JP2500149B2 - Water- and oil-repellent coating 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 water / oil repellent coating film for use in electric appliances, automobiles, industrial equipment, etc. which require water / oil repellency and a method for producing the same.

[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 is a water / oil repellent coating film formed on the surface of a substrate, and the coating film is at least hydrophilic fine particles. And a polymer containing a fluorocarbon group and a siloxane group.

In the above structure, the film having irregularities is
It is chemically bonded to the substrate by a siloxane bond.

[0008] method of manufacturing a water and oil repellent coating of the present invention comprises providing a substrate comprising a hydroxyl group on the surface, of the non-aqueous substance and surface including a fluorocarbon group and a Kuroroshi Lil groups are mixed hydrophilic microparticles solvent step applying or substance and surface including a fluorocarbon group and alkoxysilyl Lil groups, is characterized a step of applying a solvent mixed with hydrophilic particles, further comprising the step of performing a substrate various Tomo heated baking.

In the above structure, it is preferable to use metal or ceramic as the substrate containing hydroxyl groups on the surface.

In the above structure, as the substrate containing hydroxyl groups on its surface, it is also possible to use a plastic whose surface has been previously treated in a plasma atmosphere containing oxygen to make it hydrophilic.

[0011] In the above configuration, a material 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
Group) , a substituent containing Si or an oxygen atom, X is a substituent of H or an alkyl group, and p is 0 or 1 or 2).

[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
(Ethynyl group) , Si or oxygen atom-containing substituent, Y
Is H or a substituent of an alkyl group , OA is an alkoxy group (where A is H or an alkyl group), q is 0 or 1
Or 2} is preferably used.

[0013] In the above configuration, the non-aqueous solvent obtained by mixing a substance containing a fluorocarbon group and a Kuroroshi Lil _{groups, SiX s Cl 4-s (} X as a crosslinking agent for said substance
Is preferably a substituent of H or an alkyl group, and s is 0 or 1 or 2).

[0014] In the above _{configuration, SiY t (OA) 4-} t (Y is an alkyl group as a crosslinking agent to the mixed solvent to a substance containing a fluorocarbon group and alkoxysilyl lil group
Substituents, OA represents an alkoxy group, (wherein, A is H or an alkyl group) it is preferred that t adding 0 or 1 or 2).

[0015]

According to the constitution of the water / oil repellent coating film of the present invention,
A water- and oil-repellent coating formed on the surface of a substrate, wherein the coating contains at least micron-order hydrophilic fine particles,
As it is made of a polymer containing fluorocarbon and siloxane groups, it has good adhesion to the substrate, no pinholes, and the surface has small irregularities on the order of microns, and it contains fluorine, which has excellent water and oil repellency and durability. Can be used as a coating film.

[0016] According to the configuration of the manufacturing method of the present invention, using a substrate comprising a hydrophilic hydroxyl groups (-OH) on the surface, material and surface mixing hydrophilic microparticles comprising fluorocarbon groups and Kuroroshi lil group the non-aqueous solvent that, or a solvent material and the surface including a fluorocarbon group and alkoxysilyl Lil groups are mixed hydrophilic fine particles is applied, the substrate
When heat baking is carried out in an atmosphere containing water together with the OH group present on the surface of the substrate, a dehydrochlorination or dealcohol reaction occurs, and the polymer having a fluorocarbon group passes through O of the OH group present on the surface of the substrate. The fluorocarbon-based coating film chemically bonded to the substrate can be prepared in a form in which the surface incorporates hydrophilic fine particles. At this time, since the polymer having a fluorocarbon group is chemically bonded to the substrate via -O-, the adhesion is extremely excellent. Further, here, 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. Similarly, the surface of the fine particles is covered with a fluorocarbon coating film, so that a fluorocarbon coating film having arbitrary irregularities can be formed on the surface having excellent water and oil repellency.

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 having a hydroxyl group on the surface, a metal, ceramic, or glass covered with a natural oxide film can be used, but if the substance does not have an oxide film, such as plastic, the surface contains oxygen in advance. It may be treated in a plasma atmosphere 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.

Examples of the material containing a fluorocarbon group and a 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, a substituted group containing a Si or oxygen atom, X represents a substituent H or an alkyl group, p is 0 or 1
Or 2), and further a fluorocarbon group and an alkoxy group
Examples of the substance containing a ryl group include 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, substituent containing Si or 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 0 or 1 or 2} or the like can be used.

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.

[0021]

EXAMPLES Examples will be described below with reference to the drawings. The present invention is not limited to the examples below.

