirements for the substrate to which the present invention can be applied are
Of the composition formula X ′-(AlOX ′) _n-AlX '₂(However
X'is an alkoxy group, and n is an integer of 0 or more. )
A solution containing a compound represented by: or a composition formula X- (Si
OX₂)_n-SiX₃(However, X is halogen, alkoxy
Group and isocyanate group, n is an integer of 0 or more
It ) And a compositional formula X '-(AlO
X ')_n-AlX '₂(However, X'is an alkoxy group, and n is
It is an integer of 0 or more. ) With a compound represented by
Coating, attachment, adhesion, etc. of a two-component solution containing
Collectively referred to as) and withstands firing.
Just do it. As a base material that meets these conditions,
S, ceramics, aluminum oxide, aluminum,
Examples of the metal include tenless. It has heat resistance
The manufacturing method of the present invention can be applied to plastics
Of course.

When the functional film of the present invention is applied to a liquid crystal display device as a liquid crystal alignment film, the functional film can be manufactured by the following method.

First, in the same procedure as described above, the IT
A base layer is formed on a substrate on which electrodes such as O are formed (base layer forming step). Further, after forming a functional film as a liquid crystal alignment film on the underlayer (thin film forming step),
The substrate is fired (firing step).

After the baking step, in order to remove the unreacted silane compound, the substrate on which the liquid crystal alignment film is formed is washed with a cleaning agent (cleaning step). Here, as the cleaning agent, a hydrocarbon solvent containing no water, a fluorocarbon solvent,
Examples thereof include silicone-based solvents, and examples of usable petroleum-based solvents include petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, and the like.
Kerosene, ligroin, dimethyl silicone, phenyl silicone, alkyl modified silicone, polyester silicone and the like can be mentioned. As the fluorocarbon-based solvent, a CFC-based solvent, Fluorinert (manufactured by 3M Company), Aflude (manufactured by Asahi Glass Co., Ltd.) or the like can be used. These may be used alone or in combination of two or more as long as they are compatible with each other. In particular, chloroform is preferable because it has excellent drying properties after washing. Also,
N-methyl-2pyrrolidinone is excellent in removing chlorosilane polymer produced by the reaction of chlorosilane and water in the thin film forming step or the firing step.

Subsequently, after the above cleaning step, the cleaning agent is drained. That is, the substrate is pulled up so that the drainage direction of the cleaning liquid is substantially aligned with the alignment treatment direction when aligning the liquid crystal alignment film (the drainage alignment direction). As a result, the film-constituting molecules that form the liquid crystal alignment film can be tilted in the liquid draining direction and temporarily aligned. Then, the cleaning agent is removed by drying the substrate.

Next, the liquid crystal alignment film temporarily aligned in the liquid draining direction is subjected to alignment treatment. For example, when the film-constituting molecules forming the liquid crystal alignment film have a photosensitive group, the alignment treatment is performed by irradiating polarized ultraviolet light (polarization alignment step). At this time, the liquid draining direction and the polarization direction of the polarized ultraviolet rays are set so as to substantially coincide with each other. As a result, the photopolymerization reaction between the photosensitive groups enables cross-linking along the polarization direction, and the orientation of the film-constituting molecules can be fixed. Here, examples of the photosensitive group include a cinnamoyl group represented by the following chemical formula (5) and a chemical formula (6) below.
Examples include the chalconeyl group and the like.

[0095]

[Chemical 18] When these photosensitive groups are irradiated with polarized ultraviolet light, they become
Carbon-carbon double bond in formulas (5) and (6)
Of adjacent membrane components via at least one bond
The child has a cross-linked structure. Incidentally, the above-mentioned chalcone group is
Better sensitivity to polarized UV than cinnamoyl group
Considering the point, a chalcone group is used as a photosensitive group.
However, it is preferable. This reduces the amount of polarized UV irradiation
It is possible to reduce the takt time in the polarization alignment process.
Can be shortened. Polarized ultraviolet light in the above-mentioned polarization alignment process
As the irradiation conditions of, the wavelength distribution of polarized ultraviolet rays is 300 to
It only needs to be distributed around 400 nm, and the irradiation dose is
Approximately 50 to 2000 mJ / cm at a length of 365 nm²of
It should be within the range. Especially 1000mJ / cm²that's all
Then, a homogeneous orientation structure can be obtained. That
On the contrary, 100 mJ / cm ²Pretilt alignment structure with less than
Can be

On the other hand, when the film-constituting molecules constituting the liquid crystal alignment film do not have a photosensitive group, rubbing treatment is carried out instead of the photo-alignment method. Even in this case, the liquid draining direction and the rubbing processing direction are set so as to substantially coincide with each other. Accordingly, since the film-constituting molecules are oriented in the rubbing treatment direction in advance, it is not necessary to rub strongly, and the rubbing conditions can be relaxed as compared with the conventional rubbing treatment. The rubbing conditions in the rubbing treatment may be such that the width and depth of the groove portion of the rubbing are generally within the range of 0.01 to 0.5 μm.

[0097]

EXAMPLES The contents of the present invention will be specifically described below based on examples. (Example 1) This example corresponds to the functional film according to the first aspect.

X- (SiOX ₂ ) _n -SiX ₃ (provided that X
Is at least one functional group selected from the group consisting of halogen, an alkoxy group and an isocyanate group, and n
Is an integer of 0 or more. ) Is a compound represented by
i (OC ₂ H ₅ ) ₄ was prepared, and Si (OC ₂ H ₅ ) ₄ / HCl was prepared.
/ Water / Isopropyl alcohol = 1 / 0.01 / 5/2
An underlayer solution of 5 (molar ratio) was prepared. After immersing the glass plate in this underlayer solution, the glass plate is pulled up at a speed of 1 mm / sec, the underlayer solution is applied to the surface of the glass plate, and dried at 80 ° C. for 15 minutes to remove Si (OC ₂ H ₅ ) ₄ from Was formed on the surface of the glass plate.

Next, as a silane compound, C ₈ F ₁₇ C ₂ H _{4 was used.}
Prepare SiCl _3, and prepare C ₈ F ₁₇ C ₂ H ₄ SiCl ₃ / C ₈ F ₁₈
= 1/99 (volume ratio) of a silane compound solution was prepared.
The surface of the glass plate is then immersed in the silane compound solution in an anhydrous atmosphere with a relative humidity of 5% or less, and the glass plate on which the underlayer (unfired) is formed is pulled up at a speed of 1 mm / sec. A silane compound solution was applied to. After that, the solvent (C ₈ F ₁₈ ) on the surface of the glass plate was evaporated, and the glass plate was further baked at 400 ° C. for 15 minutes. Thus, the substrate A1 having the functional film was produced.

A conceptual diagram for explaining the manufacturing flow of this method is shown in FIG. FIG. 1 (a) shows that when an underlayer solution is applied to a glass plate and dried, Si (OC ₂ H ₅ ) ₄ which is an underlayer component.
Shows that OH group was introduced by hydrolysis. In addition, FIG. 1B shows that when a silane compound solution is applied to the underlayer, a silane compound (C ₈ F ₁₇ C ₂ H ₄ SiC) is used.
l ₃ ) is chemically adsorbed on the OH group. Further, FIG. 1C shows that the underlayer components are polymerized by baking the substrate.

In the following, the glass plate on which the functional film is formed is referred to as a substrate, and the method of applying the silane compound solution and then firing without firing the base layer is called the post-firing method. I will. (Comparative Example 1) An underlayer (sintered underlayer) was formed by a method in which a glass plate coated with the underlayer solution was baked at 400 ° C for 15 minutes instead of being dried at 80 ° C for 15 minutes. And 400 ℃ ・ 1 against the glass plate coated with the silane compound solution.
A substrate B1 having a functional film was produced in the same manner as in Example 1 except that the post-baking was not performed for 5 minutes.

A conceptual diagram of this method is shown in FIG. Figure 2
(A) is a glass plate when the underlayer solution is applied and dried,
The underlayer component Si (OC ₂ H ₅ ) ₄ is hydrolyzed to O
It shows that the H group was introduced. In addition, FIG.
It shows that a part of the OH groups on the surface of the underlayer was lost due to the firing of the underlayer. Further, FIG. 2C shows that a silane-based compound (C ₈ F ₁₇ C ₂ H ₄ SiCl) is added to a small OH group.
₃ ) shows the chemical adsorption.

