JP3444524B2 - Article and glass article having water- and oil-repellent coating - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an article made of a glass substrate having a water / oil repellent coating and a method for producing the article. More specifically, the present invention relates to an invention in which an undercoat layer is provided on the surface of a substrate and a water / oil repellent coating film is provided thereon.

[0002]

2. Description of the Related Art Conventionally, buildings, electric appliances, vehicles, industrial equipment, mirrors, spectacle lenses, etc. are required to have an ultra-thin film coating having heat resistance, weather resistance, wear resistance and antifouling function. . As a method for producing such a coating film for the purpose of water and oil repellency and antifouling, a method of baking a fluorocarbon polymer is currently known. In this method, the surface of the substrate is roughened with a sand brush, a wire brush, chemical etching or the like, and after applying a primer or the like,
Further, a coating material prepared by suspending a fluorocarbon-based fine powder such as polytetrafluoroethylene in ethanol is applied, and after drying, 4
A general method is to perform baking (baking treatment) at about 00 ° C. for about 1 hour, and baking the fluorocarbon polymer on the surface of the substrate.

[0003]

However, while this method is easy to manufacture, since the polymer and the substrate are merely bonded by the anchor effect, the adhesiveness to the substrate is limited and the durability is low. I was inferior in sex. Also,
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 view of the above-mentioned drawbacks of the conventional methods, an object of the present invention is to provide a method for producing a fluorine-based coating film having good adhesion to a substrate, no pinholes, and excellent water and oil repellency on the surface. It is intended to improve the performance of equipment such as buildings, electric appliances, vehicles, industrial equipment, etc., which require a heat-resistant, weather-resistant, and abrasion-resistant coating having excellent water and oil repellency.

[0005]

Means for Solving the Problems] To achieve the above object, the article having water and oil repellency coating of the present invention, the coating of repellent containing at least perfluoroalkyl group and Si, one surface of the substrate Is formed on the outermost surface of the substrate through a silica underlayer, and hydrophilic silica is formed on the other surface of the substrate.
It is characterized in that a layer is formed . Another repellent of the present invention
Articles with water-repellent coatings should be at least perfluoro.
A water- and oil-repellent coating containing an alkyl group and Si is formed on the outermost surface of one surface of the glass plate via a roughened silica base layer, and the other surface of the hydrophilic surface is hydrophilic. Siri
It is characterized in that a mosquito layer is formed . Gala of the present invention
The article has at least one surface of the glass substrate,
Perfluoroalkyl alkyl through silica underlayer
It is characterized in that it is covered with a water and oil repellent coating film formed by using silane, and a hydrophilic silica layer is formed on the other surface.

[0006] In the article, perfluoroalkyl alkyl silane of 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, X is H or an alkyl group, a cycloalkyl group, A substituent selected from an allyl 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, an ethylene group, an acetylene group, or
Is a substituent containing Si or an oxygen atom, Y is an alkyl group
Substituent, OA is preferably selected from compounds represented by alkoxy groups (wherein A is H or an alkyl group) and q is 0, 1 or 2 in order to improve antifouling property. Further, in the above-mentioned article, perfluoroalkyl alkyl
The water- and oil-repellent coating treated with silane is preferably in the form of a polymer or a monolayer.

Here, the perfluoroalkyl alkylsilane 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, it is advantageous that the surface of the substrate is roughened by the silica underlayer. Furthermore, the extent of roughening of the surface of the silica primer layer is preferable in order to improve water and oil repellency functionality If it is uneven in Mi Kuron'oda.

Further, it is preferable that the silica underlayer and the perfluoroalkylalkylsilane are treated by dehydrochlorination reaction or dealcoholization reaction in order to improve durability. In addition, it is preferable that the silica underlayer is formed by applying silicate glass on the surface of the glass substrate and then performing heat treatment or plasma ashing treatment in order to improve durability.

