JPH04239633A - Water and repelling film and manufacture thereof - Google Patents

Abstract

PURPOSE:To provide a monomolecular film coating object having high water repellency and oil repellency by chemically bonding an uneven layer mixed with fine particles and silicate glass and a polymer layer containing a fluorocarbon group and a siloxane group by a siloxane bond. CONSTITUTION:A film having an uneven surface and excellent in water repellency and oil repellency is obtained by a process forming a film having an uneven surface of a micron order by coating the surface of a substrate with a mixture of fine glass particles and silicate glass and heating and baking the coated substrate and a process thinly applying or chemically adsorbing a non-aqueous solvent mixed with a substance having a fluorocarbon group and a chlorosilane group or an alkoxysilane group on the glass film.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-containing water- and oil-repellent coating and a method for producing the same.

0002

BACKGROUND OF THE INVENTION Ultra-thin film coatings with heat resistance, weather resistance, and abrasion resistance are required for electrical appliances, automobiles, industrial equipment, mirrors, eyeglass lenses, and the like.

[0003] Conventionally, a widely used method for manufacturing a coating film for the purpose of water and oil repellency generally involves roughening the surface of an aluminum (Al) or glass substrate by blasting, wire brushing, chemical etching, etc. After roughening the surface and applying a primer etc., poly 4
A paint such as fluoroenamel made by suspending fine powder of fluorocarbon such as ethylene fluoride in ethanol, etc. is applied, dried, and then baked at approximately 400°C for approximately 1 hour to coat the surface of the substrate with fluorocarbon polymer. A burning method has been used.

0004

[Problems to be Solved by the Invention] However, while this method is easy to manufacture, there is a limit to the adhesion with the base because the polymer and the base are only bonded by an anchor effect. Since the surface of the coating film was baked at a high temperature of 400° C., the surface was flattened and a good water- and oil-repellent surface could not be obtained. Therefore, it has been unsatisfactory as a manufacturing method for appliances, automobiles, industrial equipment, etc. that require water- and oil-repellent coating films.

[0005] In order to solve the problems of the prior art, the present invention provides a fluorine-containing coating film that has good adhesion to a substrate, has no pinholes, has small irregularities on the micron order, and has excellent water and oil repellency. The purpose is to provide.

[0006]

[Means for Solving the Problems] In order to achieve the above object, the water- and oil-repellent coating of the present invention is a water- and oil-repellent coating formed on the surface of a base material, the coating comprising at least fine particles and silicate glass. It is characterized in that it is composed of a layer having irregularities in which a mixture of fluorocarbon groups and siloxane groups is mixed, and a polymer film layer or chemisorption monomolecular film layer containing a fluorocarbon group and a siloxane group.

[0007] In the above structure, a layer having irregularities on the micron order formed by coating a mixture of fine particles and silicate glass, and a fluorocarbon-based polymer film layer formed by polymerizing a substance containing a fluorocarbon group and a chlorosilane group or a fluorocarbon-based chemically adsorbed monomolecule. It is composed of a membrane layer,
It is preferable that the surface is uneven.

Next, the first method of producing a water- and oil-repellent film of the present invention includes the steps of creating irregularities on the surface of the micron order and applying a non-aqueous solvent mixed with a substance containing a fluorocarbon group and a chlorosilane group. The method is characterized by comprising a step of applying a solvent mixed with a substance containing a fluorocarbon group and an alkoxysilane group to form a fluorocarbon polymer film, and a step of performing heating baking.

In the above structure, it is preferable that the step of creating micron-order irregularities on the surface comprises a step of mixing fine particles and silicate glass and applying the mixture to the surface of the substrate, and then baking the substrates.

[0010] Furthermore, in the above structure, CF3-(
CF2)n-R-SiXpCl3-p (n is 0
or an integer, R is an alkyl group, ethylene group, acetylene group, Si or a substituent containing an oxygen atom, X is a substituent such as H or an alkyl group, and p is preferably 0, 1 or 2).

Further, in the above structure, CF3 is used as the substance containing a fluorocarbon group and an alkoxysilane group.
-(CF2)n -R-SiYq (OA)3-q
(n is 0 or an integer, R is an alkyl group, ethylene group, acetylene group, Si or a substituent containing an oxygen atom, Y is H
or a substituent such as an alkyl group, OA is an alkoxy group (
However, it is preferable to use (A is H or an alkyl group) and q is 0, 1 or 2).

Further, in the above structure, it is preferable to use metal or ceramics such as glass as the fine particles.

