JPH10309768A - Article with water repellent oil repellent film, and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a fluorine coating film having satisfactory adhesive properties with a base without pinhole and excellent water and oil repellence of a surface, and to improve performance of an equipment necessary for heat resistant, weather resistant, wear resistant coating with excellent water and oil repellence of a building, electric apparatus, vehicle or industrial equipment. SOLUTION: This article is obtained by treating a surface of a base 1 with composition containing a mixture of perfluoroalkyl with silane 3 completely hydrolyzable with alkylsilane and forming the base 1 with a non-wettable surface 4 having water repellence and oil repellence on the base selected from a group consisting of glass, ceramics, metal, plastic and inorganic film.

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 (also referred to as a non-wetting surface layer) and a method for producing the same. More specifically, when modifying the substrate surface to a non-wetting surface, the substrate surface is brought into contact with a mixture of perfluoroalkylalkylsilane and a completely hydrolyzable silane to cause a dehydrochlorination reaction or a dealcoholation reaction to effect a dehydrochlorination reaction or alcohol removal reaction. To form a water- and oil-repellent coating on the substrate.

[0002]

2. Description of the Related Art Conventionally, buildings, electrical appliances, vehicles, industrial equipment, mirrors, spectacle lenses, and the like have been required to have an ultra-thin coating having heat resistance, weather resistance, abrasion resistance and an antifouling function. . As a method for producing such a coating film for the purpose of water / oil repellency / antifouling, a method of baking a fluorocarbon polymer is known at present. In this method, the surface of the substrate is roughened with a sand brush, a wire brush, chemical etching, or the like, and after further applying a primer or the like,
Further, a paint in which a fluorocarbon-based fine powder such as polytetrafluoroethylene or the like is suspended in ethanol or the like is applied.
A method of baking (baking) at about 00 ° C. for about 1 hour and baking a fluorocarbon polymer on the surface of the substrate has been common.

[0003]

However, while this method is easy to manufacture, the polymer and the substrate are merely bonded by the anchor effect only, so that the adhesion between the polymer and the substrate is limited, and the durability is low. The sex was inferior. Also,
Since the coating film surface 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 is insufficient as a method for manufacturing an appliance, such as an electric appliance, an automobile, or an industrial device, which requires a water- and oil-repellent coating film.

In view of the above-mentioned drawbacks of the conventional method, an object of the present invention is to provide a method for forming a fluorine-based coating film having good adhesion to a substrate, no pinholes, and excellent surface water / oil repellency. Another object of the present invention is to improve the performance of equipment requiring heat-resistant, weather-resistant, and wear-resistant coatings having excellent water and oil repellency, such as buildings, electric appliances, vehicles, and industrial equipment.

[0005]

In order to achieve the above object, an article having a water- and oil-repellent coating according to the present invention is characterized in that at least a part of the surface of the substrate has a perfluoroalkylalkylsilane and a completely hydrolyzable silane. Characterized by comprising at least one substrate selected from the group consisting of a glass, ceramic, metal, plastic substrate, and a substrate coated with an inorganic coating.

Next, the method for producing a water- and oil-repellent coating of the present invention comprises the step of contacting the surface of a substrate with a mixture of a perfluoroalkylalkylsilane and a completely hydrolyzable silane. The substrate is characterized by forming a non-wetting surface on a substrate selected from the group consisting of glass, ceramic, metal, plastic, and those substrates coated with an inorganic coating.

[0007] In the article, the perfluoroalkyl
Le alkyl silane has the general formula CF_Three− (CF_Two)_n-R
-SiX_pCl_3-p(N is 0 or an integer, R is alkylene
Group, ethylene group, acetylene group, or Si, oxygen atom
X is H or an alkyl group, cycloalkyl
Or a substituent selected from an allyl group or a derivative thereof
Group, p is 0, 1 or 2), or CF_Three− (CF_Two)_n
-R-SiY_q(OA) _3-q(N is 0 or an integer, R is
Alkylene group, ethylene group, acetylene group, or Si,
A substituent containing an oxygen atom, OA is an alkoxy group (however,
A represents H or an alkyl group), and q represents 0, 1 or 2).
When selected from the compounds to be used, it is effective in improving the antifouling property.
Good.

Here, the perfluoroalkylalkylsilane is preferably at least one selected from the following compounds. (1) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ SiCl ₃ (2) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ (3) CF ₃ CH ₂ O (CH ₂ ) ₁₅ SiCl ₃ ( 4) CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si
_{Cl 3 (5) F (CF} 2) 4 (CH 2) 2 Si (CH 3) 2 (CH 2)
₉ SiCl ₃ (6) CF ₃ COO (CH ₂ ) ₁₅ SiCl ₃ (7) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ SiCl ₃ (8) F (CF ₂ ) ₈ (CH ₂ ) ₂ Si (CH _{3) 2} (CH _2)
9 SiCl ₃ (9) F (CF ₂ ) ₈ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ )
_{6 SiCl 3 (10) CF 3} CH 2 O (CH 2) 15 Si (OCH 3) 3 (11) CF 3 (CF 2) 7 (CH 2) 2 Si (OC 2 H 5) 3 (12) CF 3 (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si
(OCH ₃ ) ₃ (13) F (CF ₂ ) ₈ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ )
₉ Si (OCH ₃ ) ₃ (14) CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃

Further, if a glassy silica film is used as the inorganic coating, it is convenient to increase the durability. Further, it is preferable that the glassy silica film is formed by applying silicate glass to the surface of a glass substrate and further performing a heat treatment or a plasma ashing treatment. Furthermore, it is preferable that the outermost surface of the substrate has irregularities on the order of submicron to micron for improving the water / oil repellency.