Further, a silica underlayer is formed on the surface of the glass substrate by SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , Cl-.
(SiCl ₂ O) _n -SiCl ₃ (n is an integer) is brought into contact, and a water-repellent and oil-repellent film having excellent transparency is formed by a dehydrochlorination reaction and a hydrolysis reaction. To obtain

The method for forming a non-wetting surface on the surface of the substrate according to the present invention selects at least one surface of the glass substrate.
And a. Depositing a silica underlayer, b. The method further comprises the step of contacting the silica underlayer with a composition comprising a perfluoroalkylalkylsilane. In the above method, it is preferable to include a step of contacting the silica underlayer formed on the surface of the glass substrate with the perfluoroalkylalkylsilane and then performing a dehydrochlorination reaction or a dealcoholization reaction in order to improve durability.

Further, as a perfluoroalkylalkylsilane, a compound represented by 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, X is H or an alkyl group, a cycloalkyl group,
A substituent selected from 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 represents an alkylene group, an ethylene group, an acetylene group or Si or <br/> substituent containing an oxygen atom, Y is a substituent of the alkyl group,, OA
Is an alkoxy group (where A is H or an alkyl group),
It is preferable that q is a compound represented by 0, 1 or 2) because it can be treated in a short time.

Here, it is preferable that the perfluoroalkyl alkylsilane 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

Further, it is convenient to mix fine particles into the silicate glass at the time of forming the silica underlayer to improve the antifouling property for roughening the non-wetting surface of the substrate. Further, forming a silica underlayer by applying silicate glass on the surface of the glass substrate and then performing heat treatment or plasma ashing treatment simplifies the formation of the underlayer.

Further, SiCl ₄ , Si is formed on the surface of the glass substrate.
HCl ₃ , SiH ₂ Cl ₂ , Cl- (SiCl ₂ O) _n- S
It is convenient to form a silica underlayer having excellent transparency when it is formed by bringing at least one compound selected from iCl ₃ (n is an integer) into contact with each other and performing a dehydrochlorination reaction and a hydrolysis reaction.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Next, in the first embodiment of the present invention, a step of forming a silica underlayer on the surface of a substrate and applying a non-aqueous solvent in which a substance containing a fluorocarbon group and a chlorosilane group is mixed. Or a step of applying a solvent in which a substance containing a fluorocarbon group and an alkoxysilane group is mixed, and a step of performing heat treatment.

In the second embodiment of the present invention, the step of forming irregularities on the surface of the substrate and the step of contacting with a non-aqueous solvent mixed with a substance containing a plurality of chlorosilyl groups to form hydroxyl groups on the surface of the substrate. A step of reacting a substance containing a plurality of chlorosilyl groups with a chlorosilyl group to deposit the substance on the surface of the substrate; and washing the excess chlorosilyl group remaining on the substrate with a non-aqueous organic solvent to remove the substance. rear,
A step of reacting with water to form a silica monomolecular film (also referred to as a silica underlayer) made of a substance containing a plurality of silanol groups on the substrate, and a chlorosilane group (SiCl _n X _3-n ) at one end Group, n = 1, 2, 3, and X is a functional group, and a chlorosilane-based surfactant containing a linear fluorocarbon group at the other end is chemically adsorbed on the substrate surface to accumulate a monomolecular adsorbed film. And a process.

In the first or second embodiment of the present invention, fine particles and silicate glass are mixed and applied to the surface of the substrate in the step of forming the irregular silica silica underlayer on 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 sandblast method, a sputtering method, and a rubbing method is used.

Further, in the first or second embodiment of the present invention, a step of forming a silica underlayer (hereinafter, referred to as a silica underlayer including the silica monomolecular film) on the surface of the substrate, and a chlorosilane group at one end (SiCl _n X _3-n group, n
= 1, 2, 3, and X is a functional group), and a step of forming a chemisorption film on the substrate using a fluorosilane-based surfactant composed of a fluorocarbon-based linear molecule.

In the first or second 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 (perfluoroalkyl alkylchlorosilane based on perfluoroalkyl alkyl silane; n is 0 or an integer, R is an alkylene group, ethylene group, acetylene group, or Si, a substituent containing an oxygen atom, X is H or an alkyl group, cyclo A substituent selected from an alkyl group, an allyl group or a derivative thereof, and p is 0, 1 or 2) is used.

In the first or second embodiment of the present invention, the substance containing a fluorocarbon group and an alkoxysilane group is CF _3- (CF ₂ ) _n --R--Si.
_Yq (OA) _3-q (perfluoroalkylalkylalkoxysilane of perfluoroalkylalkylsilane; 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, OA is an alkoxy group (where A is H or an alkyl group), q
Uses 0, 1 or 2).