Comparative Example 1 is a method according to the prior art, and firing performed when forming the underlayer by this method is referred to as a pre-firing method. (Comparative Example 2) An untreated glass plate having no underlying layer was used, and the glass plate was dipped in the silane compound solution to obtain 1
The substrate was pulled up at a speed of mm / sec to evaporate C ₈ F ₁₈ to prepare a substrate C1 having a functional film according to Comparative Example 2. A conceptual diagram of this method is shown in FIG.

FIG. 3 (a) shows the existence of OH groups on the surface of the glass plate, and FIG. 3 (b) shows a small amount of O.
It shows that the silane compound (C ₈ F ₁₇ C ₂ H ₄ SiCl ₃ ) was chemisorbed to the H group.

[Film Fabrication Conditions and Durability] The above-mentioned substrate A1,
Using B1 and C1, the relationship between the presence or absence of an underlayer, the difference in firing conditions, and the contact angle was investigated. The contact angle was measured as follows. Each of the substrates A1 to C1 was rubbed with a dishwashing sponge at a load of 2 kgf for 10000 times, and during this time, the stains on the substrate were removed by ultrasonic cleaning with ethanol every 2000 times. 10 μl of water was dropped and the contact angle was measured. The measurement results are shown in FIG.

As is apparent from FIG. 4, the substrate A1 (Example 1) manufactured by the manufacturing method according to the present invention had a large initial contact angle, and the contact angle was almost decreased even by rubbing with a sponge. I couldn't do it. On the other hand, it was recognized that the substrate B1 (Comparative Example 1) according to the pre-baking method had a smaller initial contact angle than the substrate A1 and that the contact angle tended to be significantly reduced by rubbing with a sponge. Further, the substrate C1 (Comparative Example 2) having no underlying layer had a smaller initial contact angle than the substrate B1 and a large decrease in contact angle due to rubbing with a sponge.

From the above results, it was confirmed that according to the production method of the present invention, a functional film excellent in water repellency and durability could be formed.

The above results can be considered as follows.
That is, in the substrate A1, the underlayer is firmly fixed to the substrate surface, the molecules of the silane compound are chemically bonded to the underlayer uniformly and strongly, and a good quality thin film is formed. It is considered that the peeling of the thin film, which was large and did not cause a decrease in the contact angle even by rubbing, did not occur. On the other hand, it is considered that, in the substrate B1 in which the underlayer was pre-baked, the hydroxyl groups on the surface of the substrate were lost by the baking, so that a film having less uniformity and binding strength than the substrate A1 was formed. In addition, in the substrate C1 having no underlying layer, since there are few active hydrogen sites to which silane compound molecules should be bonded, a non-uniform thin film having dangling silane compound molecules that are not directly bonded to the substrate is formed. It is considered that the initial contact angle was small and the resistance to rubbing was small. (Example _{2) X- (SiOX 2) n} -SiX 3 ( wherein X
Is at least one functional group selected from the group consisting of halogen, an alkoxy group and an isocyanate group, and n
Is an integer of 0 or more. ) Is a compound represented by
A substrate D1 according to Example 2 was produced in the same manner as in Example 1 except that Si (NCO) ₄ was used instead of i (OC ₂ H ₅ ) ₄ .

[Difference in Underlayer Components and Durability] The substrate A1 according to Example 1 and the substrate D1 according to Example 2 are
It was left to stand in the air heated to 300 ° C. for 100 hours. During this period, the stains on the substrate were removed by ultrasonic cleaning with ethanol every 20 hours, and then 10 μl of water was dropped on the film formation surface to measure the contact angle. Hereinafter, this measuring method is referred to as a heating durability test method.

The measurement result is shown in FIG. It should be noted that the substrates A1 and D1 differ only in the substance forming the underlayer.

As is apparent from FIG. 5, the substrate A1 of Example 1 using Si (OC ₂ H ₅ ) ₄ as the underlying layer component.
However, the initial contact angle was larger than that of the substrate D1 of Example 2 using Si (NCO) _4, and the decrease of the contact angle with time was small. From these results, it is understood that alkoxylan is more excellent than isocyanate silane as the underlayer component in that the water repellency and durability of the functional film can be enhanced. (Example 3) As a silane compound (thin film component), C ₈ F
Instead of the _{17 C 2 H 4 SiCl 3,} C 8 F 1 7 C 2 H 4 Si (OC
_{In the same} manner as in Example 1 except that ₂ H ₅ ) ₃ was used,
A substrate E1 according to Example 3 was produced.

[Difference of Silane Compounds and Durability] Example 3
Using the substrate E1 of Example 1 and the substrate A1 of Example 1 described above, the relationship between the difference in the thin film components and the durability was examined by the above heating durability test method.

The measurement result is shown in FIG. From FIG. 6, although the initial contact angles of both substrates were the same, the substrate A1 using C ₈ F ₁₇ C ₂ H ₄ SiCl ₃ as the silane compound (Example 1)
Is a substrate E1 using C ₈ F ₁₇ C ₂ H ₄ Si (OC ₂ H ₅ ) _3.
It was confirmed that the decrease in the contact angle with time was less than that in (Example 3). From this result, as the silane compound,
It can be seen that the trichlorosilane compound is superior in terms of durability. Example 4 Example 4 was repeated in the same manner as in Example 1 except that hexamethyldisiloxane (linear silicone) was used instead of C ₈ F ₁₈ as the solvent for dissolving the silane compound. The substrate F1 according to No. 4 was manufactured.

[Difference in Solvents and Durability] Using the heating durability test method, the substrate F1 of Example 4 and the substrate A1 of Example 1 were used.
We compared the performance of.

The measurement result is shown in FIG. From FIG. 7, although the initial contact angles of both substrates were the same, C ₈ F ₁₈ was used for the substrate F1 (Example 4) using hexamethyldisiloxane as a solvent for dissolving the silane compound. Substrate A
It was confirmed that the decrease in the contact angle with time was smaller than that in Example 1 (Example 1). From this result, it is understood that hexamethyldisiloxane is excellent as a solvent for dissolving the silane compound in that a functional film having high temperature durability can be obtained.

Even when cyclohexamethyltrisiloxane (cyclic silicone) was used, the same results as above were obtained. (Example 5) As a silane compound, C ₁₀ H ₂₁ SiCl
_A substrate G1 according to Example 5 was made in the same manner as Example 1 except that ₃ was used. Example 6 A substrate H1 according to Example 6 was produced in the same manner as in Example 1 except that SiCl ₄ was used as the silane compound.

[Antifouling Test] The Substrate G1 (Example 5)
In order to compare the film performances of the substrate H1 (Example 6) and the substrate A1 (Example 1), an antifouling test was performed on each substrate. The method of the antifouling test is as follows. First, 0.2 cc of syrup consisting of sugar / soy sauce = 1/1 (weight ratio) is dropped on a substrate and baked at 300 ° C. for 15 minutes. After this, wipe off the stickiness and wipe down again, and then drop 0.2 cc of the syrup again on the substrate and
Bake at 00 ° C. for 15 minutes and wipe off stickiness in the same manner as above. This cycle was repeated until stickiness could not be wiped off, and the number of times was counted. The results are shown in Table 1.
Shown in.

[0118]

[Table 1] When the results in Table 1 are shown in order of good antifouling property in relation to the type of silane compound and antifouling property, C ₈ F ₁₇ C ₂ H ₄ SiCl ₃ (Substrate A
1) >> C ₁₀ H ₂₁ SiCl ₃ (substrate G1) >> SiCl ₄
(Substrate H1), C ₈ F ₁₇ C ₂ H ₄ SiCl ₃ and C ₁₀ H
₂₁ SiCl ₃ shows good antifouling property, especially C ₈ F ₁₇ C ₂
The antifouling property of H ₄ SiCl ₃ was excellent. On the other hand, SiCl ₄
Had almost no stain resistance.

From these results, it is preferable to use a silane compound having an alkyl group or a fluoroalkyl group in order to improve the antifouling property.

[Experiment] In the examples described above, the dipping and withdrawing in the silane compound solution was carried out in an anhydrous atmosphere. Here, in the ambient atmosphere at the time of applying the silane compound solution to the substrate on which the underlayer was formed, The effect of humidity was investigated. As an experimental method, the relative humidity of the ambient atmosphere at the time of dipping and pulling the substrate into the silane compound solution was set to 5: 1.
A substrate on which a functional film was formed was produced in the same manner as in Example 4 except that the setting was performed in 8 ways of 0, 15, 20, 25, 30, 35, and 40%. The appearance state of the substrate during and after formation of the is visually observed.