Further, the surface of the substrate and the perfluoroalkyl
It is preferable that the mixture of the alkylsilane and the completely hydrolyzable silane is treated by a dehydrochlorination reaction or a dealcoholization reaction because durability is improved. Further, as a completely hydrolyzable silane, Six _s Cl _4-s (X is H
— Or Cl (SiCl ₂ O) _n — (where n is an integer),
s is 0 or 1 or 2), or Si (OA) ₄ (A
The use of a silane selected from the group consisting of H or an alkyl group) is advantageous because scratch resistance increases. Furthermore, the combination of completely hydrolyzable silane and perfluoroalkyl alkyl silanes, perfluoroalkyl alkyl chlorosilane and SiX _s Cl _4-s (X is H- or _{Cl (SiCl 2 O) n -} ( where n is an integer) , S is 0 or a combination of 1 or 2), or perfluoroalkylalkylalkoxysilane and Si (OA)
₄ (A is H or an alkyl group). On the other hand, in the above method, the perfluoroalkylalkylsilane has the general formula 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 Si, a substituent containing an oxygen atom, X is H or an alkyl group, a cycloalkyl group, an allyl A substituent selected from the group or a derivative thereof, p is 0, 1 or 2), or CF _3- (C
F ₂ ) _n -R-SiY _q (OA) _3-q (n is 0 or an integer,
R is an alkylene group, ethylene group, acetylene group, or a substituent containing Si or an oxygen atom, OA is an alkoxy group (where A is H or an alkyl group), and q is a compound represented by 0, 1, or 2. This is preferable for obtaining a surface having excellent water and oil repellency.

Further, it is preferable to use at least one selected from the following compounds as the perfluoroalkylalkylsilane. (1) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ SiCl ₃ (2) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ (3) CF ₃ CH ₂ O (CH ₂ ) ₁₅ SiCl ₃ ( 4) CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si
_{Cl 3 (5) F (CF} 2) 4 (CH 2) 2 Si (CH 3) 2 (CH 2)
₉ SiCl ₃ (6) CF ₃ COO (CH ₂ ) ₁₅ SiCl ₃ (7) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ SiCl ₃ (8) F (CF ₂ ) ₈ (CH ₂ ) ₂ Si (CH _{3) 2} (CH _2)
9 SiCl ₃ (9) F (CF ₂ ) ₈ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ )
_{6 SiCl 3 (10) CF 3} CH 2 O (CH 2) 15 Si (OCH 3) 3 (11) CF 3 (CF 2) 7 (CH 2) 2 Si (OC 2 H 5) 3 (12) CF 3 (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si
(OCH ₃ ) ₃ (13) F (CF ₂ ) ₈ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ )
₉ Si (OCH ₃ ) ₃ (14) CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃

It is preferable to use a glassy silica film as the inorganic coating in order to improve durability. Furthermore, it is convenient to apply a silicate glass to the surface of a glass substrate and then to perform a heat treatment or a plasma ashing process for the production of the glassy silica film because the silica film can be efficiently formed.

It is preferable to further include a step of processing the outermost surface of the base into irregularities on the order of submicron to micron in order to further improve the water / oil repellency. Further, when the substrate surface is treated with a mixture of a perfluoroalkylalkylsilane and a completely hydrolyzable silane, it is advantageous in shortening the step of dehydrochlorination or dealcoholation.

Further, silanes which can be completely hydrolyzed include Six _s Cl _4-s (X is H- or Cl (Si
A substance selected from the group consisting of Cl ₂ O) _n- (where n is an integer), s is 0, 1 or 2, or Si (OA) ₄ (A is H or an alkyl group) is preferable. further,
As a combination of fully hydrolyzable silane and perfluoroalkyl alkyl silanes, perfluoroalkyl alkyl chlorosilane and SiX _s Cl _4-s (X is H- or _{Cl (SiCl 2 O) n -} ( where n is an integer), s Is a combination of 0 or 1 or 2), or a perfluoroalkyl alkylalkoxysilane and Si (OA)
₄ (A is H or an alkyl group) is preferable in that the reaction becomes the same and a uniform coating is obtained.

[0015]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A first embodiment of the present invention comprises a step of forming a silica base layer as an inorganic coating on the surface of a substrate, and a non-aqueous system in which a substance containing a fluorocarbon group and a chlorosilane group is mixed. In a step of applying a solvent, or in a non-aqueous solvent mixed with a substance containing a fluorocarbon group and a chlorosilane group, a completely hydrolyzable SiX _s Cl _4-s (X is H or alkyl) And a substituent such as a group, s is 0 or 1 or 2). Next, the second embodiment of the present invention is a step of applying a solvent mixed with a substance containing a fluorocarbon group and an alkoxysilane group, or in a solvent mixed with a substance containing a fluorocarbon group and an alkoxysilane group, completely hydrolyzable SiY _t as a crosslinking agent substances
(OA) _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
Or a step of adding 1 or 2) and a step of performing a heat treatment.

