JP2500150B2 - Water / oil repellent coating film and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a water / oil repellent fluorocarbon coating film for use in electric appliances, automobiles, industrial equipment and the like which require water / oil repellency.

[0002]

2. Description of the Related Art Ultra-thin coatings having heat resistance, weather resistance and abrasion resistance are required for electric appliances, automobiles, industrial equipment, mirrors, spectacle lenses and the like.

Conventionally, a widely used method for producing a coating film for water and oil repellency is generally to roughen the surface of an Al substrate or the like by blasting it, roughening it with a wire brush or chemical etching, etc. After treatment and application of a primer, etc., a fluorocarbon-based fine powder of polytetrafluoroethylene or the like is suspended in ethanol or the like, and a paint such as fluorine enamel is applied and dried, followed by baking at about 400 ° C. for about 1 hour ( A method of baking a fluorocarbon-based polymer on the surface of the substrate has been used.

[0004]

However, while this method is easy to manufacture, since the polymer and the substrate are merely bonded only by the anchor effect, the adhesiveness to the substrate is limited, and Since the surface of the coating film was baked at a high temperature of 400 ° C., the surface was flattened and a good water / oil repellent surface could not be obtained. Therefore, it is not sufficient as a method for producing appliances such as electric appliances, automobiles, and industrial equipment that require a water- and oil-repellent coating film.

In order to solve the above-mentioned problems of the prior art, the present invention contains fluorine, which has good adhesion to a substrate, has no pinholes, has small irregularities on the order of microns, and has excellent water / oil repellency and durability. The purpose is to provide a coating film for

[0006]

In order to achieve the above object, the water / oil repellent coating film of the present invention forms a polysiloxane thin film or a siloxane chemisorption monomolecular film on the surface of a substrate, on which a fluorocarbon group and a It has a structure in which a roughened thin film composed of a coating film in which a polymer containing a siloxane group and hydrophilic particles are mixed is chemically bonded by a siloxane bond.

Next, in the method for producing a water / oil repellent coating film of the present invention, the surface of a substrate having a hydroxyl group on the surface is brought into contact with a non-aqueous solvent in which a substance having a chlorosilyl group is mixed to form a hydroxyl group on the surface of the substrate. reaction of the chlorosilyl group
And chemically adsorbing the substance on the surface of the substrate,
Fluorocarbon group and chlorosilyl group or alkoxy
A material containing a silyl group, the surface of a mixture of hydrophilic fine particles
It has a configuration including a step of applying a non-aqueous solvent on the surface of the substrate and a step of heating and baking the substrate .

[0008] In the above configuration, as the substrate, it is preferable to use a metal or ceramic.

[0009] In the above configuration, as the substrate, it is preferable to use a hydrophilized plastics treated beforehand surface in a plasma atmosphere containing oxygen.

Further, in the above constitution, a chlorosilyl group
Is a substance having SiCl ₄ , SiHCl ₃ , SiH ₂
Cl ₂ or _{Cl- (SiCl 2 O) n -SiCl} 3,
It is preferably at least one selected from (n is an integer).

[0011] In addition the configuration, as a substance containing a fluorocarbon group and a Kuroroshi Lil group, CF ₃ - (C
_{F 2) n -R-SiX p} Cl 3-p (n is 0 or an integer,
R is an alkylene group, an ethylene group, an acetylene group (ethynyl
Same as the len group) , or a substituent containing silicon or an oxygen atom, X is H or a substituent selected from an alkyl group, a cycloalkyl group, an allyl group, and derivatives thereof, and p is 0 or 1 or 2). It is preferable.

[0012] In the above configuration, as the material containing a fluorocarbon group and alkoxysilyl Lil group, CF ₃ -
_{(CF 2) n -R-SiY} q (OA) 3-q (n is 0 or an integer, R represents an alkylene group, an ethylene group, an acetylene group
(Ethynylene group) or a substituent containing silicon or an oxygen atom, Y is a substituent selected from a hydrogen atom or an alkyl group, a cycloalkyl group, an allyl group, and derivatives thereof, OA is an alkoxy group (where A is H It is preferable to use 0 or 1 or 2) as an alkyl group) or q.

[0013] In the above configuration, the non-aqueous solvent obtained by mixing a substance having a fluorocarbon group and Kuroroshi Lil groups, SiX _s Cl as a crosslinking agent for said substance
_4-s (X is a substituent H or an alkyl group, s is 0 or 1 or 2) is preferably added.