Next, the second method for producing a water- and oil-repellent film of the present invention includes the steps of creating unevenness on the surface of the micron order, and forming a chlorosilane group (SiCln X3-n group,
a step of chemically adsorbing a fluorosilane surfactant consisting of a fluorocarbon linear chain molecule having (n=1, 2, 3, X is a functional group) onto a substrate to form a fluorocarbon chemisorbed monomolecular film. It is characterized by

[0014] In the above structure, it is preferable that the step of creating micron-order irregularities on the surface comprises a step of mixing fine particles and silicate glass and applying the mixture to the substrate surface, and then heating and baking the substrates.

[0015]

[Operation] According to the structure of the water- and oil-repellent coating of the present invention,
The coating is composed of at least a layer with irregularities in which fine particles and silicate glass are mixed, and a polymer layer or chemically adsorbed monomolecular film containing fluorocarbon groups and siloxane groups, so it has good adhesion to the substrate and has no pinholes. Moreover, it is possible to obtain a fluorine-containing coating film that has small irregularities on the micron order on its surface and has excellent water and oil repellency.

According to the manufacturing method of the present invention, fine glass particles and silicate glass are mixed and applied in advance to the surface of a substrate for forming a fluorocarbon coating film or a chemically adsorbed monomolecular film, thereby forming a glass coating having an uneven surface on the order of microns. By including the step of creating a fluorocarbon coating film, fine irregularities can be formed on the surface of the fluorocarbon coating film created in a subsequent step. Therefore, it is possible to form a fluorocarbon polymer or a chemically adsorbed monomolecular film having arbitrary irregularities on the surface and having extremely excellent water and oil repellency. In addition,
At this time, the polymer or molecule having a fluorocarbon group is chemically bonded to the substrate via -O-, and therefore has extremely excellent adhesion.

Furthermore, the roughness of the surface irregularities can be controlled by controlling the diameter and amount of fine particles added to the silicate glass.

Further, as a substance containing a fluorocarbon group and a chlorosilane group, CF3-(CF2)n-
R-SiXp Cl3-p, and as a substance containing a fluorocarbon group and an alkoxysilane group, CF3
-(CF2)n -R-SiYq (OA)3-q
It is possible to use

Furthermore, in order to adjust the hardness of the formed fluorocarbon polymer film, in the case of a non-aqueous solvent containing a substance containing a fluorocarbon group and a chlorosilane group, SiXs Cl4-s can be used as a crosslinking agent for the substance.
(X is H or a substituent such as an alkyl group, s is 0, 1, or 2), and in the case of a solvent containing a substance containing a fluorocarbon group and an alkoxysilane group, SiYt (OA) is used as a crosslinking agent. By using 4-t (Y is a substituent such as an alkyl group, OA is an alkoxy group, (A is H or an alkyl group, and t is 0, 1, or 2), the The three-dimensional crosslinking density can be adjusted, and the hardness of a fluorocarbon polymer film with arbitrary irregularities on the surface can be controlled.

[0020]

[Example] The present invention involves the process of applying a mixture of glass fine particles and silicate glass to the surface of a substrate for forming a coating film, and heating and baking both substrates to create a glass coating with an uneven surface on the micron order. and a process of applying a thin layer of a non-aqueous solvent mixed with a substance containing a chlorosilane group, or a process of applying a solvent mixed with a substance containing a fluorocarbon group and an alkoxysilane group to form a polymer film, resulting in a water-repellent surface with an uneven surface. The present invention provides a method for producing a film with excellent oiliness.

Alternatively, a step of mixing and coating glass fine particles and silicate glass on the surface of the substrate to form a glass film with an uneven surface, a step of baking the substrates by heating, and a step of applying a chlorosilane group (SiCln
The process of chemically adsorbing a fluorosilane-based surfactant consisting of a fluorocarbon-based straight chain molecule having a group (n = 1, 2, 3, X is a functional group) onto a substrate to form a monomolecular adsorption film results in a repellent surface with an uneven surface. A method for producing a water and oil repellent coating is provided.

More specifically, there is provided a water- and oil-repellent coating having an uneven surface, which is characterized in that a fluorocarbon polymer film is formed on the surface of a mixture of fine particles and silicate glass coated with an uneven film interposed therebetween, and a method for producing the same. , or a repellent with an uneven surface, which is composed of a layer coated with a mixture of glass particles and silicate glass, and a chemically adsorbed monomolecular film layer formed by polymerizing a substance containing fluorocarbon groups and chlorosilane groups. The present invention relates to a water and oil repellent coating and a method for producing the same. electrical appliances and automobiles,
The objective is to improve the performance of equipment such as industrial equipment that requires heat-resistant, weather-resistant, and wear-resistant coatings with excellent water and oil repellency.

