JP2001335693A - Aqueous emulsion containing hydrolyzed product of fluorocarbon silane, and coating having oil stain resistance and heat-resistant water repellency - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous emulsion capable of forming a coating layer having oil stain resistance together with a heat-resistant water repellency. SOLUTION: This aqueous emulsion contains a hydrolyzed product of a fluorocarbon silane, a surface active agent, an organomethoxysilane, and an acidic or alkaline aqueous solution as a pH adjuster with which pH of the emulsion is adjusted.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a fluorocarbon silane hydrolyzate-containing aqueous emulsion capable of providing a coating layer having oil- and stain-proofing properties and heat- and water-repellent properties. An aqueous emulsion containing silane and further adjusting the pH of the emulsion by containing an aqueous acid solution or aqueous alkali solution as a pH adjuster, and the emulsion, glass or metal surfaces, castings, ceramics such as pottery, bricks, concrete, Or, it is formed by coating and drying on a substrate such as stone, and is used for home appliances such as glass windows of microwave ovens and toasters, industrial applications such as automobile-related parts, and oil-fouling and anti-fouling properties of various parts in the office automation field. And heat and water repellent On Kutsugaebutsu.

[0002]

2. Description of the Related Art Various proposals have been made for a silane-containing aqueous solution capable of providing water repellency to the surface of a substrate.

Among silane-containing aqueous solutions, those which can provide a substrate with water repellency without requiring a special heat treatment include a fluorocarbon silane hydrolyzate and a surfactant for emulsifying the hydrolyzate. Have been developed (U.S. Pat. No. 5,550,18).
No. 4).

[0004] An emulsion containing a hydrolyzate of a fluorocarbon silane, a surfactant for emulsifying the hydrolyzate, and a specific silicate, wherein
Is adjusted to 7 or more, a property that can maintain excellent water repellency even under high temperature conditions, that is,
Heat and water repellency can be provided to the substrate
181355).

[0005] Further, as an emulsion which also provides excellent heat and water repellency, an emulsion containing a hydrolyzate of fluorocarbon silane emulsified by a specific nonionic surfactant and a specific silicate, An emulsion in which the pH is adjusted to 4 or more has also been proposed (JP-A-11-181355).

Both are aqueous emulsions containing a specific silicate together with a hydrofluorocarbonsilane hydrolyzate.

[0007]

Products such as a glass window of a microwave oven and a toaster provided with a coating layer formed by applying and drying such an emulsion are described below.
Although it has excellent heat and water repellency, its antifouling property against oil is insufficient. In some applications, it is strongly desired to have an antifouling property against oil as well as heat and water repellency.

An object of the present invention is to provide a fluorocarbon silane hydrolyzate-containing aqueous emulsion capable of forming a coating layer having heat resistance and water repellency as well as oil stain resistance.

[0009]

Means for Solving the Problems In order to solve such problems, the present inventors have developed an aqueous solution containing a hydrolyzate of fluorocarbon silane and an organoalkoxy silane and further having a pH adjusted by a pH adjuster. It has been found that by using an emulsion, it is possible to form a coating layer having both oil and water resistance as well as heat and water repellency.

That is, the fluorocarbon silane hydrolyzate-containing aqueous emulsion of the present invention is an aqueous emulsion containing a hydrolyzate of a fluorocarbon silane, a surfactant, an organoalkoxy silane, and a pH adjuster.

[0011]

Embedded image R _f — (CH ₂ ) _p —Si ｛— (O—CH ₂ CH ₂ ) _n —OR ¹ ｝ ₃ (1) (R _f is a perfluoroalkyl group having 3 to 18 carbon atoms or A mixture thereof, wherein a plurality of R ¹ are the same or different alkyl groups having 1 to 3 carbon atoms,
And p = 2-4 and n = 2-10)

At least one hydrolyzable fluorocarbon silane represented by the formula:
It emulsifies the hydrolyzate of the fluorocarbon silane. The fluorocarbon silane is contained in an amount of 0.1 to 20% by weight based on the total weight of the aqueous emulsion, and the weight ratio of the fluorocarbon silane to the surfactant is: 1: 1 to 10: 1, and the organoalkoxysilane is

[0013]

Embedded image _{^{R 2 n Si (OR 3)}} 4-n (2) (R 2 is a 1 to 10 alkyl group carbon atoms, more R ³ is one to three of the same carbon atom Or different alkyl groups and n = 1-3)

The organoalkoxysilane is contained in an amount having a mole fraction of 0.3 to 10 with respect to the fluorocarbon silane, and the pH adjuster is an aqueous acid solution or an aqueous alkali solution. It is characterized by that.