[0014] In the above configuration, in a solvent obtained by mixing a substance having a fluorocarbon group and alkoxysilyl Lil _{groups, SiY t (OA) 4-} t (Y substituent of the alkyl group as a crosslinking agent, OA represents an alkoxy group , (However, A is H
Or alkyl group) t is 0 or 1 or 2) is added
That it is preferable.

In the above construction, it is preferable to use metal or ceramic as the fine particles having a hydrophilic surface.

Further, in the above constitution, hydroxyl groups are formed on the surface.
Mix the surface of the substrate with a substance containing a chlorosilyl group.
Contact the combined non-aqueous solvent to form hydroxyl and chlorosilyl groups.
Is reacted, a step of depositing said material on said substrate surface, a non-aqueous organic solvent a substance having an extra said <br/> chlorosilyl groups remaining Ru on the substrate was washed away using a chlorosilyl on said substrate forming a chemically adsorbed monomolecular film of a material having a group, fluorocarbon group and Kuroroshi Li
Surface containing a substance containing a hydroxyl group or an alkoxysilyl group
A non-aqueous solvent mixed with aqueous fine particles is deposited on the substrate surface.
It is preferable to include a step of heating and a step of heating and baking the substrate .

[0017]

SUMMARY OF] According to the present invention, a polymer material is formed by polymerizing containing fluorocarbon groups and Kuroroshi lil group via a polysiloxane film, or a siloxane chemically adsorbed monomolecular film on the substrate surface, the surface hydrophilicity of the fine particles Mixed coating or fluorocarbon group and siloxane group (Si-O-
The uneven thin film consisting of a coating film in which a polymer containing a base) and fine particles whose surface is hydrophilic is chemically bonded to the surface of the substrate, so that it adheres well to the substrate, has no pinholes, and has a micron-order surface. It is possible to obtain a fluorine-containing coating film that has small irregularities and is excellent in water and oil repellency and durability.

Further, according to the method of the present invention, a substrate containing a hydroxyl group on the surface is used and a non-aqueous solvent mixed with a substance containing a plurality of chlorosilyl groups is applied to the substrate, and a plurality of hydroxyl groups and chlorosilyl groups on the surface of the substrate are applied. By reacting the chlorosilyl group of the substance containing the substance, a thin film having a large number of SiOH bonds on the surface of the substrate can be formed on the substrate. Then further solvent nonaqueous substance and a surface including a fluorocarbon group and a Kuroroshi Lil groups mixed with hydrophilic particles, or a solvent material and the surface is mixed with hydrophilic microparticles comprising fluorocarbon groups and alkoxysilyl lil group coated, substrate with the Kuroroshi Lil groups and alkoxysilyl Lil group interconversion or said Kuroroshi Lil groups and alkoxysilyl Lil groups before step by performing the heat baking (heat treatment or curing) in an atmosphere comprising a substrate various Tomo water A thin film having a large number of SiOH bonds formed on the surface of a substrate is a fluorocarbon-based coating film made of a polymer having a fluorocarbon group, which undergoes dehydrochlorination or dealcoholization reaction with a SiOH group of a thin film having a large number of SiOH bonds formed on the surface. Is chemically bonded to SiO2 via a SiO bond. The fluorocarbon-based coating film produced here can be produced in a form in which the surface incorporates hydrophilic fine particles.

On the other hand, in the step of applying a non-aqueous solvent mixed with a substance containing a plurality of chlorosilyl groups, a non-aqueous solvent mixed with a substance containing a plurality of chlorosilyl groups is applied, and the hydroxyl groups on the surface of the substrate and After reacting the chlorosilyl group of the substance containing a plurality of chlorosilyl groups, the substance containing a plurality of unreacted excess chlorosilyl groups remaining on the substrate is further removed by washing with a non-aqueous organic solvent, and further washed with water, A polysiloxane-based chemisorption monomolecular film containing a plurality of silanol groups (—SiOH) can be formed on the substrate.

In this method, the Si formed on the surface of the substrate is
OH bond is connected to the base body without fail through a siloxane bond, the non-aqueous solvent that material and the surface mixed with hydrophilic particles on the monomolecular film having SiOH bonds containing fluorocarbon groups and Kuroroshi Lil group or, the solvent material and the surface mixed with hydrophilic microparticles comprising fluorocarbon groups and alkoxysilyl drill group applying said to perform the heating baking in an atmosphere comprising a substrate various Tomo water Kuroroshi Li
Le group and alkoxysilyl Lil group interconversion or said Kuroroshi Li
And OH groups of the polysiloxane-based monomolecular film having numerous SiOH bonds formed on the substrate surface in Le group and alkoxysilyl Lil groups before step occurs dehydrochlorination or dealcoholization,
A polymer having a fluorocarbon group is chemically bonded to the substrate via a SiO bond.