According to the above-described embodiment of the present invention, since the chemisorption monomolecular film containing fluorine is formed on at least the surface of the substrate on which the silica underlayer is formed, the adhesion to the substrate is improved. It is possible to obtain a fluorine-based coating film that is good and has no pinhole, and that is excellent in water and oil repellency (non-wetting), heat resistance, weather resistance, wear resistance, and the like.

Further, in the present invention, glass fine particles and silicate glass are mixed and applied on the surface of the fluorocarbon-based coating film-forming substrate in advance and then baked to form a glassy silica underlayer having a rough surface of submicron to micron order. In addition, by including a step of roughening the substrate by etching or sandblasting the substrate itself, there is an effect that fine irregularities can be formed on the surface of the fluorocarbon coating film formed in the subsequent step. Therefore, it is possible to form a fluorocarbon-based coating film (hereinafter also referred to as a fluorocarbon-based polymer film) having arbitrary irregularities on the surface and excellent in water and oil repellency.

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

Furthermore, after the step of forming irregularities on the surface, it is brought into contact with a non-aqueous solvent in which a substance containing a plurality of chlorosilyl groups is mixed, and the chlorosilyl group of the substance containing a plurality of hydroxyl groups and the chlorosilyl group on the surface of the substrate. And a step of depositing the substance on the surface of the substrate by reacting with and a step of 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. Then, 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 a process for accumulating a monomolecular adsorption film by chemically adsorbing a chlorosilane-based surfactant containing a linear fluorocarbon group at the other end on the substrate surface is performed, a fluorocarbon-based compound with a higher molecular adsorption density will be obtained. (F It has the function of producing a chemisorption 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 and a fluorocarbon group and an alkoxysilane group include CF ₃ — (CF ₂ ) _n —R—
It is possible to use a _{SiY q (OA) 3-q} ( wherein, n, R, p, q are the same as defined above.).

Further, in order to adjust the hardness of the formed fluorocarbon polymer film, in the case of a non-aqueous solvent in which a substance containing a fluorocarbon group and a chlorosilane group is mixed, SiX _s Cl _{4 is} used as a crosslinking agent for the substance. _-s (X is H
Alternatively, in the case of a solvent in which a substituent such as an alkyl group, s is 0 or 1 or 2) is added and a substance containing a fluorocarbon group and an alkoxysilane group is mixed, SiY _t (OA) _4-t is used as a crosslinking agent. (Y is a substituent such as an alkyl group,
By using OA as an alkoxy group (where A is H or an alkyl group) and t is 0, 1 or 2), the three-dimensional crosslink density in the prepared fluorocarbon polymer film can be adjusted and formed on the surface. It has the function of controlling the hardness of the non-wetting fluorocarbon polymer film.

[0028]

EXAMPLES Examples of substrates to which the present invention can be applied include glass,
There are various materials such as ceramics, metals, and plastics, but it is most preferable to apply them to a glass substrate. An example will be described below. In addition, in the following Examples, what is simply referred to as% means% by weight.

[0029]

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 (such as plastic does not have an oxide film on its surface). In the case of a substance, the surface may be treated in advance 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.)] The surface has a diameter of 1 to 20. Micron silica particles 2 (preferably about 10 microns) 2 (for example,
Asahi Glass Co., Ltd. Microshear Agel DF10-60A or 120A) and silicate glass (for example, Shin-Etsu Chemical Co., Ltd. hard coating agent KP-1100A)
Or 1100B or Si-8000 manufactured by Tokyo Ohka Kogyo Co., Ltd.
There is 0 etc. These coating agents become a silica film by heat treatment after coating. ) Is mixed in a composition of about 1: 1 and applied by a casting method, and then the temperature is set to 50.
Heat treatment at 0 ° C for 30 minutes or plasma ashing (30
After performing 0 W for about 20 minutes), a glassy silica underlayer (hereinafter also referred to as silica underlayer) 3 having micron-order irregularities on the surface could be formed (FIG. 2). Then, the non-aqueous solvent obtained by mixing a substance containing a fluorocarbon group and a chlorosilane group _{(e.g., CF 3 - (CF 2)} n -R-SiX p Cl
_3-p (n, R, X, p are as described above) at a concentration of several percent, 90% normal hexadecane, and 1 chloroform.
(Dissolved in 0% solvent), and baking in an atmosphere containing water at a temperature of 200 ° C. for about 30 minutes exposes —OH groups on the surface of the glassy silica underlayer 3. Therefore, the chlorosilyl group and -OH group of the chlorosilane-based surfactant containing fluorine undergoes dehydrochlorination reaction on the surface,
... Si (O-) ₃ bonds are generated, and the siloxane fluorocarbon-based polymer film 4 containing fluorine is formed unevenly on the surface of the glass-like silica underlayer having micron-order unevenness on the surface in a chemically bonded state ( (Fig. 2).

