JP2001170521A - Organic film, method of manufacturing the same and film forming apparatus used therein - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method and an apparatus for manufacturing an organic film capable of being formed even on an uneven base material with high work efficiency and coating efficiency and the organic membrane free from pinhole and uniform in thickness. SOLUTION: A solution for forming an organic film containing a silane compound having a chlorosilyl group is ejected toward a base material as mist- like liquid drops in an airless state and the silane compound is adsorbed and fixed onto the surface of the base material to form the organic film. By this constitution, production cost is reduced while not only production efficiency but also workability can be enhanced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an organic thin film, a method for producing the same, and a film forming apparatus used for the same. More specifically, the present invention relates to an organic thin film formed by chemically adsorbing a silane compound having a chlorosilyl group on the surface of a substrate, a method for producing the same, and a film forming apparatus used for the same.

[0002]

2. Description of the Related Art Conventionally, an organic thin film made of a silane compound having a chlorosilyl group can improve the abrasion resistance and heat resistance of a base material on which it is formed. Useful as a coating film. This organic thin film is formed by, for example, applying a solvent in which the silane compound is dissolved in a few percent to a substrate and chemically adsorbing the solvent on the surface of the substrate.

However, silane compounds have extremely high reactivity with water, so when they come into contact with water, the following chemical reaction formula (I)
The reaction shown in FIG. That is, the chlorosilyl group (—SiCl group) in the silane compound is hydrolyzed by a dehydrochlorination reaction with the hydroxyl group (OH group), and the compound having a silanol group (—Si—OH) (R—Si (O
H) ₃ )

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Further, R-Si (OH) ₃ is polymerized as shown in the following chemical reaction formula (II) by dehydration reaction between silanol groups.

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[0005] In addition, the compound (R-Si (OH) _2- O-Si (OH) _2- R) formed by the chemical reaction formula (II) is
It polymerizes with other compounds having a silanol group to have a high molecular weight, and a polymer having a considerably large molecular weight is formed.

Accordingly, when a coating solution containing a silane compound is applied to the surface of a substrate in an environment having a high relative humidity, the silane compound in the coating solution reacts with moisture in the atmosphere to form a polymer, and the film thickness is reduced. There is a problem that an organic thin film having a non-uniform and uneven surface is formed on a substrate. In order to solve such a problem, various methods for forming a uniform organic thin film on a substrate have been proposed.

For example, in Japanese Patent Publication No. 4-256466,
A method for producing a uniform organic thin film by applying a solvent in which a chlorosilane compound is dissolved to a substrate in a dry atmosphere where the relative humidity is equal to or lower than a predetermined value is disclosed. Specifically, after the base material is immersed in a solvent in which the silane compound is dissolved for a certain period of time, the silane compound is chemically adsorbed to the base material, and the excess compound physically attached to the base material is removed from the non-aqueous system. An immersion method for preparing a monomolecular organic thin film by washing with a solvent has been proposed. However, the immersion method is not suitable for industrial production because a large amount of solvent (coating solution) is required when an organic thin film is formed on a large substrate.

To solve such a problem, Japanese Patent Application Laid-Open No. 10-1
Japanese Patent No. 80179 discloses a roll coater method in which an organic solvent is transferred to a roll in a dry atmosphere, and the transferred solvent is applied to a substrate, and then, unreacted compounds physically adsorbed to the substrate are removed. I have. According to this method, an organic thin film can be formed on the surface of a base material with a minimum amount of solvent, so that this method is suitable for forming an organic thin film on a large base material and has excellent utility. However, the solvent used is the minimum necessary, but is not suitable for applying a coating liquid to a substrate having an uneven surface or a non-flat substrate, and the development of a more useful coating method is expected. I was

By the way, if the coating is to be performed on an uneven substrate, a coating method using a spray method is also conceivable. In this spray method, a large amount of gas is blown out from a small nozzle, and a solvent (coating liquid) is discharged from the nozzle with the gas, and the solvent is atomized by turbulence generated when the gas is discharged from the nozzle. Is applied to a substrate as an object to be coated. However, when this method is diverted to the formation of an organic thin film, the following disadvantages occur. In other words, a large amount of gas needs to be sprayed simultaneously in order to make the solution (silane compound + non-aqueous solvent) for forming an organic thin film to be attached to the substrate surface into fine mist-like droplets. However, there is a disadvantage that the non-aqueous solvent is dried by the accompanying gas and volatilized. As a result, the amount of the solution for forming an organic thin film that does not reach the substrate surface and is lost in the air is large, and the solution that reaches the substrate surface becomes a solid by reacting with moisture in the air. I have. Therefore, there is a problem that it is difficult to form a uniform thin film. In addition, since the solvent is scattered in the form of a mist in the conventional spray method, the coating efficiency as a coating amount with respect to the total spray amount is 5%.
There is also a problem that the coating efficiency is low as low as 0% or less.

Further, in the conventional method, it is possible to form an organic thin film having a thickness of about a monomolecular film, but there is a problem that a pinhole is formed in the formed organic thin film. ing. Pinholes are caused by contamination or the like on a part of the substrate surface, and are generated when the silane compound cannot be covalently bonded to the contaminated part. When an organic thin film having a pinhole formed thereon is used, for example, as a dirt prevention coat, a problem occurs in that dirt adheres to the pinhole portion, and the function as the dirt prevention coat cannot be sufficiently exhibited. . In addition, since the silane compound cannot be chemically adsorbed even in a portion where the active hydrogen density is low on the surface of the base material, a pinhole may occur in this case as well as in the case where dirt is attached.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional problems, and an object of the present invention is to improve the working efficiency and the coating efficiency even for a substrate having irregularities. It is an object of the present invention to provide a possible method for producing an organic thin film and a film forming apparatus used for the method. Another object of the present invention is to provide an organic thin film having a uniform thickness by suppressing the occurrence of pinholes, a method for manufacturing the same, and a film forming apparatus used therefor.

[0012]

Means for Solving the Problems In order to solve the above-mentioned conventional problems, the present inventors have studied a method for uniformly forming an organic thin film made of a silane compound on an uneven substrate using a small amount of a solvent. . As a result, they found that it is possible to suppress the evaporation of the solvent and to improve the coating efficiency by discharging the solvent at a high pressure from the minute nozzle and applying the minute droplet-shaped solvent to the substrate. Was.

That is, in order to solve the above-mentioned problems, a first aspect of the method for producing an organic thin film of the present invention is to provide a solution for forming an organic thin film containing a silane compound having a chlorosilyl group and a non-aqueous solvent. Applying pressure, a dropletization step of forming mist-like droplets by spraying airlessly from pores in a dry atmosphere, and bringing the mist-like droplets into contact with a base material to form a mist on the surface of the base material. An adsorption step of adsorbing and fixing a group of silane compound molecules, a non-aqueous solvent removing step of volatilizing and removing the non-aqueous solvent remaining on the substrate surface, and exposing the substrate to an atmosphere containing moisture And an exposing step.

In the above method, the step of forming a droplet is a step of mistlessly spraying the solution for forming an organic thin film in the form of a mist without entraining gas, and applying a high pressure to the solution for forming an organic thin film. ,
This is a process in which fine droplets in the form of mist are formed by ejecting the fine particles (nozzles) in a certain direction. When sprayed with gas, some non-aqueous solvent evaporates in the process of the atomized droplets reaching the substrate surface, so some of the atomized droplets do not reach the substrate surface They may be lost in the air, resulting in reduced coating efficiency. But,
Since the silane compound having a SiCl group (hereinafter sometimes simply referred to as a silane compound) can be attached to the surface of the base material as fine droplets together with the non-aqueous solvent by performing the airless jetting as in the above-described process. Thus, the coating efficiency can be improved. Further, since the droplet formation step is performed in a dry atmosphere, it is possible to prevent the silane compound in the solution for forming an organic thin film from causing a dehydrochlorination reaction with moisture in the atmosphere. Therefore,
Since the solution for forming an organic thin film, which has been turned into fine droplets in the form of mist, is attached to the substrate without deactivation, the silane compound molecules can be efficiently chemically adsorbed on the surface of the substrate. Thus, a monomolecular thin film composed of a group of silane compound molecules can be formed on the surface of the base material.

Further, in the conventional immersion method, not only when the organic thin film is formed on only one substrate, but also when the organic thin film is formed on a plurality of substrates, the final substrate is completely covered. Because of the necessity of immersion, a certain amount of liquid is necessarily required. On the other hand, according to the method described above, the coating efficiency can be improved, so that the amount of liquid necessary for forming an organic thin film having a desired film thickness can be minimized and used. Therefore, in the above-described method, an organic thin film can be formed while reducing production cost and improving production efficiency. In addition, in the immersion method, since the base material is immersed in the solution, it is necessary to take some kind of contact preventing means so as not to come into contact with the solution in a region where the formation of the organic thin film is unnecessary. On the other hand, in the method according to the first embodiment, the area to be sprayed can be easily limited, so that the working efficiency can be improved. On the other hand, the conventional roll coater method is similar to the method in the first embodiment in that it can be suppressed only to the amount of liquid necessary for application to the substrate, but the conventional roll coater method can be used. The formation of the organic thin film on the surface of the substrate having the uneven surface, which was impossible with the coater method, can be easily performed by the method according to the first embodiment.

When a surface functional group having active hydrogen does not exist on a part of the substrate surface or when there is a region to which dirt is attached, the silane compound molecule is chemically adsorbed to the region. It is impossible. However, in the first embodiment, since only the non-aqueous solvent is removed by volatilization, unreacted unreacted material is present on the monomolecular film or on the surface of the base material where the silane compound molecules are exposed without being chemically adsorbed. The silane compound can be left. Therefore, when the substrate is exposed to an atmosphere containing water vapor after the non-aqueous solvent removal step (exposure step), the unreacted silane compound remaining on the substrate surface undergoes a dehydrochlorination reaction with moisture, and is physically entangled and crosslinked. Then, a portion having no surface functional group is embedded. As a result, an organic thin film in which the generation of pinholes is suppressed can be formed, so that the antifouling durability can be improved.

