JP2003145042A - Production method of coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of coating film which suppresses hydrolysis of chemical adsorption molecule until the coating film is formed by an elimination reaction. SOLUTION: On the surface of a base material 1 which has active hydrogen 2 on the surface thereof or the base material 1 which has the active hydrogen 2 applied to the surface thereof, with respect to at least the following liquid A and liquid B, the liquid A and, subsequently, the liquid B are applied or the liquid A and the liquid B are applied at the same time and, in the state of dehydrating the whole of solution, the chemical adsorption molecule included in the liquid B is covalently bonded with the surface of the base material. Therein, the liquid A is a solution prepared by mixing a nonaqueous solvent containing no active hydrogen and a metal compound 3 causing dehydration oxidation reaction. The liquid B is a coating solution prepared by dissolving at least a nonaqueous solvent containing no active hydrogen and the chemical adsorption molecule containing reactive groups on the molecular end which causes elimination reaction with the active hydrogen on the surface of the base material into the nonaqueous solvent containing no active hydrogen.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a coating film composed of an organic compound on the surface of a base material.

[0002]

2. Description of the Related Art It is required in various fields to modify the surface of a base material such as plastic, metal, ceramics, fiber, wood, concrete, and painted surface according to the purpose.

Taking plastic as an example, as a method of modifying the surface of the plastic, for example, a method of coating a fluorine-containing silane coupling agent or the like for imparting water repellency and oil repellency, and imparting lubricity. In general, a coating method such as a wax coating method, a polyvinyl alcohol coating method for imparting hydrophilicity, or a fluorocarbon polymer suspension coating method for imparting antifouling property is commonly used. Are known.

However, the coating film obtained by the conventional method has a weak binding force to the plastic, and when the surface is wiped with a cloth or washed with water repeatedly, the coating film is peeled off from the substrate and the surface treatment effect is lost. There was a problem. In addition, since the molecules of the conventional coating film are oriented in random directions, there are many pinholes in the coating film, and there is a problem that sufficient characteristics cannot be exhibited. Further, there is a problem that, for example, a transparent plastic optical material that is strongly required to have transparency cannot be used with a coating film of a fluorocarbon polymer because it lacks transparency.

Therefore, a method for producing a chemisorption monomolecular film having high peel resistance, pinhole-free film thickness of nanometer order, that is, high transparency and not impairing the gloss of the surface of the base material and the transparency of the base material is proposed. A plurality of proposals have been made by the present inventors (JP-A-4-132637, JP-A-4-22).
1630, Japanese Patent Laid-Open No. 4-377721, Japanese Patent Laid-Open No. 8-337654, etc.).

[0006]

However, in the production method proposed above, a film is formed by the dehydrochlorination reaction between a chlorosilane-based surfactant and active hydrogen on the surface of the substrate, so that a hydrochloric acid gas is produced during film production. There was a problem that occurs. There has also been an attempt to dealcoholize an alkoxysilane surfactant to form a molecular film, but there is a problem that the reaction rate is slow and film formation cannot be easily performed.
Although it is possible to use a dealcoholization catalyst, there is a problem that the surfactant is self-crosslinked by water in the air and deactivated by simply adding the dealcoholization catalyst. That is, when the surface treatment agent contains water, the surfactant itself crosslinks before reacting with the surface of the base material, and the reaction at the solid-liquid interface on the surface of the base material is hindered and the chemisorption film is formed. There is a problem that it becomes difficult to do it.

For this drawback, Japanese Patent Laid-Open No. 8-337654
In the proposal of the publication, a mixed solution containing at least an alkoxysilane-based surfactant, a non-aqueous solvent containing no active hydrogen, and a silanol condensation catalyst is brought into contact with the base material surface to form a siloxane bond on the base material surface. There is a method of forming a chemisorption film covalently bonded via.

However, according to this method, a chemisorption film can be formed in the reaction immediately after the preparation of the material, but from an industrial point of view, when the material is prepared and mixed, and the film is formed after a certain period of time, when the film is formed, Therefore, it is difficult to form a large amount of films having the same properties because the reaction proceeds from the above step, and the work of coordinating the material preparation and the film formation is required. In addition, when the material preparation site and the material consumption site are separated, it is expected that the reaction will proceed during the material transportation, and the properties of the membrane will differ depending on the reaction time, and there were only limited situations where it could be actually used. . Further, in the proposal of the above-mentioned Japanese Patent Application Laid-Open No. 8-337654, the presence of water poses a problem in film formation, and an operation in a dry atmosphere is required, which is an obstacle to film formation.

In order to solve the above-mentioned problems of the prior art, it is an object of the present invention to provide a method for producing a coating film capable of suppressing the hydrolysis of chemisorbed molecules until the coating film is formed by an elimination reaction. And

[0010]

In order to achieve the above object, the method for producing a coating film of the present invention comprises a substrate having active hydrogen on the surface or a substrate surface provided with active hydrogen at least the following: Solution A and solution B, solution A and then solution B are applied, or solution A and solution B are applied simultaneously,
It is characterized in that the chemisorbed molecules contained in the solution B are covalently bonded to the surface of the base material in a state where the entire solution is dehydrated. Solution A: a solution in which a non-aqueous solvent containing no active hydrogen and a metal compound which causes a dehydration oxide reaction are mixed together. A coating solution in which a chemisorption molecule containing a reactive group that undergoes a separation reaction is dissolved in a non-aqueous solvent that does not contain active hydrogen.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, in order to form an efficient coating film, M-NH ₂ group, M-NH group, M-OH group, M- H
Group, M-COOH group, M-CHO group, M-CONH
₂ groups, M-ROH, M-NHCOR group, M-NRH group,
M-R-NH ₂ group, M-R-NH group, M-R-OH group,
M-RH group, M-R-COOH group, M-R-CHO group,
M-R-CONH ₂ group, M-R'-ROH, M -R'-
NHCOR group, MR'-NRH group, M-SH group, M-
An H group (M is a base material constituent atom, and R and R ′ are alkyl groups or aromatics as main constituent elements) can be mentioned.

The base material is preferably resin, ceramics, glass, metal, metal oxide, fiber or paper.

Further, even if the base material has a plate shape, a film shape, a three-dimensional molding, or a thread shape, an effective coating film can be formed.

The state of the above-mentioned substrate excludes liquid, and is solid, glassy, soft material (soft material).
Is good.

When the base material and the organic compound at least partially form a chemical bond, the effect of the coating film can be exhibited.

Furthermore, the effect of the coating film, in which at least a part of the chemical bonds formed by at least a part of the base material and the organic compound forms a covalent bond, is further exerted.

The metal compound which causes the dehydration oxide reaction is selected from carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanic acid esters and titanic acid ester chelates. The coating film can be efficiently formed by using at least one substance selected. In particular, the metal compound that causes the dehydration oxide reaction is dibutyltin dioctate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, lead naphthenate, cobalt naphthenate, 2
-Iron ethylhexenoate, dibutyltin diacetate, dioctyltin bisoctylthioglycolate ester salt, dioctyltin maleate ester salt, dibutyltin maleate polymer, dibutyltin dilaurate, dibutyltin bisacetylacetate, dioctyltin bisacetyllaurate A coating film can be effectively formed with at least one selected from phthalate, stannous acetate, tetrabutyl titanate, tetranonyl titanate, bis (acetylacetonyl) dipropyl titanate, and dimethyltin mercaptopropionate polymer.

The organic compound capable of causing the elimination reaction has a structure of Xm-A-Yn, X is an organic group consisting of m at least carbon and hydrogen, and Y is composed of n carbon and hydrogen. And at least one of the n organic groups is an organic group in which A is directly bonded to oxygen, and A is Al, Si, Ge, Ti, S
One of n is a metal, and an organic compound in which m + n is the number of bonds belonging to A is mentioned as an organic compound necessary for forming a coating film.

The concentration of the metal compound causing the dehydration oxide reaction in the liquid A is 0.0001% by weight or more and 20% by weight or more.
The following are preferred. Further, the concentration of the chemisorption molecule capable of causing the elimination reaction in the liquid B is 0.1% by weight or more and 30% by weight or more.
The following are preferred.