Observation of the substrates prepared under the above-mentioned respective humidity conditions revealed that under a humidity condition of 30% or less, under an anhydrous atmosphere (5
% Or less), a substrate having an appearance similar to that of On the other hand, 4
Under a humidity condition of 0% or more, a white product which was apparently a reaction product of moisture in the atmosphere and a silane compound was confirmed. Moreover, such a white product was hardly observed at a humidity of 35%. From these things, it is preferable that the contact of the silane compound solution with the substrate is performed in an atmosphere having a relative humidity of 35% or less. (Embodiment 7) This embodiment corresponds to the functional film according to the second aspect.

X '-(AlOX') _n -AlX ' ₂ (where X'is an alkoxy group and n is an integer of 0 or more).
Al (OC ₂ H ₅ ) ₃ is prepared as a compound represented by, and under the condition of Al (OC ₂ H ₅ ) ₃ / HCl / water / isopropyl alcohol = 1 / 0.01 / 5/25 (molar ratio) A formation solution was prepared. After immersing the glass plate in this underlayer solution, the glass plate is pulled up at a speed of 1 mm / sec, the underlayer solution is applied to the surface of the glass plate, and dried at a temperature of 80 ° C. for 15 minutes to form Al.
An unbaked underlayer made of (OC ₂ H ₅ ) ₃ was formed on the surface of the glass plate.

Next, as a silane compound, C ₈ F ₁₇ C ₂ H _{4 was used.}
SiCl ₃ is prepared, C ₈ F ₁₈ is prepared as a solvent for dissolving this compound, and C ₈ F ₁₇ C ₂ H ₄ SiCl ₃ / C ₈ F is prepared.
A silane compound solution having a composition ratio (volume ratio) of ₁₈ = 1/99 was prepared. The surface of the glass plate is then immersed in the silane compound solution in an anhydrous atmosphere with a relative humidity of 5% or less, and the glass plate on which the underlayer (unfired) is formed is pulled up at a speed of 1 mm / sec. A silane compound solution was applied to. After this, the solvent on the glass plate surface (C ₈ F ₁₈ )
Was evaporated, and the glass plate was baked at 400 ° C. for 15 minutes. Thus, the substrate A2 having the functional film was produced.

FIG. 8 is a conceptual diagram for explaining the manufacturing flow of this method. FIG. 8A is a diagram schematically showing the state of the underlayer when the underlayer solution is applied to a glass plate and dried. As shown in FIG. 8A, when the underlayer solution is applied and dried at a temperature equal to or lower than the baking temperature, Al (OC ₂ H ₅ ) ₃ located near the surface of the glass plate is desorbed from OH groups on the surface of the glass plate. while bound to the alcohol reaction (-O-), the majority of Al that does not bind to OH groups of the substrate (OC ₂
The H ₅ ) ₃ molecule reacts with a small amount of moisture (for example, humidity in the air) present in the surroundings. As a result, the underlayer is bonded and fixed to the substrate, and OH groups on the surface of the underlayer increase.

FIG. 8 (b) is a schematic view showing a state in which a silane compound solution is applied to the underlayer, in which the silane compound (C ₈ F ₁₇ C ₂ H ₄ SiCl ₃ ) is formed on the underlayer surface. O
It shows a state of being chemically bonded (adsorbed) to the H group portion. Further, FIG. 8C is a diagram showing a state of the substrate after firing, showing a state in which constituent molecules of the underlayer are polymerized.

In the following, the glass plate on which the functional film is formed is referred to as a substrate, and a method of applying a silane compound solution and then performing firing without performing firing during formation of the underlayer is referred to as a post-firing method. I will. (Comparative Example 3) Instead of drying at 80 ° C for 15 minutes, the glass plate coated with the underlayer solution was replaced by 400 ° C at 15 ° C.
Except that the underlayer (sintered underlayer) was formed by a method of performing the baking for 1 minute, and that the glass plate coated with the silane compound solution was not baked at 400 ° C. for 15 minutes. A substrate B2 having a functional film was produced in the same manner as in Example 7.

A conceptual diagram of this method is shown in FIG. Figure 15
FIG. 1A is a diagram schematically showing a state in which a base layer solution is applied to a glass plate and dried, which is shown in FIG.
It is similar to (a). FIG. 15B shows a state in which the underlayer is baked, and the OH on the surface of the underlayer is caused by the baking.
It shows how some of the radicals are lost. Furthermore, FIG.
(C) is a silane-based compound (C ₈ F ₁₇ C ₂
H ₄ SiCl ₃ ) is chemically adsorbed.

Comparative Example 3 is a method according to the prior art, and the firing performed when forming the underlayer by this method is referred to as a pre-firing method. (Comparative Example 4) An untreated glass plate having no underlying layer was used, and the glass plate was dipped in the silane compound solution to obtain 1
The substrate C2 having the functional film according to Comparative Example 4 was prepared by pulling up at a speed of mm / sec to evaporate C ₈ F ₁₈ . FIG. 16 shows a conceptual diagram for explaining this method.

FIG. 16 (a) is a diagram showing a state of the glass surface, and FIG. 16 (b) is a diagram showing a state in which Al (OC ₂ H ₅ ) ₃ as an underlayer component is applied to the surface of the glass plate. is there.
As shown in FIG. 16 (b), when the glass is directly coated with the silane compound (C ₈ F ₁₇ C ₂ H ₄ SiCl ₃ ) for forming a film, a small amount of OH groups present on the glass substrate is present. Since the silane compound (C ₈ F ₁₇ C ₂ H ₄ SiCl ₃ ) is chemically adsorbed on the film, a film having a coarse density is formed.

[Film Fabrication Conditions and Durability] The above-mentioned substrate A2,
Using B2 and C2, the relationship between the presence or absence of an underlayer, the difference in firing conditions, and the contact angle was investigated. The contact angle was measured as follows. For each of the substrates A2 to C2, a dish-washing sponge was used and a load of 2 kgf was applied, and the substrate was rubbed 50,000 times. 10 μl of water was dropped and the contact angle was measured. Hereinafter, this measuring method is referred to as a rubbing durability test method. The measurement results are shown in FIG.

As is clear from FIG. 9, the substrate A2 (Example 7) manufactured by the manufacturing method according to the present invention had a large initial contact angle, and the contact angle was almost decreased even by rubbing with a sponge. I couldn't do it. On the other hand, it was confirmed that the substrate B2 (Comparative Example 3) subjected to the pre-baking method had a smaller initial contact angle than the substrate A2 and that the contact angle tended to decrease due to rubbing with a sponge. Further, the substrate C2 (Comparative Example 4) having no underlying layer had a smaller initial contact angle than the substrate B2, and the contact angle was largely reduced by rubbing with a sponge.

From the above results, it was confirmed that according to the manufacturing method of the present invention, a functional film excellent in water repellency and durability could be formed.

The above results will be considered with reference to FIGS. The excellent contact angle and rubbing durability were obtained on the substrate A2 which was not pre-baked because the OH group density on the surface of the underlayer was high during the application of the film-forming solution, so that the molecules of the silane compound were uniform on the surface of the underlayer. It is considered that this is because a high-quality thin film chemically bonded at high density is formed, and by subsequent firing, the underlying layer constituent molecules and the coating constituent molecules are polymerized to form a strong structure.

On the other hand, the rubbing durability and the like of the substrate B2 having the base layer pre-baked is inferior to that of the substrate A2 because the hydroxyl groups on the surface of the substrate are lost by the pre-baking, resulting in nonuniformity and less binding points. It is considered that this is because a film is formed. In addition, in the substrate C2 which uses the glass substrate having no underlying layer as it is, since the silane compound molecules have few active hydrogen sites to be bonded, a non-uniform thin film having dangling silane compound molecules not directly bonded to the substrate. It is considered that the initial contact angle was small and the resistance to rubbing was small as a result. (Example 8) This example corresponds to the functional film according to the third aspect.

X- (SiOX ₂ ) _n -SiX ₃ (provided that X
Is at least one functional group selected from the group consisting of halogen, an alkoxy group and an isocyanate group, and n
Is an integer of 0 or more), X'-
As a mixture (hydrolyzable) of a compound represented by (AlOX ′) _n —AlX ′ ₂ (where X ′ is an alkoxy group and n is an integer of 0 or more), Si (OC)
₂ H ₅ ) ₄ and Al (OC ₂ H ₅ ) ₃ are prepared, and when the mixing ratio of both compounds is expressed by the number of moles of Si / the number of moles of Al (numerator / denominator), 10/90, 25/75, 50/50, 75
/ 25, 90/10, 100/0 6 different mixing ratios of 2
A component-based underlayer solution was prepared. Then, an underlayer was formed using these two-component underlayer solutions. Except for this, the substrates D2, E2, F2, G2, H2, and I2 according to Example 8 were manufactured in the same manner as in Example 7.