Next, a third embodiment of the present invention comprises a step of forming irregularities on the surface of the substrate, and contacting a hydroxyl group on the surface of the substrate with a non-aqueous solvent mixed with a substance containing a plurality of chlorosilyl groups. Reacting the chlorosilyl group of the substance containing a plurality of chlorosilyl groups with the chlorosilyl group to deposit the substance on the surface of the substrate, and washing away the excess chlorosilyl group remaining on the substrate using a non-aqueous organic solvent. rear,
A step of reacting with water to form a silica monomolecular film having a siloxane bond as a main component and comprising a substance containing a plurality of silanol groups on the substrate (this film is also referred to as a silica underlayer); (SiCl _n X _3-n group, n =
(1, 2, 3, and X are functional groups) and a step of accumulating a monomolecular adsorption film by chemically adsorbing a chlorosilane-based surfactant having a linear fluorocarbon group at the other end to the substrate surface. .

In the first, second or third embodiment of the present invention, in the step of forming a silica underlayer on the surface of the substrate, fine particles and silicate glass are mixed and applied to the surface of the substrate, and then the substrates are heated. At least one method selected from a baking method, an electrolytic etching method, a chemical etching method, a sand blast method, a sputtering method, and a rubbing method is used.

In the first, second or third embodiment of the present invention, a step of forming a silica underlayer on the surface of the substrate and a chlorosilane group (SiCl _n X
Forming a chemisorption film on a substrate using a fluorosilane-based surfactant comprising a fluorocarbon-based molecule having a _3-n group, where n = 1, 2, 3, and X is a functional group.

In the first or third embodiment of the present invention, the substance containing a fluorocarbon group and a chlorosilane group is CF _3- (CF ₂ ) _n -R-SiX _p Cl.
_3-p (perfluoroalkylalkylsilane _- based perfluoroalkylalkylchlorosilane; n is 0 or an integer; R is an alkylene group, ethylene group, acetylene group, or a substituent containing Si or an oxygen atom; X is H or an alkyl group; A substituent selected from an alkyl group, an allyl group or a derivative thereof, and p is 0, 1 or 2).

In the second or third embodiment of the present invention, the substance containing a fluorocarbon group and an alkoxysilane group is CF _3- (CF ₂ ) _n -R-Si
Y _q (OA) _3-q (perfluoroalkylalkylsilane _- based perfluoroalkylalkylalkoxysilane; n is 0 or an integer, R is an alkylene group, an ethylene group, an acetylene group, or a substituent containing Si or an oxygen atom; H or a substituent selected from an alkyl group, a cycloalkyl group, an allyl group or a derivative thereof, OA is an alkoxy group (where A is H or an alkyl group), q
Is 0, 1 or 2).

According to the embodiment of the present invention, since the chemically adsorbed monomolecular film containing fluorine is formed at least through a siloxane bond on the surface of the substrate on which the silica base layer is formed, A fluorine-based coating film having good and no pinholes and having excellent water and oil repellency (non-wetting), heat resistance, weather resistance, abrasion resistance and the like can be obtained.

Further, in the present invention, glass fine particles and silicate glass are mixed and coated on the surface of a fluorocarbon-based coating film forming substrate in advance, and then baked to form a glassy silica base layer having an irregular surface with a submicron to micron order. Or a step of roughening the substrate by etching or sandblasting the substrate itself, has the effect of forming fine irregularities on the surface of the fluorocarbon-based coating film formed in a later step. Therefore, it is possible to form a fluorocarbon-based coating film (hereinafter, also referred to as a fluorocarbon-based polymer film) having any surface irregularities and extremely excellent water / oil repellency.

At this time, since the polymer having a fluorocarbon group is chemically bonded to the base via -O-, the adhesion is extremely excellent. In the method of applying fine particles, the roughness of the surface can be controlled by the diameter and the amount of fine particles added to the silicate glass.

Furthermore, after the step of forming irregularities on the surface, the substrate is brought into contact with a non-aqueous solvent in which a substance containing a plurality of chlorosilyl groups is mixed to form a hydroxyl group on the surface of the substrate and a chlorosilyl group on the substance containing a plurality of chlorosilyl groups. And a step of causing the substance to precipitate on the surface of the substrate by reacting with water and washing and removing a substance containing a plurality of excess chlorosilyl groups remaining on the substrate using a non-aqueous organic solvent, and then reacting with water. A step of forming a pure silica monomolecular film containing a plurality of silanol groups on the substrate, and a chlorosilane group (SiCl _n X _3-n group, n = 1, 2, 3, X is a functional group) at one end. If the step of chemically adsorbing a chlorosilane-based surfactant containing a linear fluorocarbon group at the other end to the substrate surface and accumulating a monomolecular adsorption film is performed, a fluorocarbon-based surfactant having a higher molecular adsorption density can be obtained. ( Fluorocarbon) has the function of producing a chemically adsorbed monomolecular film.

Further, as a substance containing a fluorocarbon group and a chlorosilane group, CF _3- (CF ₂ ) _n -R-Si
Examples of the substance containing X _p Cl _3-p , a fluorocarbon group and an alkoxysilane group include CF _3- (CF ₂ ) _n -R-
It is possible to use SiY _q (OA) _3-q (where n, R, p, and q are the same as described above).

