JP2001207162A - Liquid for water- and oil-repellent and stain-proofing treatment, and method for water- and oil-repellent and stain-proofing treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid for water- and oil-repellent and stain-proofing treatment that causes no clouding, even when it is stored for a long period of time, and provide a method for water- and oil-repellent and stain-proofing treatment using the same. SOLUTION: The objective liquid for water- and oil-repellent and stain- proofing treatment is characterized by comprising the solution A including a fluoroalkyl group-bearing silane, for example, heptadecafluorodecyltrimethoxysilane and the solution B including an acid (for example, concentrated hydrochloric acid) and a solvent (for example, i- propanol) and using them after they are mixed, and a method for water- and oil-repellent and stain-proofing treatment using the same is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a water-repellent
The present invention relates to a processing liquid used for processing an article having oil repellency and antifouling property, and a processing method thereof. In particular, the present invention relates to a water-repellent, oil-repellent and antifouling treatment liquid suitably used for articles such as glass, ceramics, plastics and metals, and a treatment method therefor.

[0002]

2. Description of the Related Art As a water-repellent treatment liquid for forming a water-repellent film on the surface of a glass plate or other articles, a water-repellent treatment liquid containing a fluoroalkylsilane compound is known.

For example, Japanese Patent Application Laid-Open No. Hei 5-31156 discloses that
A water-repellent treatment solution comprising an alcohol solution containing 1.0 to 10% by weight of a fluoroalkylsilane, 0.01 to 5% by weight of an acid catalyst, and 0.01 to 40% by weight of water is disclosed.

Japanese Patent Application Laid-Open No. 9-53065 discloses a first liquid containing a fluoroalkylsilane and a hydrophilic organic solvent.
A water-repellent treatment liquid comprising a liquid and a second liquid containing an acid and water is disclosed. Furthermore, a water-repellent treatment liquid in which the solvent of the first liquid and / or the second liquid is an alcohol or a solvent containing an alcohol is also disclosed.

Further, JP-A-9-53065 points out the following problems in the above-mentioned JP-A-5-31156. That is, when the content of the fluoroalkylsilane increases, the water-repellent effect generally improves. On the other hand, a surplus of a substance which is considered to be a hydrolyzate of fluoroalkylsilane remains on the treated surface, and the initial contact angle is significantly reduced. Furthermore, an operation of wiping this substance is required.

In order to solve this problem, Japanese Patent Laid-Open Publication No. 9-5
No. 3065, the content of fluoroalkylsilane is 1
We are considering reducing the weight to less than% by weight. However, it has been pointed out that when the content of the fluoroalkylsilane is 1% by weight or less, the water-repellent effect decreases as the storage time of the water-repellent treatment liquid elapses. In particular, it has been pointed out that when an effective amount of acid is contained, the water-repellent effect of the water-repellent treatment liquid is remarkably reduced as the storage time elapses.

Further, JP-A-10-219235 discloses that a first liquid containing a fluoroalkylsilane and a hydrophilic organic solvent is mixed with an acid, water and the hydrophilic organic solvent and / or the hydrophilic organic solvent. A water-repellent treatment liquid comprising a second liquid containing a compound having a high boiling point is disclosed.

Japanese Patent Application Laid-Open No. Hei 10-219235 proposes a processing method in which the residue of fluoroalkylsilane is wiped off without using an organic solvent.

Japanese Patent Application Laid-Open No. 9-104861 discloses a two-liquid type in which a first liquid is treated with a water-repellent treatment liquid containing fluoroalkylsilane, and then a second liquid is subjected to a finishing treatment with a lower alcohol-water solution. Are also disclosed.

[0010]

SUMMARY OF THE INVENTION The above-mentioned Japanese Patent Application Laid-Open No. 5-31 is disclosed.
According to No. 1156, when the prepared water-repellent solution is stored for a long period of time, the fluoroalkylsilane-based compound reacts and the solution becomes cloudy. When the water-repellent treatment is performed using this cloudy solution, there is a problem that the initial water-repellent performance is reduced.

[0011] Even in the processing solutions disclosed in JP-A-9-53065 and JP-A-10-219235, the above-described problem occurs when the prepared water-repellent treatment solution is stored for a long time. I do.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and has a water-repellent, oil-repellent, and antifouling treatment that does not become cloudy even if the water-repellent, oil-repellent, and antifouling treatment liquid is stored for a long period of time. The purpose is to provide a liquid. It is another object of the present invention to provide a water / oil repellent / antifouling treatment method using the treatment liquid.

In the water-repellent and oil-repellent antifouling treatment solution and method, the amount of the fluoroalkylsilane-containing silane compound containing less residue of the fluoroalkylsilane, that is, the fluoroalkylsilane-containing silane compound contained in the water-repellent and oil-repellent antifouling treatment solution is 1% by mass. % Or less, an object of the present invention is to provide a treatment liquid and a method having good water / oil / oil repellency and antifouling performance.

[0014]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive research and found the following. That is, when storing the silane compound containing a fluoroalkyl group, first, the silane compound is stored in a state where it does not contain an acid and a solvent. When stored in this manner, the water-repellent, oil-repellent, antifouling treatment liquid does not become cloudy as described above. That is, the fluoroalkyl group-containing silane compound may be stored without being hydrolyzed.

When used, a fluoroalkyl group-containing silane compound (Solution A) and a solution containing an acid and a solvent (Solution B)
And a liquid-repellent, oil-repellent, antifouling treatment liquid (hereinafter sometimes referred to as a coating liquid).

That is, the present invention is characterized in that a treatment liquid is first used as a mixture of a liquid A containing a silane compound having a fluoroalkyl group and a liquid B containing an acid and a solvent. It is an oil antifouling treatment liquid.