Furthermore, when the organic compound is an organic compound containing a fluorocarbon group, a coating film having high antifouling property can be obtained.

As the reaction represented by the dehydrated oxide reaction, dealcoholization reaction, desilanol reaction, and deesterification reaction can be mentioned.

It is convenient for the coating film that the organic compound capable of causing the elimination reaction is an alkoxysilane compound.

As the alkoxysilane surfactant containing a fluorocarbon group, CF _3- (CF ₂ ) _n- (R) _m --S
iX _p (OA) _3-p (n is 0 or an integer of 1 to 16, R is an alkylene group, a vinylene group, an ethynylene group, an arylene group, a substituent containing a silicon or oxygen atom, and m is 0.
Or 1, X is H, an alkyl group, an alkoxyl group, a substituent of a fluorine-containing alkyl group or a fluorine-containing alkoxy group, A is an alkyl group, p is 0, 1 or 2), or CF ₃ CO
_{O- (CH 2) w -SiX p} (OA) 3-p ( where, w is 1
To an integer of 15, X is H, an alkyl group, an alkoxyl group,
Examples thereof include a substituent of a fluorine-containing alkyl group or a fluorine-containing alkoxy group, A is an alkyl group, and p is an organic compound which is a substance represented by 0, 1 or 2).

As a step of exposing active hydrogen to the surface of the base material, hydrogen plasma can be exposed on the surface of the base material by performing a treatment step of oxygen plasma, corona discharge, and irradiation of ultraviolet rays in oxygen gas. , Convenient for coating film.

Further, regarding the material for forming an organic coating film, it is convenient for the coating film if the form encapsulating the organic compound capable of causing the elimination reaction is enclosed in a separate container.

Further, the organic coating film forming material becomes more convenient because the form encapsulating the organic compound capable of causing the elimination reaction is enclosed in the capsule. More specifically, in the method for forming a coating film on the surface of a base material containing active hydrogen, a solution of a metal compound that causes a dehydration oxide reaction and a non-aqueous solvent containing no active hydrogen is prepared, and at least an alkoxy compound is used. A solution of a silane-based surfactant and a non-aqueous solvent that does not contain active hydrogen is prepared, and a solution of a metal compound that causes a dehydration oxide reaction on the surface of the base material and a solution of a non-aqueous solvent that does not contain active hydrogen are brought into contact with each other. Then, a solution of an alkoxysilane-based surfactant and a non-aqueous solvent containing no active hydrogen is brought into contact with the surface of the base material. By this series of operations, the surfactant molecule is covalently bonded through a siloxane bond, and then washed with a non-aqueous solvent, whereby the surfactant molecule covalently bonded through a siloxane bond to the surface of the substrate. It is also possible to form a monomolecular film-like coating. By doing so, it is possible to efficiently form a monomolecular film-like coating film made of a surfactant covalently bonded to the surface of the base material through a siloxane bond.

In the method of forming a chemisorption film on the surface of a base material containing active hydrogen, a solution of a metal compound which causes a dehydration oxide reaction and a non-aqueous solvent containing no active hydrogen is prepared, and A solution of at least an alkoxysilane-based surfactant and a non-aqueous solvent containing no active hydrogen is prepared, and a solution of a non-aqueous solvent containing no metal compound and an active hydrogen that causes a dehydration oxide reaction on the surface of the base material is prepared. Then, a solution of an alkoxysilane surfactant and a non-aqueous solvent containing no active hydrogen is brought into contact with the surface of the base material. By this series of operations, the surfactant molecule is allowed to form a covalent bond through a siloxane bond, the non-aqueous solvent is evaporated, and then the water is reacted, whereby the surfactant is covalently bonded to the substrate surface through the siloxane bond. It is also possible to form a bonded polymer film-like coating. By doing so, it is possible to efficiently form a polymer film-like coating film made of a surfactant covalently bonded to the surface of the base material through a siloxane bond.

In the method for forming a chemisorption film on the surface of a substrate containing active hydrogen, a solution of a metal compound which causes a dehydration oxide reaction and a non-aqueous solvent containing no active hydrogen is prepared, and Hexaalkoxydisiloxane, octaalkoxytrisiloxane, dialkoxysilane,
At least one silane-based surfactant selected from trialkoxysilanes and tetraalkoxysilanes, and a solution of a non-aqueous solvent containing no active hydrogen to prepare a solution, a metal compound that causes a dehydration oxide reaction on the substrate surface A solution with a non-aqueous solvent containing no active hydrogen is contacted, and then with at least one silane-based surfactant selected from hexaalkoxydisiloxane, octaalkoxytrisiloxane, dialkoxysilane, trialkoxysilane and tetraalkoxysilane. A solution with a non-aqueous solvent containing no active hydrogen is brought into contact with the surface of the base material. By this series of operations, an underlayer film composed of a siloxane-based chemical adsorption film covalently bonded via a siloxane bond is formed, and then a second metal compound that causes a dehydration oxide reaction and a non-aqueous solvent containing no active hydrogen are formed. A solution is prepared, and a solution of at least an alkoxysilane-based surfactant and a non-aqueous solvent containing no active hydrogen is prepared, and a metal compound that causes a dehydration oxide reaction on the surface of the lower layer film and active hydrogen are included. A solution of a non-aqueous solvent that does not exist is brought into contact with the surface of the underlayer film, and then a solution of an alkoxysilane-based surfactant and a non-aqueous solvent that does not contain active hydrogen is brought into contact with the surface of the lower layer film. By this series of operations, a surface layer film made of a coating film of the second alkoxysilane-based surfactant molecule covalently bonded via a siloxane bond can be formed on the surface of the lower layer film. By doing so, it is possible to efficiently produce a coating film having a two-layer structure including a siloxane-based lower layer film and a surface layer film made of the second alkoxysilane-based surfactant in the form of a monomolecular film.

Further, regarding a method of forming a chemisorption film on the surface of a base material containing active hydrogen, at least one selected from hexaalkoxydisiloxane, octaalkoxytrisiloxane, dialkoxysilane, trialkoxysilane and tetraalkoxysilane. A solution of a silane-based surfactant and a non-aqueous solvent that does not contain active hydrogen, a solution of a metal compound that causes a dehydrated oxide reaction and a solution of a non-aqueous solvent, respectively, are prepared, and the dehydrated oxide reaction is performed on the surface of the base material. First, the solution of the metal compound to be produced and the non-aqueous solvent is contacted,
Then, a solution of at least one silane-based surfactant selected from hexaalkoxydisiloxane, octaalkoxytrisiloxane, dialkoxysilane, trialkoxysilane and tetraalkoxysilane, and a non-aqueous solvent containing no active hydrogen, and a dehydrated oxide. By bringing a solution of a metal compound causing a reaction into contact with a solution of a non-aqueous solvent to covalently bond the silane-based surfactant molecule to the surface of the base material through a siloxane bond, and then washing with a non-aqueous solvent. A monolayer siloxane-based lower layer film covalently bonded via a siloxane bond is formed on the surface of the base material, and then a solution of a second alkoxysilane-based surfactant and a non-aqueous solvent containing no active hydrogen, and dehydration. Prepare solutions of non-aqueous solvents that do not contain active hydrogen containing metal compounds that cause oxide reactions A solution of a non-aqueous solvent containing no active hydrogen containing a metal compound that causes a dehydration oxide reaction is brought into contact with the underlayer film on the surface of the substrate, and then a second alkoxysilane-based surfactant and active hydrogen are added. The second alkoxysilane-based surfactant molecule is covalently bonded through a siloxane bond by contacting with a solution containing a non-aqueous solvent, and then washed with a non-aqueous solvent to form a surface of the substrate. It is also possible to form a surface layer film of the second alkoxysilane-based surfactant molecule in the form of a monomolecular film covalently bonded via a siloxane bond. This way,
It is possible to efficiently produce a coating film having a two-layer structure including a monolayer siloxane-based lower layer film and a monolayer-shaped surface layer film made of the second alkoxysilane-based surfactant.