For example, when DF10-60A having a diameter of about 10 μm as fine particles and KP-1100A as silicate glass are dip-coated on the surface of a glass substrate and heat-treated (baked) at 350 ° C., the surface is about 10 μm (μm). A glassy silica underlayer having irregularities was obtained. After that, CF ₃ CH ₂ O (CH ₂ )
With ₁₅ SiCl _3, was dissolved at a concentration of about 1 wt% 8
A 0% n-hexadecane, 12% carbon tetrachloride, 8% chloroform solution 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, and the temperature was changed in an atmosphere containing water. : When baked at 200 ° C. for about 30 minutes, CF ₃ CH ₂ O (CH ₂ ) ₁₅ S
A bond of i (O-) ₃ was generated, and a siloxane fluorocarbon-based polymer film (also referred to as a fluorocarbon-based coating film) 4 having a thickness of 1 to 5 μm and having irregularities of about 10 μm could be produced (FIG. 2). It should be noted that this coating film was scarcely peeled off even when the goth test was conducted.

At this time, SiX _s Cl _4-s (X is a substituent such as H or an alkyl group, s is a crosslinker for the substance) is mixed in a non-aqueous solvent containing a substance containing a fluorocarbon group and a chlorosilane group. 0 or 1 or 2) is added (for example, SiCl ₄ is 3 weight percent), the bond of CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (O-) ₃ is-.
Three-dimensionally cross-linked through the bond of Si (O-) ₃ ,
A fluorocarbon coating film having a hardness about twice that of the case where SiCl ₄ was not added could be manufactured. By the way, the surface created in this way is 10 microns (μ
The wetting angle of the fluorocarbon-based coating film having irregularities of about m) to the water droplets 5 was about 130 to 140 degrees (FIG. 3).

[0032]

Example 2 Similar to Example 1, an alcohol was prepared by forming a glassy silica underlayer having an uneven surface on a substrate as shown in FIG. 1 and then mixing a substance containing a fluorocarbon group and an alkoxysilane group. solvents (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, S
i or a substituent containing an oxygen atom, Y is H or a substituent such as an alkyl group, OA is an alkoxy group (where A is H
Alkyl group), q is 0 or 1 or 2) dissolved in methanol at a concentration of several percent) and is baked at a temperature of 200 ° C. for about 30 minutes to form a glassy silica underlayer 3 on the surface. Since the -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 to form a bond of -Si (O-) ₃ on the surface, resulting in unevenness. A siloxane fluorocarbon-based polymer film containing fluorine was formed on the surface of the glassy silica underlayer in the same manner as in Example 1.

For example, CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si
(OCH ₃ ) ₃ is used to prepare an ethanol solution dissolved at a concentration of about 1%, and a polysiloxane coating film having a large number of SiOH bonds (this film is also a silica base film) is formed on the surface. When it is applied to the surface and baked at 200 ° C. for about 30 minutes, CF ₃ CH ₂ O (CH ₂ ) ₁₅
Bonds of Si (O-) ₃ were generated, and a fluorocarbon-based polymer film 4 having a thickness of 1 to 5 μm and having irregularities of about 10 μm could be manufactured (FIG. 2). It should be noted that this coating film was scarcely peeled off even when the goth test was conducted.

At this time, SiY _t (OA) _4-t (Y is a substituent such as an alkyl group and OA is an alkoxy group) as a crosslinking agent for the substance in a solvent mixed with a substance containing a fluorocarbon group and an alkoxysilane 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 ) ₁₅ The bond of Si (O-) ₃ is
-Si (O-) ₃ is three-dimensionally cross-linked through a bond, and is about 2 to 2 as compared with the case where Si (OCH ₃ ) ₄ is not added.
A fluorocarbon polymer film having a hardness of 2.5 times could be manufactured.