A specific experimental example will be explained below.

Example 1 For example, as shown in FIG. 1, a hydrophilic substrate 1 [ceramics such as glass, metal such as Al or Cu, or a plastic substrate with a hydrophilic surface (such as plastic with an oxide film on the surface)] If it is a substance that does not have a hydroxyl group, it is sufficient to treat the surface in advance in a plasma atmosphere containing oxygen at, for example, 100 W for 20 minutes to make it hydrophilic, that is, introduce hydroxyl groups to the surface.
Silica fine particles 2 with an average diameter of about 10 microns (for example, Asahi Glass's Microshayer Agel DF10-60A or 120A, etc.) and silicate glass (for example, Shin-Etsu Chemical's hard coating agent KP-1100A or 1100B, Tokyo Ohka Co., Ltd.) After mixing industrial-made Si-80000 at a concentration of about 1:1 and applying it by casting, heat treatment at 500℃ for 30 minutes or plasma ashing (300W, about 20 minutes) will cause micron-order particles to form on the surface. A glass layer 3 with unevenness can be formed. Next, a non-aqueous solvent containing a substance containing a fluorocarbon group and a chlorosilane group (for example, CF3-(CF2)n-R-
SiXp Cl3-p (n is 0 or an integer, R is a substituent containing an alkyl group, ethylene group, acetylene group, Si element or oxygen atom, X is a substituent such as H or an alkyl group, p is 0 or 1 or 2) ) dissolved in a solvent of 90% n-hexadecane and 1% chloroform at a concentration of several weight percent, and
After baking at 00°C for about 30 minutes, the glass layer 3
Since the -OH group is exposed on the surface, the chlorosilyl group of the fluorine-containing chlorosilane surfactant and the -OH group undergo a dehydrochlorination reaction to generate Si(O-)3 bonds on the surface. A siloxane fluorocarbon polymer film containing fluorine 4 is chemically bonded to the surface of the glass layer, which has irregularities on the order of microns, and is formed with irregularities (Figure 3).
.

For example, DF10-60A with a diameter of about 10 microns is used as fine particles, and KP-60A is used as silicate glass.
When dip coated using 1100A and baked at 350°C, a glass layer with irregularities of about 10 microns on the surface was obtained.

Further thereafter, CF3 CH2 O(CH
2) Using 15SiCl3, a solution of 80% n-hexadecane, 12% carbon tetrachloride, and 8% chloroform dissolved at a concentration of about 1% was prepared, and a polysiloxane coating film having many SiOH bonds was formed on the surface. When applied to the substrate surface and baked at 200°C for about 30 minutes in an atmosphere containing moisture, CF3 CH2 O(CH2)1
5Si(O-)3 bonds were formed, and a fluorocarbon polymer film 4 having a thickness of 1 to 5 microns and having irregularities of about 10 microns was manufactured (FIG. 5). In addition, this coating film hardly peeled off even when a grid test was performed.

At this time, SiXs Cl4-s (X is H or a substituent such as an alkyl group, s is 0 or 1 or 2)
(for example, 3% by weight of SiCl4), CF3 CH2 O(CH2 )15Si(
O-)3 bonds were three-dimensionally cross-linked through -Si(O-)3 bonds, making it possible to produce a fluorocarbon polymer film that was approximately twice as hard as that without adding SiCl4. .

[0028] Incidentally, the wetting angle of the fluorocarbon polymer film with water having an unevenness of about 10 microns on the surface prepared in this way was about 130 to 140 degrees.

Example 2 In the same manner as in Example 1, after forming a glass layer with an uneven surface on a substrate as shown in FIG.
For example, CF3-(CF2)n-R-SiYq
(OA)3-q (n is 0 or an integer, R is an alkyl group, an ethylene group, an acetylene 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 (however, A is H or an alkyl group), q
0 or 1 or 2) dissolved in methanol at a concentration of several percent) and baked at 200°C for about 30 minutes, the glass layer 3 has -OH groups exposed on the surface, so fluorine is removed. The alkoxy group and -OH group of the alkoxysilane surfactant containing -OH group undergo a dealcoholization reaction to generate -Si(O-)3 bonds on the surface, and a siloxane fluorocarbon polymer film containing fluorine is formed on the uneven glass layer surface. is formed in the same manner as in Example 1.