[Difference in Components of Underlayer and Rubbing Durability] The substrate A2 according to Example 7 and the substrate D2 according to Example 8 described above
The difference in durability of I2 was examined by the above-mentioned rubbing durability test method.
The measurement results are shown in FIG.

As is clear from FIG. 10, Al (OC ₂
The substrate A2 using H ₅ ) ₃ alone is Si (OC ₂ H ₅ ) ₄
The initial contact angle and rubbing durability were remarkably superior to those of the substrate I2 used alone. In addition, the contact angle decreases with time due to the following problems.
2; it increased in the order of Example 8).

From the above results, X '-(AlOX') _n-
It was found that when a compound represented by AlX ' ₂ (where X is an alkoxy group and n is an integer of 0 or more) is used alone, a functional film excellent in abrasion resistance can be obtained. . The reason why the contact angle becomes smaller by rubbing is considered to be that the molecules (C ₈ F ₁₇ C ₂ H ₄ −) forming the surface-modified film are gradually lost from the substrate surface by rubbing.
From this, the above results reflect the strength or hardness of the underlayer, and the strength or hardness of the underlayer became smaller as the blending ratio of Si increased, and as a result, the contact angle was significantly deteriorated by rubbing. It is considered to be a thing.

[Difference in Underlayer Components and Temperature Resistance] The substrate A2 according to the above Example 7 and the substrates D2 to I according to the above Example 8
The difference in temperature resistance of No. 2 was examined by the heating durability test method. Specifically, it was left to stand in the air heated to 300 ° C. for 1000 hours. During this time, the stains on the substrate were removed by ultrasonic cleaning with ethanol every 100 hours, and then 10 μl of water was dropped on the film formation surface to measure the contact angle. The measurement results are shown in FIG.

From FIG. 11, the change with time of the contact angle in the heating durability test method is as follows: Substrate I2 (100/0)> Substrate A2
(0/100)> Substrate D2 (10/90)> Substrate E2
(25/75)> Substrate F2 (50/50)> Substrate G2
It was confirmed that the order of (75/25)> substrate H2 (90/10) became smaller.

From these results, the underlayer solution was treated with X- (S
'and halogen, alkoxy group and isocyanate group, n represents 0 is an integer equal to or greater than) the compound represented _{by, X.' iOX 2) n} -SiX 3 ( where, X - (AlOX ') _n
It has been confirmed that the heat resistance in water repellency is improved by using a mixture of a compound represented by —AlX ′ ₂ (where X is an alkoxy group and n is an integer of 0 or more). Furthermore, Si / Al in the above-mentioned two-component system underlayer solution
It has been found that when the ratio is 1 or more, a functional film having more excellent heat resistance can be produced. The above results are closely related to the denseness of the underlayer, and it is considered that a substrate having a denser underlayer has better temperature resistance. (Example _{9) X- (SiOX 2) n} -SiX 3 ( where, X
Is a compound represented by halogen, an alkoxy group and an isocyanate group), and S (OC ₂ H ₅ ) ₄ instead of S
A substrate J2 according to Example 9 was produced in the same manner as the substrate H2 (Si / Al = 90/10) of Example 8 except that i (NCO) ₄ was used.

[Types of Underlayer Components and Durability] The temperature resistance of the substrate H2 according to Example 8 and the substrate J2 according to Example 9 was examined by the above heating durability test method. The result is shown in FIG.
It was shown to.

As is clear from FIG. 12, the substrate H2 of Example 8 using Si (OC ₂ H ₅ ) ₄ and Al (OC ₂ H ₅ ) ₃ as the components of the underlayer is Si (NCO) ₄ And Al (O
Compared to the substrate J2 of Example 9 using C ₂ H ₅ ) ₃ , the initial contact angle was large and the change in contact angle with time was small. From this result, it was confirmed that the use of the alkoxysilane was better than that of the two-component underlayer solution using the isocyanatesilane.
It can be seen that the component-based underlayer solution is superior in that it can enhance the water repellency and durability of the functional film. (Example 10) a silane compound (main component of the functional film), instead of the _{C 8 F 17 C 2 H 4} SiCl 3, C 8 F 17 C 2 H 4
A substrate K2 according to Example 10 was made in the same manner as Example 7 except that Si (OC ₂ H ₅ ) ₃ was used. In Example 10, a one-component underlayer was used.

[Difference of Silane Compounds and Durability] Example 1
Using the substrate K2 of No. 0 and the substrate A2 of Example 7, the relationship between the difference in the thin film component (the main agent of the functional film) and the durability was examined by the heating durability test method. The result is shown in FIG.

From FIG. 13, the initial contact angles of both substrates were the same, but as the silane compound, C ₈ F ₁₇ C ₂ H ₄ Si (O
C ₈ rather than substrate K 2 (Example 10) using C ₂ H ₅ ) ₃
It was confirmed that the substrate A2 using F ₁₇ C ₂ H ₄ SiCl ₃ (Example 7) had a significantly smaller decrease in contact angle with time. From this result, a trichlorosilane-based compound is preferable in terms of durability as the silane compound as the main component of the functional film. (Example 11) As a solvent for dissolving a silane compound,
A substrate L2 according to Example 11 was made in the same manner as Example 7 except that hexamethyldisiloxane (linear silicone) was used instead of C ₈ F ₁₈ .

[Difference in Solvents and Durability] Using the above heating durability test method, the substrate L2 of Example 11 and the substrate A of Example 7 were used.
The performance of No. 2 was compared, and the relationship between the difference in the solvent that dissolves the silane compound and the durability was examined. The results are shown in Fig. 14.

From FIG. 14, although the initial contact angles of both substrates were the same, the substrate L2 using hexamethyldisiloxane was used.
It was confirmed that (Example 11) showed less change in contact angle over time than the substrate A2 using C ₈ F ₁₈ (Example 7). From this result, hexamethyldisiloxane is preferable as the solvent for dissolving the silane compound, because a functional film excellent in high temperature durability can be obtained. The same results as above were obtained when cyclohexamethyltrisiloxane (cyclic silicone) was used. As the silane compound as a main agent (Example 12) functional film, in place of the _{C 8 F 17 C 2 H 4} SiCl 3, C 10 H 21 Si
A substrate M2 according to Example 12 was made in the same manner as Example 7 except that Cl ₃ was used. As the silane compound as a main agent (Example 13) functional film, in place of the _{C 8 F 17 C 2 H 4} SiCl 3, except for using SiCl _4, in the same manner as in Example 7, Example 13
The substrate N2 according to the above was manufactured.

[Relationship Between Type of Silane Compound and Antifouling Property] The above-mentioned substrate A2 (Example 7) and substrate M2 (Example 1) which differ only in the type of silane compound as the main ingredient of the functional film.
2) Using the substrate N2 (Example 13), the quality of the antifouling property of the substrate surface was examined by an antifouling property test.

The antifouling test was conducted as follows. First, 0.2 cc of syrup consisting of sugar / soy sauce = 1/1 (weight ratio) is dropped on a substrate and baked at 300 ° C. for 15 minutes. After that, wipe off any stickiness and drop 0.2 cc of the above syrup on the substrate again, and 300 ° C.
Bake for 15 minutes and wipe off as above. This cycle was repeated until stickiness could not be wiped off, and the number of times was counted. The results are shown in Table 2.

[0150]

[Table 2] As is clear from Table 2, the antifouling property (in order of goodness) was
2 (C ₈ F ₁₇ C ₂ H ₄ SiCl ₃ ) >> Substrate M2 (C ₁₀ H ₂₁
SiCl ₃ ) >> substrate N 2 (SiCl ₄ ), substrate N
Substrates A2 and M2 exhibited higher antifouling properties than those of No. 2, and substrate A2 was particularly excellent in antifouling properties. From this result, it can be seen that in order to enhance the antifouling property of the functional film, it is preferable to use a silane compound having an alkyl group or a fluoroalkyl group, and more preferably to use a silane compound having a fluoroalkyl group. .

[Influence of Humidity in Manufacturing Atmosphere] In Examples 7 to 13 and the like described above, dipping / pulling in the silane compound solution was performed in an anhydrous atmosphere having a relative humidity of 5% or less. But,
The level of relative humidity in the ambient atmosphere when the silane compound solution is applied greatly affects the thin film formation reaction. Therefore, an experiment was conducted to investigate the influence of humidity in the ambient atmosphere when the silane compound solution was applied to the substrate on which the underlayer was formed.