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 thus formed, the water droplet comes into contact with the fluorocarbon polymer film only at the protrusions. As shown in, the water repellency is extremely high and the wetting angle to water is about 1
It was 35 to 140 degrees.

At this time, when 10% by weight of Si (OC ₃ H ₇ ) ₄ was added as a cross-linking agent of the substance into the solvent mixed with the substance containing the fluorocarbon group and the alkoxysilane group, it was about 4 times. A fluorocarbon-based polymer film having the above hardness could be manufactured. In addition, the same coating is applied to fluorocarbon polymer (polytetrafluoroethylene).
When a non-aqueous solvent prepared by mixing a substance containing a fluorocarbon group and an alkoxysilane group in which 20% of the above fine particles are further added and dispersed is used, the hardness is the same as that of the conventional one, but the adhesiveness is extremely superior to that of the conventional one. A fluorocarbon polymer film having high water and oil repellency can 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 ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ was used, but if an ethylene group or an acetylene group is added to or incorporated in the alkyl chain portion, electron beam irradiation of about 5 megarads after coating film formation Since it can be crosslinked with, a coating film having a hardness of about 10 times can be easily obtained.

Further, as a fluorocarbon type surfactant,
In addition to the above, CF₃(CH₂) ₂Si (CH₃)
₂(CH₂)₁₅Si (OCH₃)₃, F (CF₂)₈(C
H₂)₂Si (CH₃)₂(CH₂)₉Si (OCH₃)₃, C
F₃COO (CH₂)₁₅Si (OC₂H_Five)₃Etc. are available
It

[0039]

Example 3 As in Example 1, after forming a glass-like silica underlayer having an uneven surface on a glass substrate as shown in FIG. 1, a substance containing a fluorocarbon group and a chlorosilane group was mixed. Aqueous solvent such as CF ₃ (CF ₂ )
₇ (CH ₂ ) ₂ SiCl ₃ was used to prepare a 80% n-hexadecane, 12% carbon tetrachloride, 8% chloroform solution dissolved at a concentration of about 1%, and a monomolecular film having many SiOH bonds on the surface. When the base material on which is formed is immersed for about 30 minutes, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (O
-) Water- and oil-repellent film 4 containing a bond of ₃ and containing fluorine
The (chemisorption monomolecular film) could be formed unevenly in the state of being chemically bonded to the glassy silica underlayer (FIG. 4). The water- and oil-repellent film 4 '(monomolecular film) was not peeled at all even after the goth test. Further, 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
It was 5 to 145 degrees.

Furthermore, in the above embodiment, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ S is used as the fluorocarbon type surfactant.
Although iCl ₃ was used, if an ethylene group or an acetylene group is added to or incorporated in the alkyl chain portion, it is possible to crosslink by electron beam irradiation of about 5 megarads after forming a monomolecular film, so it is possible to further improve hardness. is there.

In addition to the above-mentioned fluorocarbon surfactants, CF ₃ CH ₂ O (CH ₂ ) ₁₅ SiC is used.
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.

[0042]

Example 4 First, a glass plate that has been processed is prepared,
After washing with an organic solvent, the surface is roughened using a sand blast method, and the surface is submicron (0.1 to 1.
0) order irregularities, for example, irregularities of about 0.4 to 0.9 micron are formed. Besides this method, a chemical etching method using hydrofluoric acid or a rubbing method using sandpaper can be used. Next, a non-aqueous solvent such as CF ₃ mixed with a substance containing a fluorocarbon group and a chlorosilane group is used.
Using (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃ , prepare a solution of 80% n-hexadecane (toluene, xylene, dicyclohexyl may be used), 12% carbon tetrachloride, 8% chloroform dissolved at a concentration of about 1%. The glass plate
When immersed for about a time, a natural oxide film is formed on the surface of the glass plate, and the oxide film surface contains a large number of hydroxyl groups. Therefore, the SiCl group and the hydroxyl group of the substance containing a fluorocarbon group and a chlorosilane group are included. React to cause a dehydrochlorination reaction, and CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ S is spread over the entire glass surface.
A bond of i (O-) ₃ was generated, and it could be formed with a film thickness of about 15 angstroms in a state of being chemically bonded to the surface of the monomolecular film glass plate containing fluorine. Since the monomolecular film was extremely strongly chemically bonded, it never peeled off. When the material of the glass plate is plastic such as acrylic resin or polycarbonate resin, after the surface roughening treatment, the surface is plasma treated (300 W, about 10 minutes) to oxidize the surface to make it hydrophilic. It was possible to use a similar technique by replacing the adsorbent with a Freon solvent.