According to a second aspect of the present invention, in the water / oil repellent / antifouling treatment solution according to the first aspect, the acid contains at least one of hydrochloric acid, methanesulfonic acid, and paratoluenesulfonic acid. It is a water- and oil-repellent antifouling treatment liquid.

According to a third aspect of the present invention, the solvent is a water-repellent, oil-repellent, antifouling treatment liquid containing an organic solvent compatible with water.

According to a fourth aspect of the present invention, in the water / oil repellent / antifouling treatment liquid according to the first aspect, the solvent has 1 carbon atom.
It is a water-repellent, oil-repellent, and antifouling treatment liquid containing at least one of alcohols of 10 to 10.

According to a fifth aspect of the present invention, in the water / oil repellent / antifouling treatment solution according to the first aspect, the solvent has a carbon number of 4 or less.
A water-repellent, oil-repellent and antifouling treatment liquid containing at least one of the alkanes Nos. To 14 above.

According to a sixth aspect of the present invention, in the water-repellent, oil-repellent, antifouling treatment liquid according to the third aspect, the solvent is a water-repellent, oil-repellent, antifouling treatment liquid further containing water.

According to a seventh aspect of the present invention, in the water-repellent, oil-repellent, antifouling treatment solution according to the first aspect, the fluoroalkyl group-containing silane compound is treated with a water-repellent, oil-repellent, antifouling treatment represented by the following chemical formula 1. Liquid.

## STR1 ## _{CF 3 - (CF 2) n} -R-SiX p Y 3-p ·· (1) ( wherein, n represents 0 to 12 integer, preferably 3 to 12 integer, R represents a carbon atom X is H or a monovalent hydrocarbon group having 1 to 4 carbon atoms (eg, an alkyl group), wherein X is a divalent organic group having 1 to 10 groups (eg, a methylene group or an ethylene group) or a group containing a silicon atom and an oxygen atom. , Cycloalkyl group, allyl group) or a substituent selected from derivatives of these groups, or hydrogen, p is 0, 1 or 2, Y is an alkoxyl group having 1 to 4 carbon atoms, an acyloxy group, or a halogen atom. )

According to an eighth aspect of the present invention, in the water-repellent, oil-repellent and antifouling treatment solution according to the first aspect, the fluoroalkyl group-containing silane compound is contained in a proportion of 0.01 to 5% by mass of the treatment solution. Water-repellent, oil-repellent and antifouling treatment liquid.

According to a ninth aspect of the present invention, in the water-repellent, oil-repellent and antifouling treatment solution according to the first aspect, the acid is contained such that the acid concentration of the treatment solution is 0.0001 to 1N. It is a water-repellent, oil-repellent, antifouling treatment liquid.

According to a tenth aspect of the present invention, in the water-repellent, oil-repellent and antifouling treatment liquid according to the third aspect, the alcohol is contained in a proportion of 1 to 99% by mass of the treatment liquid. It is an antifouling treatment liquid.

According to an eleventh aspect of the present invention, in the water-repellent, oil-repellent and antifouling treatment liquid according to the fourth aspect, the alkane is contained in a proportion of 1 to 99% by mass of the treatment liquid. It is an antifouling treatment liquid.

According to a twelfth aspect of the present invention, in the water-repellent, oil-repellent and antifouling treatment liquid according to the fifth aspect, the water is contained in a proportion of 0.1 to 5% by mass of the treatment liquid. It is an oil repellent and antifouling treatment liquid.

According to a thirteenth aspect of the present invention, in the water-repellent, oil-repellent and antifouling treatment solution according to the first aspect, the solution A further comprises a polysiloxane compound or a water represented by SiR _n X _(4-n). It is a water-repellent, oil-repellent, antifouling treatment liquid containing a decomposable silane compound. (However, R: an alkyl group having 1 to 5 carbon atoms, n = 0 to 3, X; an alkoxyl group, a halogen, an acetoxyl group, or an isocyanate group)

The invention of the processing method is described in claim 14.
(1) a step of preparing a liquid A containing a fluoroalkyl group-containing silane compound, (2) a step of preparing a liquid B comprising an acid and a solvent, (3) the liquid A and the liquid B A step of preparing a water-repellent, oil-repellent and antifouling treatment liquid by mixing the liquids; and (4) a step of applying the water-repellent, oil-repellent and antifouling treatment liquid to the surface of the article. This is an antifouling treatment method.

Further, there is provided a water-repellent, oil-repellent, antifouling treatment method using the treatment liquid according to any one of claims 2 to 13.

Furthermore, in the water / oil / oil repellent / antifouling treatment method according to the fourteenth aspect, the article is one of glass, ceramics, plastic, and metal.

Further, in the water / oil repellent / antifouling treatment method according to claim 14, the coating method is a hand coating method, a dip coating method, a flow coating method, a curtain coating method, a spin coating method, a spray coating method. , A bar coating method, a roll coating method, or a brush coating method.

Further, as an invention of a water-repellent, oil-repellent, and soil-repellent treated article, a water-repellent, oil-repellent, stain-repellent and / or soil-repellent treatment method according to claims 14 to 27 is provided. It is a processed article.

According to the present invention, there is provided a two-part mixed water / oil repellent / antifouling treatment liquid comprising a liquid A containing a fluoroalkyl group-containing silane compound and a liquid B containing an acid and a solvent. It can also be grasped as.

Further, in the two-part mixed type water-repellent, oil-repellent and antifouling treatment liquid, the liquid A contains substantially no acid and / or solvent, and the liquid B contains a fluoroalkyl group-containing silane compound. It can also be understood as a two-liquid mixed type water-repellent, oil-repellent, antifouling treatment liquid not containing.

In the present invention, it is preferable that the solution A substantially consists of only a silane compound containing a fluoroalkyl group.

Further, in the present invention, the solution A is substantially
It may be composed of only a fluoroalkyl group-containing silane compound and a polysiloxane compound or a hydrolyzable silane compound represented by SiR _n X _(4-n) .