On the other hand, as described above, since unreacted silane compounds remain on the monomolecular film, when these silane compounds are exposed to an atmosphere containing moisture, they polymerize to form siloxane compounds. Is formed. Accordingly, an organic thin film having a large thickness can be formed, and heat resistance can be improved.

Further, in place of the non-aqueous solvent removing step and the exposing step, a step of volatilizing and removing the non-aqueous solvent remaining on the substrate surface in an atmosphere containing moisture can be performed. As a result, the unreacted silane compound remaining on the monomolecular film can be polymerized by a dehydrochlorination reaction with an OH group to form a polymer layer on the monomolecular film. Can be further improved.

Further, in place of the non-aqueous solvent removing step,
A removing step of removing the silane compound and the non-aqueous solvent that are not chemically bonded to the substrate can be performed by spraying a dry gas on the substrate.

As a result, the unreacted silane compound and the non-aqueous solvent other than the silane compound molecules chemically adsorbed to the substrate are removed from the surface of the substrate, so that a monomolecular film-like An organic thin film can be formed. That is, according to the above method, a monomolecular organic thin film can be formed on the surface of the base material with good workability and reduced production cost.

In order to solve the above-mentioned problems, a second aspect of the method for producing an organic thin film of the present invention is to provide a solution for forming an organic thin film containing a silane compound having a chlorosilyl group and a non-aqueous solvent. A droplet forming step of forming mist droplets, and contacting the organic thin film forming solution which has become the mist droplets with moisture, thereby polymerizing at least a part of the droplets, and forming a silane compound and A polymerization step of forming polymerizable droplets composed of a siloxane compound polymer, and bringing the polymerizable droplets into contact with a substrate to adsorb and fix a group of silane compound molecules and the siloxane compound polymer on the surface of the substrate. A non-aqueous solvent removing step of volatilizing and removing the non-aqueous solvent remaining on the substrate surface.

In the above-mentioned method, the polymerization step includes contacting mist-like droplets containing a silane compound, which have been produced in the droplet formation step, with the moisture in the atmosphere by, for example, exposing it to the atmosphere. This is a step of forming polymerizable droplets in which at least the surface layer portion of the droplets is made of a siloxane compound polymer. In the surface layer portion that has reacted with moisture to form a siloxane compound polymer, a silanol group and a chlorosilyl group are coexisting. This is because some chlorosilyl groups and O
This is because HCl was eliminated by the dehydrochlorination reaction with the H group, and as a result, it was changed to a silanol group. In addition, since the inside of the polymerizable droplet does not come into contact with moisture, it contains an unreacted silane compound.

The adsorption step is a step of forming a film by adsorbing polymerizable droplets on the surface of the substrate, thereby chemically adsorbing silane compound molecules or siloxane compound polymers on the surface of the substrate. When unreacted silane compound molecules adhere to the substrate surface, the chlorosilyl groups in the silane compound molecules and the surface functional groups having active hydrogen on the substrate surface undergo a dehydrochlorination reaction, thereby causing chemical adsorption. Further, when the siloxane compound polymer adheres to the surface of the base material, the chlorosilyl group in the siloxane compound polymer and the surface functional group having active hydrogen on the base material surface are chemically adsorbed by a dehydrochlorination reaction. Alternatively, the silanol group and the surface functional group undergo a dehydration reaction to chemically adsorb.

Further, in the non-aqueous solvent removing step, the non-aqueous solvent remaining on the surface of the substrate is volatilized and removed, so that a group of silane compound molecules and a siloxane compound polymer are formed on the surface of the substrate. Can be formed into an organic thin film composed of a mixed film formed by chemical adsorption and a polymer layer formed on the mixed film. Here, even if there is a region where the surface functional group does not exist, or a region where dirt or the like is present, in a part of the substrate surface,
In the above method, an organic thin film can be formed while suppressing generation of pinholes. That is, as described above, when there is no surface functional group or the like on the substrate surface, the silane compound molecule having a chlorosilyl group cannot be chemically adsorbed on the substrate surface, but such a portion is not polymerizable. The droplets are embedded, and these polymerizable droplets are combined with other polymer or monomolecular film constituting the organic thin film by a dehydration reaction. Therefore, generation of pinholes can be suppressed, and an organic thin film having excellent antifouling durability can be formed.

Therefore, according to the method of manufacturing an organic thin film according to the second aspect, it is possible to form an organic thin film in which the production cost is reduced, the production efficiency is improved, and the occurrence of pinholes is suppressed. .

In addition, instead of the non-aqueous solvent removing step, a non-aqueous solvent is obtained by blowing a dry gas onto the substrate to form a polymer of the silane compound and siloxane compound not chemically bonded to the substrate. A removing step for removing may be performed.

According to the above-described method, the solution for forming the organic thin film remaining on the surface of the substrate is immediately removed by spraying a dry gas onto the substrate, so that a group of silane compound molecules and siloxane An organic thin film composed of a mixed film formed by chemical adsorption of a compound polymer can be formed.

The droplet forming step may be a step of applying high pressure to the solution for forming an organic thin film and jetting airlessly from fine holes to form mist-like droplets.

Thus, it is possible to prevent the non-aqueous solvent in the droplets jetted from the pores from being dried and volatilized, thereby further improving the coating efficiency as a coating amount with respect to the total spray amount. be able to.

The diameter of the pores is 10 μm or more and 100 μm or more.
m and the pressure applied to the organic thin film forming solution is 100 N / cm ² or more and 1000 N / c or more.
It is preferably within a range of m ² or less. By forming the solution for forming an organic thin film into droplets under such conditions, it is possible to generate droplets having a particle size suitable for forming an organic thin film having a uniform thickness.

The average diameter of the droplets exceeds 0 μm.
It is preferable that it is within the range of 100 μm or less. By controlling the average particle diameter of the droplets within the above numerical range, the amount of application can be controlled, and an organic thin film having a uniform film thickness can be formed.

Further, in order to solve the above-mentioned problems, in an organic thin film forming apparatus used in the method of manufacturing an organic thin film according to the present invention, the organic thin film forming apparatus includes the organic thin film forming solution. Having a main body for storing a liquid, a pressure generator for applying pressure to the organic thin film forming solution, and at least one pore for injecting the organic thin film forming solution pressurized by the pressure generating device. It is characterized by further comprising a device.

According to the above configuration, the spraying device applies a high pressure to the solution for forming an organic thin film by the pressure generating device, and mistlessly sprays the fine particles through the pores without gas. In the process before reaching the substrate surface, the non-aqueous solvent can be attached to the substrate surface without evaporating. Thereby, the coating efficiency can be improved. Further, by improving the coating efficiency, it is possible to minimize the amount of liquid necessary for forming an organic thin film having a desired thickness. Therefore, an organic thin film can be formed while reducing production cost and improving production efficiency. Further, according to the above configuration, the operability can be improved, for example, the area to be sprayed can be easily limited as compared with the immersion method. Further, the organic thin film can be formed even on a substrate having an uneven surface, and in this regard, the working efficiency can be further improved.

Further, after the solution for forming an organic thin film is formed into droplets by the spraying device and sprayed on the substrate, a dry gas is blown on the substrate to leave the silane compound remaining without being adsorbed on the surface of the substrate. And a removing device for removing the non-aqueous solvent.

According to the above construction, the unreacted silane compound and the non-aqueous solvent remaining on the surface of the base material are immediately removed by blowing the dry gas onto the base material. Can be formed.

The apparatus for forming an organic thin film further comprises an external air shielding means capable of installing the spraying device and the solvent removing apparatus therein, and a humidity control device capable of controlling the inside of the external air shielding means to a predetermined humidity. Can be provided.

According to the above construction, the solution for forming the organic thin film is formed into fine droplets by setting the dry atmosphere by the humidity controller so that the relative humidity inside the outside air shielding means becomes a predetermined value. When sprayed on a substrate, it is possible to prevent the solution for forming an organic thin film that has been made into microdroplets from reacting with moisture in the atmosphere. Accordingly, the silane compound having a chlorosilyl group can be chemically adsorbed on the surface of the base material, and a monomolecular organic thin film composed of a group of silane compound molecules can be formed. On the other hand, by setting the internal humidity to be higher than the outside air by the humidity control device, the droplets sprayed from the spraying device are brought into contact with moisture, and at least a part of the droplets are polymerized to be polymerizable. It can be a droplet. Further, when the polymerizable droplets come into contact with the base material, a group of silane compound molecules and a mixed film formed by chemisorption of the siloxane compound polymer and a polymer layer formed on the mixed film are formed. Organic thin film can be formed.

In order to solve the above problems, an organic thin film according to the present invention is an organic thin film formed on a substrate surface,
The organic thin film is composed of a monomolecular film formed by chemically adsorbing a group of silane compound molecules to the base material through a siloxane bond, and a polymer layer formed on the monomolecular film and formed of a siloxane compound polymer. Wherein the polymer layer covers a region of the substrate on which the silane compound molecules are not chemically adsorbed.

If there is a region on the substrate where no surface functional group having active hydrogen exists, for example, a silane compound molecule having a chlorosilyl group cannot be chemically adsorbed.
This can cause pinholes. However, according to the above configuration, the organic thin film provided on the base material has no pinholes and has a high surface coverage. Therefore, it is possible to prevent the organic thin film from deteriorating due to the pinhole. For example, when an organic thin film is formed to impart an antifouling function to a substrate, even when dirt adheres to the organic thin film having the above-described structure since there is no pinhole,
It can be easily removed. Also, when dirt is removed with a cloth or the like, the organic thin film is not deteriorated from the pinhole portion, so that the antifouling durability is excellent.