For example, CF3 CH2 O(CH2 )
Prepare an ethanol solution containing 15Si(OCH3)3 at a concentration of about 1%, and add Si to the surface.
When applied to the surface of a substrate on which a polysiloxane coating film with many OH bonds is formed and baked at 200°C for about 30 minutes, CF3 CH2 O(CH2)15Si(
O-)3 bonds were generated, and a fluorocarbon polymer film with a thickness of 1 to 5 microns and an unevenness of about 10 microns was manufactured. In addition, this coating film hardly peeled off even when a grid test was performed.

At this time, SiYt (OA)4-t (Y is a substituent such as an alkyl group, OA is an alkoxy group, ( However, if A is H or an alkyl group) and t is 0, 1, or 2) (for example, 5 weight percent of Si(OCH3)4), CF3 CH2 O(CH2 )15S
The i(O-)3 bond is three-dimensionally cross-linked via the -Si(O-)3 bond to form Si(OCH3)4
A fluorocarbon polymer film was produced that was about 2 to 2.5 times as hard as that without the addition of fluorocarbon.

By the way, when a water droplet 5 is dropped on the fluorocarbon polymer film prepared in this manner, the surface of which has irregularities of about 10 microns, the water droplet comes into contact with the fluorocarbon polymer film only at the protrusions, so as shown in FIG. As shown in Figure 2, the water repellency was extremely high, and the wetting angle with respect to water was approximately 135 to 140 degrees.

At this time, if 10% by weight of Si(OC3 H7)4 is added as a crosslinking agent for the above substance into a solvent containing a substance containing a fluorocarbon group and an alkoxysilane group, the hardness is approximately 4 times higher. A fluorocarbon-based polymer film of 100% was produced.

[0034] In addition, when similar coating was performed using a non-aqueous solvent mixed with a substance containing a fluorocarbon group and an alkoxysilane group, in which 20% of fine particles of a fluorocarbon polymer (polytetrafluoroethylene) were further dispersed. Although the hardness was the same as before, we were able to produce a fluorocarbon polymer film with extremely superior adhesion and water and oil repellency compared to conventional methods.

Furthermore, in the above example, C was used as a reagent.
F3 CH2 O(CH2)15Si(OCH3)
3, CF3 (CF2)7 (CH2)2 Si
(OC2 H5 )3 was used, but if an ethylene group or acetylene group is added or incorporated into the alkyl chain part, it can be crosslinked by electron beam irradiation of about 5 megarads after the coating film is formed, so it can be made about 10 times harder. A coating film can also be easily obtained.

In addition to the above-mentioned fluorocarbon surfactants, CF3 (CH2)2 Si(C
H3)2 (CH2)15Si(OCH3)3,
F(CF2)8(CH2)2Si(CH3
)2 (CH2)9 Si(OCH3)3,
CF3 COO(CH2)15Si(OC2 H5
)3 etc. can be used.

Example 3 In the same manner as in Example 1, after forming a glass layer with an uneven surface on a substrate as shown in FIG. 1, a nonaqueous solvent containing a substance containing a fluorocarbon group and a chlorosilane group, For example, CF3 (CF2)7 (CH2)2 SiCl
3 to prepare a solution of 80% n-hexadecane, 12% carbon tetrachloride, and 8% chloroform dissolved at a concentration of about 1%, and then remove the substrate on which a monomolecular film with many SiOH bonds was formed on the surface. When immersed for about a minute, CF3 (CF2)7 (CH2)2 Si(
O-)3 bonds were generated, and a fluorine-containing water- and oil-repellent film 4 (chemically adsorbed monomolecular film) could be formed in an uneven manner while chemically bonded to the glass layer (FIG. 4). In addition, this water- and oil-repellent film 4
(Monolayer) did not peel off at all even when a grid test was performed. Further, in this case, since the fluorocarbon groups were formed on the surface in an oriented state, the surface energy was extremely low, and the wetting angle with respect to water was 135 to 145 degrees.

Furthermore, in the above examples, CF3 (CF2)7 (C
H2)2SiCl3 was used, but if an ethylene group or acetylene group is added to or incorporated into the alkyl chain portion, the hardness can be further improved because it can be crosslinked by electron beam irradiation at about 5 megarads after monomolecular film formation. It is possible.