In the method of forming a chemisorption film on the surface of a base material containing active hydrogen, a mixed solution containing a non-aqueous solvent having no active hydrogen and a metal compound which causes a dehydration oxide reaction is prepared. A solution containing at least one silane-based surfactant selected from hexaalkoxydisiloxane, octaalkoxytrisiloxane, dialkoxysilane, trialkoxysilane, and tetraalkoxysilane and a non-aqueous solvent having no active hydrogen is prepared. First, a solution containing a metal compound that causes a dehydrated oxide reaction is brought into contact with the surface of the base material, and then hexaalkoxydisiloxane, octaalkoxytrisiloxane,
By contacting a solution comprising at least one silane-based surfactant selected from dialkoxysilane, trialkoxysilane and tetraalkoxysilane with a non-aqueous solvent having no active hydrogen, the silane-based interface on the surface of the base material. The activator molecule is covalently bonded via a siloxane bond, and then washed with a non-aqueous solvent to form a monomolecular siloxane-based lower layer film covalently bonded via a siloxane bond on the surface of the substrate. A solution consisting of a second alkoxysilane-based surfactant and a non-aqueous solvent having no active hydrogen is prepared, and first, a dehydration oxide reaction is caused with the same non-aqueous solvent having no active hydrogen as previously prepared. A solution containing a metal compound is brought into contact with the surface of the base material,
Then, a solution of the second alkoxysilane-based surfactant and a non-aqueous solvent having no active hydrogen is brought into contact with the surface of the base material to covalently bond the surfactant molecule through a siloxane bond. After evaporating the non-aqueous solvent, the alkoxy group of the second alkoxysilane-based surfactant remaining on the surface is reacted with water to form a polymer film in the form of a polymer film covalently bonded to the substrate surface via a siloxane bond. It is preferable to form a surface layer film made of the coating film of the second alkoxysilane-based surfactant molecule.
This makes it possible to efficiently produce a coating film having a two-layer structure including a siloxane-based lower layer film in the form of a chemisorption monomolecular film and a surface layer film made of the second alkoxysilane-based surfactant in the form of a polymer film.

In the method for forming a chemisorption film on the surface of a substrate containing active hydrogen, a solution containing a non-aqueous solvent having no active hydrogen and a metal compound which causes a dehydration oxide reaction is prepared, and Hexaalkoxydisiloxane,
A solution of at least one silane-based surfactant selected from octaalkoxytrisiloxane, dialkoxysilane, trialkoxysilane, and tetraalkoxysilane-based surfactant and a non-aqueous solvent having no active hydrogen is prepared. First, a solution containing a metal compound that causes a dehydration oxide reaction is brought into contact with the surface of the base material, and then hexaalkoxydisiloxane, octaalkoxytrisiloxane, dialkoxysilane, trialkoxysilane and tetraalkoxysilane surfactants. A solution of at least one silane-based surfactant selected from the above and a non-aqueous solvent having no active hydrogen is contacted. By this operation, the silane-based surfactant is covalently bonded to the surface of the base material through a siloxane bond, the non-aqueous solvent is evaporated, and the alkoxy group of the surfactant molecule remaining on the surface is reacted with water. By doing so, a polysiloxane-based lower layer film covalently bonded via a siloxane bond is formed on the surface of the base material. Then, a solution comprising a second alkoxysilane-based surfactant and a non-aqueous solvent having no active hydrogen is prepared, and first, a solution containing a metal compound which causes the same dehydration oxide reaction as previously prepared is added to the above-mentioned group. The second alkoxysilane-based surfactant molecule is brought into contact with a lower layer film of the material surface, and then a solution of the second alkoxysilane-based surfactant and a non-aqueous solvent having no active hydrogen is brought into contact with the second alkoxysilane-based surfactant molecule. A surface layer film of the second alkoxysilane-based surfactant molecule in the form of a monomolecular film covalently bonded to the surface of the substrate by covalent bonding via a bond and then washing with a non-aqueous solvent. Can also be formed. This makes it possible to efficiently manufacture a coating film having a two-layer structure including a polysiloxane-based lower layer film and a surface layer film made of the second alkoxysilane-based surfactant in the form of a monomolecular film.

In the method for forming a coating film on the surface of a substrate containing active hydrogen, a solution containing a non-aqueous solvent having no active hydrogen and a metal compound which causes a dehydration oxide reaction is prepared, Preparation of a solution comprising at least one silane-based surfactant selected from alkoxydisiloxane, octaalkoxytrisiloxane, dialkoxysilane, trialkoxysilane and tetraalkoxysilane-based surfactant and a non-aqueous solvent having no active hydrogen To do. First, a solution containing a metal compound that causes a dehydration oxide reaction is brought into contact with the surface of the base material, and further, hexaalkoxydisiloxane, octaalkoxytrisiloxane, dialkoxysilane, trialkoxysilane, and tetraalkoxysilane surfactant. A solution consisting of at least one silane-based surfactant selected from the above and a non-aqueous solvent having no active hydrogen is brought into contact. By this operation, the silane-based surfactant molecule is covalently bonded to the surface of the base material through a siloxane bond, the non-aqueous solvent is evaporated, and the alkoxy group of the surfactant molecule remaining on the surface is replaced with water. By reacting, a polysiloxane-based lower layer film covalently bonded to the surface of the base material through a siloxane bond is formed. Next, a solution containing a second alkoxysilane-based surfactant and a non-aqueous solvent having no active hydrogen is prepared, and first, a solution containing the metal compound that causes the dehydrated oxide reaction prepared above is added to the surface of the base material. Then, a solution of the second alkoxysilane-based surfactant and a non-aqueous solvent having no active hydrogen is contacted. By this operation, a covalent bond is formed in the surfactant molecule through a siloxane bond, the non-aqueous solvent is evaporated, and then the alkoxy group of the second alkoxysilane surfactant molecule remaining on the surface is replaced with water. It is also possible to form a surface layer film of the above-mentioned second alkoxysilane-based surfactant molecule in the form of a polymer film covalently bonded via a siloxane bond to the surface of the inner layer film on the surface of the base material. By doing so, it is possible to efficiently manufacture a coating film having a two-layer structure including a polysiloxane-based lower layer film and a surface layer film made of the polymer-like second alkoxysilane-based surfactant.

Further, in the method for forming a chemisorption film on the surface of a substrate containing active hydrogen, a solution containing a non-aqueous solvent containing no active hydrogen and a metal compound which causes a dehydration oxide reaction is prepared, and A solution containing at least one silane-based surfactant selected from hexaalkoxydisiloxane, octaalkoxytrisiloxane, dialkoxysilane, trialkoxysilane and tetraalkoxysilane and a non-aqueous solvent containing no active hydrogen is prepared. First, a solution containing a metal compound that causes a dehydration oxide reaction is brought into contact with the surface of the substrate, and then at least one selected from hexaalkoxydisiloxane, octaalkoxytrisiloxane, dialkoxysilane, trialkoxysilane and tetraalkoxysilane. It is also possible to form a siloxane-based coating film covalently bonded via a siloxane bond to the surface of the base material by contacting a solution containing one silane-based surfactant and a non-aqueous solvent containing no active hydrogen. By doing so, a siloxane-based molecular film having excellent hydrophilicity can be efficiently formed.

Further, in the method for forming a coating film on the surface of a substrate containing active hydrogen, a solution containing a non-aqueous solvent containing no active hydrogen and a metal compound which causes a dehydration oxide reaction is prepared, A solution containing at least one silane-based surfactant selected from alkoxydisiloxane, octaalkoxytrisiloxane, dialkoxysilane, trialkoxysilane and tetraalkoxysilane and a non-aqueous solvent containing no active hydrogen is prepared. First, a solution containing a metal compound that causes a dehydration oxide reaction is brought into contact with the surface of the base material, and then hexaalkoxydisiloxane, octaalkoxytrisiloxane,
A solution containing at least one silane-based surfactant selected from dialkoxysilanes, trialkoxysilanes and tetraalkoxysilanes and a non-aqueous solvent containing no active hydrogen is brought into contact. By this operation, a covalent bond is formed on the surface of the base material through the siloxane bond of the silane-based surfactant molecule, and then the surface of the base material is covalently bonded through the siloxane bond by washing with a non-aqueous solvent. It is also possible to form a monomolecular siloxane-based film.
By doing so, a siloxane-based coating film having excellent hydrophilicity can be efficiently formed.