As the silane compound containing a fluoroalkyl group used in the present invention, a silane compound containing a fluoroalkyl group and containing an alkoxyl group, an acyloxy group or a chlorine group can be preferably used. The compound represented by the chemical formula (1) can be mentioned. From among these, a single substance or a combination of plural substances can be used.

[0039]

## STR1 ## _{CF 3 - (CF 2) n} -R-SiX p Y 3-p ·· (1) ( wherein, n represents 0 to 12 integer, preferably 3 to 12 integer, R represents a carbon atom X is H or a monovalent hydrocarbon group having 1 to 4 carbon atoms (eg, an alkyl group), wherein X is a divalent organic group having 1 to 10 carbon atoms (eg, a methylene group or an ethylene group) or a group containing a silicon atom and an oxygen atom. , Cycloalkyl group, allyl group) or a substituent selected from these derivatives,
Or hydrogen, p is 0, 1 or 2, and Y is 1 carbon atom.
To 4 alkoxyl groups, acyloxy groups, or halogen atoms)

Specific examples of the compound of the above formula (1) include the following.

## STR2 ## C ₆ F ₁₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃

Embedded image C ₇ F ₁₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃

Embedded image C ₈ F ₁₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃

Embedded image C ₉ F ₁₉ CH ₂ CH ₂ Si (OCH ₃ ) ₃

Embedded image C ₁₀ F ₂₁ CH ₂ CH ₂ Si (OCH ₃ ) ₃

Embedded image C ₆ F ₁₃ CH ₂ CH ₂ SiCl ₃

[Image Omitted] C ₇ F ₁₅ CH ₂ CH ₂ SiCl ₃

Embedded image C ₈ F ₁₇ CH ₂ CH ₂ SiCl ₃

Embedded image C ₉ F ₁₉ CH ₂ CH ₂ SiCl ₃

Embedded image C ₁₀ F ₂₁ CH ₂ CH ₂ SiCl ₃

Embedded image

Embedded image C ₈ F ₁₇ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃

Embedded image C ₈ F ₁₇ CH ₂ CH ₂ Si (OCOCH ₃ ) ₃

Embedded image

Among these, C₈F₁₇CH_TwoCH_TwoSi
(OCH_Three)_Three (Heptadecafluorodecyltrimethodine
Silane) and C₈F₁₇CH_TwoCH_TwoSi (CH_Three)
(OCH _Three)_TwoIs particularly preferably used.

The silane compound containing a fluoroalkyl group is
It is preferable that it is contained at a ratio of 0.01 to 5% by mass of the treatment liquid. Further, it is preferably contained in a proportion of 1% by mass or less. Even with this ratio, a good water-repellent, oil-repellent, antifouling effect can be obtained. Therefore, surplus hydrolyzate of fluoroalkylsilane rarely remains on the treated surface. For this reason, the work of wiping it is unnecessary or reduced. Further, since the fluoroalkyl group-containing silane compound is an expensive raw material, a smaller amount is more advantageous in terms of cost.

If the ratio of the fluoroalkyl group-containing silane compound to the treatment liquid is small and the coating method is inappropriate, the water / oil / oil repellency / antifouling performance may be insufficient.
Therefore, it is preferable that the content is 0.1% by mass or more.

The fluoroalkyl group-containing silane compound may be highly viscous or solid, and may not be easily mixed with the solution B. Therefore, in the present invention,
It is preferable to use a fluoroalkyl group-containing silane compound having low viscosity.

The water-repellent, oil-repellent, stain-proofing article according to the present invention basically exhibits a water-repellent, oil-repellent, stain-proofing function by the fluoroalkyl group of the fluoroalkyl group-containing silane compound. That is, if it has water repellency, it also has oil repellency and antifouling property at the same time.

The acid used in the present invention acts as a catalyst for the hydrolysis reaction. The type is not particularly limited. It is preferable to use hydrochloric acid, methanesulfonic acid, p-toluenesulfonic acid, or the like because a water-repellent and stain-resistant coating exhibiting high weather resistance can be obtained.

In the present invention, it is preferable that the concentration of the acid is represented by a normality and is contained in the treatment solution at 0.0001 to 1N. If the acid concentration is low and the coating method is inappropriate, the water / oil / oil repellency and antifouling performance may be insufficient. Therefore, 0.005N or more is preferable. Also, the higher the acid concentration, the better the water-repellent, oil-repellent, and antifouling treatment generally becomes possible. On the other hand, when using volatile hydrochloric acid, if the acid concentration is too high, it is necessary to handle it carefully. Therefore, an acid concentration of 0.2N or less is preferred.

In order to hydrolyze the solution A and the solution B, water may be further added to the solution B in a range of 0 to 5% by mass. When the proportion of water is large, the wiping property may be deteriorated depending on the composition of the treatment liquid. Therefore, the content is preferably 2% by mass or less.

The solvent contained in the solution B is not particularly limited as long as the solvent can easily dissolve acid or water. For example, alcohol solvents having 1 to 10 carbon atoms, particularly ethanol, 1-propanol, 2-propanol, n-butanol, i-butanol, s-butanol, t-butanol, etc., have a high evaporation rate at room temperature. It is preferably used. Acetone can be used as a solvent because it can be mixed with water at any ratio.

A non-polar solvent may be used in place of the alcohol solvent. For example, when a nonpolar solvent such as an alkane containing a hydrocarbon having 4 to 14 carbon atoms is used, the hydrolyzed fluoroalkylsilane compound tends to easily react with the article surface, which is preferable. Further, both the alcohol solvent and the non-polar solvent may be used.