In addition to the above-mentioned fluorocarbon surfactants, CF3 CH2 O(CH2)1
5SiCl3, CF3(CH2)2Si(CH
3)2(CH2)15SiCl3, F(C
F2 )8 (CH2 )2 Si(CH3 )2 (
CH2)9 SiCl3, CF3COO(CH2
)15SiCl3 etc. can be used.

[0040]

[Effect of the invention] As explained above, if the present invention is used, A
Fluorocarbon-based polymer films or monomolecular films with excellent water and oil repellency are chemically bonded to the substrates to form high-density coatings on ceramics of metals and metal oxides such as L, Cu, and stainless steel, as well as glass and plastic substrates. Can be formed without pinholes. Therefore, it is possible to provide a high-performance fluorocarbon coating that is extremely durable and has excellent water and oil repellency.

[Brief explanation of the drawing]

FIG. 1 is a process cross-sectional conceptual diagram for explaining the manufacturing process of the water- and oil-repellent coating of the present invention.

FIG. 2 is a process cross-sectional conceptual diagram for explaining the manufacturing process of the water- and oil-repellent coating of the present invention.

FIG. 3 is a conceptual cross-sectional view of a case where water droplets are dropped on the water- and oil-repellent coating of the present invention.

FIG. 4 is a conceptual cross-sectional view of a water- and oil-repellent coating according to another embodiment of the present invention, enlarged to the molecular level.

FIG. 5 is a conceptual cross-sectional view of a water- and oil-repellent coating enlarged to the molecular level of part A in FIG. 2;

[Explanation of symbols]

Claims (9)

[Claims] 1. A water- and oil-repellent coating formed on the surface of a substrate, the coating comprising at least a layer having irregularities in which fine particles and silicate glass are mixed, and a polymer film layer containing a fluorocarbon group and a siloxane group; A water- and oil-repellent coating characterized by being composed of a chemically adsorbed monolayer. 2. A layer having irregularities on the micron order formed by coating a mixture of fine particles and silicate glass, and a fluorocarbon-based polymer film layer or a fluorocarbon-based chemically adsorbed monomolecular film layer formed by polymerizing a substance containing a fluorocarbon group and a chlorosilane group. 2. The water- and oil-repellent coating according to claim 1, which has an uneven surface. 3. A step of creating micron-order unevenness on the surface and a step of applying a non-aqueous solvent mixed with a substance containing a fluorocarbon group and a chlorosilane group, or a step of applying a solvent mixed with a substance containing a fluorocarbon group and an alkoxysilane group. A method for producing a water- and oil-repellent coating, comprising the steps of forming a fluorocarbon polymer film and performing heating baking. 4. The method according to claim 3, wherein the step of creating irregularities on the order of microns on the surface comprises a step of mixing fine particles and silicate glass and applying the mixture to the substrate surface, and then heating and baking the substrates. A method for producing a water- and oil-repellent coating. 5. CF3-(CF2)n-R- as a substance containing a fluorocarbon group and a chlorosilane group;
SiXp Cl3-p (n is 0 or an integer, R is an alkyl group, an ethylene group, an acetylene group, a substituent containing Si or an oxygen atom, X is a substituent such as H or an alkyl group,
5. The method for producing a water- and oil-repellent coating according to claim 3, wherein p is 0, 1 or 2). 6. CF3-(CF2)n- as a substance containing a fluorocarbon group and an alkoxysilane group;
R-SiYq (OA)3-q (n is 0 or an integer,
R is an alkyl group, ethylene group, acetylene group, Si or a substituent containing an oxygen atom, Y is a substituent such as H or an alkyl group, OA is an alkoxy group (however, A is H or an alkyl group), q is 0 or 5. The method for producing a water- and oil-repellent coating according to claim 3, wherein the method uses 1 or 2). 7. The method for producing a water- and oil-repellent coating according to claim 3 or 4, wherein metal or ceramic such as glass is used as the fine particles. 8. A step of creating unevenness on the surface of the micron order, and forming a chlorosilane group (SiCln
n group, n = 1, 2, 3, X is a functional group), chemically adsorbing a fluorosilane surfactant consisting of a fluorocarbon linear chain molecule onto a substrate to form a monomolecular adsorption film. A method for producing a characteristic water- and oil-repellent coating. 9. The water- and oil-repellent coating according to claim 8, wherein the step of creating irregularities in the order of microns on the surface comprises a step of mixing fine particles and silicate glass, applying the mixture to the surface of the substrate, and then baking the substrate with heat. manufacturing method.