Further, according to the above configuration, since the organic thin film is thicker than the monomolecular film, it has excellent heat resistance. In the case of a monomolecular film, the film constituent molecules may be desorbed by heating, but in the present invention, since the polymer layer is further formed on the monomolecular film, the silane compound molecule can be easily removed. This is because detachment can be prevented.

In order to solve the above-mentioned problem, another organic thin film according to the present invention is an organic thin film formed on a substrate surface, wherein the organic thin film is composed of a silane compound molecule and a siloxane compound polymer. A thin film composed of a mixed film obtained by chemically adsorbing the base material through a siloxane bond to the base material, and a polymer layer formed on the mixed film and made of a siloxane compound polymer. Is characterized by covering a region on the base material where the silane compound molecule and the siloxane compound polymer are not chemically adsorbed.

According to the above structure, the polymer layer covers even the region where the silane compound molecule and the siloxane compound polymer cannot be chemically adsorbed, so that there is no pinhole in the organic thin film provided on the substrate. Therefore, it is possible to suppress the organic thin film from being deteriorated due to the pinhole. In addition, since a polymer layer is further formed on the mixed film formed by chemisorption on the base material, it is possible to prevent the silane compound molecules and the like from being easily desorbed even when the base material is heated. And excellent heat resistance can be obtained.

[0043]

Embodiments of the present invention will be described below. However, unnecessary parts are omitted, and
Some parts are shown enlarged or reduced for ease of explanation. The above applies to the following drawings.

(Embodiment 1) First, a method for producing an organic thin film according to the present invention will be described below. Embodiment 1
Corresponds to the first aspect of the present invention.

The method for producing an organic thin film according to the present invention comprises applying a pressure to a silane compound having a chlorosilyl group and a solution for forming an organic thin film containing a non-aqueous solvent, and subjecting the solution to airless injection from pores in a dry atmosphere. A droplet forming step of forming mist-like droplets, and an adsorbing step of adsorbing and fixing the silane compound on the surface of the substrate by bringing the solution for forming an organic thin film into a mist-like droplet into contact with a substrate. And a non-aqueous solvent removing step of volatilizing and removing the non-aqueous solvent remaining on the surface of the base material, and an exposing step of exposing the base material to an atmosphere containing moisture.

The droplet forming step is a step of converting the solution for forming an organic thin film into mist-like droplets. Specifically, by compressing the solution for forming an organic thin film, the expansion force of the compressed solution for forming an organic thin film is increased to a certain level, and the expansion force is rapidly released to form a droplet. In addition to the action of separation, the particles collide with the outside air, which is a stationary fluid, to be atomized into mist-like droplets. Here, as a method of forming the organic thin film forming solution into mist-like liquid droplets, a method of adding a compressed gas and spraying the organic thin film forming solution may be considered. The disadvantage is that the non-aqueous solvent in the solution is evaporated by the compressed gas. Therefore, as described above, droplet formation by airless jetting is preferable in the present invention.

The significance of making the solution for forming an organic thin film into mist-like droplets is that spraying can be efficiently performed over a wide area on an object to be coated, and the coating efficiency can be improved. is there. The average particle size of the droplets exceeds 0 μm and
It is preferably within a range of 0 μm or less. If the average particle diameter of the liquid droplets exceeds 100 μm, it is difficult to precisely control the amount of the liquid droplets to be deposited on the surface of the base material and to form a uniform organic thin film.

This droplet formation step is performed in a dry atmosphere. This is to prevent the chlorosilyl group of the silane compound contained in the organic thin film forming solution from reacting with moisture in the air and to maximize the adsorption rate of the silane compound to the substrate. Details will be described later.)
The above-mentioned dry atmosphere refers to an environment in which the relative humidity is, for example, about 35% or less.
The process is performed in a dry gas such as dry nitrogen or dry helium.

The solution for forming an organic thin film includes a silane compound having a chlorosilyl group and a non-aqueous solvent. The silane compound having a chlorosilyl group is not particularly limited, and various compounds such as a compound having a long fluorinated carbon chain and a compound having a hydrocarbon chain can be used depending on the intended use. More specifically, for example, CF ₃ (CF ₂ ) ₇ C ₂ H ₄ SiCl ₃ can be exemplified.

The non-aqueous solvent is not particularly limited as long as it is a solvent comprising a component which disperses the silane compound and does not extremely deactivate the silane compound. Specifically, for example, a solvent containing one or more of solvents selected from a fluorocarbon solvent, a silicone solvent, and the like can be used. As a result, an organic thin film forming solution composed of a compound or the like containing a large amount of a chlorosilyl group as an activating group can be obtained, and its reactivity can be maintained in a high state. As the fluorocarbon solvent,
Examples thereof include n-perfluorooctane. Octamethylcyclotetrasiloxane and the like can be exemplified as the silicone-based solvent. When a solvent having a relatively low boiling point is used as the non-aqueous solvent, the organic thin film can be evaporated at room temperature without performing heat treatment after the formation of the organic thin film, and the handleability can be improved. In the case where an organic thin film is formed on the surface of a base material on which adsorbed water is present, it is preferable to use, as the non-aqueous solvent, a solvent that exhibits a certain degree of solubility (absorbency) with respect to the adsorbed water. . The reason will be described later.

The adsorbing step is a step in which mist-like droplets are brought into contact with the surface of a substrate to chemically adsorb silane compound molecules on the surface of the substrate. As described above, since the solution for forming an organic thin film is in the form of droplets in the form of a mist, it can be attached even on a non-planar substrate surface,
It is possible to spray efficiently over a wide area on a substrate as an object to be coated. Therefore, work efficiency can be significantly improved. Further, since the airless spray is used, evaporation of the non-aqueous solvent can be prevented, and application efficiency can be improved. Furthermore, by improving the coating efficiency,
Since the application can be performed with the total spray amount suppressed to a minimum, the production cost can be reduced and the production efficiency can be improved. Also,
The amount of the organic thin film forming solution to be adhered to the substrate can be controlled by appropriately changing the total spray amount in the droplet formation step.

Examples of the substrate include those having a plurality of surface functional groups having active hydrogen such as hydroxyl groups (—OH) on the surface thereof, and those having adsorbed water in addition to the surface functional groups. Can be used. Specifically, for example, glass, ceramic, plastic, metal, fiber,
Those made of materials such as leather and paper are exemplified.

Here, the state when the silane compound molecule having a chlorosilyl group is chemically adsorbed on the substrate surface will be described.
This will be described in detail with reference to FIG. In FIG. 1,
As an example of a silane compound, CF ₃ (CF ₂ ) ₇ C ₂ H ₄ S
The case where iCl ₃ (hereinafter abbreviated as FS-17) is used is shown. When the droplet composed of the organic thin film forming solution adheres to the surface of the substrate 12, the silane compound molecules 11 in the organic thin film forming solution are absorbed by the adsorbed water 13 on the substrate 12.
Alternatively, a dehydrochlorination reaction occurs with an OH group as a surface functional group having active hydrogen, and HCl is eliminated. As a result, silanol groups are introduced to form silanol compound molecules 14 (FIG. 1).
(B)). Since the amount of the adsorbed water 13 on the substrate surface is as small as about several layers of water molecules in thickness, it is absorbed by the non-aqueous solvent. In the absorption process, the silanol compound molecules 14 undergo a dehydration reaction between the OH groups and the molecules on the surface of the substrate 12 to form a monomolecular film 15 on the substrate 12 (FIG. 1C).
reference).

When the non-aqueous solvent in the solution for forming an organic thin film is a solvent that hardly absorbs adsorbed water and the silane compound has a functional group exhibiting water repellency (hydrophobicity), Reacts with the adsorbed water to form a silanol compound, which cannot float on the surface of the base material due to the action of the functional group exhibiting water repellency, and floats on the adsorbed water surface. In this case, if the adsorbed water on the base material surface is removed, a dehydration reaction between the surface functional group having active hydrogen on the base material surface and the silanol group can be performed. Can be adsorbed. Further, when there is no adsorbed water on the substrate surface, the silane compound chemically adsorbs by dehydrochlorination reaction with the OH group on the substrate surface to form a monomolecular film.

The non-aqueous solvent removing step is a step of removing the non-aqueous solvent remaining on the surface of the substrate 12 by volatilizing. By performing this step, the monomolecular film 15 can be formed.
Unreacted silane compound molecules 11 remain on the upper surface by physical adsorption. On the other hand, in a region where the surface functional group having active hydrogen such as an OH group does not exist on the surface of the base material 12, FIG.
As shown in (a), the unreacted silane compound molecules 11 and silanol compound molecules 14 are physically adsorbed, etc.
2 Adhered to the surface.

Further, the substrate 12 on which the monomolecular film 15 and the like are formed is placed in an atmosphere containing moisture (relative humidity of 40% or more).
Exposure step. As a result, the unreacted silane compound molecules 11 physically adsorbed on the monomolecular film 15 react with water and polymerize to form a polymer layer 16 made of a siloxane compound polymer (FIG. 1C). reference).
Further, in a region where the surface functional group having active hydrogen does not exist on the surface of the base material 12 and the unreacted silane compound is physically adsorbed or the like, the chlorosilyl group in the silane compound is replaced with the OH group as described above. Polymerization is carried out by the dehydrochlorination reaction to produce a siloxane compound polymer. This polymer cross-links with the film constituent molecules constituting the monomolecular film 15 and the polymer layer 16 formed on the monomolecular film 15 (see FIG. 2B).
Accordingly, the region where the surface functional group having active hydrogen does not exist on the surface of the base material 12 is filled with the siloxane compound polymer, so that an organic thin film in which the generation of pinholes is suppressed can be formed. Accordingly, deterioration of the organic thin film such as peeling caused by the pinhole can be prevented, and an organic thin film having excellent durability can be formed.