In the method of forming a coating film on the surface of a substrate containing active hydrogen, a solution containing a non-aqueous solvent having no active hydrogen and a metal compound which causes a dehydration oxide reaction is prepared, and A solution comprising at least one silane-based surfactant selected from hexaalkoxydisiloxane, octaalkoxytrisiloxane, dialkoxysilane, trialkoxysilane and tetraalkoxysilane-based surfactant and a non-aqueous solvent having no active hydrogen. Prepare. First, a solution containing a metal compound that causes a dehydration oxide reaction is brought into contact with the surface of the base material, and then hexaalkoxydisiloxane, octaalkoxytrisiloxane, dialkoxysilane, trialkoxysilane and tetraalkoxysilane surfactants. A solution consisting of at least one silane-based surfactant selected from the above and a non-aqueous solvent having no active hydrogen is brought into contact. By this series of operations, a covalent bond is formed on the surface of the base material via the silane-based surfactant through a siloxane bond,
After evaporating the non-aqueous solvent, by reacting the alkoxy group of the surfactant molecule remaining on the surface with water,
It is also possible to form a polysiloxane film covalently bonded to the surface of the base material through a siloxane bond. By doing so, a polysiloxane coating film having excellent hydrophilicity can be efficiently formed.

As the non-aqueous solvent, a hydrocarbon solvent containing no water or a fluorocarbon solvent can be used. In the above method and solution, the water content of the solution is preferably 10 ppm or less. This is because the alkoxysilane surfactant and the metal compound that causes the dehydration oxide reaction are kept stable and the reactivity of the solution is kept long.

In the above-mentioned method and adsorbent, the amount of the alkoxysilane-based surfactant present is 0.1 to 30% by weight, and the metal compound causing the dehydration oxide reaction is 100% by weight of the mixed solution. Abundance of 0.0001 ~
7.5% by weight (0.1 to 25% by weight relative to the surfactant), the amount of the non-aqueous solvent containing no active hydrogen is 6
It is preferably in the range of 2.5 to 99.8999% by weight.

According to the above method of the present invention, in the method for forming a coating film on the surface of a substrate containing active hydrogen, at least a non-aqueous solvent containing no active hydrogen and a metal compound which causes a dehydration oxide reaction. First, a solution and a solution consisting of an alkoxysilane-based surfactant and a non-aqueous solvent containing no active hydrogen, first, a solution containing a non-aqueous solvent containing no active hydrogen and a metal compound that causes a dehydration oxide reaction, The coating film covalently bonded to the surface of the base material through a siloxane bond by contacting the surface of the material with a solution of an alkoxysilane-based surfactant and a non-aqueous solvent containing no active hydrogen. Can be formed. This makes it possible to realize a method for producing a chemisorption film in which harmful hydrochloric acid gas is not generated during the production of the film and the reaction rate is practically sufficient. Further, the reactivity of the silanol condensation reaction liquid and the reaction liquid containing the alkoxysilane-based surfactant can be maintained for a long time, and a uniform coating film can be realized every time the coating film is formed.

Further, according to the organic coating film forming material of the present invention, it is possible to provide a reaction material useful for a method for producing a coating film. Further, according to a preferred constitution of the method of the present invention, the surface of the substrate is previously treated with hexaalkoxydisiloxane, octaalkoxytrisiloxane, dialkoxysilane, trialkoxysilane or tetraalkoxysilane before the reaction step of forming the coating film. For example, it has the effect of providing high density silanol bonds on the surface of the substrate.

Further, in the above-mentioned constitution, as the metal compound which causes the dehydration oxide reaction, a carboxylic acid metal salt, a carboxylic acid ester metal salt, a carboxylic acid metal salt polymer, a carboxylic acid metal salt chelate, a titanate ester,
Alternatively, when titanate ester chelates are used, the reaction controllability is remarkably better than when an acid catalyst is used. If the alkoxysilane surfactant contains a fluorocarbon group, the water and oil repellency of the formed film can be improved. In particular,
Alkoxysilane surface active agent containing a fluorocarbon _{group, CF 3 - (CF 2)} n - (R) m -SiX p (OA) 3-p
(N, R, m, X, A and p are as described above), or C
_{F 3 COO- (CH 2) w} -SiX p (OA) 3-p (w,
When a substance represented by X, A, and p is as described above), a higher density chemisorption film can be produced.

Furthermore, the use of a water-free hydrocarbon solvent or fluorocarbon solvent as the non-aqueous solvent has the effect of producing a high-density coating film without impairing the reaction activity. In particular, a fluorocarbon-based solvent has a low specific heat and thus has a high evaporation rate, which is convenient for forming a polymer film.

Further, in the case where the base material, such as plastic or synthetic fiber, has a low content of active hydrogen on the surface, the surface of the substrate is previously treated with a plasma containing oxygen or a corona atmosphere to make it hydrophilic. According to the preferable constitution of the method, it becomes possible to suitably form the highly functional coating film of the method of the present invention on the surface of the polymer compound, which was relatively difficult by the conventional method.

[0043]