Therefore, it is possible to prepare a fluorocarbon-based coating film in which the adhesion is extremely excellent and the surface incorporates hydrophilic fine particles. At this time, if the thickness of the fluorocarbon-based coating film is made thinner than the diameter of the fine particles whose surface is hydrophilic, naturally the surface becomes uneven due to the hydrophilic fine particles, and at this time, the surface becomes hydrophilic. Since the surface of the fine particles is covered with a fluorocarbon coating film as well as the surface of the substrate, a fluorocarbon coating film having arbitrary irregularities on the surface having extremely excellent water and oil repellency can be prepared.

At this time, the roughness of the surface irregularities can be controlled by the diameter and the amount of the fine particles to be added. Further, as the substrate containing a hydroxyl group on the surface, a metal or ceramic covered with a natural oxide film can be used. However, if the substance does not have an oxide film, such as plastic, a plasma atmosphere containing oxygen on the surface in advance is used. It may be treated with to make it hydrophilic.

Further, as the fine particles having a hydroxyl group on the surface, metal, ceramic, glass, etc. covered with a natural oxide film can be used. May be treated with a plasma atmosphere containing oxygen to make it hydrophilic.

[0024]

The present invention will be described more specifically with reference to the following examples.

The substance containing a plurality of chlorosilyl groups used in the present invention includes SiCl ₄ , SiHCl ₃ , and S.
_{iH 2 Cl 2, Cl- (SiCl} 2 O) n -SiCl 3
(N is an integer) It is possible to use such as the material containing a fluorocarbon group and a Kuroroshi Lil groups, CF <sub>3
- (CF 2) n -R-</sub> SiX p Cl 3- p (n is 0 or an integer, R represents an alkylene group, an ethylene group, an acetylene group
(Ethynylene group) or a substituent containing Si or an oxygen atom,
X is a substituent such as H or an alkyl group, p is 0 or 1 or 2), further fluorocarbon groups and alkoxysilane Li
The material containing Le _{group, CF 3 - (CF 2)} n -R-
SiY _q (OA) _3-q (n is 0 or an integer, R is an alkyl
Ren group, ethylene group, acetylene group (ethynylene group) or a substituent containing Si or an oxygen atom, Y is a substituent such as H or an alkyl group, OA is an alkoxy group (where A is H or an alkyl group), q is It is possible to use 0 or 1 or 2).

Furthermore, in order to adjust the hardness of the formed fluorocarbon-based coating film, in the case of the non-aqueous solvent obtained by mixing a substance containing a fluorocarbon group and a Kuroroshi Lil groups, SiX _s Cl as a crosslinking agent for said substance
_4-s (X is a substituent such as H or an alkyl group, s is 0 or 1 or 2) used by adding, in the case of solvents mixed with material containing fluorocarbon groups and alkoxysilyl Lil groups, as crosslinking agent SiY _t (OA) _{4 -t} (Y is a substituent such as an alkyl group, OA is an alkoxy group, where A is H or an alkyl group) t is 0 or 1 or 2 and is a fluorocarbon The three-dimensional crosslink density in the system coating film can be adjusted, and the hardness of the fluorocarbon coating film having any irregularities on the surface can be controlled.

A description will be given below with reference to FIGS. 1 and 20.
In the examples,% means% by weight unless otherwise specified.

Example 1 As shown in FIG. 1, a hydrophilic substrate 1 {ceramics such as glass, a metal such as Al or Cu, a plastic substrate having a hydrophilic surface (a substance having no oxide film on the surface such as plastic) In that case, the surface may be treated in advance in a plasma atmosphere containing oxygen, for example, at 100 W for 20 minutes to make it hydrophilic, that is, to introduce hydroxyl groups into the surface.)} And prepare a plurality of chlorosilyl groups. A substance (eg, SiCl ₄ , or SiHCl ₃ , SiH ₂ Cl ₂ , Cl- (SiCl ₂
O) _n -SiCl _{3 (n} is an integer). In particular, Cl- (Si
If Cl ₂ O) _n -SiCl ₃ is used, a non-aqueous solvent (for example, 1 weight percent dissolved in a chloroform solvent) mixed with a surface is rendered effective.