A container for storing and distributing the above-mentioned liquid A and liquid B will be described. First, the liquid B contains an acid and a solvent (specifically, an alcohol, an alkane, or even water). Therefore, it is preferable that the container be made of a material that does not deteriorate over a long period of time after the components are injected. Specifically, high-density polyethylene, polytetrafluoroethylene (Teflon (trade name)) resin,
A container made of a material such as glass is exemplified. Of these, high-density polyethylene is most preferably used in view of cost, safety, and ease of processing.

The form of the container is preferably one having good airtightness, and is preferably a container having a screw hole for easy handling, or a structure that can be sealed by a polyethylene container. A structure that can be sealed and sealed is particularly preferable because it can prevent liquid leakage and can prevent the influence of moisture in the outside air.

Since the amount of the solution A may be smaller than that of the solution B,
A preferred form is to enclose a single dose in a pipette-shaped container. Also, the liquid B is preferably sealed in a polyethylene container into which a single dose can be injected. At this time, the treatment liquid may be adjusted by directly mixing the liquid A in the container of the liquid B, or by mixing the liquid A and the liquid B in another mixing container. Further, it is preferable that a nozzle of the mixed processing liquid can be attached to the container of the processing liquid so that the coating operation can be easily performed.

As a coating method, a method in which a coating liquid is applied to a cotton cloth, paper, sponge, or the like, and the liquid is applied to glass by hand or the like is simple and preferably used. Further, a method such as a dip coating method, a flow coating method, a curtain coating method, a spin coating method, a spray coating method, a bar coating method, a roll coating method, or a brush coating method may be used.

The coating liquid according to the present invention basically comprises
It is prepared by mixing a fluoroalkyl group-containing silane compound (Solution A) and an acid catalyst to a solvent and stirring for 10 seconds to 60 minutes (Solution B) and stirring the mixture for 10 seconds to 60 minutes.

The life of the coating solution thus prepared is relatively long. However, when the amount of the acid catalyst is relatively small or the amount of water is relatively large, there is a possibility that the hydrolysis and polycondensation reaction may proceed excessively in the coating solution before application, and therefore it is preferable to apply the solution within one day after preparation. . After applying this coating liquid to the surface of the article, the article is dried at room temperature for 10 seconds to 10 minutes to evaporate the solvent, thereby obtaining a water-repellent, oil-repellent, antifouling treated article.

In the treatment method according to the present invention, the coating liquid can be applied to the surface of an article, and the applied wet film and substrate can be dried at room temperature while being left as it is. In order to further enhance the bonding between the coating liquid and the surface of the article, a heat treatment at about 200 ° C. or lower may be performed.

The processing method according to the present invention can be applied to transparent or opaque plate-like bodies, rod-like bodies, and other various shaped articles such as glass, ceramics, plastics and metals. Among these, the present invention is preferably applied to articles such as window glass for automobiles, side mirrors, and architectural glass sheets such as show windows, which are particularly required to have transparency.

When the surface of the article has few hydrophilic groups, it is preferable to perform a hydrophilic treatment. That is, the hydrophilicity-imparting treatment is performed by previously treating the surface of the article with a plasma or corona atmosphere containing oxygen, or irradiating the article surface with ultraviolet rays having a wavelength of about 200 to 300 nm in an atmosphere containing oxygen. . After performing such a hydrophilicity-imparting treatment, it is preferable to perform a water / oil repellent / antifouling treatment.

In the water / oil / oil repellent / antifouling treatment article of the present invention, in order to further improve durability, a metal oxide layer is formed as a base layer on the article surface, and then the water / oil / oil repellent / antifouling treatment is performed. May be done.

As a method of forming the underlayer, for example,
There is a method of forming a metal oxide layer containing silica as a main component by using a sol-gel method. Furthermore, the sputtering method and C
A silica layer may be formed by a VD method, or a metal oxide layer of silica-alumina, silica-titania, silica-zirconia, or the like may be formed. Furthermore, a method called liquid phase film forming method (LPD method), in which ammonia or the like is added to a solution of saturated hydrosilicofluoric acid to precipitate a silica layer, can also be mentioned. Further, the surface shape of the underlayer may be any shape such as smoothness, unevenness, and porous shape.

[0062]

Embodiments of the present invention will be described below. In each of Examples and Comparative Examples, the following chemicals and materials were used.

* Fluoroalkyl group-containing silane compound Heptadecafluorodecyltrimethoxysilane: CF
₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , manufactured by Shin-Etsu Chemical Co., Ltd .;

* Additives-Polydimethylsiloxane: "KF96" manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter abbreviated as "DMS". Tetraethoxysilane: Si (OC ₂ H ₅ ) ₄ , hereinafter abbreviated as “TEOS”.

* Solvent Acetone: manufactured by Katayama Chemical Co., Ltd. i-Propyl alcohol: manufactured by Katayama Chemical Co., Ltd.
A ". T-Butyl alcohol: manufactured by Katayama Chemical Co., Ltd.
OH ". -Isoalkane mixture: "Isosol 200 (trade name)", (The hydrocarbon has 4 to 10 carbon atoms, and the main component is a hydrocarbon having 8 carbon atoms (from the catalog)) "Isosol 300 (trade name)"", (The hydrocarbon has 6 to 14 carbon atoms, and the main component is a hydrocarbon having 12 carbon atoms (from catalog)). Hereinafter, I20
0, abbreviated as I300. -Ethanol + n-propanol + IPA: Solmix AP-7 (trade name), manufactured by Nippon Kasei, hereinafter abbreviated as "AP7".

* Acid catalyst ・ Hydrochloric acid: concentrated hydrochloric acid (35% by weight), 1N, 0.1N hydrochloric acid, manufactured by Kanto Chemical, Kanto Chemical ・ oxalic acid: manufactured by Kanto Chemical ・ p-toluenesulfonic acid: manufactured by Tokyo Kasei PTS "
Abbreviated. -Methanesulfonic acid: manufactured by Tokyo Chemical Industry, hereinafter abbreviated as "MS".・ Nitric acid: 1N nitric acid, manufactured by Kanto Chemical ・ Oleic acid: manufactured by Tokyo Chemical Industry

The acid concentration in the present specification is the number of moles of hydrogen ions when the degree of dissociation of the added acid is 100%, and is the sum of the volumes of all the compounds contained in the treatment liquid before mixing. This is the divided value.