EXAMPLES The present invention will be described in more detail below with reference to examples. First, the present invention can be widely applied to the following uses. (A) Example of base material; base material is metal, ceramics, glass,
Alternatively, it can be applied to materials made of plastic, wood and stone. The surface may be painted. (B) Examples of knife: kitchen knife, scissors, knife, cutter, chisel, razor, clipper, saw, canna, chisel, awl, awl, bite, drill blade, mixer blade, juicer blade, milling Machine blade, lawn mower blade, punch, pusher, stapler blade, can opener blade, surgical knife, etc. (C) Examples of needles: acupuncture needles, sewing needles, sewing needles, tatami needles,
Injection needles, surgical needles, safety pins, etc. (D) Examples of ceramic products: products made of ceramics, glass, ceramics or enamel. For example, sanitary ware (eg, toilet bowl, washbasin, bath, etc.), tableware (eg, bowl, plate, bowl, teacup, cup, bottle, coffee kettle, pot, mortar, cup, etc.), vase (basin, flowerpot,
(A vase, etc.), aquarium (aquarium for aquaculture, aquarium for appreciation, etc.), chemical experiment equipment (beaker, reaction vessel, test tube, flask, etc.)
Petri dish, cooling tube, stirring rod, stirrer, mortar, vat, syringe), roof tile, tile, enamel tableware, enamel basin, enamel pot. (E) Examples of mirrors: hand mirrors, full-length mirrors, bathroom mirrors, washroom mirrors,
Automotive mirrors (rear view mirrors, side mirrors), half mirrors, show window mirrors, department store product section mirrors, etc. (F) Examples of molding members: press molding dies, cast molding dies, injection molding dies, transfer molding dies, vacuum molding dies, blow molding dies, extrusion dies. , Inflation molding die, fiber spinning die, calendering roll, etc. (G) Examples of ornaments: watches, jewels, pearls, sapphires, rubies, emeralds, garnets, cat's eyes, diamonds, topaz, blood stones, aquamarine,
Sardonyx, turquoise, agate, marble, amethyst, cameo, opal, crystal, glass, ring, bracelet, brooch, tie pin, earring, necklace, precious metal decoration product, platinum, gold, silver, copper, aluminum, titanium, tin Or their alloys, stainless steel, eyeglass frames, etc. (H) Examples of food molding molds: cake baking molds, cookie baking molds, bread baking molds, chocolate molding molds, jelly molding molds, ice cream molding molds, oven plates, ice trays and the like. (I) Examples of cookware: pots, kettles, kettles, pots, frying pans, hot plates, grills for cooking grilled foods, oil drainers, octopus grilled plates, etc. (J) Examples of paper: gravure paper, water / oil repellent paper, poster paper,
High-quality pamphlet paper, etc. (k) Examples of resins: polyolefins such as polypropylene and polyethylene, polyvinyl chloride, polyvinylidene chloride,
Polyamide, polyimide, polyamideimide, polyester, aramid, polystyrene, polysulfone, polyether sulfone, polyphenylene sulfide, phenol resin, furan resin, urea resin, epoxy resin, polyurethane, silicon resin, ABS resin, methacrylic resin,
Acrylic ester resin, polyacetal, polyphenene oxide, etc. (l) Examples of home appliances: televisions, radios, tape recorders, audios, CDs, refrigerators for freezing-related equipment, refrigerators, air conditioners, juicers, mixers, fan blades. , Lighting fixtures, dials, perm dryers, etc. (M) Examples of sports equipment: skis, fishing rods, pole vaults, boats, yachts, jet skis, surfboards, golf balls, bowling balls, fishing lines, fishnets,
Fishing float etc. (N) Examples applied to vehicle parts: (1) ABS resin: lamp cover, instrument panel, interior parts, motorcycle protector (2) Cellulose plastic: car mark, steering wheel (3) FRP (fiber reinforced resin): Exterior bumper, engine cover (4) Phenolic resin: Brake (5) Polyacetal: Wiper gear, gas valve, carburetor parts (6) Polyamide: Radiator fan (7) Polyarylate: Directional lens, instrument plate lens,
Relay housing (8) Polybutylene terephthalate: Rear end, front fender (9) Polyamino bismaleimide: Engine parts, gear box, wheel, suspension drive system (10) Methacrylic resin is a lamp cover lens, instrument panel and cover, center mark (11 ) Polypropylene is bumper (12) Polyphenylene oxide: radiator grill, wheel cap (13) Polyurethane: bumper, fender, instrument panel, fan (14) Unsaturated polyester resin: body, fuel tank, heater housing, instrument panel (o) Examples of office supplies: fountain pens, ballpoint pens, sharp pencils, pencil cases, binders, desks, chairs, bookshelves, racks, telephone stands, rulers, drafting tools, etc. (P) Examples of building materials: roofing materials, outer wall materials, interior materials. As roof material, kiln roof tiles, slate roof tiles, galvanized iron (galvanized iron plate), etc.
Outer wall materials include wood (including processed wood), mortar, concrete, ceramic sizing, metal sizing, bricks, stone materials, plastic materials, and metal materials such as aluminum. Interior materials include wood (including processed wood), metal materials such as aluminum, plastic materials, paper, and fibers. (Q) Examples of stone materials: granite, marble, granite, etc. For example, buildings, building materials, works of art, figurines, baths, tombstones, monuments, gateposts, stone walls, sidewalk paving stones, etc. (R) Examples of musical instruments and audio equipment: musical instruments such as percussion instruments, string instruments, keyboard instruments, woodwind instruments, brass instruments, and acoustic equipment such as microphones and speakers. Specifically, percussion instruments such as drums, cymbals, violins, cellos, guitars, koto, pianos, flutes, clarinet, shakuhachi and horns, string instruments, keyboard instruments, woodwind instruments, brass instruments, and microphones, speakers, Audio equipment such as earphones. (S) Others, such as a thermos bottle, a vacuum system, an insulator for electric power transmission, a high voltage-resistant insulator having a high water and oil repellency and antifouling effect such as a spark plug, a semiconductor device and its manufacturing member, a magneto-optical recording device and the like. Manufacturing member, magnetic recording device and manufacturing member thereof, optical circuit and manufacturing member thereof, precision channel and manufacturing member thereof, precision molding die and manufacturing member thereof, laminated electronic component and manufacturing member thereof, semiconductor manufacturing apparatus and member thereof.

The present invention will be described in detail below with reference to specific examples and schematic drawings. In the following examples,% means% by weight unless otherwise specified.

Example 1 For example, an automobile windshield plate 1 was prepared as a substrate having active hydrogen exposed on its surface. The surface was washed by an appropriate method to expose active hydrogen 2 (FIG. 1). Then, a chloroform solution containing 0.1% of dibutyltin diacetate as a metal compound for causing a dehydration oxide reaction was prepared and dropped on the glass plate 1 to make the surface wet with the solution 3 (FIG. 2). . It should be noted that FIG. 2 shows active hydrogen 2 as a layer as a schematic diagram and clarifies that the solution 3 is attached thereon, which may be different from the current state. Next, a normal decane solution containing 1% of triethoxysilane (heptadecafluoro-1,1,2,2-tetrahydrodecyl) containing a fluorocarbon group as an alkoxysilane-based surfactant was prepared, and the solution was added to the above solution. The substrate was immersed for 1 hour. At the time of immersion, the chloroform solution was almost dry. After soaking for 1 hour, the plate was thoroughly washed with chloroform, washed with water, and then dried with a nitrogen gun. As a result, they were covalently bonded to the surface of the glass plate 1 (heptadecafluoro-1,1,2,2-tetrahydrodecyl).
A coating film 4 made of triethoxysilane was formed (FIG. 3).

When the contact angle of water on the surface of the coating film was evaluated, the fluorocarbon group was exposed on the surface.
A contact angle of 2 degrees was obtained. Further, the contact angle of the glass surface on which the coating film was not formed was 10 degrees or less (below the measurement limit of the measuring instrument), clearly showing that the coating film was formed on the glass surface.

An important factor in this experiment is a process in which an alkoxysilane-based surfactant is brought into contact with a glass substrate in a state in which dibutyltin diacetate as a metal compound causing a dehydration oxide reaction is distributed on the surface of the glass substrate. The dibutyltin diacetate that causes the dehydration oxide reaction must be capable of reacting with the alkoxysilane surfactant and active hydrogen on the substrate surface. The reaction proceeds only with the active hydrogen on the surface in the state where the water content is completely absent, but the reaction proceeds even if there is no water even if there is no active hydrogen on the surface of the substrate. In order to prevent this, it is necessary to place dibutyltin diacetate on the surface of the substrate in advance.

In Example 1, heptadecafluoro-1,
1,2,2-tetrahydrodecyl) triethoxysilane was used as the coating film material, but the organic compound capable of causing the elimination reaction has a structure of Xm-A-Yn, and X is m at least carbon, An organic group consisting of hydrogen, Y is an organic group consisting of n carbons and hydrogen, and at least one of the n organic groups is an organic group in which A is directly bonded to oxygen. Group, A is Al, S
One of i, Ge, Ti, and Sn, and m + n
Is an organic compound which is the number of bonds belonging to A as long as it is an organic compound necessary for forming a coating film. More specifically, an alkoxysilane surfactant containing a fluorocarbon group is CF ₃ — (CF ₂ ) _n -(R) _m -SiX _p (OA) _3-p
(N, R, m, X and A are as described above), or CF _{3
COO- (CH 2) w -SiX p} (OA) 3- p (w, X,
A and p may be an organic compound which is a substance represented by the above).