For example, when Cl- (SiCl ₂ O) ₂ -SiCl ₃ is used as the substance containing a plurality of trichlorosilyl groups, a hydrophilic OH group is formed on the surface of the substrate 1 and the dehydrochlorination reaction occurs on the surface. Occurs, and the molecule is fixed to the surface of the substrate through the —SiO— bond as shown in (Chemical formula 1) below.

[0030]

Embedded image After that, when dried in an atmosphere containing water, the Cl group that has not reacted with the substrate reacts with water and undergoes a dehydrochlorination reaction, so that the coating film 2 made of polysiloxane as shown in FIG. 2 is formed. The coating film formed at this time was --Si at the substrate interface.
It is difficult to peel off because it is bonded via the O- chemical bond. Further, here, the coating film of polysiloxane has SiO 2 on the surface.
Has many H bonds.

[0031] Thus addition, nonaqueous solvent mixed with microparticles comprising hydrophilic OH groups on the material and the surface including a fluorocarbon group and a black <br/> rosiglitazone Lil group (e.g., CF ₃ - (C
_{F 2) n -R-SiX p} Cl 3-p (n is 0 or an integer,
R is an alkylene group, an ethylene group, an acetylene group (ethynyl
Ren group) or a substituent containing Si or an oxygen atom, X is a substituent such as H or an alkyl group, and p is 0 or 1 or 2).
90% normal hexadecane at a concentration of a few percent,
Chloroform dissolved in a solvent of 10%) is applied (FIG. 3), and baking is performed at 200 ° C. for about 30 minutes in an atmosphere containing water. Then, since the -OH group is exposed on the surface of the polysiloxane coating and the fine particles having a hydrophilic surface, the chlorosilyl group and -OH group of the chlorosilane-based surfactant containing fluorine undergoes a dehydrochlorination reaction to the surface. …
A bond of Si (O-) ₃ is generated, and the siloxane fluorocarbon-based polymer film 3 containing fluorine is formed in a state of being chemically bonded to the lower polysiloxane coating film and the fine particles (FIG. 4).

For example, CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si
Cl ₃ 1% and silica fine particles 4 containing hydrophilic OH groups on the surface having a diameter of 0.5 to 50 μm (more preferably 1 to 10 μm) were dissolved at a concentration of about 10% 80
% N-hexadecane, 12% carbon tetrachloride, 8% chloroform solution was prepared and applied to the surface of the substrate on which the polysiloxane coating film having a large number of SiOH bonds was formed, and the temperature was 200 ° C. in an atmosphere containing water. After baking for about 30 minutes, CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (O
−) ₃ bonds were generated, and a fluorocarbon-based coating film having a thickness of 1 to 5 μm (μm) having an unevenness of 0.5 to 50 μm (more preferably 1 to 10 μm) was manufactured (FIG. 5). . It should be noted that this coating film did not peel off at all even after the goth test.

[0033] At this time, fluorocarbon groups and black <br/> as a crosslinking agent for said material in a non-aqueous solvent obtained by mixing a substance containing a Russian Lil group SiX _s Cl _4-s (X is H or an alkyl group such as Of the substituent, s is 0 or 1 or 2) (for example, SiCl ₄ is 3% by weight), the bond of CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (O-) ₃ is ... ... Si (O-) are three-dimensionally crosslinked via the binding of _3, could be produced approximately twice the fluorocarbon-based coating film hardness compared with the case without the addition of SiCl _4.

By the way, the wetting angle of water of the fluorocarbon coating film having the irregularities of about 10 microns formed on the surface is about 140 to 15
It was 0 degrees.

On the other hand, as shown in FIG. 6, the hydrophilic substrate 1
When (FIG. 6) is immersed for about 1 hour in a non-aqueous solvent mixed with a substance containing a plurality of trichlorosilyl groups, for example, a solution of 1% by weight in a chloroform solvent, hydrophilic OH groups are present on the surface of the substrate 1. Therefore, a dehydrochlorination reaction occurs on the surface, and molecules are adsorbed and fixed as shown in (Chemical formula 2) below.

[0036]

Embedded image After that, when washed with a non-aqueous solvent such as chloroform and further washed with water, Cl- (Si not reacting with the substrate is
Cl ₂ O) ₂ -SiCl ₃ molecules are removed, and a chemisorption monomolecular film 5 of polysiloxane such as (Chemical Formula ₃ ) and (Chemical Formula 4) shown below is obtained on the substrate surface (FIG. 7).

[0037]

Embedded image

[0038]

Embedded image The monomolecular film 5 formed at this time is different from the substrate in -SiO-.
Since it is completely bonded through the chemical bond of, it does not come off. The obtained monomolecular film has SiOH on the surface.
Has many bonds.