Example 1 For example, 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 (an oxide film is formed on the surface such as plastic). If there is no substance, the surface may be preliminarily treated in a plasma atmosphere containing oxygen, for example, with 100 W for 20 minutes to make it hydrophilic, that is, to introduce hydroxyl groups into the surface (FIG. 1)}, and non-aqueous solvents mixed with silica fine particles 2 containing OH groups of hydrophilic material and a surface comprising Kuroroshi Lil group _{(e.g., CF 3 - (CF 2)} n -R-Si
X _p Cl _3-p (n is 0 or an integer, R represents an alkylene group,
An ethylene group, an acetylene group (ethynylene group) , a substituent containing Si or an oxygen atom, X is H or a substituent of an alkyl group , and p is 0 or 1 or 2 in several weight percent (hereinafter, referred to as weight). (% Is simply expressed in%) (normal hexadecane 90%, chloroform 10% dissolved in a solvent) is applied (FIG. 2), and baking is performed in an atmosphere containing water at 200 ° C. for about 30 minutes. Base 1
Since the -OH group is exposed on the surface of the fine particles having a hydrophilic surface, the chlorosilyl group and -OH group of the chlorosilane-based surfactant containing fluorine undergoes a dehydrochlorination reaction on the surface.
Bonds of Si (O-) ₃ are generated, and a siloxane fluorocarbon-based polymer film 3 containing fluorine is formed on the surfaces of the substrate and the fine particles in a state of being chemically bonded to the substrate (FIG. 3).

For example, CF ₃ CH ₂ O (CH ₂ ) ₁₅ S
Dissolving or suspending 1% of iCl ₃ and 0.5% to 50 μm (more preferably 1 to 10 μm) in diameter of silica fine particles 2 containing a hydrophilic —OH group at a concentration of about 10%. 80% n-hexadecane, 12%
A solution of carbon tetrachloride and 8% chloroform was prepared and applied on the surface of a substrate on which a polysiloxane coating film having a large number of SiOH bonds was formed on the surface, and then 200
When baked at ℃ for 30 minutes, CF ₃ CH ₂ O
(CH ₂ ) ₁₅ Si (O-) ₃ bonds are generated,
A fluorocarbon-based coating film 3 having a thickness of 1 to 5 μm and having an unevenness of 5 to 50 μm (more preferably 1 to 10 μm) was produced (FIG. 4). A of this FIG.
FIG. 3 is an enlarged view of the part. It should be noted that this coating film was not peeled off at all even after the goth test.

[0024] 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 weight percent), the bond of CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (O-) ₃ is ... Si. It was three-dimensionally crosslinked through the (O-) ₃ bond, and a fluorocarbon-based coating film having a hardness about twice that of the case where SiCl ₄ was not added could be manufactured.

By the way, the wetting angle of the fluorocarbon-based coating film having the irregularities of about 10 microns formed on the surface as described above is about 130 to 14
It was 0 degrees.

In the above embodiment, the reagent used is CF ₃ C.
H ₂ O (CH ₂ ) ₁₅ SiCl ₃ , CF ₃ (CF ₂ )
_{Although 5} (CH ₂ ) ₂ SiCl ₃ was used, if an ethylene group or an acetylene group (ethynylene group) is added to or incorporated in the alkyl chain portion, it can be crosslinked by electron beam irradiation of about 5 megarads after forming a coating film. Furthermore, a coating film 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 SiCl ₃ , F (CF ₂ ) ₄
(CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₉ SiC
l ₃ , CF ₃ COO (CH ₂ ) ₁₅ SiCl _3, etc. can be used.

[0027] Example 2 For example, as shown in FIG. 5, a hydrophilic substrate 11 in the same manner as in Example 1, particles 12 containing the hydrophilic -OH groups on the material and the surface including a fluorocarbon group and alkoxysilyl lil group the mixed alcohol solvent _{(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) , 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 or 1 or 2}. 6), after baking at 200 ° C. for about 30 minutes, the substrate 11 and the fine particles 12 having a hydrophilic surface
-OH group is exposed on the surface, the alkoxy group of the fluorine-containing alkoxysilane-based surfactant and the -OH group undergo a dealcohol reaction, and the surface of the substrate ... Si (O-) ₃
Is generated, and the siloxane fluorocarbon-based polymer film 13 containing fluorine is formed on the surface of the substrate and the fine particles in a state of being chemically bonded to the substrate (FIG. 7).

For example, CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si
1% of (OCH ₃ ) ₃ and 0.5 to 50 μm (more preferably 1 to 10 μm) in diameter of the silica fine particles 12 containing a hydrophilic —OH group are dissolved at a concentration of about 10% or A suspended ethanol solution was prepared, coated on the surface of the substrate, and baked at 200 ° C. for about 30 minutes to obtain CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (O−) ₃
Was produced, and a fluorocarbon-based coating film 13 having a thickness of 1 to 5 μm and having an unevenness of 0.5 to 50 μm (more preferably 1 to 10 μm) was produced (FIG. 8). FIG. 7 is an enlarged view of part B of FIG. It should be noted that this coating film did not peel off at all even after the goth test.

[0029] 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 A group (where A is H or an alkyl group) t is 0 or 1 or 2) (for example, Si (OCH ₃ ) ₄ is 5 weight percent), CF ₃ CH ₂ O (CH ₂ ) The bond of ₁₅ Si (O-) ₃ is three-dimensionally cross-linked through the bond of Si (O-) _{3 and} is about 2-2.5 as compared with the case where Si (OCH ₃ ) ₄ is not added. A fluorocarbon coating film having double the hardness could be manufactured.

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.