More specifically, in addition to this, C
H₃-(CH₂)_r-SiX_p(OA) _3-pAnd CH₃-(CH
₂)_s-O- (CH₂)_t-SiX_p(OA_3-p, CH₃−
(CH₂)_u-Si (CH₃)₂-(CH₂)_v-SiX_p(O
A)_3-p, CF₃COO- (CH₂)_w-SiX_p(OA)
_3-p(Here, as a preferable range, r is 1 to 25 and s is 0.
-12, t is 1-20, u is 0-12, v is 1-20,
w represents 1 to 25. X is H, alkyl group, alkoxy
Group, fluorine-containing alkyl group or fluorine-containing alkoxy group
A substituent, A is an alkyl group, p is 0, 1 or 2), etc.
It can be used. The following are specific molecules.
is there. CH₃CH₂O (CH₂)₁₅Si (OCH₃)₃ CF₃CH₂O (CH₂)₁₅Si (OCH₃)₃ CH₃(CH₂)₂Si (CH₃)₂(CH₂)₁₅Si (OC
H₃)₃ CH₃(CH₂)₆Si (CH₃)₂(CH₂)₉Si (OC
H₃)₃ CH₃COO (CH₂)₁₅Si (OCH₃)₃ CF₃(CF₂)_Five(CH₂)₂Si (OCH₃)₃ CF₃(CF₂)₇-C₆H_Four-Si (OCH₃)₃ CH₃CH₂O (CH₂)₁₅Si (OC₂H_Five)₃ CH₃(CH₂)₂Si (CH₃)₂(CH₂)₁₅Si (OC
₂H_Five)₃ CH₃(CH₂)₆Si (CH₃)₂(CH₂)₉Si (OC₂
H_Five)₃ CF₃(CH₂)₆Si (CH₃)₂(CH₂)₉Si (OC₂
H_Five)₃ CH₃COO (CH₂)₁₅Si (OC₂H_Five)₃ CF₃COO (CH₂)₁₅Si (OC₂H_Five)₃ CF₃COO (CH₂)₁₅Si (OCH₃)₃ CF₃(CF₂)₉(CH₂)₂Si (OC₂H_Five)₃ CF₃(CF₂)₇(CH₂)₂Si (OC₂H_Five)₃ CF₃(CF₂)_Five(CH₂)₂Si (OC₂H_Five)₃ CF₃(CF₂)₇C₆H_FourSi (OC₂H_Five)₃ CF₃(CF₂)₉(CH₂)₂Si (OCH₃)₃ CF₃(CF₂)_Five(CH₂)₂Si (OCH₃)₃ CF₃(CF₂)₇(CH₂)₂SiCH₃(OC₂H_Five)₂ CF₃(CF₂)₇(CH₂)₂SiCH₃(OCH₃)₂ CF₃(CF₂)₇(CH₂)₂Si (CH₃)₂OC₂H_Five CF₃(CF₂)₇(CH₂)₂Si (CH₃)₂OCH₃ It should be noted that in the coating film manufacturing method of the present invention,
The preferable content of the lucoxysilane surfactant is 0.1.
~ 30%.

Examples of the metal compound which causes the dehydration oxide reaction in the method of the present invention include carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanic acid esters,
Alternatively, titanic acid ester chelates can be used, and in particular, as a silanol condensation catalyst, stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, dioctanesan is used. Stannous, lead naphthenate, cobalt naphthenate, 2
-Carboxylic acid metal salts such as iron ethylhexenoate, dioctyltin bisoctylthioglycolic acid ester salts, carboxylic acid ester metal salts such as dioctyltin maleic acid ester salts, dibutyltin maleate polymer, dimethyltin mercaptopropionate polymer, etc. Carboxylic acid metal salt polymers, carboxylic acid metal salt chelates such as dibutyltin bisacetylacetate and dioctyltin bisacetyllaurate, titanate esters such as tetrabutyl titanate and tetranonyl titanate, or bis (acetylacetonyl) dipropyl titanate. It is more preferable to use the titanate ester chelates.

In particular, when a carboxylic acid metal salt and a carboxylic acid metal salt chelate were used, a stable chemisorption film was obtained. The preferable addition amount of the metal compound that causes the dehydration oxide reaction is 0.1 to 25 with respect to the surfactant.
%.

As the non-aqueous solvent containing no active hydrogen,
Hydrocarbon-based solvents, fluorocarbon-based solvents, and silicone-based solvents that do not contain water can be used, but those having a boiling point of 50 to 200 ° C. are particularly easy to use. In addition to petroleum-based solvents, those specifically usable are petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine,
Examples thereof include isoparaffin, normal paraffin, decalin, industrial gasoline, kerosene, ligroin, dimethyl silicone, phenyl silicone, alkyl modified silicone, polyether silicone, cyclic silicone and the like. The fluorocarbon-based solvent includes chlorofluorocarbon-based solvent, Fluorinert (product of 3M Company), Aflude (product of Asahi Glass Co., Ltd.) and the like. These may be used alone or in combination of two or more if necessary.

If the reaction is carried out immediately, an aqueous solvent may be applicable as a solvent for the metal compound that causes the dehydration oxide reaction and the organic compound that can cause the elimination reaction. In addition, not only the reaction between the base material and the organic compound but also the reaction between the organic compounds occurs at the same time, and when the structure in which the respective molecular chains are entangled is developed, it is often effective to use the aqueous solvent.

The substrate which can be used in the present invention includes
Examples thereof include a substrate containing active hydrogen on the surface, that is, a substrate having a hydroxyl group (-OH), for example, a metal such as Al, Cu or stainless steel, glass, ceramics, paper, natural fiber, leather or other hydrophilic substrate. If the substance does not have a hydroxyl group on the surface, such as plastic or synthetic fiber, the surface is preliminarily set to 20 W at 100 W in a plasma atmosphere containing oxygen.
A high-concentration hydroxyl group can be provided on the surface by treatment for about a minute or by corona treatment. The active hydrogen is not limited to the hydroxyl group (-OH) but -COO having active hydrogen.
It may be a functional group such as H, --CHO, ═NH, --NH2. However, in the case of a polyamide resin or a polyurethane resin, an imino group (-NH) is present on the surface, and an alkoxysilyl group (-of an organic compound capable of causing a elimination reaction with active hydrogen of this imino group (-NH). No surface treatment is particularly required because a dealcohol reaction with SiOA) forms a siloxane bond (—SiO—). For example,
If the base material is nylon or polyurethane 11,
As shown in (a), a large amount of imino groups 12 (containing active hydrogen) are exposed on the surface, so that the coating film 13 can be formed by the same method as that for the glass plate (FIG. 2).
(B)).

(Embodiment 2) As a base material having active hydrogen exposed on the surface, an aluminum vapor deposition film 12 was formed on a slide glass 11.
Substrate 1 on which a silicon oxide film 13 is formed
Prepared 4. Ultraviolet-ozone treatment was performed to wash the surface of the substrate to expose active hydrogen (FIG. 4). Then, a chloroform solution containing 0.1% of dibutyltin diacetate as a metal compound for causing a dehydration oxide reaction was prepared and dropped on the substrate 14 to make the surface wet with the solution. Next, a normal hexadecane solution containing 1% of octadecyltriethoxysilane containing a fluorocarbon group as an alkoxysilane-based surfactant was prepared, and the substrate was immersed in the solution for 2 hours. At the time of immersion, the chloroform solution was almost dry. Two
After soaking for a time, it was thoroughly washed with chloroform, washed with water, and then dried with a nitrogen gun. As a result, the substrate 14
A coating film 16 made of octadecyltriethoxysilane covalently bonded to the surface was formed (FIG. 5).

The infrared absorption spectrum of the coating film of the substrate was measured by a reflection measurement method using a Fourier infrared spectrophotometer. Figure 6 shows the spectrum. 2900
Absorption related to symmetrical stretching vibration and antisymmetric stretching vibration of a methyl group and a methylene group was observed at wave numbers of 3000 wave numbers. From this, it was confirmed that the coating film 16 was formed on the substrate.

(Comparative Example 1) As a conventional technique, Japanese Patent Laid-Open No.
Chemical adsorption films or chemisorption monomolecular films described in JP-A-132637, JP-A-4-221630, JP-A-4-368721 and the like were prepared and compared.

Using the substrate used in Example 2, the same UV-ozone treatment as in Example 2 was performed to wash the surface of the substrate. The active hydrogen was exposed. Then, a 1% normal hexadecane-chloroform mixed solution of octadecyltrichlorosilane was prepared in an atmosphere dried with dry nitrogen gas, and the substrate was immersed in the solution. After soaking for 2 hours, wash the substrate with chloroform,
The substrate was taken out from the dry nitrogen gas atmosphere. afterwards,
The infrared absorption spectrum was measured by the method described in Example 2. As shown in FIG. 7, absorptions associated with symmetrical stretching vibrations and antisymmetric stretching vibrations of a methyl group and a methylene group were observed at 2900 to 3000 wave numbers, and formation of a chemisorption film was confirmed.