[0015] In the above-mentioned aqueous emulsion containing hydrolyzate of fluorocarbon silane, the aqueous acid solution contains phosphoric acid,
It is preferably an aqueous solution of boric acid, hydrochloric acid, nitric acid, sulfuric acid, acetic acid or formic acid, and the alkaline aqueous solution is preferably an aqueous solution of ammonia, pyridine, sodium hydroxide or potassium hydroxide.

In any of the above aqueous emulsions containing hydrolyzate of fluorocarbon silane, the organoalkoxysilane is preferably an organomethoxysilane.

Another aspect of the present invention is a coating having oil- and stain-proofing properties and heat- and water-repellent properties, wherein at least one surface of a substrate is coated with any one of the above-mentioned aqueous fluorocarbon silane hydrolyzate-containing emulsions and dried. And a coating layer formed by the above-mentioned method.

[0018]

DETAILED DESCRIPTION OF THE INVENTION The aqueous emulsion of the present invention contains a hydrolyzate of a fluorocarbon silane.

The hydrolyzable fluorocarbon silane used to form the aqueous emulsion includes:

[0020]

Embedded image R _f — (CH ₂ ) _p —Si ｛— (O—CH ₂ CH ₂ ) _n —OR ¹ ｝ ₃ (1)

Wherein R _f is a perfluoroalkyl group having 3 to 18 carbon atoms or a mixture thereof;
The plurality of R ¹ are the same or different alkyl groups having 1 to 3 carbon atoms, and p = 2 to 4 and n = 2
At least one fluorocarbon silane of from 10 to 10 is used. Preferably, R _f is a mixed perfluoroalkyl group having an average of 8 to 12 carbon atoms, R ¹ is a methyl group, and p = 2 and n =
2-4. More preferably, n = 2-3.

Specifically, a preferred fluorocarbon silane is perfluoroalkylethyltris (2- (2-methoxyethoxy) ethoxy) silane when n is 2, and (2- (2-methoxyethoxy) ethoxy) silane when n is 3. (2- (2-methoxyethoxy) ethoxy) ethoxy) silane.
Such a fluorocarbon silane can be produced by a known method. Two or more fluorocarbon silanes may be used as a mixture.

The surfactant used in the present invention includes:
It is a surfactant having an HLB value sufficiently high to suppress self-condensation of a hydrofluorocarbonsilane hydrolyzate.
Surfactants include anionic, cationic, nonionic,
And surfactants of any type, amphoteric, but preferred surfactants have an HLB value of greater than 12, more preferably greater than 16. When using surfactants with HLB values between 12 and 16, very large amounts of surfactant are usually required to stabilize the emulsion. As long as the surfactant has an HLB value sufficiently high to suppress the self-condensation of the fluorocarbon silane hydrolyzate, two or more surfactants having compatibility may be used in combination.

The HLB value of the nonionic surfactant can be calculated by a calculation formula created by Mr. Griffin of Atlas (currently ICI America) in the United States. At present, there is no method for calculating the HLB value by calculation. However, Atlas has focused on the fact that emulsifiability changes sensitively when the HLB value changes, and has established and announced a method for experimentally determining the HLB value by emulsification experiments using standard oils. A method for experimentally determining the HLB value has been established by companies other than Atlas, but it has been clarified that the HLB value of the anionic or cationic type is larger than 16 regardless of the method used. .

Specifically, R _f '-CH2CH2-O-
_{(CH 2 CH 2 O) 11} -H, C 9 H 19 -C 6 H 4 -O- (C
H ₂ CH ₂ O) nonionic surfactants such as ₅₀ -H, R _{f
'-CH 2 CH 2 SCH 2} CH (OH) CH 2 N (CH 3) 3
⁺ Cl ^- cationic surfactants, such as, C ₁₂ H ₂₅ (OCH
^{_{2 CH 2) 4 OSO 3 -}} NH 4 +, C 12 H 27 -C 6 H 4 -SO 3 -
Examples include anionic surfactants such as Na ⁺ . R _f ′ is a perfluoroalkyl group, usually 3
It has １８18 carbon atoms.

Preferred surfactants are nonionic surfactants having polyethylene glycol in the molecular chain.