If the non-aqueous solvent removal step is performed in an atmosphere containing water (relative humidity of 40% or more), the chlorosilyl group in the unreacted silane compound is removed from the OH group together with the volatilization of the non-aqueous solvent. Polymerization can be carried out by a hydrochloric acid reaction to produce a polymer comprising a siloxane compound. As a result, a polymer layer 16 can be further formed on the monomolecular film 15 formed on the surface of the substrate 12.

(Embodiment 2) The present Embodiment 2 is different from the method of producing an organic thin film according to Embodiment 1 in that an organic thin film remaining on the surface of a substrate is replaced with a non-aqueous solvent removing step. The difference is that a removing step of spraying a dry base on the forming solution to remove the forming solution is performed and a step of exposing the base to an atmosphere in which moisture is present is not performed.

By performing the removal step, the unreacted silane compound and the non-aqueous solvent remaining on the monomolecular thin film composed of the silane compound chemically adsorbed on the substrate surface can be removed. As shown in (1), a monomolecular organic thin film can be formed.

(Embodiment 3) Embodiment 3 corresponds to the second aspect of the present invention, and differs from the first aspect in the following points.

That is, in the method for producing an organic thin film according to the present invention, an organic thin film forming solution in which a silane compound having a chlorosilyl group as a terminal group is dissolved in a non-aqueous solvent is used.
A droplet forming step of forming mist-like droplets, and by contacting the organic thin film forming solution that has become the mist-like droplets with moisture,
A polymerization step of polymerizing at least a part of the surface portion of the liquid droplet to form a polymerizable liquid droplet, and bringing the polymerizable liquid droplet into contact with a substrate to adsorb and fix the polymerizable liquid droplet on the surface of the substrate. And a non-aqueous solvent removing step of volatilizing and removing the non-aqueous solvent remaining on the substrate surface.

The droplet forming step is a step of converting the solution for forming an organic thin film into mist-like droplets 21 (see FIG. 4A). Specifically, a pressure is applied to the solution for forming an organic thin film. In addition, a method of injecting airlessly from a fine hole, a method of injecting air with gas, and the like are included.

In the polymerization step, the solution for forming an organic thin film which has been formed into mist-like droplets in the droplet formation step is brought into contact with moisture to polymerize at least a part of the surface portion of the droplets. This is a step of generating the polymerizable droplet 22 (FIG. 4).
(B)). As a method of bringing the droplets into contact with moisture, for example, a method of exposing the droplets to an atmosphere containing water vapor set to have a predetermined relative humidity and the like can be mentioned. When the droplet comes into contact with moisture, the chlorosilyl group and the OH group in the silane compound undergo a dehydrochlorination reaction, so that a siloxane compound polymer is formed at least on the surface layer of the droplet. This siloxane compound polymer has a chlorosilyl group and a silanol group. Also, since the water does not reach the inside of the droplet,
The droplet contains an unreacted silane compound. In addition,
The relative humidity is preferably in the range of 30% to 100%, and more preferably in the range of 70% to 90%.

In the adsorption step, the polymerizable droplet 22
This is a step of causing chemical adsorption by contacting the surface. More specifically, it is as follows. That is, when the polymerizable droplet 22 adheres to the surface of the substrate 12, in the siloxane compound polymer constituting the surface portion of the polymerizable droplet 22, the chlorosilyl group undergoes a dehydrochlorination reaction with the OH group in the adsorbed water 13. As a result, it changes to a silanol group. Further, also in the silane compound existing inside the polymerizable droplet 22, the chlorosilyl group reacts with the OH group to introduce a silanol group and change to a silanol compound. The base material 12
The non-aqueous solvent absorbs the adsorbed water 13 because the amount of the adsorbed water 13 existing on the surface is very small and the thickness is only about several layers of water molecules. In the absorption process, the siloxane compound polymer and the silanol compound molecule undergo a dehydration reaction between OH groups as surface functional groups present on the surface of the substrate 12 and between the molecules, and are bound and fixed on the substrate 12 and mixed. A film 23 is formed. In a region where the OH group or the like does not exist in the base material 12, the surface of the substrate 12 is covered by a polymer or the like made of a siloxane compound by physical adsorption (see FIG. 5).

The non-aqueous solvent removing step is a step of removing the non-aqueous solvent remaining on the surface of the substrate 12 by volatilizing. By performing this step, a region where a group of silane compound molecules is chemically adsorbed to form a monomolecular film and a region where the siloxane compound polymer is chemically adsorbed are mixed on the surface of the substrate 12. The mixed film 23 is formed (see FIG. 4C). Further, on the mixed film 23, a polymer layer 2 in which a siloxane compound polymer is physically entangled.
4 is formed. In the polymer layer 24, a silane compound polymer constituting the polymer layer 24 is fixed by bonding to a silane compound molecule or a siloxane compound polymer constituting the mixed film 23 through a siloxane bond. On the other hand, in a region where there is no surface functional group having active hydrogen on the surface of the base material 12,
The siloxane compound polymer is physically adsorbed and covers the surface of the substrate 12. In addition, this siloxane compound polymer,
The mixed film 23 and the polymer layer 24 are bonded and fixed by a siloxane compound. As a result, the region where the surface functional group having active hydrogen does not exist on the surface of the base material 12 is filled with the siloxane compound polymer, so that an organic thin film in which the generation of pinholes is suppressed can be formed. It is possible to prevent the organic thin film from deteriorating, such as peeling, which is caused by the above, and to form an organic thin film having excellent durability.

Further, in place of the non-aqueous solvent removing step,
By spraying the substrate with a dry gas, a removal step of removing the silane compound and the siloxane compound polymer not chemically bonded to the surface of the substrate and the non-aqueous solvent can be performed. In this case, it is deposited on the mixed film 23,
Since the siloxane compound polymer and the remaining non-aqueous solvent are removed, an organic thin film composed of the mixed film 23 is formed on the base material (see FIG. 5B). Therefore,
An organic thin film having a small thickness is formed as compared with the removing step of removing only the non-aqueous solvent.

In the case where the non-aqueous solvent in the solution for forming an organic thin film is a solvent that hardly absorbs adsorbed water and the silane compound has a water-repellent (hydrophobic) functional group, the siloxane compound The polymer may not reach the surface of the substrate 12 due to the action of the functional group exhibiting water repellency, and may float on the adsorbed water surface. On the other hand, the unreacted silane compound reacts with the adsorbed water to become a silanol compound, and, like the siloxane compound, floats on the adsorbed water surface by the action of a functional group exhibiting water repellency. In this case, if the adsorbed water on the surface of the base material 12 is removed, a dehydration reaction between the surface functional group having active hydrogen on the surface of the base material 12 and the silanol group can be performed. And can be chemically adsorbed. When no water is present on the surface of the substrate 12, the siloxane compound polymer and the unreacted silane compound undergo a dehydrochlorination reaction with OH groups on the surface of the substrate to chemically adsorb to form a composite film.

Here, the reason why the method for producing an organic thin film according to the present embodiment includes a polymer as a film component and enables formation of an organic thin film having a uniform thickness will be described below. .

When the average particle size of the polymerizable droplet is R, the surface area of the polymerizable droplet is S, and the volume is V, the total amount of the polymer in the polymerizable droplet is (k ₁ × S) It can be expressed as. Here, k ₁ is a constant determined by the type of the silane compound, the type of the non-aqueous solvent, the relative humidity of the atmosphere, and the arrival time from when the droplet is sprayed from the nozzle to when it reaches the substrate 12. Therefore, the concentration of the polymer present in the polymerizable droplet can be represented by the following formula (1).

(Equation 1)

On the other hand, in the conventional immersion method,
The concentration of the polymer can be calculated from the ratio between the surface area and the volume of the solution for forming an organic thin film filled in the container. For example, assuming that the container has a cubic shape with one side L, the concentration of the polymer is represented by the following equation (2).

(Equation 2) Here, k ₂ in the formula is a constant determined by the type of the silane compound, the type of the non-aqueous solvent, the relative humidity of the atmosphere, and the immersion time of the substrate in the organic thin film forming solution.

Further, in the conventional roll coater method,
The concentration of the polymer can be calculated from the ratio of the surface area (that is, the surface area of the roll) of the solution for forming an organic thin film transferred to the roll to the volume. For example, assuming that the radius of the roll is r, the length of the roll in the long side direction is l, and the thickness of the organic thin film forming solution transferred to the roll is d, the concentration of the polymer is represented by the following formula (3). expressed.

(Equation 3) Here, k ₃ in the formula is a constant determined by the type of the silane compound, the type of the non-aqueous solvent, the relative humidity of the atmosphere, and the number of rotations of the roll.

In the immersion method, the minimization of L is limited due to the size of the substrate on which the organic thin film is formed. Therefore, there is a limit to increasing the concentration of the polymer represented by the formula (2).

Also in the roll coater method, it is in principle difficult to make the thickness of the organic thin film forming solution to be transferred as thin as possible. Therefore, also in this case, the above equation (3)
As is clear from the above, there is a limit to increasing the concentration of the polymer.

On the other hand, in the method for producing an organic thin film according to the present embodiment, the smaller the average particle size of the droplets in the formation of the mist in the droplet formation step, It is presumed that it easily reacts with water to change into a polymer composed of a siloxane compound. Further, since the average particle diameter of the droplets can be reduced without limit in principle, the average particle diameter R of the polymerizable droplets can be similarly reduced. Therefore, the above equation (1)
The concentration of the polymer represented by can be increased both theoretically and practically. That is,
In the method for manufacturing an organic thin film according to the present embodiment, an organic thin film containing a large amount of a polymer as a film component can be formed. Further, by controlling R to about 100 μm or less and controlling the total spray amount,
Since the amount of polymerizable droplets adhering to the surface can be precisely controlled, an organic thin film having a uniform film thickness can be formed. As described above, when the film component contains a large amount of a polymer, an organic thin film in which pinholes are suppressed can be obtained. Therefore, antifouling durability can be improved. Further, for example, an organic thin film having a larger thickness than a monomolecular film can be formed. Therefore, the heat resistance can be improved.