* Substrate • Glass substrate: glass plate of soda-lime silicate glass composition by float method (size: 150 × 150 × 3 mm)

* Method of evaluating water-repellent, oil-repellent and antifouling performance [Contact angle of water] In order to evaluate the performance of the water-repellent, oil-repellent and antifouling treated article, a contact angle of water was measured as a representative characteristic. Using a contact angle meter (CA-DT, manufactured by Kyowa Interface Science Co., Ltd.), 2
A water drop having a mass of mg was dropped on the surface of the treated article and measured as a static contact angle at that time. The larger the value of the contact angle, the better the static water repellency.

[Weather resistance] The treated article is irradiated with ultraviolet rays,
The weather resistance was examined. Using a UV resistance tester (“I-Super UV Tester W-13”, manufactured by Iwasaki Electric Co., Ltd.), the UV intensity was set to 76 ± ² mW / cm ² , the black panel temperature was 48 ± 2 ° C., the irradiation was 20 hours, the darkness was 4 In a time cycle, ion-exchanged water was showered every hour for 30 seconds, and ultraviolet rays were irradiated for a total of 200 hours. After the irradiation, the contact angle of water on the treated article was measured by the method described above.

Example 1-1 This Example 1-1 is a case of a solution A consisting only of FAS and a solution B consisting only of hydrochloric acid (catalyst) and alcohol. The following procedure is performed. (1) As a fluoroalkylsilane group-containing compound, F
Prepare 5 g of AS and use it as solution A. (2) 5 g of concentrated hydrochloric acid as an acid catalyst was added to i-propanol 90
g) and mixed to obtain solution B. (3) The above solution A and solution B were mixed and left to stand after about 5 minutes to obtain a coating solution. (4) On a washed glass substrate, 1 ml of the above coating solution was applied to a cotton cloth and applied. (5) Excess coating liquid was wiped off with a new cotton cloth to obtain a treated glass.

The initial contact angle of water of the obtained water repellent glass was 109 degrees, and the contact angle of water after the weather resistance test was 95 degrees. In addition, each mixing ratio of the liquid A and the liquid B is shown in Table 1 by mass%. Table 1 also shows the initial contact angle and the contact angle after the weather resistance test. However, (%) in the table
Represents (mass%) (same in all tables below).

The treated glass was attached to a sliding reciprocating abrasion tester (manufactured by Shinto Kagaku Co., Ltd.), and a dry cloth was used to load 0.3 k.
The surface was slid reciprocally 5,000 times under the condition of g / cm ² , and its wear resistance was examined. Thereafter, the contact angle of water on the treated glass was measured by the method described above. The contact angle after the abrasion test was 101 degrees.

The above solution A and solution B were mixed at room temperature for 1 hour.
Left for months. However, there was no change in the appearance of each of the solution A and the solution B. Further, the solution A and the solution B were mixed, but no turbidity occurred. Further, the same water-repellent treatment was performed using this, but the water-repellent performance was not changed.

In each of the following embodiments, A
The solution and the solution B were left at room temperature, and there was no change in the appearance of each. Further, the solution A and the solution B were mixed, but no turbidity occurred.

As is clear from Example 1-1, it can be seen that the solution B constituting the treatment solution according to the present invention only needs to be composed of an acid catalyst and an alcohol solvent.

[0077]

[Table 1] ---------------------------------------------- ------------------------ Solution A | Solution B | After initial weathering Example FAS | Acid catalyst Water IPA Acetone AP7 tBuOH I300 I200 | CA CA (% ) | (%) (%) (%) (%) (%) (%) (%) (%) | (°) (°) ----------------- -------------------------------------------------- --- 1-1 5.0 | c-HCl 5.0 − 90.0 − − − − − | 109.0 95.0 ---------------------------- ------------------------------------------ 2-1 5.0 | c-HCl 1.0 − − − 54.0 − 40.0 − | 109.4 96.2 2-2 1.0 | c-HCl 1.0 − − − 58.0 − 40.0 − | 109.4 95.8 2-3 0.5 | c-HCl 1.0 − − − − 58.5 − 40.0 − | 109.2 94.2 2 -4 0.1 | c-HCl 1.0 − − − 58.9 − 40.0 − | 107.6 93.8 2-5 0.05 | c-HCl 1.0 − − − 58.95 − 40.0 − | 107.8 94.0 2-6 0.02 | c-HCl 1.0 − − − 58.98 − 40.0 − | 107.2 93.7 2-7 0.01 | c-HCl 1.0 − − − 58.99 − 40.0 − | 107.3 93.0 ------------------------- --------------------------------------------- 3-1 1.0 | c-HCl 5.0 − − − 54. 0 − 40.0 − | 109.2 96.6 | 0.38N | 3-2 1.0 | c-HCl 1.0 − − − 58.0 − 40.0 − | 109.4 95.8 | 0.075N | 3-3 1.0 | 1N-HCl 1.0 − − − 58.0 − 40.0 − | 108.9 93.0 | 0.0077N | 3-4 1.0 | .1N-HCl 1.0 − − − 58.0 − 40.0 − | 107.5 93.7 | 0.00077N | ------------------- -------------------------------------------------- -4-1 1.0 | Oxalic acid 0.1---58.9-40.0-| 107.2 80.0 4-2 1.0 | PTS 0.18---58.82-40.0-| 108.2 93.6 4-3 1.0 | MS 0.09---58.91-40.0- | 109.2 93.3 4-4 1.0 | 1N-HNO ₃ 1.0 − − − 58.0 − 40.0 − | 108.1 83.3 --------------------------- -------------------------------------------

[Examples 2-1 to 2-7] In Examples 2-1 to 2-7, the solvent contained in the solution B was changed from i-propanol to "AP-7" in Example 1-1. And "ISOSOL 300"
In this example, and the amount of “FAS” is further changed. Each mixing ratio is shown in Table 1 by mass%. Table 1 also shows the initial contact angle and the contact angle after the weather resistance test. In each case, the initial contact angle and the contact angle after the weather resistance test were good.