The content of fluorocarbon silane in the aqueous emulsion is at least 0.1% by weight, preferably 2 to 20% by weight, more preferably 7 to 15% by weight, based on the total weight of the emulsion. If it is less than 0.1% by weight, the water repellency is insufficient, while if it is more than 20% by weight, the stability of the aqueous emulsion tends to be impaired.

The weight ratio of the fluorocarbon silane to the surfactant is from 1: 1 to 10: 1, preferably from 10: 1.
The ratio is 2 to 10: 5, and more preferably 10: 3. If the proportion of the surfactant is too low, the aqueous emulsion cannot be kept stable.On the other hand, if the proportion is too high, the hydrophilic group may remain on the substrate even after drying, resulting in good water repellency. Can not do.

The aqueous emulsion of the present invention contains a component which is copolymerized with a hydrolyzed fluorocarbon silane in order to improve the heat and water repellency. Conventionally, in a fluorocarbon hydrolyzate-containing aqueous emulsion, Si (OCH ₃ ) ₄ , Si (O
_{CH 2 CH 3) 4, Si} - {(OCH 2 CH 2) m OCH 3} 4
A silicate such as (m = 1 to 3) is used. However, the present inventors have studied various silicon compounds in order to improve the antifouling property against oil. As a result, by adding an organoalkoxysilane together with a hydrolyzable fluorocarbon silane, the oil resistant and oil repellent is maintained while maintaining the heat and water repellency. It has been found that soiling can be improved.

The organoalkoxysilane is

[0031]

Embedded image R ² _n Si (OR ³ ) _4-n (2) (R ² is an alkyl group having 1 to 10 carbon atoms, and a plurality of R ³ are the same having 1 to 3 carbon atoms. Or different alkyl groups and n = 1-3)

And organomethoxysilane is particularly preferred.

The organoalkoxysilane is used in such an amount that the molar fraction to the fluorocarbon silane is from 0.3 to 10. When the mole fraction is less than 0.3, the oil resistance and oil repellency and heat repellency of the coating layer are insufficient.
If it is larger than 0, the aqueous emulsion gels and the heat-resistant water repellency of the coating layer is impaired.

From the viewpoint of easy handling of the aqueous emulsion, the aqueous emulsion is preferably stable. In order to obtain a stable emulsion, the molar ratio of the organoalkoxysilane to the fluorocarbonsilane is preferably from 0.3 to 5. Preferably, 0.4 to 2 is more preferable.

The aqueous emulsion of the present invention comprises a hydrolyzate of a fluorocarbon silane, a surfactant, an organomethoxysilane, and a pH adjuster.

Compared to aqueous emulsions that do not contain a pH adjuster, ie, to which no aqueous acid or alkali solution is added, the aqueous emulsions whose pH has been adjusted according to the invention are:
Surprisingly, it has been found that the oil stain resistance is improved.

The pH adjusting agent is an aqueous acid solution such as phosphoric acid, boric acid, hydrochloric acid, sulfuric acid, nitric acid, acetic acid and formic acid, and an aqueous alkali solution such as ammonia, pyridine, sodium hydroxide and potassium hydroxide. Of these, phosphoric acid is preferred. A coating layer formed by applying an emulsion whose pH has been adjusted with phosphoric acid can further improve oil and stain resistance and can maintain heat and water repellency over a long period of time.

When an aqueous acid solution is used as the pH adjuster, the pH of the aqueous emulsion is preferably 4.5 or lower, more preferably 2.0 to 4.5.

When an aqueous alkaline solution is used as the pH adjuster, the pH of the aqueous emulsion is preferably 7.
It is contained in an amount of 0 or more, more preferably 7.0 to 12.0.

The aqueous emulsion of the present invention is prepared by adding conventional additives such as a pigment, a biocide, an ultraviolet absorber, and an antioxidant, to the stability of the emulsion, and to the oil and stain resistance and heat and water repellency of the coating layer. Can be contained in a range that does not affect the content.

The method for preparing the aqueous emulsion of the present invention is not particularly limited. However, a fluorocarbon silane is added after dissolving a surfactant in water, and if necessary, other additives are added. Alternatively, a method of adding an organoalkoxysilane after adding an aqueous alkali solution is preferable.

In order to suppress the self-condensation of the fluorocarbon silane and keep it in a hydrolyzed state, it is preferable to add the fluorocarbon silane after dissolving the surfactant, and further to add the fluorocarbon silane while stirring by a conventional stirring technique. Preferably, the fluorocarbon silane is added slowly.