For reference, in the roll coater method, since the organic thin film forming solution is applied by bringing the roll into contact with the base material, the film forming surface of the base material is a curved surface. In addition, there is a problem that the coating itself is difficult because the roll does not conform to the curved surface. Even if the roll is made of a resilient material so that it can conform to a curved surface, it is difficult to coat uniformly because the contact pressure varies depending on the location. Further, since the rolls are usually set horizontally, there are restrictions on the method of transporting the base material during formation. In contrast, in the method for producing an organic thin film according to the present embodiment, the solution for forming an organic thin film is formed into droplets and chemically adsorbed on the surface of the substrate, so that the surface of the substrate has an uneven surface. It is also possible to form an organic thin film having a uniform thickness.

From the above considerations, it can be seen that the method for producing an organic thin film according to the present embodiment can form an organic thin film containing a large amount of a polymer as a film component, as compared with the conventional method. .

(Embodiment 4) The present invention also relates to an organic thin film forming apparatus used in the method of manufacturing an organic thin film according to any one of Embodiments 1 to 3. The organic thin film forming apparatus includes:
A spraying device is provided as a main component thereof. FIG.
FIG. 1 is an explanatory view schematically showing a spraying device as a main configuration in an organic thin film forming apparatus according to the present invention. FIG. 7 is a cross-sectional view schematically showing a tip portion of the spray gun 2 in the spray device.

As shown in FIGS. 6 and 7, a spray gun 41 as a spray device according to the present invention comprises a main body 45.
, A tip 46 having a nozzle (pore) 50 and an opening / closing shutter 51, a high-pressure gas tank 43 as a pressure generating device, and a pulse controller 44.

The main body 45 is provided with a solution 5 for forming an organic thin film.
2 is a structure that can be stored in a closed state. Body 45
Is supplied from a storage tank or the like (not shown). The kinematic viscosity of the organic thin film forming solution 52 is 0.2 to 5000 cSt (25 ° C.).
And more preferably in the range of 0.5 to 2 cSt. If the kinematic viscosity is within the above numerical range, a droplet having a desired particle size (0 to 100 μm) can be obtained.

The nozzle 50 is a jet port for jetting (discharging) the organic thin film forming solution 52 stored in the main body 45. Although the diameter of the nozzle 50 is not particularly limited, it is necessary to reduce the diameter in order to improve atomization. On the other hand, if the diameter is too small, the discharge amount becomes small, and the coating efficiency is reduced. , Within the optimal range. In the present invention, for example, 10
It is set to be in the range of μm to 100 μm. The shape of the nozzle is not particularly limited, and may be appropriately changed as needed.

The opening / closing shutter 51 is an opening / closing device for opening / closing the nozzle 50, and is provided with a drive mechanism (not shown) for executing the opening / closing operation.

The high-pressure gas tank 43 is a tank for intermittently supplying pressurizing air 53 for applying pressure to the organic thin film forming solution 52 filled in the spray gun 41. The pressurizing air 53 is supplied to the spray gun 41 via a flow path 47, and the supply amount of the pressurizing air 53 is controlled by an adjusting valve 42. The channel 47 has an optimally designed structure so that the pressure is effectively applied to the organic thin film forming solution by the pressurizing air 53. Pressurizing air 5
As 3, it is preferable to use a dry gas, and specific examples include nitrogen gas, helium gas, argon gas, and carbon dioxide gas. This is because, if moisture is contained in the pressurizing air 53, the silane compound in the solution for forming an organic thin film reacts with moisture to deactivate the solution. The nozzle 50 has a diameter of 10 to 100 μm,
The kinematic viscosity of the solution for forming an organic thin film is 0.2 to 5000 cSt.
(25 ° C.), the solution 52 for forming an organic thin film filled in the spray gun 41 is filled with 100 N / cm ^{2 to} 1000 N / cm ² .
The present inventors have found that the supply of pressurized air so that a pressure of about N / cm ² is applied can control the particle size of the atomized droplets of the solution for forming an organic thin film to about 100 μm or less.

The pulse controller 44 is a control means for controlling the opening / closing operation of the opening / closing shutter 51 in accordance with a control signal. The pulse controller 44 receives data such as the surface condition of the substrate to be coated and the thickness of the organic thin film to be formed. The spray amount is adjusted based on the amount. In addition, when the organic thin film forming solution 52 is exposed to the atmosphere, there is a concern that it may be deactivated due to the reaction with moisture in the atmosphere. Therefore, it is preferable to use a spray gun 41 having excellent airtightness.

The spray gun 41 having the above configuration
As described below, the solution for forming an organic thin film is atomized and sprayed as described below. That is, when the opening / closing shutter 51 closes the nozzle 50 under the control of the pulse controller 44, the solution 52 for forming an organic thin film filled in the front end portion 46 is supplied with pressurized air as shown in FIG. 5
3 and are compressed. Next, when the opening / closing shutter 51 opens the nozzle 50 under the control of the pulse controller 44, the solution 52 for forming an organic thin film, whose liquid pressure has been increased by being compressed, is rapidly released, and is ejected at a higher speed than the nozzle 50. You. At this time, the organic thin film forming solution 52 sprayed from the nozzle 50 becomes a conical liquid film 54. The liquid film 54 functions to separate into droplets as it expands in a wide angle, and is crushed into fine particles from the forefront in the jetting direction of the liquid film 54 by collision with outside air which is a stationary fluid. Into droplets 55. At this time, the spray pattern formed by the mist droplets 55 is a wide-angle conical spray flow. Therefore, it is suitable for forming a coating over a wide area.

As described above, the spray gun 4 according to the present invention
1 is sprayed by airless spray without gas (airless spray), so that it is possible to prevent the non-aqueous solvent in the solution for forming an organic thin film from drying before reaching the surface of the substrate 12. In addition, since the particle size of the droplet 55 is controlled to about 100 μm or less, it is possible to form an organic thin film having a uniform film thickness on the base material 12 by appropriately setting the spray amount as needed. Become.

Further, the apparatus for forming an organic thin film according to the present invention may be provided with a moving device for relatively moving the substrate 12 as the object to be coated and the spraying device (spray gun 41). For example, as shown in FIG. 8, a pair of opposing pulleys 62
An endless annular belt 61 is wound around 62,
The belt 61 includes a moving device 60 having a configuration in which the belt 61 is stretched linearly between the pulleys 62. The spray gun 4 is fixed to the belt 61 by fixing means (not shown).
1 is fixed. The pulleys 62 are connected to a pulse motor 63 for driving them. The pulse motor 63 is designed to be able to rotate forward and backward. Further, a control means 64 for controlling the pulse motor 63 is connected thereto. The belt 6
As 1, for example, a timing belt can be exemplified.

The moving device 60 operates as described below. That is, a control signal is sent from the control means 64 to drive the pulse motor 63 so that the pulleys 6
By rotating the belt 2 in the same direction, the belt 61 is rotated in the direction indicated by the arrow A. Accordingly, the spray gun 41 can also be moved on the base material 12 in the direction indicated by the arrow A in a timely manner. In this way, by creating a relative movement state between the spray gun 41 and the substrate 12, it is possible to sequentially spray the organic thin film forming solution even on the substrate 12 having a large area. Gun 4
When 1 is in the fixed state, the limited spray area can be enlarged. Further, a translation device (not shown) for translating the translation device 60 in the direction indicated by the arrow B may be provided. This makes it possible to spray two-dimensionally on the base material 12. Further, the moving device 60 may be provided with up-and-down elevating means (not shown) for elevating the moving device 60 up and down. Thereby, the nozzle 50 in the spray gun 41 is
In addition, the separation distance from the base material 12 can be appropriately adjusted as needed, and the spray gun 41 is moved three-dimensionally, so that an organic thin film can be formed even on a box-shaped one.

In the apparatus for forming an organic thin film according to the present invention, after the organic thin film forming solution is sprayed on the substrate 12, the organic thin film forming solution remaining on the substrate surface is removed. For removing the solvent. More specifically, as shown in FIG. 9, an air gun 71 that blows out a dry gas to remove a silane compound or the like that is not chemically bonded to the substrate can be suitably used.

Further, the apparatus for forming an organic thin film according to the present invention can install the spray gun 41, the moving device 60 and the like inside, and has a shielded space to prevent the contact with the outside air. An outside air shielding means may be provided.

The outside air shielding means is not particularly limited in its shape and material as long as it can shield the spray gun 41 and the substrate 12 of the present invention from outside air. For example, as shown in FIG. 10, a humidity control container 72 or the like in which the internal temperature and humidity can be controlled can be exemplified. The humidity control container 72 includes a humidity control device (not shown) for controlling internal humidity and the like. When the inside of the humidity control container 72 is set to a high temperature and a high humidity by this humidity control device, it can be suitably used in the method of manufacturing an organic thin film according to the third embodiment. On the other hand, if the inside of the humidity control container 72 is controlled to a low humidity so that the humidity does not exceed a predetermined value and the humidity control container 72 is used, the first embodiment can be used.
Alternatively, it can be suitably used in the manufacturing method according to the second embodiment. In this case, the humidity control container 72
Further, an inert gas supply means for supplying an inert gas (for example, dry air, dry nitrogen or dry helium) which is inert to the organic thin film forming solution may be provided. In addition,
As the outside air shielding means, a high-temperature high-humidity tank, a chamber, or the like can be used in addition to the humidity control container described above. Further, a room for mounting an organic thin film forming apparatus capable of controlling the humidity and temperature inside can also be used as the outside air shielding means.