As is apparent from this embodiment, the “FA
Even when the proportion of “S” is 1% by mass or less of the treatment liquid, a good water-repellent, oil-repellent, antifouling effect can be obtained. In these cases, little or no residual residual hydrolyzate of “FAS” was observed on the treated surface. For this reason, the work of wiping it was unnecessary or reduced.

[Examples 3-1 to 3-4] Examples 3-1 to 3-4 are examples in which the hydrochloric acid concentration is changed based on Example 2-2. Specifically, the acid concentration is increased from 0.00077N to 0.3.
8N. In each case, the initial contact angle and the contact angle after the weather resistance test were good. In this example, the specified number [N] of the acid as the coating liquid was calculated by the method described above, and also shown in Table 1.

As is clear from this example, it is understood that excellent water-repellent, oil-repellent, antifouling treatment can be performed in a wide range of acid concentrations.

[Examples 4-1 to 4-4] Examples 4-1 to 4-4 are examples in which the type of acid catalyst is changed based on Example 2-2. In each case, the initial contact angle was good. The contact angle after the weather resistance test was slightly smaller in the case of oxalic acid and 1N nitric acid.

As is clear from this example, it is understood that good water-repellent, oil-repellent, antifouling treatment can be performed even with various acid catalysts.

Among various acid catalysts, hydrochloric acid, methanesulfonic acid and paratoluenesulfonic acid are particularly preferably used.

[Examples 5-1 to 5-4] Examples 5-1 to 5-4 were based on Example 4-3, that is, MS was used as an acid catalyst, and the concentration of water was further changed. It is an example. In each case, the initial contact angle and the contact angle after the weather resistance test were good (see Table 2).

As is apparent from this example, even when the solution B further contains water as a solvent, good water / oil / oil repellent / antifouling treatment can be performed.

[0087]

[Table 2] ---------------------------------------------- ------------------------ Solution A | Solution B | After initial UV Example FAS | Acid catalyst Water IPA Acetone AP7 tBuOH I300 I200 | CA CA (% ) | (%) (%) (%) (%) (%) (%) (%) (%) | (°) (°) ----------------- -------------------------------------------------- --- 5-1 1.0 | MS 0.12 − − − 58.88 − 40.0 − | 108.3 95.3 5-2 1.0 | MS 0.12 1.0 − − 57.88 − 40.0 − | 108.6 95.1 5-3 1.0 | MS 0.12 2.0 − − 56.88 − 40.0 − | 107.9 94.8 5-4 1.0 | MS 0.12 4.0 − − 54.88 − 40.0 − | 108.5 95.0 ----------------------------- ----------------------------------------- 6-1 1.0 | PTS 0.25 − 58.75 − − − 40.0 − | 108.3 95.5 6-2 1.0 | PTS 0.25 − − 58.75 − − 40.0 − | 107.8 96.3 6-3 1.0 | PTS 0.25 − − − 58.75 − 40.0 − | 108.6 95.9 6-4 1.0 | PTS 0.25 − − − − 58.75 40.0 − | 108.7 96.0 ----------------------------------------- ----------------------------- 7-1 5.0 | c-HCl 5. 0 − − − 50.0 − 40.0 − | 107.8 97.0 7-2 5.0 | c-HCl 5.0 − − − 50.0 − − 40.0 | 108.4 96.4 -------------------- -------------------------------------------------- 8-1 1.0 | MS 0.12 − − − 93.88 − 5.0 − | 107.5 96.6 8-2 1.0 | MS 0.12 − − − 88.88 − 10.0 − | 109.4 96.8 8-3 1.0 | MS 0.12 − − − 78.88 − 20.0 − | 109.2 95.5 8-4 1.0 | MS 0.12 − − − 58.88 − 40.0 − | 108.3 95.3 8-5 1.0 | MS 0.12 − − − 18.88 − 80.0 − | 107.6 96.0 8-6 1.0 | MS 0.12 − − − 8.88 − 90.0 − | 109.4 95.9 8-7 1.0 | MS 0.12 − − − 3.88 − 95.0 − | 107.9 96.0 ------------------------------- ---------------------------------------

[Examples 6-1 to 6-4] Examples 6-1 to 6-4 are based on Example 4-2, that is, PTS is used as an acid catalyst, and a solvent contained in solution B is further used. "Isosol 30
0 "and a combination of acetone and various alcohols. In each case, the initial contact angle and the contact angle after the weather resistance test were good (see Table 2).

As is evident from this example, good water / oil / oil repellency / antifouling treatment can be achieved even with a combination of alkane, acetone and alcohols having various carbon numbers as the solvent in the solution B.

[Examples 7-1 to 7-2] The examples 7-1 to 7-2
In the solvent contained in the liquid, "ISOSOL 300"
This is an example in which the types of alkanes of “200” and “200” are compared. The liquid B also contains “AP7”. In each case, the initial contact angle and the contact angle after the weather resistance test were good (see Table 2).

As is clear from this example, even when the type of the alkane used as the solvent in the solution B is changed, it is possible to perform a good water-repellent, oil-repellent, antifouling treatment.