The aqueous emulsion of the present invention can be applied to any substrate and can provide excellent water repellency and oil and stain resistance. Since the aqueous emulsion of the present invention provides a heat- and water-repellent coating layer, it can be used particularly under high-temperature conditions such as metal plates such as aluminum and stainless steel, glass plates, ceramic tiles, bricks, concrete, and stones. It can be applied to a suitable substrate to form a coating having excellent oil stain resistance and heat and water repellency.

The application of the aqueous emulsion to the substrate is performed by a known method such as a dipping method, a spray method, a spin coating method, and a roll coating method. In particular, since it is often required to form a coating layer on a glass substrate without impairing the transparency, the dipping method is preferable from the viewpoint that the transparency is not impaired.

Heating may be performed to accelerate the drying process. Usually, drying is carried out in a temperature range of 100 to 350 ° C for 5 minutes to
Performed over 24 hours.

Before applying the aqueous emulsion of the present invention to a substrate, a silicon compound is applied to form an underlayer, and the emulsion is applied over the underlayer to provide a heat and water repellency for a long time. It can be maintained.

The substrate coated with the aqueous emulsion is optionally washed with water after drying to remove the remaining surfactant.

[0048]

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

The components used in the following Examples and Comparative Examples are as follows.

The fluorocarbon silane is represented by R _f- (C
H ₂ ) ₂ —Si ｛— (O—CH ₂ CH ₂ ) ₂ —OCH ₃ ｝ ₃ , and R _f is F (CF ₂ ) _k CH ₂ CH ₂ (k = 6, 1
K = 8, 62 to 64% by weight; k = 10,2
3 to 30% by weight; k = 12 to 18, 2 to 6% by weight).

The surfactant is R _f '-CH ₂ CH ₂ -O-
Is represented by _{(CH 2 CH 2 O) 11} -H, R f ' is 3 to 18
Nonionic surfactant which is a perfluoroalkyl group having two carbon atoms.

The organoalkoxysilane is represented by (CH ₃ )
Si (OCH ₃ ) ₃ .

Examples 1 to 3 A surfactant was dissolved in water in an amount of 30 parts by weight per 100 parts by weight of fluorocarbon silane, and then 10% by weight of fluorocarbon silane, based on the total weight of the aqueous emulsion, was dissolved. Is added slowly with stirring by a conventional stirring technique to suppress the self-condensation of the fluorocarbon silane and keep it in a hydrolyzed state. Then, while measuring the pH of the emulsion with a pH meter, the pH adjuster shown in Table 1 is added. Was added, and the addition was terminated when the pH reached a predetermined value shown in Table 1. Further, (CH ₃ ) Si for fluorocarbon silane
(CH) so that the molar fraction of (OCH ₃ ) ₃ is 0.45.
₃ ) Si (OCH ₃ ) ₃ was added to prepare an aqueous emulsion.

Thereafter, the aqueous emulsion was stirred for 2 to 4 hours, and then applied to a glass plate (2.5 cm × 5.0 cm, thickness 3 mm) to prepare a test piece.

The application of the aqueous emulsion was carried out by dip coating. Dip coating lowers the specimen into an aqueous emulsion at a rate of 300 mm / min,
The holding was performed for 5 minutes in this state, and the lifting was performed at a speed of 50 mm / min. Drying after coating is 6 hours at 200 ° C.
Performed over 0 minutes.

On the surface of the coating layer of the obtained test piece, 2 μl of pure water was applied.
Then, the contact angle was measured by a contact angle meter (manufactured by Kyowa Interface Science). Table 1 shows the measurement results.

Further, 10 mg of chicken oil was sprayed on the surface of the coating layer of the test piece with a spray and baked at 250 ° C. for 60 minutes. After the burnt oil was wiped off with gauze five times, it was visually observed how much burned dirt was removed. Table 1 shows the measurement results.

(Comparative Examples 1-2) In Comparative Examples 1-2, tetrakis [2] was used in place of the organomethoxysilane of Example 1.
-(2-methoxyethoxy) ethyl] silicate (Si
Except for using (DEGM) ₄ ), a fluorocarbon silane hydrolyzate-containing aqueous emulsion having the same composition as in Example 1 was prepared according to the same procedure, a test piece was prepared, and a water-repellent and oil-resistant stain-proof was similarly prepared. A sex test was performed. Table 1 shows the results.