As an experimental method, the relative humidity of the ambient atmosphere at the time of dipping / pulling up the substrate in the silane compound solution was set to 8 kinds of 5, 10, 15, 20, 25, 30, 35, 40%. Except for the above, a substrate on which a functional film is formed is manufactured in the same manner as in Example 11 above, and the appearance state of the substrate during and after the formation of the functional film is visually observed.

Observation of the substrates produced under the above-mentioned respective humidity conditions revealed that under a humidity condition of 30% or less, under an anhydrous atmosphere (5
% Or less), a substrate having an appearance similar to that of On the other hand, 4
Under a humidity condition of 0% or more, a white product which was apparently a reaction product of moisture in the atmosphere and a silane compound was observed. From these things, it is preferable that the contact of the silane compound solution with the substrate is performed in an atmosphere having a relative humidity of 35% or less. Next, examples in which the functional film of the present invention is applied to a liquid crystal alignment film will be described. (Example 14) A liquid crystal display element according to this example was manufactured by the method described below. First, as shown in FIG.
A first substrate 3 having a first electrode group 1 formed in a matrix and a transistor group 2 driving the electrodes.
A base layer 7 was formed on the top.

That is, X- (SiOX ₂ ) _n -SiX ₃
(However, X is at least one functional group selected from the group consisting of halogen, an alkoxy group and an isocyanate group, and n is an integer of 0 or more.) As a compound represented by Si (OC ₂ H ₅ ). ₄ is prepared and Si (OC
₂ H ₅ ) ₄ / HCl / water / isopropyl alcohol = 1 /
An underlayer solution of 0.01 / 5/25 (molar ratio) was prepared. Then, this underlayer solution was applied to a region of the first substrate 3 where the first electrode group 1 was formed using a printing machine. The coating film at this time was made to have a thickness of about 1 μm. Further, this coating film is dried at 80 ° C. for 15 minutes to remove S
An unfired underlayer 7 made of i (OC ₂ H ₅ ) ₄ was formed on the surface of the first substrate 3 (underlayer forming step).

Next, C was used as a silane compound.₆H_Five-CH
= CH-CO-C₆H_Four-O- (CH ₂)₆-O-SiCl
₃As a solvent for dissolving this compound.
Prepare oxamethyldisiloxane, 10^-3mol / L
 C₆H_Five-CH = CH-CO-C₆H_Four-O- (CH₂)
₆-O-SiCl₃/ Hexamethyldisiloxane silane
A compound solution was prepared. And the relative humidity is 5% or less
Under this anhydrous atmosphere, the silane compound solution was added to the underlayer.
A printing machine is used for the first substrate 3 on which 7 (unbaked) is formed.
And applied (thin film forming step). The thickness of the applied liquid film is about
It was 1 μm. After this, the melt remaining on the surface of the first substrate 3
The agent (hexamethyldisiloxane) is evaporated and
The first substrate 3 is baked at 300 ° C. for 15 minutes to align the liquid crystal.
The film 4 was formed (firing process).

After the above firing step, the first substrate 3 having the liquid crystal alignment film 4 formed thereon was immersed in chloroform, which is a non-aqueous solvent, and washed (washing step). Further, the first substrate 3 was pulled up from chloroform in a state of standing in a desired direction and the chloroform was drained (a draining alignment step). As a result, the molecules forming the liquid crystal alignment film 4 were able to be aligned while being inclined in the liquid draining direction opposite to the pulling direction.

After the liquid draining alignment step, polarized ultraviolet rays of 400 mJ / cm ² (wavelength: 365 nm) were irradiated so that the liquid draining direction and the polarization direction were the same direction (polarization aligning step). As a result, the molecules forming the functional film as the liquid crystal alignment film 4 were cross-linked at the photosensitive group along the polarization direction. In this way, a functional film as the liquid crystal alignment film 4 in which the film constituent molecules were aligned in the polarization direction was formed on the first substrate 3.

On the other hand, regarding the second substrate 6 on which the color filter group 13 and the second electrode 14 are sequentially provided,
By performing the same steps as described above, the base layer 5 and the liquid crystal alignment film 5 that has been subjected to the alignment treatment in a predetermined direction were formed.

Further, beads were scattered on the first substrate 3, and the adhesive 8 containing a spacer was applied to the edge portion of the substrate 3 so that the application shape was a frame shape. Then, the first
The first electrode group 1 and the second electrode 14 were opposed to each other in parallel, and the first substrate 3 and the second substrate 6 were bonded so that the cell gap became about 5 μm. At this time, the alignment treatment direction of the liquid crystal alignment film 4 provided on the first substrate 3 and the second substrate 6
The alignment was performed so that the relative crossing angle with the alignment treatment direction in the liquid crystal alignment film 5 provided above was 90 °.

Next, the first substrate 3 and the second substrate 6
In between, a liquid crystal material was injected to form a liquid crystal layer 10 having a TN orientation with a twist angle of 90 °. Further, on the outer surfaces of the first substrate 3 and the second substrate 6, polarizing plates 11 and 12 whose optical axis directions are set so as to be in a normally white mode are provided. As described above, the TN type liquid crystal display element O according to this example was manufactured.

FIG. 18 shows a conceptual diagram for explaining the manufacturing flow of this method. FIG. 18A is a diagram schematically showing the state of the underlayer 7 when the underlayer solution is applied to the first substrate 3 and dried. As shown in FIG. 18A, when the underlayer solution is applied and dried at a temperature equal to or lower than the baking temperature, first, Si (OC ₂₎ located near the surface of the first substrate 3 is firstly formed.
H ₅ ) ₃ is OH on the surface of the first substrate 3 and the first electrode group 1
The majority of Si (OC ₂₎ does not bond with the OH group of the first substrate 3 while being dealcoholized with the group to bond (-O-).
The H ₅ ) ₃ molecule reacts with a small amount of moisture (for example, humidity in the air) present in the surroundings. As a result, the underlayer 7 is bonded and fixed to the first substrate 3, and the OH on the surface of the underlayer 7 is
The group increases.

FIG. 18B is a schematic view showing a state in which a silane compound solution is applied to the underlayer 7, and the silane compound (C ₆ H ₅ —CH═CH—CO—C ₆ H _{4) is used.} -O
- (CH ₂₎ a ₆ -O-SiCl ₃₎ is underlying layer 7 surface OH
It shows a state of being chemically bonded (adsorbed) to the base portion. Further, FIG. 18C is a diagram showing a state of the substrate after firing, showing a state in which constituent molecules of the underlayer 7 are polymerized.

FIG. 18D is a schematic view showing a state in which the silane compound chemically adsorbed on the surface of the underlayer 7 is liquid-distributed and aligned, and the constituent molecules of the liquid crystal alignment film 5 are arranged in the liquid-discharging direction of the cleaning liquid. It shows a state of being inclined and oriented. Further, FIG. 18 (e) is a diagram showing an alignment state of the liquid crystal alignment film 5 after the polarization alignment step, in which the photosensitive groups in the constituent molecules of the liquid crystal alignment film 5 are arranged along the direction parallel to the polarization direction. Shows a cross-linked state. (Comparative Example 5) For the first and second substrates coated with the underlayer solution, instead of drying at 80 ° C for 15 minutes, 3
A base layer (baking base layer) was formed by a method of baking at 00 ° C. for 15 minutes, and post baking at 400 ° C. for 15 minutes was performed on the first and second substrates coated with the silane compound solution. Example 14 above, except not performed
A TN type liquid crystal display element P was manufactured in the same manner as in. (Comparative Example 6) Using the first and second substrates having no underlying layer at all, the silane compound solution was applied to these substrates in the same manner as in Example 7, and hexamethyldisiloxane was evaporated to align the liquid crystal. A functional film as a film was formed. Further, a TN type liquid crystal display element Q according to Comparative Example 6 was manufactured in the same manner as in Example 14.

[Film Fabrication Conditions and Display Characteristics] Using the above-mentioned liquid crystal display elements O, P and Q, the initial alignment of the liquid crystal and the contrast for evaluating the display characteristics were examined. The results are shown in Table 3.
Also described in.

[0165]

[Table 3] As is clear from this table, it was confirmed that the liquid crystal display element O using the functional film of the present invention as a liquid crystal alignment film had no alignment defects.