[0039] Thus addition, the non-aqueous solvent that material and the surface mixed with hydrophilic microparticles comprising fluorocarbon groups and black <br/> rosiglitazone Lil groups, _{e.g., CF 3 (CF 2) 7} (CH 2)
The ₂ SiCl ₃ and 1%, 80% n diameter dissolved at a concentration of the silica fine particles 4 to about 10% comprising a hydrophilic OH groups on the surface of 0.5 to 50 microns (more preferably 1 to 10 microns) -Hexadecane, 12% carbon tetrachloride, 8
% Chloroform solution is prepared and applied on the surface of the substrate on which a monomolecular film having many SiOH bonds is formed.
Baking is performed at 200 ° C. for about 30 minutes in an atmosphere containing water. Thereby, CF ₃ (CF ₂ ) ₇ (CH ₂ )
A bond of ₂ Si (O-) ₃ is generated (FIG. 8), and 0.5 to
The fluorocarbon-based coating film 6 containing fine particles having a thickness of 1 to 20 μm and having irregularities of 50 μm (more preferably 1 to 10 μm) could be formed in a state of being chemically bonded to the lower polysiloxane monomolecular film (FIG. 9). ). It should be noted that this coating film did not peel off at all even after the goth test.

[0040] At this time, if had been 15% by weight of SiCl ₄ as a crosslinking agent for the material in the non-aqueous solvent obtained by mixing a substance containing a fluorocarbon group and a black <br/> rosiglitazone Lil groups, about 5 A fluorocarbon coating film having double the hardness could be manufactured.

Further, using a nonaqueous solvent mixed with material containing the same when performing coating, fluorocarbon polymers fluorocarbon group and Kuroroshi Lil groups was further added 20% dispersion microparticles (polytetrafluoroethylene) However, it was possible to manufacture a fluorocarbon-based coating film having unevenness on the surface, which was extremely excellent in adhesiveness as compared with the conventional one.

Furthermore, in the above embodiment, CF ₃ CH ₂ O (CH ₂ ) ₁₅ was used as the fluorocarbon surfactant.
SiCl ₃ and CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ S
iCl ₃ was used, but if an ethylene group or acetylene group (ethynylene group) is added to or incorporated in the alkyl chain part, it can be crosslinked by electron beam irradiation of about 5 megarads after forming the coating film, so hardness of about 10 times more The coating film of is also easily obtained.

In addition to the above fluorocarbon surfactants, CF ₃ (CH ₂ ) ₂ Si (CH ₃ )
₂ (CH ₂ ) ₁₅ SiCl ₃ , CF ₃ (CF ₂ ) ₃ (CH
₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ SiCl ₃ , CF
₃ COO (CH ₂ ) ₁₅ SiCl ₃ etc. were available.

Example 2 For example, as shown in FIG. 11, a hydrophilic substrate 11 is mixed with a substance containing a plurality of trichlorosilyl groups as in FIG. 1, and a non-aqueous solvent (for example, 1% by weight dissolved in a chloroform solvent) is used. ) And pull up.

For example, when Cl- (SiCl ₂ O) ₂ -SiCl ₃ is used as the substance containing a plurality of trichlorosilyl groups, the surface of the substrate 11 has hydrophilic OH groups, so that the dehydrochlorination reaction occurs on the surface. As a result, the molecule is fixed to the substrate via the —SiO— bond as shown in (Chemical Formula 5) below.

[0046]

Embedded image After that, when dried in an atmosphere containing water, the Cl group that has not reacted with the substrate reacts with water to perform a dehydrochlorination reaction, so that the coating film 1 made of polysiloxane as shown in FIG.
2 is formed. In addition, since the coating film formed at this time is bonded via the -SiO- chemical bond at the substrate interface, it is difficult to peel off. The formed polysiloxane coating film has many SiOH bonds on its surface.

[0047] Thus further alcohol solvent to material and surface including a fluorocarbon group and alkoxysilyl Lil groups mixed with microparticles comprising hydrophilic OH groups (e.g., CF ₃ -
_{(CF 2) n -R-SiY} q (OA) 3-q (n is 0 or an integer, R represents an alkylene group, an ethylene group, an acetylene group
(Ethynylene group) or a substituent containing Si or an oxygen atom, Y is a substituent such as H or an alkyl group, OA is an alkoxy group (where A is H or an alkyl group), and q is 0.
Alternatively, 1 or 2) is applied in methanol at a concentration of several percent) (FIG. 13) and baked at 200 ° C. for about 30 minutes to form a polysiloxane coating and fine particles whose surface is hydrophilic- Since the OH group is exposed, the alkoxy group of the fluorine-containing alkoxysilane-based surfactant and the -OH group undergo a dealcohol reaction to cause the surface ...
A bond of Si (O-) ₃ is generated, and a siloxane fluorocarbon-based polymer film 13 containing fluorine is formed in a state of being chemically bonded to the lower polysiloxane coating film 12 and the fine particles (FIG. 14).