(Comparative Example 3) In Comparative Example 3, a water repellency and antifouling resistance test were carried out in the same manner as in Example 1 by using a glass plate as a test piece. Table 1 shows the results.

Comparative Examples 4 and 5 In Comparative Example 4, tetrakis [2-
(2-methoxyethoxy) ethyl] silicate (Si
Using (DEGM) ₄ ), without adding a pH adjuster, a fluorocarbon silane hydrolyzate-containing aqueous emulsion having the same composition as in Example 1 was prepared according to the same procedure, and a test piece was prepared. Water repellency and oil stain resistance tests were performed. Table 1 shows the results.

In Comparative Example 5, a fluorocarbon silane hydrolyzate-containing aqueous emulsion having the same composition as in Example 1 was prepared according to the same procedure except that no pH adjuster was added, and a test piece was prepared. Water repellency and oil stain resistance tests were performed. Table 1 shows the results.

[0062]

[Table 1]

In Example 1, although a small amount of oil remained in the state of being spread on the glass, it could be almost completely wiped off, and the wiping was easy. In Example 2, it was harder to wipe than Example 1, but almost no scorching was obtained. In Example 3, dirt could be almost completely and easily wiped off.

On the other hand, the uncoated glass of Comparative Example 3 did not burn off any oil even when wiped. In Comparative Examples 1, 2 and 4 containing silicate, the oil remained in a state of being spread on the glass. Comparative Example 5, which contains an organomethoxysilane but does not contain a pH adjuster,
The oil has been left extended.

From the above results, the water repellency of the surface of the coating layer is good in both the case of using organomethoxysilane and the case of using silicate. It can be seen that remarkably improved by adjusting to acidic or alkaline. Further, when the pH is adjusted to be acidic, it can be seen that the use of phosphoric acid achieves a further improvement in oil stain resistance.

(Examples 4 and 5) An aqueous emulsion was prepared in the same manner as in Example 1, and a glass plate (2.5 cm × 5.0 c) was prepared.
m, thickness 3 mm) to prepare a test piece.

On the surface of the coating layer of the obtained test piece, 2 μl of pure water was applied.
Then, the contact angle was measured by a contact angle meter (manufactured by Kyowa Interface Science). Table 2 shows the measurement results.

Further, the test piece was placed in an oven at 330 ° C., and after 6 hours and 10 hours, the contact angle was measured in the same manner. Table 2 shows the measurement results.

(Comparative Examples 6 to 8) An aqueous emulsion was prepared in the same manner as in Example 1 except that a silicon compound shown in the following Table 2 was used instead of the organomethoxysilane, and a glass plate (2.5 cm × (5.0 cm, thickness 3 mm) to prepare a test piece, and the contact angle was measured in the same manner as in Example 4. Table 2 shows the measurement results.

[0070]

[Table 2]

In Example 4, at 330 ° C. for 6 hours and 1 hour
Even after the elapse of 0 hours, the water-repellent angle of the surface of the coating layer was equal to or greater than that before aging, and it can be seen that an excellent heat-resistant water-repellent coating layer was obtained.

As in Comparative Examples 6 to 8, even when a silicon compound other than organomethoxysilane was used, the initial water repellency was almost the same as that of Example 4, and a water-repellent coating layer was formed. You can see that. However, despite the inclusion of phosphoric acid as in Example 4, at 330.degree.
The values of the water repellent angle after 0 hour have been considerably reduced in all the comparative examples, and it can be seen that the formed coating layer does not have the heat-resistant water repellency.

In the same manner as in Example 4, an aqueous emulsion containing an organomethoxysilane was used.
Indicates that even when hydrochloric acid is contained as a pH adjuster, the formed coating layer has good heat and water repellency.

Example 6 An aqueous emulsion was prepared in the same manner as in Example 1, and an aluminum plate (2.5 cm × 5.0) was prepared.
JIS1100 cm, 1 mm thick) to prepare a test piece.

On the surface of the coating layer of the obtained test piece, 2 μl of pure water was applied.
Then, the contact angle was measured by a contact angle meter (manufactured by Kyowa Interface Science). Table 3 shows the measurement results.

Further, the test piece was placed in an oven at 370 ° C., and after 40 hours, the contact angle was measured in the same manner. Table 3 shows the measurement results.