On the other hand, the initial alignment of the liquid crystal of the liquid crystal display device Q and the display characteristics are considerably deteriorated because the electrode material ITO on the surfaces of the first and second substrates has active hydrogen which becomes an adsorption site of a silane compound. It is considered that this is because there are almost no surface hydroxyl groups having. Therefore, it can be said that the effect of the present invention of increasing the number of adsorption sites for the silane compound to be adsorbed to the underlayer is extremely high even when used as a liquid crystal alignment film.

The inventors of the present application also examined the initial alignment and the contrast of the liquid crystal display element manufactured by the same method as in Example 14 except that the washing step and the liquid draining alignment step were not performed. Further, a liquid crystal display element manufactured by the same method as in Example 14 was examined in the same manner except that the liquid draining direction in the liquid draining alignment step and the polarization direction in the polarization aligning step were different. As a result, it was found that the molecules constituting the liquid crystal alignment film are aligned in the polarization direction, and the liquid crystal molecules in the vicinity of the liquid crystal alignment film are also aligned in the polarization direction. Was not obtained. Therefore, it was found that the characteristics of the liquid crystal display element O can be approximated by increasing the irradiation amount of polarized ultraviolet rays in the polarization alignment step as compared with the case of the above-described Example 14. From the above, it was found that the irradiation amount of the polarized ultraviolet light can be reduced as compared with the conventional photo-alignment method by making the drainage direction of the cleaning agent parallel to the polarized direction of the polarized ultraviolet light in advance. This is because, as a result of preliminarily preliminarily preliminarily aligning the film-constituting molecules of the liquid crystal alignment film so as to be parallel to the polarization direction by draining the cleaning agent before irradiation with polarized ultraviolet light, It is considered that the anisotropic photoreaction of the photosensitive group was apt to occur, and thereby the polarized UV irradiation dose could be reduced.

The underlayer solution X- (SiOX ₂ ) _n- S
iX ₃ (where X is a halogen, an alkoxy group and an isocyanate group, n is an integer of 0 or more) and X ′-(AlOX ′) _n —AlX ′ ₂ (where X ′ is an alkoxy group) A liquid crystal display device was produced in the same manner as in Example 7 by changing the composition of the compound capable of being hydrolyzed with the compound represented by the formula (4). The initial alignment and display characteristics of the liquid crystal are shown.

X- (SiOX ₂ ) _n -SiX ₃ (wherein X is at least one functional group selected from the group consisting of halogen, an alkoxy group and an isocyanate group, and n is an integer of 0 or more). A compound represented by
Si 'as a mixture (hydrolyzable) composed of a compound represented by X'-(AlOX ') _n -AlX' ₂ (where X'is an alkoxy group and n is an integer of 0 or more).
When (OC ₂ H ₅ ) ₄ and Al (OC ₂ H ₅ ) ₃ were prepared and the mixing ratio of both compounds was changed to prepare a liquid crystal display element in the same manner as in Example 14, the liquid crystal display element was also prepared. It has been found that it exhibits almost the same initial orientation and display characteristics as O. (Example 15) As a silane compound (thin film component), C _{6
H 5 -CH = CH-CO-} C 6 H 4 -O- (CH 2) 6 -O
In place of —SiCl ₃ (containing a chalcone group), C ₆ H ₅ —
CH = CH-CO-O- ( CH 2) 6 -O-SiCl
Example 14 except that ₃ (containing cinnamoyl group) was used.
Similarly to the above, a TN type liquid crystal display element R according to Example 15 was manufactured. (Example 16) As a silane compound (thin film component), C _{6
H 5 -CH = CH-CO-} C 6 H 4 -O- (CH 2) 6 -O
Instead of —SiCl ₃ (containing a chalconeyl group), C ₁₀ H ₂₁
Example 1 except that SiCl ₃ (no photosensitive group) was used
In the same manner as in Example 4, a TN type liquid crystal display element S according to Example 16 was manufactured.

[Difference of Silane Compounds and Display Characteristics] Example 1
5 and the TN type liquid crystal display element R according to Example 16;
Using S and the liquid crystal display element O according to Example 14 above,
The contrast was investigated as the initial alignment and display characteristics of the liquid crystal. The results are also shown in Table 4.

[0171]

[Table 4] As is clear from Table 4, the silane compound having a chalcone group is superior to the one having a cinnamoyl group in the initial alignment and display characteristics of liquid crystal.
However, it was found that even in the case of a liquid crystal alignment film made of a silane compound having a cinnamoyl group, the initial alignment state and display characteristics of liquid crystal molecules can be improved by increasing the irradiation amount of polarized ultraviolet light. It is considered that this is because the sensitivity of the photosensitive group to polarized ultraviolet light is chalconyl group> cinnamoyl group. Further, in the liquid crystal display element S including the liquid crystal alignment film made of a silane compound having no photosensitive group, it was found that the liquid crystal molecules were not aligned in a desired direction and the alignment characteristics were deteriorated. From the above, it is considered that in the liquid crystal display elements O and R, liquid crystal molecules were aligned as a result of polymerization of the photosensitive groups along the deflection direction due to irradiation of polarized ultraviolet light. (Example 17) A TN type liquid crystal display element T was produced in the same manner as in Example 14 except that the polarization alignment step was replaced with the rubbing alignment step. In addition, the rubbing direction in the rubbing treatment is parallel to the liquid cutting orientation direction, and a nylon cloth (fiber warp 16 to 20 μm, hair length 3 mm) is used,
The surface of the liquid crystal alignment film was rubbed with a push-in of 0.4 mm and a speed of 500 m / min.

[Alignment Method and Display Characteristics] The TN type liquid crystal display element T according to Example 17 and the T according to Example 14 described above.
Using the N-type liquid crystal display element O, the initial alignment of the liquid crystal and the contrast as the display characteristics were examined. The results are shown in Table 5.
Also described in.

[0173]

[Table 5] As is clear from Table 5, a lot of rubbing lines were observed on the surface of the liquid crystal alignment film under the microscope observation, but like the liquid crystal alignment film O, the liquid crystal molecules were aligned in a desired direction, and no alignment defect was confirmed. It was Also, display characteristics with high contrast were obtained.

As the silane compound (thin film component),
_{C 6 H 5 -CH = CH-} CO-C 6 H 4 -O- (CH 2) 6 -
Instead of O—SiCl ₃ (containing a chalconeyl group), C ₁₀ H
_{By using 21} SiCl ₃ (no photosensitive group), it was examined whether or not the presence of the photosensitive group in the liquid crystal display element T affects the initial alignment of liquid crystal molecules and display characteristics. As a result, even when C ₁₀ H ₂₁ SiCl ₃ was used, the same initial alignment as that of the liquid crystal display element T was exhibited and the display characteristics were obtained. Therefore, it was confirmed that the initial alignment of the liquid crystal molecules was due to the rubbing treatment.

The inventors of the present application also examined the initial alignment and the contrast of the liquid crystal display element manufactured by the same method as in Example 14 except that the washing step and the liquid-draining alignment step were not performed. A liquid crystal display device manufactured by the same method as in Example 14 was examined in the same manner except that the liquid draining direction in the liquid draining alignment step and the rubbing treatment direction in the rubbing step were different. As a result, it was found that the molecules constituting the liquid crystal alignment film were aligned in the rubbing treatment direction, and as a result, the liquid crystal molecules in the vicinity of the liquid crystal alignment film were also aligned in the rubbing treatment direction. Orientation and display characteristics were not obtained. Therefore, it was found that the characteristics of the liquid crystal display element T of Example 17 were approximated by changing the rubbing conditions in the rubbing process and rubbing strongly. However, rubbing debris was observed on the surface of the liquid crystal alignment film at this time. From the above, by making the drainage direction of the cleaning agent parallel to the rubbing treatment direction in advance, it is possible to prevent rubbing more strongly than in the conventional rubbing treatment and prevent the liquid crystal alignment film from being scraped off. Do you get it. This is because, as a result of preliminarily preliminarily aligning the film-constituting molecules of the liquid crystal alignment film in parallel with the rubbing treatment direction by draining the cleaning agent before performing the rubbing treatment, the film-constituting molecules are removed during the rubbing treatment. This is because the orientation process is easier.

[Experiment 2] In the embodiment described above, the case where the non-aqueous solvent was used as the cleaning agent in the cleaning step was described. In this experiment, water was used as the cleaning agent. As an experimental method, a liquid crystal alignment film was formed in the same manner as in Example 14 except that water was used as the cleaning agent in the cleaning step. Further, the appearance state of the formed liquid crystal alignment film was visually observed.