If an organic thin film is formed using the apparatus for forming an organic thin film having the above configuration, the coating efficiency can be improved. In addition, since the coating efficiency is high, the amount of the organic thin film forming solution used can be suppressed, and the production cost can be reduced.

In the immersion method, when it is desired to form an organic thin film only on a desired region of the substrate surface, it is necessary to protect the other region from contact with the organic thin film forming solution. . However, in the present invention, since it is sufficient to spray only the region where the film is to be formed, the complexity of the operation in the above case can be reduced. Furthermore, while the immersion method requires a relatively long immersion time, the spraying time in the spraying method is completed in a short time, thereby improving the productivity.

In this embodiment, FIG.
However, the present invention is not limited to this. For example, as shown in FIG. 11, a tip portion 81 having a nozzle is horizontally provided on a main body portion 45. The spraying device 80 having the above configuration may be used. The spraying device 80 may be further provided with elevating means for raising and lowering the same. Thus, for example, when it is desired to form an organic thin film on the inner surface of the cylindrical base material 82, the organic thin film forming solution is formed while the base device 82 is being rotated at a constant speed and the spray device 80 is moved up and down. By spraying, a uniform organic thin film can be formed on the inner surface of the substrate 82. Therefore, the organic thin film forming apparatus according to the present invention has an effect that an organic thin film can be manufactured on a substrate having any shape by a method suitable for industrial production regardless of the shape of the substrate.

[0094]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the contents of the present invention will be specifically described based on embodiments.

(Example 1) First, preparations described below were performed before forming an organic thin film on the surface of a substrate. That is,
As a base material, tempered glass having a size of 5 cm square and 3 mm thickness, a 3-inch silicon wafer, and a surface having irregularities as shown in FIG.
Three types of mm stainless steel substrates were prepared. Each of these substrates was subjected to ultrasonic cleaning using an alkaline surfactant, and then rinsed with pure water.

On the other hand, FS-17 (C
F ₃ (CF ₂ ) ₇ C ₂ H ₄ SiCl ₃ was prepared and dissolved in a silicone solvent (octamethylcyclotetrasiloxane) so as to have a concentration of 1 vol% to prepare a solution for forming an organic thin film.

The apparatus shown in FIG. 6 was used as an organic thin film producing apparatus.
%). The high-pressure gas tank 43 was filled with dry nitrogen gas obtained by evaporating liquid nitrogen. The diameter of the nozzle 50 in the spray gun 41 is about 50 μm,
The spray gun 41 was installed such that the distance from the nozzle 50 to the substrate was about 10 cm. Further, the inside of the spray gun 41 was filled with a solution for forming an organic thin film, and the opening / closing shutter 51 was kept closed.

The production of the organic thin film was performed as follows.
First, an organic thin film made of FS-17 was formed on the surface of the tempered glass. That is, a pressure of about 400 N / cm ² is applied to the organic thin film forming solution filled in the spray gun 41 by the high-pressure gas tank 43, and the opening / closing shutter 5 is opened.
1 was opened for only 10 seconds. Thus, the solution for forming an organic thin film was sprayed onto the tempered glass from the nozzle 50. At this time, the total amount of the sprayed solution for forming an organic thin film was about 4 ml. Further, assuming that a range in which the solution for forming an organic thin film is sprayed from the spray gun 41 onto the tempered glass is a spray region, the spray region is formed in a circular shape having a diameter of about 20 cm.

Subsequently, dry nitrogen was sprayed on the tempered glass using an air gun to remove the organic thin film forming solution remaining on the surface of the tempered glass.

The above operation was similarly performed for a silicon wafer and a stainless steel substrate, and an organic thin film was formed on each substrate surface. The organic thin film formed on each substrate as described above is hereinafter referred to as the organic thin film A of the present invention.

Here, as a result of visually observing the tempered glass, the silicon wafer, and the stainless steel substrate on which the organic thin film made of FS-17 was formed, a uniform organic thin film was formed on the surface of each substrate. It was confirmed that. In particular, it was confirmed that a good organic thin film was formed even on a stainless steel substrate having an uneven surface.

Further, with respect to the method for producing the organic thin film in this example, the coating efficiency was examined for the method. The method for calculating the coating efficiency is as follows.

First, a glass substrate having a size of 30 cm square was prepared, and its weight W ₀ (mg) was measured. Next, immediately after the organic thin film forming solution was sprayed on the glass substrate by a spray gun for 60 seconds, the weight W ₁ (mg) of the glass substrate was measured.
Was measured. Then, a value obtained by subtracting the W ₀ from W _1, the coating amount of the applied solution for forming an organic thin film on a substrate (= W ₁ -
W ₀ (mg)). The spray amount W _s (mg) of the solution for forming an organic thin film actually sprayed from the spray gun
Was determined by measuring the amount of decrease in the organic thin film forming solution present inside the spray gun. The coating efficiency is determined by the ratio of the amount of coating applied to the glass substrate to the amount of spraying ((W
₁₋ W ₀ ) / W _s ) was multiplied by 100 for calculation. As a result of the calculation, the coating efficiency was 85%. That is, considering that the coating efficiency in the conventional spray method is 50%, the coating efficiency was high in the method for producing an organic thin film according to the present invention.

Comparative Example 1 In this comparative example, an organic thin film was formed on the surface of the tempered glass by a dipping method. Specifically, in a dry atmosphere, octamethylcyclotetrasiloxane in which FS-17 was dissolved at 1 vol% was placed in a petri dish having a diameter of 15 cm and a depth of 3 cm, and the tempered glass was immersed therein for 1 hour. Thereafter, the tempered glass was washed with a 300 ml beaker containing octamethylcyclotetrasiloxane to remove unreacted FS-
17 mag was removed. The organic thin film produced as described above is hereinafter referred to as a comparative organic thin film.

[Test] The organic thin film made of FS-17 has a low energy surface because it has a fluorocarbon chain, and can be applied as an antifouling film like a fluorine coat used in a frying pan or the like. Therefore, in this example, a test was performed on the durability and other physical properties of this film as a stain prevention film. Specifically, four characteristics listed below were examined.

(1) Water Repellency The water repellency of the organic thin film to pure water was evaluated by measuring the static contact angle of water at room temperature. In the present embodiment, since CF ₃ groups are present on the film surface side of the organic thin film formed on the base material, if the organic thin film is formed on the base material surface, the water repellency of the base material against pure water is high. Become. In other words, as a result of the measurement of the contact angle, the larger the contact angle with respect to pure water,
It can be estimated that the surface coverage of the organic thin film on the substrate is high,
It can be determined whether the film is useful as an antifouling film. Note that an organic thin film formed on tempered glass was used as a sample used for the measurement.

(2) Antifouling durability The durability of the organic thin film against the antifouling property was evaluated as follows. That is, 0.5 ml of a mixture of sugar and soy sauce mixed at a ratio of 1: 1 (weight ratio) was dropped on tempered glass having an organic thin film formed thereon, and the mixture was baked at 300 ° C. for 20 minutes. Thereafter, the substrate was cooled to room temperature, and then the burned sugar soy sauce was removed with a wet cloth. This operation was repeated several times until the burnt sugar soy sauce could not be removed. Then, the number of removals of the sugar soy sauce was evaluated as an evaluation standard for antifouling durability. Note that an organic thin film formed on tempered glass was used as a sample used for the measurement.

(3) Heat Resistance The heat resistance of the organic thin film was evaluated as follows. That is, the tempered glass on which the organic thin film was formed was heated in an oven and left at 300 ° C. for 100 hours. Next, after cooling to room temperature, the static contact angle of water at room temperature was measured. As a result of this measurement, it can be said that the larger the contact angle after heat resistance, the higher the heat resistance of the organic thin film. Note that an organic thin film formed on tempered glass was used as a sample used for the measurement.

(4) Film Thickness The film thickness, which is a basic characteristic of the thin film, was measured by an ellipsometry method. Note that an organic thin film formed on a silicon wafer was used as a sample used for the measurement.

[Results] The results of the various tests listed above are shown in Table 1 below.

[Table 1]

As can be seen from the results in Table 1, when the organic thin film A of the present invention and the comparative organic thin film were compared, the water repellency and the water repellency were higher.
The antifouling durability, heat resistance, and film thickness were almost the same values. However, in the production of the organic thin film A of the present invention, the workability was significantly improved. In other words, the solution for forming an organic thin film has high reactivity to atmospheric moisture,
Care must be taken in its handling, but if it is not used, the spraying device used in Example 1 can be easily stored by storing it in a storage tank or the like. However, in the immersion method in Comparative Example 1, storage was accompanied by difficulty. Furthermore, while the immersion method required about 1 hour of immersion time, the spray method according to Example 1 required a very short spray time of about 10 seconds, which enabled a dramatic improvement in production efficiency. It was found that industrial productivity could be further improved. The coating efficiency was as high as 85%, and the amount of the organic thin film forming solution used was lower than the amount used in the dipping method in the comparative example. These facts have made it possible to reduce production costs.

Example 2 The method for producing an organic thin film according to Example 2 is different from the method for producing the organic thin film A according to Example 1 in that an organic thin film forming solution is applied to each substrate. (Tempered glass, silicon wafer, stainless steel substrate), after spraying, volatilize the silicone solvent present in the substrate,
Except that these substrates were exposed to an atmosphere at a relative humidity of 60%, they were produced in the same manner as in Example 1 above. The organic thin film according to the second embodiment thus manufactured is hereinafter referred to as an organic thin film B of the present invention.