For example, CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si
(OCH ₃ ) ₃ 1% and an ethanol solution in which silica fine particles 14 having a hydrophilic OH group and having a diameter of 0.5 to 50 μm (more preferably 1 to 10 μm) are dissolved at a concentration of about 10%. And adjust SiOH on the surface.
When it is applied to the surface of a substrate on which a polysiloxane coating film having many bonds is formed and baked at 200 ° C. for about 30 minutes, CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (O-) ₃ bonds are generated. , A fluorocarbon-based coating film having a thickness of 1 to 5 μm and a roughness of 0.5 to 50 μm (more preferably 1 to 10 μm) was produced (FIG. 1).
5). It should be noted that this coating film did not peel off at all even after the goth test.

[0049] At this time, substituents such _{SiY t (OA) 4-t} (Y is an alkyl group as a crosslinking agent for the material in the solvent obtained by mixing a substance containing a fluorocarbon group and alkoxysilyl Lil group, OA is alkoxy If a group (where A is H or an alkyl group) and t is 0, 1 or 2 is added (for example, Si (OCH ₃ ) ₄ is 5 weight percent), CF ₃ CH ₂ O (CH ₂ ) is added. The bond of ₁₅ Si (O-) ₃ is three-dimensionally cross-linked through the bond of Si (O-) ₃ and is about twice as large as that in the case where Si (OCH ₃ ) ₄ is not added. It was possible to manufacture a fluorocarbon coating film having a hardness of.

By the way, the wetting angle of the fluorocarbon-based coating film thus formed, which has irregularities of about 10 microns, to water is about 135 to 14
It was 0 degrees.

Further, the hydrophilic substrate 11 (FIG. 16) is dipped in a non-aqueous solvent (for example, 1% by weight dissolved in a chloroform solvent) mixed with a substance containing a plurality of trichlorosilyl groups for about 1 hour.

For example, when Cl- (SiCl ₂ O) ₂ -SiCl ₃ is used as the substance containing a plurality of trichlorosilyl groups, the surface of the substrate 11 has a hydrophilic OH group and a dehydrochlorination reaction occurs on the surface. Molecules are adsorbed and fixed as shown in (Chemical Formula 6) below.

[0053]

[Chemical 6] After that, when washed with a non-aqueous solvent such as chloroform and further washed with water, Cl- (Si not reacting with the substrate is
Cl ₂ O) ₂ —SiCl ₃ molecules are removed, and a polysiloxane monomolecular film 15 of (Chemical formula 7), (Chemical formula 8) shown below is obtained on the surface of the substrate (FIG. 17).

[0054]

[Chemical 7]

[0055]

Embedded image In addition, the monomolecular film 15 formed at this time is made of -SiO
Since it is completely bonded through the chemical bond of-, it never peels off. The obtained monomolecular film has S on the surface.
Has many iOH bonds.

[0056] Thus further solvent material and the surface containing fluorocarbon groups and alkoxysilyl Lil groups mixed with hydrophilic particles, such as _{CF 3 (CF 2) 7 (} CH 2) 2 Si
1% of (OC ₂ H ₅ ) ₃ and 0.5 to 50 μm (more preferably 1 to 10 μm) in diameter of the silica fine particles 14 containing hydrophilic OH groups are dissolved at a concentration of about 10%. Prepared methanol solution, and
When it is applied to the surface of a substrate on which a monomolecular film having a large number of H bonds is formed (FIG. 18) and baked at 200 ° C. for about 30 minutes, CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (O−) ₃ Bonds were generated, and a fluorocarbon-based coating film 16 having a thickness of 1 to 10 μm and having irregularities of 0.5 to 50 μm (more preferably 1 to 10 μm) was formed (FIGS. 19 to 20). Since this coating film 16 was formed in a state of being chemically bonded to the lower polysiloxane monomolecular film, it did not peel off at all even after the go-th test. At this time, again, the fluorocarbon group and the alkoxy group are
When 10% by weight of Si (OC ₃ H ₇ ) ₄ was added as a cross-linking agent for a substance containing a rilyl group, a fluorocarbon coating film having about 4 times the hardness could be produced. .