Comparing the infrared absorption spectrum shown in FIG. 6 of Example 2 with the infrared absorption spectrum shown in FIG. 7 of Comparative Example 1, the methylene inverse symmetric stretching vibration, the methylene inverse symmetric stretching vibration, and the methyl antisymmetric stretching were found to have almost the same wave number. The absorption spectra of vibration and methyl symmetrical stretching vibration were observed, and their intensities were almost the same. Since the infrared absorption spectrum of octadecyltriethoxysilane used in Example 2 is different from the spectra shown in FIGS. 7 and 8, obviously no bulk-shaped coating film was formed, and the comparison was made. Since Example 1 is known as a method for forming a monomolecular film, a spectrum close to the spectrum of Clay 1 was obtained on that day or in Example 2. Therefore, the coating film of the present invention is also a monomolecular film or a monomolecular film. It is assumed that the state is close to.

Example 3 According to the method shown in Example 1,
A chloroform solution containing 0.1% dibutyltin diacetate was prepared. Separately, heptadecafluoro-1,
1,2,2-Tetrahydrodecyltrimethoxysilane [CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ ] was added to 1
% Normal decane solution was prepared. Each of the above solutions was left in a warm bath at 70 ° C for 5 days. After that, the chloroform solution was dropped on the glass plate used in Example 2 to make the surface wet with the solution, and then the glass substrate was immersed in a normal decane solution for 1 hour. Then, the substrate was washed twice with chloroform and dried to form a coating film.

(Comparative Example 2) As a conventional example, Japanese Patent Laid-Open No. 8-8
According to the method disclosed in Japanese Patent Publication No. 337654, heptade cuff
Luoro-1,1,2,2-tetrahydrodecyltrimetho
Xysilane [CF ₃(CF₂)₇(CH₂)₂Si (OC
H₃)₃], And n-dibutyltin diacetate to 0.
1% and n-deca as a non-aqueous solvent containing no active hydrogen.
A solution was prepared by mixing 9% with 94.9%. The solution
Was left in a warm bath at 70 ° C for 5 days. Performed on that solution
The glass substrate used in Example 2 was immersed for 1 hour. afterwards,
The substrate is washed twice with chloroform, dried and coated.
Formed a coating film.

Water droplets were dropped on the glass substrates prepared in Examples 3 and 2, and the contact angle of the water droplets was measured. As a result, the contact angle of the glass substrate prepared by the method of Comparative Example 2 was 7
The contact angle of the glass substrate prepared by the method of Example 3 was around 110 degrees, while it was around 0 degrees. Further, the contact angles formed by the water droplets when the coating film was formed on the glass substrate immediately after preparing the solutions of Example 3 and Comparative Example 2 were all about 115 degrees. Numerical values are shown in Table 1 including a comparative example.

[0063]

[Table 1]

Example 4 An acetonitrile solution of dioctyltin dilaurate was prepared as a metal compound material, and an acetonitrile solution of nonadecyltriethoxysilane was prepared as an organic compound material. The above-mentioned two solutions were simultaneously prepared and dripped on the glass substrate exposed with active hydrogen after pre-cleaning so that the solution was spread over the entire surface of the glass substrate. After standing at room temperature for 1 hour, the glass substrate was washed with pure acetonitrile and dried. As a result, a coating film starting from octadecyltriethoxysilane was formed on the surface of the glass substrate. When the contact angle of this coating film with water was measured, it was 107 degrees.
Since the contact angle of water on the surface of the glass substrate exposed with active hydrogen was below the measurement limit (10 degrees or less), it was clearly confirmed that the coating film was formed.

(Example 5) Coating on transparent acrylic plate
A wing film was formed. Acrylic plate is treated with oxygen plasma
The surface of the Arrill plate is oxidized and cleaned by a processing device, and active hydrogen is added.
Was formed on the surface of the acrylic plate. Next, dioctyl tin di
Prepare a 2% ethyl alcohol solution of acetate and
Fluorohexyltriethoxysilane [CF₃(CF₂)
₃CH₂CH ₂Si (OCH₂CH₃)₃] Fluorocarbon solution
Medium (product name HFE7200: manufactured by Sumitomo 3M Limited)
Prepare a 2% solution according to
The solution was dropped so that the solution spreads on the body. After the solution has dried
Again wash the acrylic board with pure HFE7200 and dry
Let

The contact angle of water with respect to this acrylic plate was measured to confirm the formation of a coating film. The contact angle of the acrylic plate is 75 to 80 degrees and is 25 after the oxygen plasma treatment.
While the contact angle after forming the coating film was about 120 °, the formation of the fluorocarbon coating film was clearly confirmed.

Example 6 A stainless steel plate was prepared as a base material, and pre-cleaning was performed to clean the surface and expose active hydrogen. Next, a 0.1% fluorocarbon solution of tetrabutyl titanate (solvent: PF5080, manufactured by Sumitomo 3M) was prepared. In addition, a 2% fluorocarbon solution of pentadecafluoroethyltriethoxysilane (solvent: PF50
80, manufactured by Sumitomo 3M) was adjusted.

The above stainless steel substrate was immersed in a tetrabutyl titanate solution for 10 minutes, and then the substrate was taken out and dried. Next, the above substrate was immersed in a pentadecafluoroethyltriethoxysilane solution, taken out after 30 minutes, and
Dried. In this operation, a coating film using pentadecafluoroethyltriethoxysilane as a starting material was formed.

Next, writing was performed on the surface of the stainless steel substrate with an oil-based marker as an example of stains. The oil-based magic formed fine oil droplets, which could be scraped off with a dry cloth when the oil droplets were not dry. Even when the oil droplets were dried, stains could be easily removed by pressing a cloth soaked in water diluted with neutral detergent against the oil droplets and scraping off. From this, it was confirmed that the stainless substrate having the coating film provided with the antifouling effect.

(Example 7) A coating film similar to that of Example 6 was formed on a heat-resistant ceramic plate, a solution prepared by mixing 50% of sugar and soy sauce having the coating film formed thereon was dropped, and the solution was dried by a dryer. The solution was heated and solidified. The heat-solidified body remained in a fixed state, but the stain could be removed by rubbing it several times with a wet cloth containing water. From the above, it was confirmed that the ceramic plate having the coating film provided with antifouling property.

Comparative Example 3 The ceramic plate used in Example 7 was subjected to an operation of forming a fixed substance composed of sugar and soy sauce without forming a coating film, and removing dirt with a wet cloth. No dirt could be wiped off with the number of floors wiped off completely when it was removed with No. 7, and even at about 5 times the number of floors wiped out, the dirt was only spread and spread on the ceramic plate. By the above comparative examination, the effect of antifouling property was further confirmed.

(Embodiment 8) An artificial oil film is formed on the vehicle-mounted glass on which the coating film used in Embodiment 1 is formed,
The wiping performance was confirmed. The oil film could be removed very easily by rubbing the glass plate on which the oil film was formed with a sponge towel containing a thin aqueous solution of a neutral detergent and further washing the glass surface with water. As a comparison, when the same operation was performed on an uncoated glass plate, the oil film slightly decreased, but it could not be completely removed, and further, the glass in the part where the oil film was not formed was contaminated with the oil film. As a result, it was confirmed that the glass on which the coating film was formed was effective as an antifouling property.

Further, the glass surface from which the oil film was removed was restored to water repellency by the effect of the coating film, and the effect as water repellent glass was confirmed.

(Embodiment 9) A solution 22 made of a metal compound which causes a dehydration oxide reaction is sealed in one of the tubes 21 having a double structure, and the other is an organic material capable of causing a desorption reaction which becomes a coating film. A solution 23 composed of a compound was enclosed, and both tubes could be ejected at the same time by pressing a tube during coating (FIG. 8). With this material, it becomes possible to form the coating film as shown in the above-mentioned embodiment relatively easily.

Although no reference was made to the control of water content in any of the examples, it is necessary to reduce the water content in the reaction atmosphere as much as possible in the case of forming a film at the monomolecular film level. It is better to circulate dry nitrogen or dry air in the glove box to carry out the reaction under the dry condition as much as possible.

In the present embodiment, it is described that the active hydrogen necessary for forming the coating film is exposed by cleaning the glass, metal and ceramics. By forming a base layer using tetrachlorosilane, etc.,
Since more active hydrogen can be contained, these underlayers may be used if necessary.

Although the example of the tube having the double structure has been introduced in the ninth embodiment, the double structure is not required as long as the two liquids can be simultaneously supplied. For example, if either solution can be enclosed in a microcapsule or the like, it is not necessary to have a double structure.