Observation of the substrate produced in the above-mentioned washing step revealed a white product apparently due to the reaction between water and the silane compound, and it could not be removed. For these reasons, it is preferable to use a non-aqueous solvent containing no water as the solvent in the washing step. (Example 18) A liquid crystal display device was manufactured in the same manner as in Example 14 except that N-methyl-2-pyrrolidinone was used instead of chloroform as the cleaning agent in the cleaning step.

In this example, the removability of the unreacted silane compound present in excess was observed in the washing step. It was found that the N-methyl-2-pyrrolidinone used in this example was superior to the chloroform used in Example 14 in its removability. Therefore, the use of N-methyl-2-pyrrolidinone in the washing step can improve the mass productivity in consideration of the safety of the chemical solution. (Example 19) As a silane compound (thin film component), C _{6
H 5 -CH = CH-CO-} C 6 H 4 -O- (CH 2) 6 -O
-SiCl ₃ (containing a chalcone group) at a mixing ratio of 1 mo
A liquid crystal display element U according to the present Example 19 was produced in the same manner as in the above Example 14 except that a mixture containing 1% of C ₈ F ₁₇ C ₂ H ₄ SiCl ₃ was used. (Example 20) 100 mJ / c instead of 400 mJ / cm ² as the irradiation amount of polarized ultraviolet rays in the polarization alignment step.
A TN type liquid crystal display element V according to this example was manufactured in the same manner as in Example 14 except that m ² was used. (Example 21) Instead of 400 mJ / cm ² as the irradiation amount of polarized ultraviolet rays in the polarization orientation step, 1000 mJ /
A TN type liquid crystal display element W according to this example was manufactured in the same manner as in Example 14 except that the size was changed to cm ² .

[Liquid Crystal Alignment Mode] The liquid crystal display element U according to Example 19, the liquid crystal display element V according to Example 20, the liquid crystal display element W according to Example 21, and the liquid crystal display element O according to Example 14 described above. For and, the pretilt angles of the liquid crystal molecules near the liquid crystal alignment film were examined. The results are also shown in Table 6 below.

[0180]

[Table 6] From the above, it was confirmed that a liquid crystal alignment film capable of homeotropic alignment can be obtained by mixing a silane compound having a fluoroalkyl group of 5 mol% or less with the silane compound.

Further, in the functional film of the present invention, it is possible to obtain a liquid crystal alignment film capable of homogeneous alignment by irradiating polarized UV with a dose of 1 J / cm ² (wavelength: 365 nm) or more in the polarization alignment step. Was confirmed. further,
It has been confirmed that when the irradiation amount is 100 mJ / cm ² or less, pretilt alignment with a pretilt angle of 5 to 10 ° which is optimum for TN liquid crystal can be achieved.

[0182]

As described above, according to the present invention, a base layer having hydroxyl groups or the like is formed on a substrate such as a glass plate, and the surface of the base layer is chemically treated with a silane compound without firing. A manufacturing method of adsorbing and then firing is adopted. With such a manufacturing method, a large amount of active hydrogen can be present on the surface of the underlayer, so that the silane compound molecules can be chemically bonded at a high density by contact with the silane compound.

In the present invention, the base layer is strongly solidified and firmly bound to the base material by firing at the final stage of production. According to such a production method of the present invention, a functional film formed by uniformly and strongly bonding and fixing to a substrate can be formed. With such a functional film, a desired surface such as water repellency or liquid crystal alignment property can be obtained. The modifying effect is exerted for a long time.

Furthermore, in the present invention, X- (SiOX) _n-
SiX ₂ (where X is a halogen, an alkoxy group and an isocyanate group, and n is an integer of 0 or more) is used as the underlayer forming component. By using this compound, an extremely solid underlayer can be formed. As a result, a functional film having excellent water repellency and abrasion resistance can be obtained.

Furthermore, in another embodiment of the present invention, X '-(A
lOX ') _n -AlX' ₂ (where X'is an alkoxy group,
n is an integer of 0 or more. ) Is used as the underlayer-forming component, an extremely firm underlayer can be formed by using this compound, and as a result, a functional film excellent in water repellency and rubbing durability can be obtained.

In still another embodiment of the present invention, X '
_{- (AlOX ') n -AlX'} 2 (. Where, X is an alkoxy group, n represents an integer of 0 or more) and, X- (SiO
X _{2) n} -SiX ₃ (where, X is a halogen, an alkoxy group and an isocyanate group, n represents an integer of 0 or more.)
A two-component underlayer-forming component mixed with and is used, which makes it possible to obtain an excellent functional film in which the desired surface-modifying effect such as water repellency does not easily deteriorate due to heat.

Further, when a liquid draining drying method or a polarized light irradiation method using ultraviolet rays is applied to the functional film, a liquid crystal alignment film having desired liquid crystal alignment characteristics can be obtained.

Furthermore, by using such a liquid crystal alignment film according to the present invention, a liquid crystal display device having excellent display performance can be provided.

It should be noted that X '-(A
lOX ') _n -AlX' ₂ is used alone,
It can be suitably applied to, for example, cooking utensils that require scrubbing. In addition, X '-(AlOX') _n -AlX ' ₂ and X
- (SiOX ₂₎ manufacturing method using a two-component undercoat layer forming solution with _n -SiX _3, for example electric iron base can be preferably applied to portions of, thereby the iron over a long period crease smoothing function is hardly degraded give To be

[Brief description of drawings]

FIG. 1 is a conceptual diagram for explaining a method for producing a functional film according to the present invention.

FIG. 2 is a conceptual diagram for explaining a method of manufacturing a functional film according to a conventional method.

FIG. 3 is a conceptual diagram for explaining a method of manufacturing a functional film according to a conventional method in which an underlayer is not formed.

FIG. 4 is a graph showing the relationship between the number of rubbing and the contact angle.

FIG. 5 is a graph showing changes with time in contact angle in a heating durability test.

FIG. 6 is a graph showing changes with time in contact angle in a heating durability test.

FIG. 7 is a graph showing a change in contact angle over time in a heating durability test.

FIG. 8 is a conceptual diagram for explaining a method for producing a functional film according to the present invention.

FIG. 9 is a graph showing the relationship between the number of rubbing and the contact angle.

FIG. 10 is a graph showing the relationship between the number of rubbing and the contact angle.

FIG. 11 is a graph showing a change in contact angle over time in a heating durability test.

FIG. 12 is a graph showing changes with time in contact angle in a heating durability test.

FIG. 13 is a graph showing changes in contact angle over time in a heating durability test.

FIG. 14 is a graph showing a change in contact angle with time in a heating durability test.

FIG. 15 is a conceptual diagram for explaining a method of manufacturing a functional film according to a conventional method.

FIG. 16 is a conceptual diagram for explaining a method for manufacturing a functional film according to a conventional method in which an underlayer is not formed.

FIG. 17 is a schematic sectional view showing a configuration of a liquid crystal display element according to the present invention.

FIG. 18 is a conceptual diagram for explaining a method for manufacturing a liquid crystal alignment film according to the present invention.

[Explanation of symbols]

1 First electrode group 2 transistor group 3 First substrate 4 Liquid crystal alignment film 6 Second substrate 7 Underlayer 10 Liquid crystal layer 14 Second electrode

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI G02F 1/1333 505 G02F 1/1333 505 1/1337 530 1/1337 530 (72) Inventor Naoko Takebe 1006 Kadoma, Kadoma, Osaka Prefecture Address: Matsushita Electric Industrial Co., Ltd. (56) Reference JP-A-5-86353 (JP, A) JP-A-7-328538 (JP, A) JP-A-11-167114 (JP, A) (58) Survey Areas (Int.Cl. ⁷ , DB name) B05D 1/00-7/26 B32B 1/00-35/00 C03C 17/30 C09D 183/10 C09D 185/00 G02F 1/1333 505 G02F 1/1337 530

Claims (30)