Further, in order to adjust the hardness of the formed fluorocarbon polymer film, in the case of a non-aqueous solvent mixed with a substance containing a fluorocarbon group and a chlorosilane group, SiX _s Cl _{4 is} used as a crosslinking agent for the substance. _-s (X is H
Or a substituent such as an alkyl group, s is used with the addition of 0 or 1 or 2), in the case of solvents mixed with material containing fluorocarbon groups and alkoxysilane _{groups, SiY t (OA) 4-} t as a crosslinking agent (Y is a substituent such as an alkyl group,
OA is an alkoxy group (where A is H or an alkyl group) and t is 0, 1 or 2), whereby the three-dimensional crosslink density in the prepared fluorocarbon polymer film can be adjusted and formed on the surface. This has the effect of controlling the hardness of the non-wetting fluorocarbon polymer film.

[0027]

The substrates to which the present invention can be applied include glass,
Although there are various types such as ceramics, metals, and plastics, it is most preferable to apply to a glass substrate. This will be described below with reference to an example. In the following examples, the unit “%” means “% by weight”.

[0028]

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 (a plastic-like surface having no oxide film). If it is a substance, 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, a hydroxyl group may be introduced into the surface.)] Micron silica particles 2 (preferably about 10 microns) (for example,
Micro Shear Gel DF10-60A or 120A manufactured by Asahi Glass Co., Ltd.) and silicate glass (for example, hard coating agent KP-1100A manufactured by Shin-Etsu Chemical Co., Ltd.)
Or 1100B or Si-8000 manufactured by Tokyo Ohka Kogyo Co., Ltd.
0 magnitude. These coating agents are converted into a silica coating by heat treatment after coating. ) Was mixed at a composition of about 1: 1 and applied by a casting method.
Heat treatment for 30 minutes or plasma ashing (300W,
After about 20 minutes, a glass-like silica underlayer 3 (hereinafter, also referred to as a silica underlayer) 3 having irregularities on the order of microns was formed on the surface (FIG. 2). Next, a non-aqueous solvent mixed with a substance containing a fluorocarbon group and a chlorosilane group (for example, CF _3- (CF ₂ ) _n -R-SiX _p Cl)
_3-p (n, R, X, and p are as described above) was dissolved at a concentration of several percent in a solvent of 90% normal hexadecane and 10% chloroform, and applied at 200 ° C. in an atmosphere containing water at 200 ° C. After baking for about 30 minutes, the surface of the glassy silica base layer 3 has exposed -OH groups. Therefore, the chlorosilyl group of the fluorine-containing chlorosilane-based surfactant and the -OH group undergo a dehydrochlorination reaction, and the surface is dehydrochlorinated. , ... Si
The bond of (O-) ₃ was generated, and the siloxane fluorocarbon-based polymer film 4 containing fluorine was formed unevenly on the surface of the glass-like silica base layer having irregularities on the order of microns on the surface (FIG. 2). ).

For example, DF10-60A having a diameter of about 10 μm as fine particles and KP-1100A as a silicate glass are dip-coated on the surface of a glass substrate and heat-treated (baked) at 350 ° C. to give a surface of about 10 μm (μm). A glassy silica underlayer having irregularities was obtained. After that, CF ₃ CH ₂ O (CH ₂ )
Dissolved at a concentration of about 1% by weight using ₁₅ SiCl ₃ 8
A solution of 0% n-hexadecane, 12% carbon tetrachloride and 8% chloroform was prepared and applied to the surface of a substrate on which a polysiloxane coating film having a large number of SiOH bonds was formed. , when the order of 30 minutes _{baking, CF 3 CH 2 O (CH} 2) 15 Si (O-) 3
Is formed, and has a roughness of about 10 microns.
A 5-micron-thick siloxane fluorocarbon polymer film (also referred to as a fluorocarbon coating film) 4 was produced (FIG. 2). In addition, this coating film hardly peeled off even when the goth test was performed.

At this time, in a non-aqueous solvent mixed with a substance containing a fluorocarbon group and a chlorosilane group, SiX _s Cl _4-s (X is a substituent such as H or an alkyl group, and s is 0 or 1 or 2; especially when S is 0, and s is 1 or 2 and X is H or Cl
In the case of a substance represented by (SiCl ₂ O) _n- (where n is an integer), it is a silane that can be completely hydrolyzed. ) Added (e.g., when the SiCl ₄ 3% by weight) to _{keep, CF 3 CH 2 O (CH} 2) 15 Si (O-) 3 3 binding via binding -Si (O-) ₃ of The fluorocarbon-based coating film was cross-dimensionally cross-linked to have a hardness approximately twice that of the case where SiCl ₄ was not added. Incidentally, the wetting angle of the fluorocarbon coating film having irregularities of about 10 μm (μm) on the surface formed in this way with respect to the water droplet 5 was about 130 to 140 degrees (FIG. 3).

[0031]

Example 2 As in Example 1, as shown in FIG. 1, after forming a glassy silica base layer having an uneven surface on a substrate, an alcohol containing a substance containing a fluorocarbon group and an alkoxysilane group was mixed. Solvent (for example, 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, S
i is a substituent containing 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 0 or 1 or 2) dissolved in methanol at a concentration of several percent), and baked at 200 ° C. for about 30 minutes to form a glassy silica underlayer 3 on the surface. Since the OH group is exposed, the alkoxy group of the fluorine-containing alkoxysilane-based surfactant and the -OH group undergo a dealcoholization reaction to form -S on the surface.
Bonds of i (O-) ₃ were generated, and a siloxane fluorocarbon-based polymer film containing fluorine was formed on the surface of the uneven glassy silica underlayer in the same manner as in Example 1.