When a similar coating is performed,
In case of performing with a nonaqueous solvent mixed with material containing a fluorocarbon-based polymer further 20% dispersion the added fluorocarbon group and alkoxysilyl Lil based fine particles (polytetrafluoroethylene), hardness becomes conventional parallel However, it was possible to manufacture a fluorocarbon-based coating film having extremely excellent adhesion as compared with the conventional one.

Furthermore, in the above embodiment, CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃ , CF is used as a reagent.
₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ was used, but ethylene group or acetylene group was added to the alkyl chain portion.
If a (ethynyl group) is added or incorporated, the coating can be crosslinked by electron beam irradiation at about 5 megarads after the coating is formed, so that a coating having a hardness of about 10 times can be easily obtained.

In addition to the above fluorocarbon surfactants, CF ₃ (CH ₂ ) ₂ Si (CH ₃ )
_{2 (CH 2) 15 Si (} OCH 3) 3, CF 3 (CF 2)
₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (O
CH ₃ ) ₃ , CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H
₅ ) _3rd grade is available.

According to the above examples, the surface of the substrate is treated with a compound having a chlorosilyl group to form a polysiloxane film. As a compound having a fluorocarbon group and a siloxane group thereon, for example, a surfactant such as a trichlorosilane compound or a trialkoxysilane compound is used, and a thin film chemically bonded to the surface of the substrate by reacting with the -OH group on the surface. To form. At this time, hydrophilic fine particles are present in order to enhance adhesion. This makes it possible to obtain a coating film containing fluorine, which has good adhesion to the substrate and is excellent in water and oil repellency and durability.

[0061]

As described above, according to the method of the invention of the present application, the hydrophilic substrate having a water-repellent and oil-repellent film on the surface 1 to 1 is excellent.
It is possible to form a fluorocarbon-based coating film having unevenness of 0 micron in a state where it is chemically bonded to a substrate with high density without pinholes, with a uniform thickness and very thin. Therefore, a high-performance fluorocarbon coating film having extremely high durability can be obtained.

[Brief description of drawings]

FIG. 1 is an enlarged conceptual view of a substrate at a molecular level before a processing step according to a first embodiment of the present invention.

FIG. 2 is an enlarged conceptual diagram at a molecular level during a processing step of the first embodiment of the present invention.

FIG. 3 is an enlarged conceptual view at a molecular level during a processing step of the first embodiment of the present invention.

FIG. 4 is an enlarged conceptual diagram at the molecular level after the processing steps of the first embodiment of the present invention.

FIG. 5 is an enlarged conceptual diagram of a water / oil repellent film obtained according to the first embodiment of the present invention.

FIG. 6 is an enlarged conceptual diagram of the molecular level of the substrate before the processing step showing the first embodiment of the present invention.

FIG. 7 is an enlarged conceptual diagram at a molecular level during a processing step of the first embodiment of the present invention.

FIG. 8 is an enlarged conceptual diagram at a molecular level during a processing step of the first embodiment of the present invention.

FIG. 9 is an enlarged conceptual view at the molecular level after the processing steps of the first embodiment of the present invention.

FIG. 10 is an enlarged conceptual view of a water / oil repellent film obtained according to the first embodiment of the present invention.

FIG. 11 is an enlarged conceptual view of the substrate at the molecular level before the processing step of the second embodiment of the present invention.

FIG. 12 is an enlarged conceptual view of the molecular level during the processing steps of the second embodiment of the present invention.

FIG. 13 is an enlarged conceptual view at the molecular level during the processing steps of the second embodiment of the present invention.

FIG. 14 is an enlarged conceptual view at the molecular level after the processing steps of the second embodiment of the present invention.

FIG. 15 is an enlarged conceptual view of a water / oil repellent film obtained according to the second embodiment of the present invention.

FIG. 16 is an enlarged conceptual diagram of the molecular level of the substrate before the processing step showing the second embodiment of the present invention.

FIG. 17 is an enlarged conceptual view of the molecular level during the processing steps of the second embodiment of the present invention.

FIG. 18 is an enlarged conceptual view at the molecular level during the treatment process of the second embodiment of the present invention.

FIG. 19 is an enlarged conceptual diagram at the molecular level after the treatment process of the second embodiment of the present invention.

FIG. 20 is an enlarged conceptual view of a water / oil repellent film obtained according to the second embodiment of the present invention.