[0031] At this time, if had been Si a (OC ₃ H _{7) 4} was added 10% by weight as a cross-linking agent of the substance in the solvent obtained by mixing a substance containing a fluorocarbon group and alkoxysilyl Lil groups, about 4 A fluorocarbon coating film having double the hardness could be manufactured.

Further, the solvent of the nonaqueous mixed with material containing fluorocarbon groups and alkoxy <br/> silyl group was further 20% dispersion additive microparticles of similar coating a fluorocarbon polymer (polytetrafluoroethylene) When used, the hardness was almost the same as the conventional one, but a fluorocarbon coating film having much better adhesion than the conventional one could be manufactured.

Furthermore, in the above embodiment, C was used as a reagent.
_{F 3 CH 2 O (CH 2} ) 15 Si (OCH 3) 3, CF 3
(CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ was used, but an ethylene group or an acetylene group (eth
By adding or incorporating a ( tinylene group) , it is possible to crosslink by electron beam irradiation at about 5 megarads after forming the coating film, so that a coating film having a hardness of about 10 times can be easily obtained.

Besides the above-mentioned fluorocarbon surfactants, CF ₃ (CH ₂ ) ₂ Si (CH ₃ )
_{2 (CH 2) 15 Si (} OCH 3) 3, F (CF 2)
₄ (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.

[0035]

As described above, according to the present invention, a fluorocarbon-based coating film having a water-repellent and oil-repellent film having an unevenness of 1 to 10 μm on the surface of the hydrophilic substrate is chemically bonded to the substrate. It can be formed very thin with a uniform thickness and no pinholes. Therefore, it is possible to provide a high-performance fluorocarbon-based coating film having high water / oil repellency and extremely high durability.

[Brief description of drawings]

FIG. 1 is a conceptual sectional view for explaining a manufacturing process according to a first embodiment of the present invention.

FIG. 2 is an enlarged cross-sectional view of the same at the molecular level.

FIG. 3 is an enlarged cross-sectional view of the same at a molecular level, and FIG.
FIG. 3 is an enlarged cross-sectional view of a molecular level of the part.

FIG. 4 is a conceptual cross-sectional view for explaining the coating film of Example 1 of the present invention.

FIG. 5 is a sectional conceptual view for explaining a manufacturing process according to a second embodiment of the present invention.

FIG. 6 is an enlarged cross-sectional view of the same at the molecular level.

FIG. 7 is an enlarged cross-sectional view of the same at the molecular level, showing B of FIG.
FIG. 3 is an enlarged cross-sectional view of a molecular level of the part.

FIG. 8 is a conceptual cross-sectional view for explaining a coating film according to a second embodiment of the present invention.

[Explanation of symbols]

 1,11 Hydrophilic substrate 2,12 Fine particles 3,13 Water and oil repellent coating

Claims (9)

(57) [Claims] 1. A water- and oil-repellent coating formed on the surface of a substrate, wherein the coating is an uneven film formed of at least hydrophilic fine particles and a polymer containing a fluorocarbon group and a siloxane group. A water and oil repellent coating characterized by. 2. The water and oil repellent coating film according to claim 1, wherein the uneven film layer is chemically bonded to the substrate by a siloxane bond. Wherein providing a substrate comprising a hydroxyl group on the surface, fluorocarbon groups and processes or fluorocarbon groups and alkoxysilyl Lil group substance and the surface is coated with the non-aqueous solvent obtained by mixing hydrophilic microparticles comprising Kuroroshi lil group A method for producing a water- and oil-repellent coating film, comprising: a step of applying a solvent in which a substance containing is mixed with fine particles having a hydrophilic surface; and a step of heating and baking the substrate . 4. The method for producing a water / oil repellent coating film according to claim 3, wherein a metal, silica or ceramic is used as the substrate having a hydroxyl group on the surface. 5. The method for producing a water / oil repellent coating film according to claim 3, wherein a plastic whose surface is previously treated with a plasma atmosphere containing oxygen to make it hydrophilic is used as the substrate having a hydroxyl group on the surface. 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, a substituted group containing a Si or oxygen atom, X represents a substituent H or an alkyl group, p is 0 or 1
Alternatively, the method of producing a water- and oil-repellent coating according to claim 3, which uses 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, a substituted group containing a Si or oxygen atom, Y is a substituent H or an alkyl group, OA is an alkoxy group (where A is H or an alkyl group), q
Is 0 or 1 or 2), and the method for producing a water and oil repellent coating film according to claim 3. 8. A fluorocarbon group and a non-aqueous solvent obtained by mixing a substance containing an Kuroroshi Lil _{group, SiX s Cl 4-s (} X is <br/> substituent H or an alkyl group as a crosslinking agent for said substance , S is 0 or 1 or 2) is added.
A method for producing the water- and oil-repellent coating described. 9. SiY _t as a crosslinking agent in a solvent obtained by mixing substances comprising fluorocarbon groups and alkoxysilyl Lil <br/> group
The water- and oil-repellent property according to claim 3, wherein (OA) _4-t (Y is a substituent of an alkyl group , OA is an alkoxy group (where A is H or an alkyl group), and t is 0, 1 or 2). Method of manufacturing coating film.