[Examples 8-1 to 8-7] Examples 8-1 to 8-7 are based on Example 5-1 in the solvent contained in the solution B.
This is an example in which the mixing ratio of “isosol 300” as an alkane and “AP7” as an alcohol is changed. In each case, the initial contact angle and the contact angle after the weather resistance test were good (see Table 2).

As is clear from this example, even if the mixing ratio of the alkane and the alcohol as the solvent in the solution B is changed, good water / oil / oil repellency / antifouling treatment can be performed.

[Examples 9-1 to 9-2] In each of the examples described above, the solution A was only "FAS". In this example, polydimethylsiloxane and tetraethoxysilane were further added to the solution A. The acid catalyst was MS.
In each case, the initial contact angle and the contact angle after the weather resistance test were good (see Table 3).

In Example 9-1, the liquid A was further added with polydimethylsiloxane as an example of a polysiloxane compound. At this time, a water droplet having a diameter of 5 mm was placed on the surface of the processing substrate, the substrate was tilted, and the angle at which the water droplet started rolling was evaluated as the falling angle. In this example, it was as good as 8.5 degrees. The falling angle of Example 5-1 described above for comparison was 12.3 degrees. From this result, it was found that when polydimethylsiloxane was added to the treatment liquid, falling of water droplets was further facilitated.

In Example 9-2, the above solution A was added to SiR _n X
_As an example of the hydrolyzable silane compound represented by _(4-n) , tetraethoxysilane is added. When tetraethoxysilane is added, an SiO ₂ film can be simultaneously formed. When this substrate was subjected to the abrasion resistance test described above, the contact angle after the abrasion test was as good as 103.1 degrees. The contact angle after the wear test of Example 5-1 described above for comparison was 92.3 degrees. From this result,
For this reason, it was found that the obtained water-repellent, oil-repellent, antifouling treatment film was excellent in durability (wear resistance).

[0097]

[Table 3] ---------------------------------------------- ------------------------ Liquid A | Liquid B | After initial UV fall After wear Example FAS additive | Acid catalyst AP7 I300 | CA CA Angle CA (%) (%) | (%) (%) (%) | (°) (°) (°) (°) --------------------- ------------------------------------------------- 9 -1 0.5 DMS 0.2 | MS 0.12 58.88 40.0 | 108.3 95.3 8.5 − 9-2 0.5 TEOS 0.2 | MS 0.12 58.88 40.0 | 108.3 95.3 − 103.1 ------------------- -------------------------------------------------- -

[Examples 10-1 to 10-4] The above Examples 4-1 to 4-4
Then, “AP7” and “ISOSOL 3
In the combination solvent “00”, the type of the acid catalyst was changed. In Examples 10-1 to 10-4, "A
This is an example in which the type of the acid catalyst is changed in the solvent in which "P7" and "ISOSOL 300" are combined. In each case, the initial contact angle was good. The contact angle after the weather resistance test was slightly smaller in the case of 1N hydrochloric acid and 1N nitric acid (see Table 4).

As is clear from this example, the "AP
It can be seen that even with a solvent in which the combination of "7" and "ISOSOL 300" is used, even with various acids, good water / oil repellency / antifouling treatment can be performed.

[0100]

[Table 4] ---------------------------------------------- ------------------------ Solution A | Solution B | After initial UV Example FAS | Acid catalyst Water IPA Acetone AP7 tBuOH I300 I200 | CA CA (% ) | (%) (%) (%) (%) (%) (%) (%) (%) | (°) (°) ----------------- -------------------------------------------------- --- 10-1 1.0 | c-HCl 1.0 − − − − 50.0 48.0 − | 109.2 89.5 10-2 1.0 | 1N-HCl 1.0 − − − − 50.0 48.0 − | 107.6 85.5 10-3 1.0 | 1N-HNO ₃ 1.0 − − − − 50.0 48.0 − | 108.1 83.3 10-4 1.0 | PTS 0.18 − − − − 49.8 48.0 − | 108.2 91.6 10-5 1.0 | MS 0.09 − − − − − 49.91 48.0 − | 109.0 91.0 ----- -------------------------------------------------- --------------- 11-1 1.0 | Oleic acid 0.1 1.0 − − − 49.9 48.0 − | 107.2 80.0 11-2 1.0 | PTS 0.18 1.0 − − − 48.8 48.0 − | 108.1 91.5 11-3 1.0 | MS 0.09 1.0---48.81 48.0-| 109.2 91.3 --------------------------------- ------------------------------------- 12-1 1.0 | 1N-HCl 1.0 − 48.0 − − − 50.0 − | 107.9 92.3 12-2 1.0 | 1N-HCl 1.0 − − 48.0 − − 50.0 − | 106.8 89.8 12-3 1.0 | 1N-HCl 1.0 − − − − 48.0 50.0 − | 106.3 92.9- -------------------------------------------------- ------------------ 13-1 1.0 | 1N-HCl 1.0 − 48.0 − − − − 50.0 | 110.9 92.2 13-2 1.0 | 1N-HCl 1.0 − − 48.0 − − − 50.0 | 105.1 91.5 13-3 1.0 | 1N-HCl 1.0 − − − − 48.0 − 50.0 | 105.9 91.5 ------------------------- ---------------------------------------------

[Examples 11-1 to 11-4] The above Examples 5-1 to 5-4
Then, MS was used as an acid catalyst, and the concentration of water was further changed. In Examples 11-1 to 11-4, in the solvent in which "AP7" and "tBuOH" contained in the solution B were combined, moisture was basically added to an acid containing no moisture. In each case, the initial contact angle was good. The contact angle after the weather resistance test was slightly smaller in the case of oleic acid (see Table 4).

As is evident from this example, even if water is added to an acid basically containing no water in solution B,
It can be seen that good water-repellent, oil-repellent, antifouling treatment is possible.