In addition, although the specific examples relating to the water repellency and the oil repellency are described in this example, in addition to these, devices and device process members up to the nanometer level,
It can also be used as a device molding member.

[0079]

As described above, according to the present invention, when a coating film is produced on the surface of a substrate by a desorption reaction, the presence of a metal compound which causes a dehydration oxide reaction allows the formation of a coating film. Moreover, the hydrolysis of the chemisorption molecule can be suppressed. Thereby, as a result of improving the performance of the material, the film quality can be remarkably improved. Further, in the film using the conventional chlorosilane-based material, a film having practical durability could be formed, but the hydrogen chloride gas generated during the formation process can be completely eliminated in the present invention,
In addition, it is possible to form a coating film that is as practical as a film formed of a conventional chlorosilane material. Further, as a result, it has become possible to provide an excellent coating film forming material, a practical antifouling glass, an antifouling metal, an antifouling ceramics and a water repellent glass.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view for explaining a first embodiment of the present invention in which active hydrogen is exposed and which is enlarged to a molecular level of an automobile windshield plate.

FIG. 2 illustrates a first embodiment of the present invention, which is expanded to a molecular level at the stage of applying a solution of a metal compound that causes a dehydration oxide reaction on an automobile windshield plate exposed with active hydrogen. FIG.

FIG. 3 is a schematic cross-sectional view enlarged to a molecular level showing a state in which a coating film is formed on an automobile windshield plate for explaining the first embodiment of the present invention.

FIG. 4 is a schematic view showing a second embodiment of the present invention in which a vapor-deposited aluminum film and a silicon oxide film are formed on a slide glass, and active hydrogen is exposed on the surface of the glass. FIG.

FIG. 5 is a schematic sectional view enlarged to a molecular level showing a state where a coating film is formed on a substrate for explaining a second embodiment of the present invention.

FIG. 6 is an infrared absorption spectrum drawing showing a state in which a coating film is formed on a substrate for explaining a second embodiment of the present invention.

FIG. 7 is an infrared absorption spectrum drawing of a state in which a chemisorption film was formed on the substrate in Comparative Example 1 performed for comparison with the second example of the present invention.

FIG. 8 is a schematic view of a tube for supplying a material for explaining a ninth embodiment of the present invention.

[Explanation of symbols]

1 Car windshield plate 2 active hydrogen 3 Metal compound solution that causes dehydration oxide reaction 4 coating film 11 slide glass 12 Aluminum vapor deposition film 13 Silicon oxide film 14 board 15 active hydrogen 16 coating film 21 tubes 22 Solution consisting of metal compounds 23 Solution consisting of organic compounds

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Claims (15)

[Claims] 1. A substrate having active hydrogen on its surface or a substrate having active hydrogen applied to the surface thereof, at least the following A:
Solution B and solution B are applied after application of solution A or solution B, or solutions A and B are applied simultaneously and the entire solution is dehydrated,
A method for producing a coating film, wherein the chemisorption molecule contained in the solution B is covalently bonded to the surface of the base material. Solution A: a solution in which a non-aqueous solvent containing no active hydrogen and a metal compound which causes a dehydration oxide reaction are mixed, and a solution B: at least a non-aqueous solvent containing no active hydrogen and active hydrogen on the surface of the base material and desorption at the molecular end. A coating solution in which a chemisorption molecule containing a reactive group that undergoes a separation reaction is dissolved in a non-aqueous solvent that does not contain active hydrogen. 2. The active hydrogen of the substrate is M-NH.
₂ , M-NH group, M-OH group, M-H group, M-COO
H group, M-CHO group, M-CONH ₂ group, M-ROH,
M-NHCOR group, M-NRH group, M-R-NH ₂ group,
M-R-NH group, M-R-OH group, M-RH group, M-R
-COOH group, M-R-CHO group, M-R-CONH ₂
Group, M-R'-ROH, M-R'-NHCOR group, M-
R'-NRH group, M-SH group, and M-H group (M is a constituent atom of the base material, R and R'are the main constituents are alkyl groups,
The method for producing a coating film according to claim 1, wherein the coating film is at least one selected from a fluoroalkyl group or an aromatic group. 3. The base material is resin, ceramics, glass,
The method for producing a coating film according to claim 1, which is at least one selected from metals, metal oxides, fibers, papers, and plastics. 4. The method for producing a coating film according to claim 1, wherein the shape of the base material is at least one selected from a plate shape, a film shape, a three-dimensional molded product, and a thread shape. 5. The metal compound which causes a dehydration oxide reaction in the liquid A is a carboxylic acid metal salt, a carboxylic acid ester metal salt, a carboxylic acid metal salt polymer, a carboxylic acid metal salt chelate, a titanic acid ester and a titanic acid. The method for producing a coating film according to claim 1, which is at least one substance selected from ester chelates. 6. The metal compound causing a dehydration oxide reaction in the liquid A is dibutyltin dioctate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, lead naphthenate, naphthenic acid. Cobalt, iron 2-ethylhexenoate, dibutyltin diacetate, dioctyltin bisoctylthioglycolate ester salt, dioctyltin maleate ester salt, dibutyltin maleate polymer, dibutyltin dilaurate, dibutyltin bisacetylacetate, dioctyltin At least one selected from bisacetyl laurate, stannous acetate, tetrabutyl titanate, tetranonyl titanate and bis (acetylacetonyl) dipropyl titanate, and dimethyltin mercaptopropionate polymer. A method for producing a coating film according to claim 5. 7. The organic compound capable of causing the elimination reaction in the liquid B has a structure of Xm-A-Yn, X is an organic group consisting of m at least carbon and hydrogen, and Y is n. Is an organic group consisting of carbon and hydrogen, and at least one of n organic groups is an organic group in which A is directly bonded to oxygen, and A is Al, Si, Ge, T
The method for producing a coating film according to claim 1, wherein the coating film is an organic compound having at least one metal selected from i and Sn, and m + n is the number of bonds belonging to A. 8. The method for producing a coating film according to claim 7, wherein the organic compound is an organic compound containing a fluorocarbon group. 9. The concentration of the metal compound which causes the dehydration oxide reaction in the solution A is 0.0001% by weight or more and 20% by weight or less, and the chemical adsorption molecule capable of causing the elimination reaction in the solution B is The method for producing a coating film according to claim 1, wherein the concentration is 0.1% by weight or more and 30% by weight or less. 10. The method for producing a coating film according to claim 1, wherein the reaction represented by the dehydrated oxide reaction is a dealcoholization reaction, a silanol reaction, or a deesterification reaction. 11. The method for producing a coating film according to claim 1, wherein the organic compound capable of causing the elimination reaction is an alkoxysilane compound. 12. The alkoxysilane surfactant, wherein the alkoxysilane compound contains a fluorocarbon group.
The method for producing a coating film according to item 1. 13. alkoxysilane surface active agent containing a fluorocarbon _{group, CF 3 - (CF 2)} n - (R) m -SiX p
(OA) _3-p (n is 0 or an integer of 1 to 16, R is an alkylene group, a vinylene group, an ethynylene group, an arylene group,
A substituent containing a silicon or oxygen atom, m is 0 or 1, X is a substituent of H, an alkyl group, an alkoxyl group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group, A is an alkyl group, and p is 0, 1 or 2 ), Or CF ₃ COO-
_{(CH 2) w -SiX p (} OA) 3-p ( where, w is 1 to 1
An integer of 5, X is H, an alkyl group, an alkoxyl group, a fluorine-containing alkyl group or a substituent of a fluorine-containing alkoxy group, A
The method for producing a coating film according to claim 12, wherein is a substance represented by an alkyl group and p is 0, 1 or 2). 14. The method for producing a coating film according to claim 1, wherein the means for applying active hydrogen to the surface of the base material is a treatment by oxygen plasma, corona discharge, or ultraviolet irradiation in oxygen gas. 15. The method for producing a coating film according to claim 1, wherein the chemisorption molecule capable of causing the elimination reaction is encapsulated in a capsule.