The surface of each substrate on which the organic thin film B of the present invention was formed was visually observed, and it was confirmed that a uniform organic thin film was formed.

Further, in the same manner as in Example 1, various characteristics and the film thickness of the organic thin film B of the present invention were examined. The results are shown in Table 1 above. As is clear from Table 1, the water repellency, antifouling durability and heat resistance of the organic thin film B of the present invention were all smaller than those of the comparative organic thin film according to Comparative Example 1 formed by the immersion method. It turns out that it is high. Also,
The thickness was larger than that of the comparative organic thin film. Further, it was found that the workability was also good for the same reason as in Example 1.

The water repellency of the organic thin film B of the present invention was high because the organic thin film B was formed by forming a monomolecular film on tempered glass and further forming a polymer layer comprising a siloxane compound on the monomolecular film. It is considered that the unevenness of the film surface is larger than that of a normal monomolecular film due to the configuration, and as a result, the initial contact angle is increased.

Further, the durability of the sugar soy sauce baking was higher than that of the comparative organic thin film, which indicates that the antifouling durability was excellent. It is considered that this is because a region where the film constituent molecules are not adsorbed on the surface of the tempered glass is covered with the polymer composed of the siloxane compound, so that a thin film without pinholes is formed. More specifically, in the comparative organic thin film, dirt such as sugar soy sauce sticks to the portion where the pinholes are present, making it difficult to remove. Therefore, by strongly rubbing this portion with a wet cloth, a large mechanical stress is applied to the film. Therefore, as the number of tests increases, the film is peeled from this portion to cause deterioration (see FIG. 13A). On the other hand, as shown in FIG. 13B, since the organic thin film B of the present invention covers the whole of the tempered glass, the sugar soy sauce adheres only to the film that is easily removed. Therefore, the sugar soy sauce can be removed only by lightly rubbing with a wet cloth, so that there is little mechanical stress on the membrane. Therefore, even if the number of tests is increased, the film is not peeled off and hardly deteriorates.
Therefore, it is considered that the result as shown in Table 1 was obtained.

Further, the contact angle to water after the heat resistance test at 300 ° C. is larger than that of the comparative organic thin film.
This indicates that the heat resistance is excellent. This is for the following reason (see FIG. 14). That is,
When a comparative organic thin film is formed on tempered glass,
When the heat resistance test is performed, Na ⁺ contained in the tempered glass precipitates as shown in FIG. As a result of the Na ⁺ breaking the siloxane bond to desorb the film constituent molecules, the organic thin film is degraded and the water repellency is reduced (FIG. 14B).
reference). On the other hand, in the organic thin film B of the present invention,
Monomolecular film on the glass outermost surface formed by chemisorption, although siloxane bonds are broken in part by Na ^+, since until the polymer layer formed on the monomolecular film Na ⁺ is not diffused, polymer The siloxane bonds in the layer are not destroyed. For this reason, the organic thin film B of the present invention is less likely to be thermally degraded than the comparative organic thin film.

Example 3 The method for producing an organic thin film according to Example 3 is different from the method for producing the organic thin film A in Example 1 in that an organic thin film is prepared under an atmosphere having a relative humidity of about 80%. Example 1 except that the solution was formed by spraying a thin film forming solution.
It was produced in the same manner as described above. Specifically, the first embodiment
The spray device used in the above was installed in a humidity control container (humidity control device), and the relative humidity was controlled to be 80%, and the organic thin film was placed on each substrate (tempered glass, silicon wafer, stainless steel substrate). Formed. Example 3
In the above, the organic thin film forming solution remaining on each substrate was not removed by an air gun or the like. The organic thin film according to the third embodiment thus manufactured is hereinafter referred to as an organic thin film C of the present invention.

As a result of visually observing the surface of each substrate on which the organic thin film C of the present invention was formed, it was confirmed that a uniform organic thin film was formed.

Further, in the same manner as in Example 1, various characteristics and the film thickness of the organic thin film C were examined. The results are shown in Table 1 above. As is clear from Table 1, the water repellency, antifouling durability and heat resistance of the organic thin film C of the present invention are all superior to those of the comparative organic thin film formed by the immersion method. You can see that. Further, the film thickness was larger than that of the comparative organic thin film. Further, it was found that the workability was also good for the same reason as in Example 1.

The organic thin film C of the present invention is excellent in water repellency, antifouling durability and heat resistance for the same reason as described in the second embodiment.

Example 4 The method for producing an organic thin film according to Example 4 differs from the method for producing an organic thin film C according to Example 3 in that an organic thin film forming solution was applied to each substrate. After spraying, it was produced in the same manner as in Example 3 except that dry nitrogen was sprayed on the solution for forming an organic thin film present on each substrate. Example 4 produced in this way
Hereinafter, the organic thin film according to the present invention is referred to as the present organic thin film D.

The surface of the base material on which the organic thin film D of the present invention was formed was visually observed, and it was confirmed that a uniform organic thin film was formed.

Further, in the same manner as in Example 1, various characteristics and the film thickness of the organic thin film D of the present invention were examined. The results are shown in Table 1 above. As is clear from Table 1, the water repellency, antifouling durability and heat resistance of the organic thin film D of the present invention are all higher than those of the comparative organic thin film according to Comparative Example 1 formed by the immersion method. You can see that. further,
It was also found that workability was good for the same reason as in Example 1. The reason why the film thickness is smaller than that of the organic thin film C of the present invention according to Example 3 is that the organic thin film forming solution remaining on the substrate after the spraying of the organic thin film forming solution is removed. I can guess.

Example 5 The method for producing an organic thin film according to Example 5 is different from the method for producing the organic thin film A according to Example 1 of the present invention except for the following points. It was prepared in the same manner as in Example 1. That is, when the solution for forming an organic thin film is sprayed onto a substrate as an object to be coated, the solution is sprayed while moving the spraying device at a speed of 60 cm / s in the longitudinal direction of the substrate, and the organic material according to the present embodiment is sprayed. A thin film was formed.
The size of the tempered glass as a substrate and the stainless steel substrate having irregularities were both 5 cm × 20 cm. If the substrate has a wider area than the spray area, when forming an organic thin film using an apparatus having no moving means,
Mist droplets ejected from nozzles (solution for forming organic thin film)
Adhered to only a part of the substrate, and it was difficult to form a uniform organic thin film over the entire surface of the substrate.
However, as in this embodiment, if the spraying device is sprayed onto the substrate while moving the spraying device in a timely manner using a moving device, the droplets can adhere to the entire substrate and form a uniform organic thin film. It has become possible. The organic thin film produced as described above is hereinafter referred to as an organic thin film E of the present invention.

Further, in the same manner as in Example 1, various characteristics and the film thickness of the organic thin film E were examined. The results are shown in Table 1 above. As is clear from Table 1, the organic thin film E according to Example 5 exhibited almost the same water repellency, antifouling durability and heat resistance as the organic thin film A according to Example 1 above. Therefore, the organic thin film E of the present invention can significantly improve workability and reduce the production cost, as in the case of manufacturing the organic thin film A of the present invention according to the first embodiment. An organic thin film could be formed uniformly. Further, it was found that the workability was also good for the same reason as in Example 1.

Example 6 The method for producing an organic thin film according to Example 6 is different from the method for producing an organic thin film C according to Example 3 of the present invention except for the following points. 3 was produced in the same manner. That is, when the organic thin film forming solution was sprayed on the base material, the organic thin film according to the present example was formed by spraying while moving the spraying device at a speed of 60 cm / s in the longitudinal direction of the base material. The size of the tempered glass as the substrate and the stainless steel substrate having irregularities were both 5 cm × 20 cm. As in the present embodiment, if the spraying device is sprayed onto the substrate while moving the spraying device in a timely manner using a moving device, the droplets can be attached to the entire substrate, and as a result, the entire surface of the substrate can be covered. A uniform organic thin film could be formed. The organic thin film produced as described above is referred to as the present organic thin film F.

Further, in the same manner as in Example 1, various characteristics and the film thickness of the organic thin film F of the present invention were examined.
The results are shown in Table 1 above. As is apparent from Table 1, the organic thin film F of the present invention exhibited almost the same water repellency, antifouling durability and heat resistance as the organic thin film C of the present invention according to Example 3 above. Further, it was found that the workability was also good for the same reason as in Example 1.

Example 7 The method for producing an organic thin film according to Example 7 is different from the method for producing the organic thin film A according to Example 1 in that n-perfluorooctane is used as a non-aqueous solvent. Except for using, was prepared in the same manner as in Example 1. Since n-perfluorooctane hardly dissolves water, when preparing a solution for forming an organic thin film in which 1 vol% of FS-17 is dissolved, there is little danger that water is mixed as an impurity and the handleability is excellent. The organic thin film produced in this example is hereinafter referred to as the present organic thin film G.

Further, in the same manner as in Example 1, various characteristics and the film thickness of the organic thin film G of the present invention were examined. The results are shown in Table 1 above. Thus, it was found that the organic thin film G of the present invention was superior in heat resistance as compared with the comparative organic thin film. Further, similarly to the case where the organic thin film A of the present invention according to the first embodiment is manufactured, workability is remarkably improved, production cost can be reduced, and the organic thin film is formed uniformly over the entire surface of the base material. I was able to.
Further, it was found that the workability was also good for the same reason as in Example 1.

Example 8 The method for producing an organic thin film according to Example 8 is different from the method for producing the organic thin film C according to Example 3 in that n-perfluorooctane is used as a non-aqueous solvent. Was prepared in the same manner as in Example 3 except that was used. Since n-perfluorooctane hardly dissolves water, there is little danger of water being mixed as impurities when preparing a solution for forming an organic thin film in which 1 vol% of FS-17 is dissolved, and it is easy to handle. The organic thin film according to the seventh embodiment manufactured in this manner is hereinafter referred to as the present organic thin film H.