For example, CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si
Using (OCH ₃ ) ₃ , an ethanol solution dissolved at a concentration of about 1% was prepared, and a substrate on which a polysiloxane coating film having many SiOH bonds (this film is also a silica base film) was formed. When applied on the surface and baked at 200 ° C. for about 30 minutes, CF ₃ CH ₂ O (CH ₂ ) ₁₅ S
Bonds of i (O-) ₃ were generated, and a fluorocarbon polymer film 4 having a thickness of 1 to 5 microns having irregularities of about 10 microns was produced (FIG. 2). In addition, this coating film hardly peeled off even when the goth test was performed.

At this time, SiY _t (OA) _4-t (Y is a substituent such as an alkyl group, OA is an alkoxy group) is used as a crosslinking agent for the substance in a solvent in which a substance containing a fluorocarbon group and an alkoxysilane group is mixed. (Where A is H or an alkyl group) t is 0 or 1 or 2;
Is a completely hydrolyzable silane. ) (For example, 5% by weight of Si (OCH ₃ ) ₄ ), the bond of CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (O—) ₃ is changed to that of —Si (O—) ₃ . Cross-linking was performed three-dimensionally through the bond, and a fluorocarbon polymer film having a hardness about 2 to 2.5 times as high as that obtained when Si (OCH ₃ ) ₄ was not added was produced.

By the way, when the water droplet 5 is dropped on the fluorocarbon polymer film having the irregularities of about 10 microns on the surface formed as described above, the water droplet comes into contact with the fluorocarbon polymer film only at the protruding portion. The water repellency is extremely high as shown in Fig.
35 to 140 degrees.

At this time, when 10% by weight of Si (OC ₃ H ₇ ) ₄ is added as a cross-linking agent to a solvent containing a substance containing a fluorocarbon group and an alkoxysilane group, about four times as much A fluorocarbon-based polymer film having a hardness of 5 was produced. In addition, a similar coating is formed using a fluorocarbon polymer (polytetrafluoroethylene).
When a non-aqueous solvent mixed with a substance containing a fluorocarbon group and an alkoxysilane group in which 20% of the fine particles were further dispersed and added was used, the hardness was almost the same as the conventional one, but the adhesion was extremely excellent as compared with the conventional one. A fluorocarbon polymer film having high water and oil repellency was produced.

Further, in the above embodiment, C was used as the reagent.
F ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃ , CF ₃ (CF
₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ was used, but if an ethylene group or an acetylene group was added to or incorporated in the alkyl chain portion, electron beam irradiation of about 5 megarads after coating film formation And a coating film having a hardness of about 10 times can be easily obtained.

As a fluorocarbon-based surfactant,
In addition to the above, CF_Three(CH_Two) _TwoSi (CH_Three)
_Two(CH_Two)_FifteenSi (OCH_Three)_Three, F (CF_Two)₈(C
H_Two)_TwoSi (CH_Three)_Two(CH_Two)₉Si (OCH_Three)_Three, C
F_ThreeCOO (CH_Two)_FifteenSi (OC_TwoH_Five)_ThreeEtc. are available
You.

[0038]

Example 3 As in Example 1, as shown in FIG. 1, a glassy silica base layer having an uneven surface was formed on a glass substrate, and then a mixture containing a substance containing a fluorocarbon group and a chlorosilane group was prepared. Aqueous solvents such as CF ₃ (CF ₂ ) ₇
Using (CH ₂ ) ₂ SiCl ₃ , a solution of 80% n-hexadecane, 12% carbon tetrachloride and 8% chloroform dissolved at a concentration of about 1% was prepared, and a monomolecular film having many SiOH bonds on the surface was prepared. When the formed base material is immersed for about 30 minutes, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (O
−) Water- and oil-repellent film 4 containing ₃ bonds and containing fluorine
(Chemically adsorbed monomolecular film) could be formed unevenly in a state chemically bonded to the glassy silica base layer (FIG. 4). The water- and oil-repellent film 4 '(monomolecular film) did not peel off at all even when the cross test was performed. In this case, since the fluorocarbon group is formed on the surface in an oriented state, the surface energy is extremely low, and the wetting angle to water is 13
5 to 145 degrees.

Further, in the above embodiment, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ S was used as the fluorocarbon surfactant.
Although iCl ₃ was used, if an ethylene group or an acetylene group is added to or incorporated into the alkyl chain portion, it can be cross-linked by electron beam irradiation of about 5 megarads after forming a monomolecular film, so that the hardness can be further improved. is there.

In addition to the above-mentioned fluorocarbon surfactants, CF ₃ CH ₂ O (CH ₂ ) ₁₅ SiC
l ₃ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si
Cl ₃ , F (CF ₂ ) ₈ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (C
_{H 2) 9 SiCl 3, CF} 3 COO (CH 2) 15 SiCl 3 and the like can be used.