(57) [Claims] 1. An X- (SiOX ₂ ) _n -Si film on the surface of a substrate.
X ₃ (where X is at least one functional group selected from the group consisting of halogen, an alkoxy group and an isocyanate group, and n is an integer of 0 or more),
An underlayer forming step of contacting an underlayer solution containing a compound capable of being hydrolyzed and drying it to form an underlayer, and bringing a solution containing a silane compound into contact with the substrate surface on which the underlayer is formed. A method for producing a functional film, comprising: a thin film forming step of forming a thin film by chemically adsorbing a silane compound on the surface of a base material; and a baking step of baking the base material after the thin film forming step. 2. X ′-(AlOX ′) _n —A on the surface of the substrate.
1X ′ ₂ (where X ′ represents an alkoxy group and n is an integer of 0 or more) is brought into contact with a base layer solution containing a hydrolyzable compound, and the base layer solution is dried. And a base layer forming step of forming a film, and a film is formed by contacting a film forming solution containing a silane compound to the surface of the base material on which the base layer is formed and chemically adsorbing silane compound molecules on the surface of the base material. A method for producing a functional film, comprising: a forming step; and a baking step of baking the base material after the film forming step. 3. X- (SiOX ₂ ) _n- Si is formed on the surface of the base material.
A hydrolyzable compound represented by X ₃ (wherein X is at least one functional group selected from the group consisting of a halogen, an alkoxy group and an isocyanate group, and n is an integer of 0 or more); X '-(AlO
X ') _n -AlX' ₂ ( _where X'is an alkoxy group and n is an integer of 0 or more) and a hydrolyzable compound is contained in the underlayer solution containing a binary mixture. And a base layer forming step of forming a base layer by drying and contacting a film forming solution containing a silane compound on the base material surface on which the base layer is formed to bring the silane compound molecules onto the base material surface. A method for producing a functional film, comprising: a film forming step of forming a film by being chemically adsorbed onto the film; and a baking step of baking the substrate after the film forming step. 4. The molar ratio of Si to Al of the binary mixture, Si / Al, is set to 1 or more.
3. The method for producing a functional film according to item 3 . Characterized in that wherein said X- (SiOX ₂₎ a compound represented by _n -SiX ₃ is an alkoxysilane, claim 1, as claimed in any one of claims 2 or claim 3 Method for manufacturing functional film. 6. in dry the underlying layer forming step, the functional film according to any one of claims 1 to 5, characterized in that evaporating the solvent contained in the undercoat layer solution Production method. 7. The drying in the base layer forming step is performed 30 times.
The method for producing a functional film according to claim 6 , wherein the method is performed at a temperature lower than 0 ° C. 8. The firing step comprises polymerizing and solidifying constituent molecules in the underlayer.
The method for producing a functional film according to any one of claims 1 to 6 . 9. The method for producing a functional film according to claim 8 , wherein the firing in the firing step is performed at a temperature of 300 ° C. or higher. As claimed in claim 10, wherein the silane compound for film formation, which comprises using the trichlorosilane compound, method for producing a functional membrane according to any one of claims 1 to 9. As claimed in claim 11, wherein the silane compound for film formation, which comprises using a silane compound having an alkyl group or a fluoroalkyl group, function according to any one of claims 1 to 10 Of a flexible film. 12. A non-aqueous solvent is used as a solvent for the film-forming solution, according to any one of claims 1 to 11.
1. A method for producing a functional film according to any one of 1. 13. The non-aqueous solvent is silicone.
The method for producing the functional film according to claim 12 . 14. The contact of the film-forming solution for the substrate surface, and performing a relative humidity of 35% in the following atmosphere functionality according to any one of claims 1 to 13 Membrane manufacturing method. 15. After the firing process, the production of a functional film according to any one of claims 1 to 14, characterized in that it comprises a cleaning step of removing the silane compound molecule unadsorbed Method. 16. The method for producing a functional film according to claim 15 , wherein a non-aqueous solvent is used as a cleaning agent in the cleaning step. 17. The chloroform is used as the non-aqueous solvent in the washing step.
16. The method for producing the functional film according to 16 . 18. The method for producing a functional film according to claim 16 , wherein N-methyl-2pyrrolidinone is used as the non-aqueous solvent in the cleaning step. 19. A pair of substrates having a liquid crystal alignment film inside at least one of them, a liquid crystal layer provided between the substrates, the liquid crystal layer having a predetermined alignment structure by the liquid crystal alignment film. the manufacturing method of a liquid crystal display device having a, on the _{substrate, X- (SiOX 2) n -SiX} 3 ( wherein X is halogen, at least one functional group selected from the group consisting of alkoxy group and an isocyanate group ,
n is an integer of 0 or more. ), An underlayer forming step of contacting an underlayer solution containing a compound capable of being hydrolyzed and drying to form an underlayer; and a silane compound on the surface of the substrate on which the underlayer is formed. A thin film forming step of forming a liquid crystal alignment film by contacting a solution containing the same and chemically adsorbing silane compound molecules on the substrate surface, a baking step of baking the substrate, and an alignment treatment step of aligning the liquid crystal alignment film. And a method for manufacturing a liquid crystal display device, comprising: 20. A pair of substrates having a liquid crystal alignment film inside at least one of them, a liquid crystal layer provided between the substrates, the liquid crystal layer having a predetermined alignment structure by the liquid crystal alignment film. In the method for producing a liquid crystal display device including: X ′-(AlOX ′) _n —AlX ′ ₂ (where X ′ represents an alkoxy group and n is an integer of 0 or more) on the substrate. An underlayer forming step of contacting an underlayer solution containing a compound capable of being hydrolyzed and drying to form an underlayer, and a solution containing a silane compound on the surface of the substrate on which the underlayer is formed. A thin film forming step of forming a liquid crystal alignment film by chemically adsorbing silane compound molecules on the substrate surface, a baking step of baking the substrate, an alignment treatment step of aligning the liquid crystal alignment film, Equipped with Method of manufacturing a crystal display element. 21. A pair of substrates having a liquid crystal alignment film inside at least one of them, and a liquid crystal layer provided between the substrates, the liquid crystal layer having a predetermined alignment structure by the liquid crystal alignment film. the manufacturing method of a liquid crystal display device having a, on the _{substrate, X- (SiOX 2) n -SiX} 3 ( wherein X is halogen, at least one functional group selected from the group consisting of alkoxy group and an isocyanate group ,
n is an integer of 0 or more. ), Which can be hydrolyzed, and X ′-(AlOX ′) _n -Al
X _'2 (however, X' is an alkoxy group, n represents an integer of 0 or more.) Contacting an underlying layer solution containing represented by comprising a compound capable of hydrolyzing 2-component mixture, dried And a base layer forming step of forming a base layer, and a solution containing a silane-based compound is brought into contact with the substrate surface on which the base layer is formed to chemically adsorb silane-based compound molecules on the substrate surface to form a liquid crystal alignment film. A method of manufacturing a liquid crystal display device, comprising: a thin film forming step of forming; a baking step of baking the substrate; and an alignment treatment step of aligning the liquid crystal alignment film. 22. A washing process for removing unadsorbed silane compound molecules after the firing process, according to claim 19 , 20 or 21.
7. A method for manufacturing a liquid crystal display device according to item 1. 23. The method for manufacturing a liquid crystal display device according to claim 22 , wherein a non-aqueous solvent is used as a cleaning agent in the cleaning step. 24. The method of manufacturing a liquid crystal display device according to claim 23 , wherein chloroform is used as the non-aqueous solvent. 25. The non-aqueous solvent, N-methyl-
The method for manufacturing a liquid crystal display device according to claim 23 , wherein 2 pyrrolidinone is used. 26. After the cleaning step, a liquid draining alignment step of draining the cleaning agent in a desired liquid draining direction to align the silane compound molecules constituting the liquid crystal alignment film in the liquid draining direction. method of manufacturing a liquid crystal display device according to any one of claims 19 to claim 25, characterized in that it comprises. 27. the alignment treatment step, by rubbing of claim 19 to claim 26, characterized in that a rubbing orientation step of orienting the at silane compound molecule in the desired direction to the liquid crystal alignment film A method for manufacturing the liquid crystal display element according to any one of the above. 28. When the liquid crystal alignment film comprises a group of silane-based compound molecules having a photosensitive group, in the alignment treatment step, the surface of the substrate on which the liquid crystal alignment film is formed is irradiated with polarized light, by crosslinking reaction system compound molecules each other, any one of claims 19 to claim 26, characterized in that a polarization orientation step of applying alignment regulating force capable of orienting the liquid crystal molecules in a specific direction A method for manufacturing a liquid crystal display device according to item 1. 29. The method of manufacturing a liquid crystal display device according to claim 28 , wherein the light intensity of the polarized light irradiated in the polarization alignment step is 1 J / cm ² or more at a wavelength of 365 nm. 30. A solution containing the silane compound is added to the solution.
claims 1-9 or claims, characterized in that mixing the silane compound having a mol% or less of the fluoroalkyl group
29. The method for manufacturing a liquid crystal display element according to any one of 28 .