An attempt was made to use this glass plate for actual use, but the adhesion of dirt could be greatly reduced as compared with the untreated one, and even if it did, it could be easily removed by rubbing with a brush. At this time, no scratches were formed. Further, even oil and fat stains could be removed only by washing with water. The wettability to water is similar to that of a lotus leaf, and the wetting angle is 155.
It was degree.

[0044]

Albeit in Example 5 Hydrophilic case of the aluminum plate 6 small proportion containing a hydroxyl group, the surface was electrolytically etched to form a 0.5 to 0.8 microns about irregularities on the surface. Other than this method, a chemical etching method using hydrofluoric acid, a sputtering method using plasma in vacuum, a rubbing method using sandpaper, etc. can be used. All metals can be used in the same way, but if the material is plastic such as acrylic resin or polycarbonate resin,
After roughening the surface, the same technique can be used by treating the surface with plasma for 200 W for 10 minutes to oxidize the surface to make it hydrophilic.

Next, a substance containing a plurality of chlorosilyl groups (for example, SiCl ₄ , or SiHCl ₃ , SiH ₂ C)
_{l 2, Cl- (SiCl 2 O} ) n -SiCl 3 (n is an integer), in particular, the use of SiCl _4, since the molecule is active also large for small hydroxyl group, the greater the effect of uniformly hydrophilize the aluminum plate surface ) Are mixed in a non-aqueous solvent, for example, a chloroform solvent at a concentration of 1% by weight.
When it is immersed for about 0 minutes, hydrophilic -O will appear on the aluminum plate surface.
Since there are some H groups, a dehydrochlorination reaction occurs on the surface and a chlorosilane monomolecular film of a substance containing a plurality of chlorosilyl groups is formed.

For example, when SiCl ₄ is used as the substance containing a plurality of chlorosilyl groups, a small amount of hydrophilic --OH groups are exposed on the surface of the aluminum plate, so that a dehydrochlorination reaction occurs on the surface and Cl ₃ SiO-- Molecules such as Cl ₂ Si (O—) ₂ are fixed to the surface via —SiO— bonds.

After that, when washed with a non-aqueous solvent such as chloroform and further washed with water, SiCl ₄ molecules which have not reacted with the aluminum plate are removed, and (OH) ₃ SiO- or (OH) is attached to the surface of the aluminum plate. A siloxane monomolecular film 7 (pure silica underlayer) of ₂ Si (O-) ₂ or the like was obtained.

Since the monomolecular film formed at this time is completely bonded to the aluminum plate through a chemical bond of -SiO-, it never peels off. Moreover, the obtained monomolecular film has many SiOH (silanol) bonds on the surface.
About three times as many as the initial hydroxyl groups are generated.

Therefore, a non-aqueous solvent mixed with a substance containing a fluorocarbon group and a chlorosilane group, for example, C
With _{F 3 (CF 2) 7 (} CH 2) 2 SiCl 3, 80% n- hexadecane dissolved at a concentration of about 1%, 12% carbon tetrachloride, and adjust the 8% chloroform solution, Si on the surface
Immersing an aluminum plate on which a silica monolayer having many OH bonds is formed for about 1 hour, CF
A bond of ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (O-) ₃ is generated, and the polymer film 4 containing fluorine is chemically bonded to the lower siloxane monomolecular film, and about 1 is spread over the entire surface of the aluminum plate.
It could be formed with a film thickness of 5 nm (FIG. 5). The polymer film was not peeled at all even after the peeling test. The wetting angle with water was about 155 degrees.