[0041]

Embodiment 4 First, a processed glass plate is prepared.
After washing with an organic solvent, the surface is roughened using a sand blast method and submicron (0.1 to 1.
0) Form irregularities on the order of, for example, 0.4 to 0.9 microns. Note that, other than this method, a chemical etching method using hydrofluoric acid or a rubbing method using sandpaper can be used. Next, a non-aqueous solvent mixed with a substance containing a fluorocarbon group and a chlorosilane group, for example, CF
_{Using 3} (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ , a solution of 80% n-hexadecane (toluene, xylene, dicyclohexyl), 12% carbon tetrachloride and 8% chloroform dissolved at a concentration of about 1% Adjust the glass plate to 2
When the glass plate is immersed for about an hour, a natural oxide film is formed on the surface of the glass plate, and the surface of the oxide film contains a large number of hydroxyl groups. Therefore, the SiCl group of the substance containing a fluorocarbon group and a chlorosilane group and the hydroxyl group React with each other to cause a dehydrochlorination reaction, and CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ S
A bond of i (O-) ₃ was generated, and a monomolecular film containing fluorine was formed to a thickness of about 15 angstroms in a state of being chemically bonded to the surface of the glass plate. In addition, since the monomolecular film was very strongly chemically bonded, it did not peel off at all. When the material of the glass plate is a plastic such as an acrylic resin or a polycarbonate resin, after the surface is roughened, the surface is plasma-treated (300 W, about 10 minutes) to oxidize the surface to make it hydrophilic. A similar technique could be used by replacing the adsorbed liquid with a Freon solvent.

An attempt was made to actually use this glass plate, but the adhesion of dirt could be greatly reduced as compared with the case where the glass plate was not treated, and even if it adhered, it could be easily removed by rubbing with a brush. At this time, no scratch was made. In addition, the removal of oil and fat stains was possible only by washing with water. The wettability to water is similar to that of a lotus leaf, and the wetting angle is 155.
Degree.

[0043]

Embodiment 5 In the case of an aluminum plate 6 which is hydrophilic but has a small proportion of hydroxyl groups, the surface is electrolytically etched to form irregularities of about 0.5 to 0.8 microns. In addition to this method, a chemical etching method using hydrofluoric acid, a sputtering method using plasma in a vacuum, a rubbing method using sandpaper, or the like can be used. All metals can be used in the same way, but when the material is plastic such as acrylic resin or polycarbonate resin, the surface is roughened, and the surface is oxidized and hydrophilically treated by plasma treatment at 200 W for about 10 minutes. By doing so, a similar technique can be used.

Next, a substance containing a plurality of chlorosilyl groups (eg, SiCl ₄ , SiHCl ₃ , SiH ₂ C
If l ₂ , Cl— (SiCl ₂ O) _n —SiCl ₃ (n is an integer), particularly SiCl ₄ , the molecules are small and the activity toward hydroxyl groups is large, so that the effect of uniformly hydrophilizing the surface of the aluminum plate is large. ) In a non-aqueous solvent, for example, a 1% by weight solution in a chloroform solvent.
When the aluminum plate is immersed for about a minute, a dehydrochlorination reaction occurs on the surface of the aluminum plate because some OH groups are present on the surface, and a chlorosilane monomolecular film of a substance containing a plurality of chlorosilyl groups is formed.

[0045] For example, with the use of the SiCl ₄ as the substance containing a plurality of chlorosilyl groups, because the aluminum plate surface is a small amount of hydrophilic OH groups are exposed, dehydrochlorination reaction occurs Cl ₃ SiO- Ya at the surface Cl ₂ Si (O-) molecules as in ₂ is fixed to the surface via -SiO- bonds.

Thereafter, by washing with a non-aqueous solvent such as chloroform and further washing with water, SiCl ₄ molecules that have not reacted with the aluminum plate are removed, and (OH) ₃ SiO— or (OH) ₂ Si (O-) siloxane monomolecular film 7 composed mainly of siloxane bonds ₂ such
(Pure silica underlayer) was obtained.

Since the monomolecular film formed at this time is completely bonded to the aluminum plate through the chemical bond of -SiO-, it does not peel off at all. Moreover, the obtained monomolecular film has many SiOH (silanol) bonds on the surface.
About three times the number of the original hydroxyl groups are generated.

Then, a non-aqueous solvent mixed with a substance containing a fluorocarbon group and a chlorosilane group, for example, CF
_{Using 3} (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ , an 80% n-hexadecane, 12% carbon tetrachloride, 8% chloroform solution dissolved at a concentration of about 1% was prepared, and a SiO 2 solution was formed on the surface.
When an aluminum plate on which a silica monomolecular film having many H bonds is formed is immersed for about 1 hour, CF ₃ (C
A bond of F ₂ ) ₇ (CH ₂ ) ₂ Si (O—) ₃ is generated, and the fluorine-containing polymer film 4 is chemically bonded to the underlying siloxane monomolecular film, and has a thickness of about 15 nm over the entire surface of the aluminum plate.
(FIG. 5). This polymer film did not peel at all even when a peeling test was performed. The wetting angle with water was about 155 degrees.

Further, in the above embodiment, the fluorocarbon
CF as a surfactant_Three(CF_Two) ₇(CH_Two)_TwoSiC
l_ThreeWas used, but as the fluorocarbon surfactant
Other than CF_ThreeCH_TwoO (CH_Two)_FifteenSiCl_Three, CF
_Three(CH_Two)_TwoSi (CH_Three)_Two(CH_Two)_FifteenSiCl_Three, F
(CF_Two)_Four(CH_Two)_TwoSi (CH_Three)_Two(CH_Two)₉SiC
l_Three, CF_ThreeCOO (CH_Two)_FifteenSiCl_Three, CF_Three(C
F_Two)_Five(CH_Two)_TwoSiCl_ThreeEtc. are available.