[Explanation of symbols]

 1,11 Hydrophilic substrate 2,12 Polysiloxane coating film 3,6,13,16 Fluorocarbon coating film 4,14 Hydrophilic fine particles on surface 5,15 Polysiloxane monomolecular film

Claims (11)

(57) [Claims] 1. A polysiloxane thin film or a siloxane chemisorption monomolecular film is formed on the surface of a substrate, and a polymer having a fluorocarbon group and a siloxane group is mixed on the surface of the film, and the surface is coated with hydrophilic fine particles. A water and oil repellent coating film in which a thin film is chemically bonded by a siloxane bond. To 2. A surface of the substrate having a hydroxyl group on the surface, is anti <br/> response hydroxyl and the chlorosilyl groups of the substrate surface in contact with a non-aqueous solvent obtained by mixing a substance having a chlorosilyl group, the A step of chemically adsorbing a substance on the surface of the substrate, a fluorocarbon group and a chlorosilyl group or an alkoxy group
A material containing a silyl group, the surface of a mixture of hydrophilic fine particles
A method for producing a water / oil repellent coating film, which comprises the step of applying a non-aqueous solvent to the surface of a substrate and the step of baking the substrate by heating. Wherein as the substrate, a manufacturing method of a water-repellent, oil-repellent coating film according to claim 2, wherein a metal or ceramic. 4. A as a base, the production method according to claim 2 water and oil repellent coating film according to use hydrophilicized treated beforehand surface in a plasma atmosphere containing oxygen plastic. 5. The substance having a chlorosilyl group is SiC.
l ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , or Cl-
Selected from _{(SiCl 2 O) n -SiCl 3} (n is an integer)
At least one method of manufacturing a water and oil repellent coating film according to claim 2, wherein that. As substances including 6. fluorocarbon group and Kuroroshi Lil _{group, CF 3 - (CF 2)} n -R-SiX p
Cl _3-p (n is 0 or an integer, R represents an alkylene group, an ethylene group, an acetylene group or silicon-substituted group containing an oxygen atom,, X is H or an alkyl group, a cycloalkyl group, an allyl group, and of these The method for producing a water / oil repellent coating film according to claim 2, wherein a substituent selected from derivatives and p is 0 or 1 or 2). As substances including 7. A fluorocarbon group and alkoxysilyl Lil <br/> _{group, CF 3 - (CF 2)} n -R-Si
_{Y q (OA) 3-q} (n is 0 or an integer, R represents an alkylene <br/> group, an ethylene group, an acetylene group or silicon-substituted group containing an oxygen atom, Y is a hydrogen atom or an alkyl group, a cycloalkyl A substituent selected from an alkyl group, an allyl group, and derivatives thereof, OA is an alkoxy group (where A is H
Alternatively, the alkyl group) and q are 0, 1 or 2), and the method for producing a water / oil repellent coating film according to claim 2. 8. A fluorocarbon group and Kuroroshi lil group
In a non-aqueous solvent mixed with a substance having SiX _s Cl _4-s (X is H or an alkyl group ) as a crosslinking agent for the substance.
Substituents, s is 0 or 1 or 2) A method of manufacturing water- and oil-repellent coating film according to claim 2, wherein the addition of. 9. A solvent obtained by mixing a substance having a fluorocarbon group and alkoxysilyl Lil <br/> group, Si as a crosslinking agent
The water repellent according to claim 2, wherein Y _t (OA) _4-t (Y is a substituent of an alkyl group , OA is an alkoxy group, (where A is H or an alkyl group), t is 0, 1 or 2). Method for producing oil repellent coating film. 10. The method for producing a water / oil repellent coating film according to claim 2, wherein metal or ceramic is used as the fine particles having a hydrophilic surface. 11. The surface of a substrate having a hydroxyl group on the surface,
Contacting the non-aqueous solvent obtained by mixing a substance having a chlorosilyl group, by reacting a hydroxyl group and chlorosilyl groups, a step of depositing said material on said substrate surface, residual Ru extra wherein on said substrate using a non-aqueous organic solvent black <br/> washed remove substances having a Roshiriru group, forming a formed of material chemically adsorbed monomolecular film having a chlorosilyl groups on the substrate, the fluorocarbon group and Kuroroshi drill or alkoxy
Mix a substance containing a silyl group and fine particles with a hydrophilic surface.
A method for producing a water / oil repellent coating film, which comprises a step of depositing a non-aqueous solvent on the surface of a substrate and a step of baking the substrate by heating.