Furthermore, in the above embodiment, fluorocarbon is used.
CF as a system surfactant₃(CF₂) ₇(CH₂)₂SiC
l₃Was used as the fluorocarbon surfactant.
CF besides things₃CH₂O (CH₂)₁₅SiCl₃, CF
₃(CH₂)₂Si (CH₃)₂(CH₂)₁₅SiCl₃, F
(CF₂)_Four(CH₂)₂Si (CH₃)₂(CH₂)₉SiC
l₃, CF₃COO (CH₂)₁₅SiCl₃, CF₃(C
F₂)_Five(CH₂)₂SiCl₃Etc. are available.

In the fifth embodiment, a glass plate is used instead of the aluminum plate, and when a substance containing a fluorocarbon group and a chlorosilane group is chemically adsorbed, it remains hydrophilic in order to provide an antifogging effect. By forming an organic solvent-insoluble hydrophilic coating (for example, an aqueous solution of Poval (polyvinyl alcohol) or pullulan to have a thickness of several microns) on the surface to be left (for example, the inner surface), it is possible to The hydrophilic coating was washed off with water to obtain a light-transmitting glass having a water-repellent, oil-repellent and antifouling monomolecular film on the surface and a monomolecular film (silica film made of siloxane) having hydrophilic hydroxyl groups on the inner surface. The antifogging effect was confirmed with this glass, but the glass surface that remained hydrophilic was extremely wettable by water and did not fog at all.

Also, the length of the molecule of the adsorption reagent was changed.
Are mixed (for example, F (CF₂)₈(CH₂)₂S
i (CH₃)₂(CH₂)₉SiCl₃And F (CF₂)
₈(CH₂)₂Si (CH₃)₂(CH₂)₆SiCl₃,is there
I'm CF₃(CF₂)₇(CH₂) ₂SiCl₃And CF₃
(CF₂)_Five(CH₂)₂SiCl₃The combination of
(3: 1 to 1: 3) If it is adsorbed, the molecular surface of the member is
It is possible to make it uneven with a bell, further improving water and oil repellency
Get better.

[0053]

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

[Brief description of drawings]

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

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

FIG. 3 is a conceptual cross-sectional view when 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 for explaining the manufacturing process of the monomolecular film water- and oil-repellent coating in Example 3 of the present invention.

5 is a conceptual diagram of a cross section of a water- and oil-repellent coating obtained by enlarging a portion A in FIG. 2 to a molecular level in Example 5. FIG.

[Explanation of symbols]

1 glass substrate 2 fine particles 3 Silicate glass film 4 Polymer film water and oil repellent film 4'monomolecular film water and oil repellent film 5 water drops 6 Aluminum plate 7 Siloxane monolayer

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-4-288349 (JP, A) JP-A-2-311332 (JP, A) JP-A-60-40254 (JP, A) JP-A-5- 238781 (JP, A) JP 2-248480 (JP, A) JP 58-147483 (JP, A) JP 62-3046 (JP, A) JP 1-315431 (JP, A) JP 63-175671 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C03C 15/00-23/00 B32B 1/00-35/00 C09K 3/18

Claims (6)

(57) [Claims] 1. At least a perfluoroalkyl group and S
coating repellent containing i is being formed through a silica primer layer on the outermost surface of one side of the substrate, the other surface of the substrate has hydrophilic silica layer is formed
Articles having a water- and oil-repellency coating, characterized in that that. 2. At least a perfluoroalkyl group and S
A water- and oil-repellent coating containing i is formed on the outermost surface of one surface of the glass plate through a roughened and roughened silica underlayer, and a hydrophilic silica layer is formed on the other surface. An article having a water and oil repellent coating characterized by being formed . 3. A glass substrate, at least one surface of which is covered with a water- and oil-repellent coating formed by using a perfluoroalkylalkylsilane through a silica underlayer, and the other surface is hydrophilic. Silica layer is formed
Glass article, characterized in that is. 4. The glass article according to claim 3 , wherein the surface of the substrate is roughened by the silica underlayer. 5. The glass article according to claim 4 , wherein the degree of roughening of the silica underlayer is in the order of micron. 6. The silica underlayer comprises SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ and Cl- (S) on the surface of a glass substrate.
_{iCl 2 O) n -SiCl 3 (} n is contacting at least one compound selected from an integer) An article according to any one of claims 3 to 5 which is formed by processing dehydrochlorination.