In the fourth embodiment, when a glass plate is used instead of an aluminum plate and a substance containing a fluorocarbon group and a chlorosilane group is chemically adsorbed, the glass plate is kept hydrophilic to impart an anti-fogging effect. By forming an organic solvent-insoluble hydrophilic coating (for example, by applying an aqueous solution of poval (polyvinyl alcohol) or pullulan to a thickness of several microns) on the surface to be left (for example, the inner surface), The hydrophilic film was washed away with water to obtain a light-transmitting glass having a water-repellent, oil-repellent, antifouling monomolecular film on the surface and a monomolecular film (silica film composed of siloxane) having a hydrophilic hydroxyl group on the inner surface. The antifogging effect of this glass was confirmed, but the glass surface left hydrophilic remained extremely wet with water and did not fog at all.

In addition, the length of the molecule of the adsorption reagent was changed.
(For example, F (CF_Two)₈(CH_Two)_TwoS
i (CH_Three)_Two(CH_Two)₉SiCl_ThreeAnd F (CF_Two)
₈(CH_Two)_TwoSi (CH_Three)_Two(CH_Two)₆SiCl_Three,is there
Well, CF_Three(CF_Two)₇(CH_Two) _TwoSiCl_ThreeAnd CF_Three
(CF_Two)_Five(CH_Two)_TwoSiCl_ThreeThe composition
3: 1 to 1: 3) If adsorbed, the surface of the member becomes
It is possible to make it uneven with a bell, further improving water and oil repellency
Get better.

[0052]

As described above, when the method of the present invention is used, ceramics of metals and metal oxides such as Al, Cu, and stainless steel, or glass and plastic substrates can be used.
An excellent fluorocarbon monomolecular film having a water- and oil-repellent film can be formed at a high density without pinholes in a state of being chemically bonded to a substrate. Therefore, there is an effect that a high-performance fluorocarbon-based coating having extremely high durability and excellent water and oil repellency can be provided.

[Brief description of the drawings]

FIG. 1 is a conceptual cross-sectional view illustrating a manufacturing process of a water / oil repellent coating of Example 1 of the present invention.

FIG. 2 is a conceptual cross-sectional view illustrating a manufacturing process of a water- and oil-repellent coating of Example 1 of the present invention.

FIG. 3 is a conceptual cross-sectional view showing a case where a water droplet is dropped on the water- and oil-repellent coating of Example 1 of the present invention.

FIG. 4 is a conceptual cross-sectional view of a water- and oil-repellent coating enlarged to a molecular level in order to explain a manufacturing process of a monomolecular film-shaped water- and oil-repellent coating in Example 3 of the present invention.

FIG. 5 is a conceptual cross-sectional view of a water- and oil-repellent coating in which a portion A in FIG. 2 is enlarged to a molecular level in Example 5 of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Fine particles 3 Silicate glass film 4 Polymer film-like water- and oil-repellent film 4 'monomolecular film-like water- and oil-repellent film 5 Water droplet 6 Aluminum plate 7 Siloxane monomolecular film

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09D 183/08 C09D 183/08 C09K 3/18 102 C09K 3/18 102 104 104

Claims (18)