(Comparative Examples 9 to 12) An aqueous emulsion was prepared in the same manner as in Example 1 except that silicon compounds shown in Table 3 below were used instead of organomethoxysilane.
Aluminum plate (2.5cm × 5.0cm, thickness 1mm
JIS 1100) to prepare a test piece, and the contact angle was measured in the same manner as in Example 6. Table 3 shows the measurement results.

[0078]

[Table 3]

In both Example 6 and Comparative Examples 9 to 12, the initial water-repellent angles were almost the same, and it was found that all the coating layers were excellent in water-repellent properties. However, in Comparative Examples 9 to 11 containing silicate, the value of the water repellent angle was significantly reduced after lapse of 40 hours at 370 ° C., whereas in Example 6, 3
After 40 hours at 70 ° C., the water repellent angle was kept at 100 degrees or more. From these results, it can be seen that by using organomethoxysilane, an excellent heat- and water-repellent coating layer can be provided and the durability is also excellent.

In Comparative Example 12, after 40 hours at 370 ° C., the value of the water repellent angle was significantly reduced. From these results, it can be seen that good heat resistance of the water-repellent coating layer cannot be obtained without using a pH adjuster even when organomethoxysilane is used.

[0081]

The aqueous emulsion containing hydrolyzate of fluorocarbon silane according to the present invention can realize a coating layer having both heat and water repellency and oil and stain resistance. The coating formed by applying the aqueous emulsion of the present invention can easily remove oil stains and can maintain excellent water repellency even when used under high temperature conditions.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/16 C09D 5/16 183/04 183/04 183/08 183/08 (72) Inventor Satoko Iwato 19-2 Kiyohara Industrial Park, Utsunomiya City, Tochigi Prefecture F-term (Reference) 4D002 CH051 CH052 DD018 DE058 DF008 DF038 DH028 DK008 EF038 EU048 EV087 EV257 EX036 FD312 FD317 GH02 4J038 DF022 DL031 DL031 HA376 HA416 HA476 JA37 JB01 JB26 JC14 KA09 MA08 MA10 NA04 NA05 NA07 NA14 PA18 PB05 PC02 PC03 PC04

Claims (4)

[Claims] 1. A hydrolyzate of a fluorocarbon silane,
An aqueous emulsion containing a surfactant, an organoalkoxysilane, and a pH adjuster, wherein the fluorocarbon silane is represented by the following formula: R _f- (CH ₂ ) _p -Si ｛-(O-CH ₂ CH ₂ ) _n —OR ¹ ｝ ₃ (1) (R _f is a perfluoroalkyl group having 3 to 18 carbon atoms or a mixture thereof, and a plurality of R ¹ are the same or different alkyl groups having 1 to 3 carbon atoms. And
And p = 2 to 4 and n = 2 to 10). At least one hydrolyzable fluorocarbon silane represented by the formula: wherein the surfactant emulsifies the hydrolyzate of the fluorocarbon silane. The fluorocarbon silane is contained in an amount of 0.1 to 20% by weight based on the total weight of the aqueous emulsion, and the weight ratio of the fluorocarbon silane to the surfactant is 1: 1 to 10: 1. the organoalkoxysilane is ## STR2 ## ^{_{R 2 n Si (OR 3)}} 4-n (2) (R 2 is a 1 to 10 alkyl group carbon atoms, more R ³ is a carbon atom 1 to 3 identical or different alkyl groups, and n = 1 to 3), wherein the organoalkoxysilane is Le Oro mole fraction for carbon silane is contained in an amount of 0.3 to 10, wherein the pH adjusting agent, a fluorocarbon silane hydrolyzate-containing aqueous emulsions, characterized in that the aqueous acid solution or aqueous alkali solution. 2. The aqueous acid solution is an aqueous solution of phosphoric acid, boric acid, hydrochloric acid, nitric acid, sulfuric acid, acetic acid or formic acid, and the alkaline aqueous solution is an aqueous solution of ammonia, pyridine, sodium hydroxide, or potassium hydroxide. The aqueous emulsion containing a hydrolyzate of fluorocarbon silane according to claim 1, wherein: 3. The aqueous emulsion containing a hydrolyzed fluorocarbonsilane according to claim 1, wherein the organoalkoxysilane is an organomethoxysilane. 4. A coating layer formed by applying and drying the fluorocarbon silane hydrolyzate-containing aqueous emulsion according to any one of claims 1 to 3 on at least one surface of a substrate. An oil- and stain-resistant and heat- and water-repellent coating characterized by the following characteristics.