Further, in the same manner as in Example 3, various characteristics and the film thickness of the organic thin film H of the present invention were examined. The results are shown in Table 1 above. As is clear from Table 1, the organic thin film H of the present invention exhibited almost the same water repellency, antifouling durability and heat resistance as the organic thin film C of the present invention according to Example 3 above. Further, similarly to the case where the organic thin film A of the present invention according to the first embodiment is manufactured, workability is remarkably improved, production cost can be reduced, and the organic thin film is formed uniformly over the entire surface of the base material. I was able to. Further, it was found that the workability was also good for the same reason as in Example 1.

[0133]

The present invention is embodied in the form described above, and has the following effects.

That is, according to the method for producing an organic thin film of the present invention, a solution for forming an organic thin film containing a silane compound having a chlorosilyl group is sprayed aerobically into mist-like droplets, and the silane is deposited on the surface of the substrate. Since the organic thin film is formed by adsorbing and fixing the compound, the production cost can be reduced, the production efficiency can be improved, and the organic thin film can be formed with improved workability. .

Further, according to another method for preparing an organic thin film of the present invention, a solution for forming an organic thin film containing a silane compound having a chlorosilyl group is formed into mist-like droplets, and then the droplets are brought into contact with moisture. Since at least a part of the droplet is polymerized to be polymerized and the polymerized droplet is adsorbed and fixed on a substrate to form an organic thin film, the same effect as described above is exerted.

Further, according to the film forming apparatus used in the method for producing an organic thin film of the present invention, the solution for forming an organic thin film containing a silane compound having a chlorosilyl group is formed into droplets and sprayed on the substrate in an airless manner. Since a film is formed by adsorbing and fixing the silane compound on the surface of the base material, an organic thin film having a uniform thickness can be formed with good workability and improved application efficiency. Furthermore, by improving the coating efficiency, it is possible to minimize the amount of liquid necessary for forming an organic thin film having a desired film thickness, thereby reducing the production cost and improving the production efficiency. Can be formed.

Further, according to the organic thin film of the present invention, a monomolecular film in which a group of silane compound molecules is chemically adsorbed to the base material through a siloxane bond and a monomolecular film formed on the monomolecular film, And a polymer layer formed of the union, and the polymer layer covers a region of the substrate on which the silane compound molecules are not chemically adsorbed. Further, according to another organic thin film of the present invention, a mixed film in which a group of silane compound molecules and a siloxane compound polymer are chemically adsorbed to the base material by a siloxane bond, and a mixed film formed on the mixed film, And a polymer layer made of a compound polymer. The polymer layer covers a region on the base material where the silane compound molecule and the siloxane compound polymer are not chemically adsorbed. Therefore, from each of the above configurations,
An effect of being able to provide an organic thin film having excellent antifouling durability and heat resistance and a uniform film thickness is provided.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view for explaining a manufacturing process of an organic thin film according to a first embodiment of the present invention.

FIG. 2 is a schematic sectional view showing a main part of the organic thin film according to the first embodiment.

FIG. 3 is a sectional view showing an organic thin film according to a second embodiment of the present invention.

FIG. 4 is a schematic cross-sectional view for explaining a manufacturing process of an organic thin film according to a third embodiment of the present invention.

FIG. 5 is a schematic sectional view showing a main part of an organic thin film according to the third embodiment.

FIG. 6 is an explanatory diagram schematically showing an organic thin film forming apparatus according to a fourth embodiment of the present invention.

FIG. 7 is a schematic sectional view showing a main part of the organic thin film forming apparatus.

FIG. 8 is a sectional view schematically showing a moving device in the organic thin film forming apparatus.

FIG. 9 is a sectional view schematically showing a removing device in the organic thin film forming apparatus.

FIG. 10 is a cross-sectional view schematically showing a spraying device and a chamber in the organic thin film forming apparatus.

FIG. 11 is a perspective view showing another organic thin film forming apparatus according to the fourth embodiment.

FIG. 12 is a perspective view showing a surface state of a stainless steel base material used in the example of the present invention.

13 is an explanatory view showing a state in which dirt is attached to an organic thin film formed on a tempered glass. FIG. 13 (a) shows a case of a comparative organic thin film, and FIG. 13 (b) shows the present invention. The case of an organic thin film is shown.

FIG. 14 is an explanatory view showing how a comparative organic thin film formed on a tempered glass is deteriorated by a heat resistance test. FIG. 14 (a) shows a state in which Na ⁺ is precipitated by heating, and FIG. (B) shows how the constituent molecules of the comparative organic thin film are desorbed.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 11 Silane compound molecule 12, 82 Base material 13 Adsorbed water 14 Silanol compound molecule 15 Monomolecular film 16 Polymer layer 21 Droplet 22 Polymerizable droplet 23 Mixed film 24 Polymer layer 41, 80 Spray gun (spray device) 42 Adjustment Valve 43 High-pressure gas tank (pressure generating device) 44 Pulse controller 45 Main body 46 Tip 47 Air flow passage 50, 81 Nozzle (pore) 51 Opening / closing shutter 52 Organic thin film forming solution 53 Pressurizing air 54 Liquid film 55 Droplet 60 Moving device 61 Belt 62 Pulley 63 Pulse motor 64 Control means 71 Air gun device 72 Humidity control container (outside air blocking means)

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4D075 AA02 AA76 BB24Z BB57Z BB60Z BB79Z BB93Z CA02 CA18 DA06 DC13 DC19 EA05 EB42 EC08 EC30 4F033 QA01 QB02Y QB03X QB16Y QB18 QD02 QD03 QD02 QF02B

Claims (13)

[Claims] 1. A silane compound having a chlorosilyl group,
And applying a pressure to the solution for forming an organic thin film containing a nonaqueous solvent and a non-aqueous solvent. An adsorption step of adsorbing and fixing a group of silane compound molecules on the surface of the base material by contacting the base material, and a non-aqueous solvent removal step of volatilizing and removing the non-aqueous solvent remaining on the base material surface Exposing the substrate to an atmosphere containing moisture. 2. The method according to claim 1, wherein a step of volatilizing and removing the non-aqueous solvent remaining on the surface of the base material in an atmosphere containing moisture is performed in place of the non-aqueous solvent removing step and the exposing step. Item 2. The method for producing an organic thin film according to Item 1. 3. A removing step of removing the non-aqueous solvent and the silane compound not chemically bonded to the substrate by blowing a dry gas on the substrate instead of the non-aqueous solvent removing step. Claim 1 characterized by the following:
3. The method for producing an organic thin film according to item 1. 4. A silane compound having a chlorosilyl group,
And forming the organic thin film forming solution containing the non-aqueous solvent into a mist-like liquid droplet, and contacting the mist-like liquid organic thin film forming solution with moisture to form a droplet. Polymerizing at least a portion of the polymerizable polymer to form polymerizable droplets comprising a silane compound and a siloxane compound polymer; and contacting the polymerizable droplets with a substrate to form a silane compound molecule on the surface of the substrate. An organic thin film, comprising: an adsorption step of adsorbing and fixing the aggregate group and the siloxane compound polymer; and a non-aqueous solvent removal step of volatilizing and removing the non-aqueous solvent remaining on the substrate surface. Method. 5. Instead of the non-aqueous solvent removing step, by blowing a dry gas onto the substrate, the silane compound and the siloxane compound polymer not chemically bonded to the substrate are mixed with the non-aqueous solvent. The method for producing an organic thin film according to claim 4, further comprising a removing step of removing. 6. The method according to claim 4, wherein the droplet forming step is a step of applying pressure to the organic thin film forming solution and spraying airlessly from fine pores to form mist-like droplets.
Or the method for producing an organic thin film according to claim 5. 7. The pores have a diameter of 10 μm or more and 100 μm or more.
μm or less, and the pressure applied to the organic thin film forming solution is 100 N / cm ² or more and 1000 N /
cm ² or less.
The method for producing an organic thin film according to claim 3. 8. The method according to claim 1, wherein an average particle diameter of the droplet is in a range from more than 0 μm to 100 μm or less. Method. 9. An apparatus for forming an organic thin film used in the method of manufacturing an organic thin film according to claim 1, wherein a body for storing the organic thin film forming solution is provided. A pressure generator for applying pressure to the organic thin film forming solution, and a spray device having at least one pore for injecting the organic thin film forming solution pressurized by the pressure generator. Characteristic organic thin film forming equipment. 10. The organic thin film forming solution is formed into droplets by the spray device and sprayed on the substrate, and then dried gas is sprayed on the substrate to remain on the substrate surface without being adsorbed. 10. The apparatus for forming an organic thin film according to claim 9, further comprising a removing device for removing the silane compound and the non-aqueous solvent. 11. The apparatus for forming an organic thin film further includes an outside air shielding unit in which the spraying device and the removing unit can be installed, and a humidity control device for controlling the inside of the outside air shielding unit to a predetermined humidity. The organic thin film forming apparatus according to claim 9 or 10, wherein: 12. An organic thin film formed on a surface of a base material, wherein the organic thin film is a monomolecular film in which a group of silane compound molecules is chemically adsorbed to the base material by a siloxane bond; A thin film formed on the film and comprising a polymer layer made of a siloxane compound polymer, wherein the polymer layer covers a region on the substrate on which the silane compound molecules are not chemically adsorbed. An organic thin film, characterized in that: 13. An organic thin film formed on a surface of a base material, wherein the organic thin film is a mixed film in which a group of silane compound molecules and a siloxane compound polymer are chemically adsorbed to the base material by a siloxane bond. A thin film formed on the mixed film and comprising a polymer layer made of a siloxane compound polymer. The polymer layer is formed by chemically adsorbing the silane compound molecule and the siloxane compound polymer on the base material. An organic thin film characterized by covering an unexposed area.