[Claims] At least a portion of the surface of a substrate is treated with a composition comprising a mixture of a perfluoroalkylalkyl silane and a fully hydrolyzable silane,
Moreover, an article having a water- and oil-repellent coating composed of at least one substrate selected from a glass, ceramic, metal, plastic substrate, and a substrate coated with an inorganic coating. 2. The perfluoroalkylalkylsilane has the general formula CF ₃ — (CF 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, or a substituent containing Si or an oxygen atom, and X is H
Or a substituent selected from an alkyl group, a cycloalkyl group, an allyl group or a derivative thereof, p is 0, 1 or 2), or CF _3- (CF ₂ ) _n -R-SiY _q (OA)
_3-q (n is 0 or an integer, R is an alkylene group, an ethylene group, an acetylene group, or a substituent containing Si or an oxygen atom, X is H or an alkyl group, a cycloalkyl group, an allyl group, or a derivative thereof. OA is an alkoxy group (where A is H or an alkyl group), q
Is 0, 1 or 2). The article having the water / oil repellent coating according to claim 1. 3. The article having a water / oil repellent coating according to claim 1, wherein the perfluoroalkylalkylsilane is at least one selected from the following compounds. (1) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ SiCl ₃ (2) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ (3) CF ₃ CH ₂ O (CH ₂ ) ₁₅ SiCl ₃ ( 4) CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si
_{Cl 3 (5) F (CF} 2) 4 (CH 2) 2 Si (CH 3) 2 (CH 2)
₉ SiCl ₃ (6) CF ₃ COO (CH ₂ ) ₁₅ SiCl ₃ (7) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ SiCl ₃ (8) F (CF ₂ ) ₈ (CH ₂ ) ₂ Si (CH _{3) 2} (CH _2)
9 SiCl ₃ (9) F (CF ₂ ) ₈ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ )
_{6 SiCl 3 (10) CF 3} CH 2 O (CH 2) 15 Si (OCH 3) 3 (11) CF 3 (CF 2) 7 (CH 2) 2 Si (OC 2 H 5) 3 (12) CF 3 (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si
(OCH ₃ ) ₃ (13) F (CF ₂ ) ₈ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ )
₉ Si (OCH ₃ ) ₃ (14) CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃ 4. The article having a water- and oil-repellent coating according to claim 1, wherein the inorganic coating is a glassy silica film. 5. The water-repellent material according to claim 1, wherein the glassy silica film is formed by applying a silicate glass to a surface of a glass substrate and further performing a heat treatment or a plasma ashing treatment. An article having an oily coating. 6. The article having a water- and oil-repellent coating according to claim 1, wherein the outermost surface of the substrate has irregularities on the order of submicron to micron. 7. The method according to claim 1, wherein the surface of the substrate and the mixture of the perfluoroalkylalkylsilane and the completely hydrolyzable silane are treated by a dehydrochlorination reaction or a dealcoholation reaction. An article having a water and oil repellent coating. 8. The fully hydrolyzable silane is Six _s
Cl _4-s (X is H- or Cl (SiCl ₂ O) _n- (where n is an integer), s is 0 or 1 or 2), or S
The article having a water / oil repellent coating according to any one of claims 1 to 7, wherein the article is selected from the group consisting of i (OA) ₄ (A is H or an alkyl group). 9. The combination of a perfluoroalkylalkyl silane and a completely hydrolyzable silane is a combination of a perfluoroalkylalkylchlorosilane and Six _s Cl.
_4-s (X is H— or Cl (SiCl ₂ O) _n — (where n is an integer), s is 0 or 1 or 2), or a combination of perfluoroalkylalkylalkoxysilane and Si (OA) ₄ (A The article having a water- and oil-repellent coating according to claim 8, which is selected from a combination of H and an alkyl group). 10. A method comprising contacting the surface of a substrate with a mixture of a perfluoroalkylalkylsilane and a fully hydrolyzable silane, said substrate being coated with a glass, ceramic, metal, plastic, and inorganic coating. Forming a non-wetting surface on a substrate selected from the group consisting of: 11. A perfluoroalkylalkylsilane having the general formula CF ₃ — (CF ₂ ) _n —R—Six _p Cl
_3-p (n is 0 or an integer, R is an alkylene group, ethylene group, acetylene group, or a substituent containing Si or an oxygen atom, X is H or an alkyl group, a cycloalkyl group, an allyl group, or a derivative thereof. Substituents, p is 0, 1 or 2), or CF _3- (CF ₂ ) _n -RS
iY _q (OA) _3-q (n is 0 or an integer, R is an alkylene group, an ethylene group, an acetylene group, or a substituent containing Si or an oxygen atom, and OA is an alkoxy group (where A is H or an alkyl group) , Q is selected from the compounds represented by 0, 1 or 2). 12. The method according to claim 10, wherein the perfluoroalkylalkylsilane is at least one selected from the following compounds. (1) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ SiCl ₃ (2) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ (3) CF ₃ CH ₂ O (CH ₂ ) ₁₅ SiCl ₃ ( 4) CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si
_{Cl 3 (5) F (CF} 2) 4 (CH 2) 2 Si (CH 3) 2 (CH 2)
₉ SiCl ₃ (6) CF ₃ COO (CH ₂ ) ₁₅ SiCl ₃ (7) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ SiCl ₃ (8) F (CF ₂ ) ₈ (CH ₂ ) ₂ Si (CH _{3) 2} (CH _2)
9 SiCl ₃ (9) F (CF ₂ ) ₈ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ )
_{6 SiCl 3 (10) CF 3} CH 2 O (CH 2) 15 Si (OCH 3) 3 (11) CF 3 (CF 2) 7 (CH 2) 2 Si (OC 2 H 5) 3 (12) CF 3 (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si
(OCH ₃ ) ₃ (13) F (CF ₂ ) ₈ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ )
₉ Si (OCH ₃ ) ₃ (14) CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃ 13. The method according to claim 10, wherein the inorganic coating is a vitreous silica film. 14. The glassy silica film is formed by applying silicate glass to the surface of a glass substrate, and further performing a heat treatment or a plasma ashing treatment.
3. The method according to 3. 15. The method according to claim 10, further comprising the step of processing the outermost surface of the base into irregularities on the order of submicron to micron.
15. The method according to 14. 16. The method according to claim 10, wherein the substrate surface and a mixture of a perfluoroalkylalkylsilane and a completely hydrolyzable silane are subjected to a dehydrochlorination reaction or a dealcoholation reaction. 17. S as a completely hydrolyzable silane
iX _s Cl _4-s (X is H- or Cl (SiCl ₂ O) _n -
The method according to any one of claims 10 to 16, wherein (n is an integer), s is 0 or 1 or 2, or Si (OA) ₄ (A is H or an alkyl group). 18. Perfluoroalkyl alkylsila
The combination of silane and fully hydrolyzable silane
Oroalkyl alkylchlorosilane and SiX _sCl_4-s
(X is H- or Cl (SiCl_TwoO)_n− (Where n is
Integer), s is 0 or a combination of 1 or 2), or
Fluoroalkyl alkylalkoxysilane and Si
(OA)_Four(A is H or an alkyl group)
18. The method of claim 17, wherein the method is performed.