[Examples 12-1 to 12-3] The above Examples 6-1 to 6-4
In this example, the acid catalyst was “PTS”, the solvent contained in the solution B was “Isosol 300”, a combination of acetone and various alcohols. In Examples 12-1 to 12-3, 1N hydrochloric acid was used as the acid catalyst, and the solvent contained in the solution B was a combination of "ISOSOL 300", acetone, and various alcohols. In each case, the initial contact angle and the contact angle after the weather resistance test were good (see Table 4).

As is evident from this example, good water-repellent, oil-repellent and antifouling treatment can be achieved even when "Isolzol 300", acetone and various alcohols are used as the solvent in the solution B.

[Examples 13-1 to 13-3] Examples 13-1 to 13-13
-3 is the same as in Examples 12-1 to 12-3 except that "Isolzol 300"
This is an example. In each case, the initial contact angle and the contact angle after the weather resistance test were good (see Table 4).

As is clear from this example, it is understood that good water-repellent, oil-repellent, and soil-repellent treatment can be performed even when "ISOSOL 200", acetone, and various alcohols are used as the solvent in the solution B.

[Examples 14-1 to 14-2] Examples 14-1 to 14-2
-2 is the solvent contained in the solution B in the above Examples 4-2 and 4-3, where "AP7" is IPA and "ISOSOL 30
This is an example in which the ratio of “0” is changed. In each case, the initial contact angle and the contact angle after the weather resistance test were good (see Table 5).

[0108]

[Table 5] ---------------------------------------------- ------------------------ Solution A | Solution B | After initial UV Example FAS | Acid catalyst Water IPA Acetone AP7 tBuOH I300 I200 | CA CA (% ) | (%) (%) (%) (%) (%) (%) (%) (%) | (°) (°) ----------------- -------------------------------------------------- --- 14-1 1.0 | PTS 0.18 − 48.82 − − − 50.0 − | 107.1 94.5 14-2 1.0 | MS 0.09 − 48.91 − − − 50.0 − | 108.5 95.6 ------------- -------------------------------------------------- ------- 15-1 5.0 | c-HCl 5.0 − − − 40.0 − 50.0 − | 108.8 95.6 15-2 5.0 | c-HCl 1.0 − − − 43.0 − 50.0 − | 109.0 95.4 15-3 5.0 | c-HCl 0.1 − − − 43.9 − 50.0 − | 109.4-15-4 5.0 | 1N-HCl 1.0 − − − 44.0 − 50.0 − | 109.7 95.1 ---------------- -------------------------------------------------- ---- 16-1 5.0 | 1N-HCl 1.0 − − − 44.0 − 50.0 − | 109.7 95.1 16-2 2.0 | 1N-HCl 1.0 − − − 47.0 − 50.0 − | 108.7 92.8 16-3 1.0 | 1N-HCl 1.0 − − − 48. 0 − 50.0 − | 108.0 92.8 ------------------------------------------- ---------------------------

[Examples 15-1 to 15-4] The above Examples 3-1 to 3-4
In the example, when the concentration of “FAS” was 1.0% by mass, the concentration of hydrochloric acid was changed. In Examples 15-1 to 15-4, the concentration of “FAS” was 5.0% by mass. This is an example in which the hydrochloric acid concentration was changed in the above case. In each case, the initial contact angle and the contact angle after the weather resistance test were good (see Table 5).

As is clear from this example, it is understood that good water-repellent, oil-repellent, antifouling treatment can be performed in a wide range of acid concentrations.

[Examples 16-1 to 16-3] The above Examples 2-1 to 2-7
Then, when the concentration of concentrated hydrochloric acid is 1.0% by mass,
Although "FAS" was changed, in Examples 16-1 to 16-3, when the concentration of the acid catalyst was adjusted to 1.0% by mass with 1N hydrochloric acid, the "FAS" concentration was changed. is there. In each case, the initial contact angle and the contact angle after the weather resistance test were good (see Table 5).

As is clear from this example, it is understood that excellent water-repellent, oil-repellent, antifouling treatment can be performed in a wide range of "FAS" concentration.

[Example 17-1] In Example 1-1, the type of the solvent contained in the solution B was changed from "i-propanol" to "Isosol 300", and the acid was changed to "concentrated hydrochloric acid".
Was changed to "methanesulfonic acid". Each mixing ratio is shown in Table 6 by mass%. Table 6 also shows the initial contact angle and the contact angle after the weather resistance test. In each case, the initial contact angle and the contact angle after the weather resistance test were good.

As is apparent from Example 17-1, it is sufficient that the solution B constituting the treatment liquid according to the present invention should be composed of an acid catalyst and an alkane solvent.

[0115]

[Table 6] ---------------------------------------------- ------------------------ Solution A | Solution B | After initial weathering Example FAS | Acid catalyst Water IPA Acetone AP7 tBuOH I300 I200 | CA CA (% ) | (%) (%) (%) (%) (%) (%) (%) (%) | (°) (°) ----------------- -------------------------------------------------- --- 17-1 5.0 | MS 0.12 − − − − − 94.88 − | 108.4 95.2 ------------------------------ ----------------------------------------

As is clear from the embodiments described above, it is preferable that the solvent contained in the solution B contains at least one alcohol compatible with water. Further, since alkanes are soluble in alcohols, it is preferable that the alkanes are used together with alcohols when the alkanes are contained in the solvent.

In the above embodiments, a glass substrate is used as a substrate. However, even when an article made of ceramics, plastic, or metal is processed using the same processing liquid, the same water and oil repellency is obtained. An antifouling effect was obtained.

Comparative Example 1 (1) As a compound having a fluoroalkylsilane group, F
5 g of AS is dissolved in 45 g of i-propanol to obtain solution a. (2) 5 g of concentrated hydrochloric acid is dissolved in 45 g of i-propanol and mixed to obtain a solution b. (3) The above-mentioned liquid a and liquid b were mixed and left to stand about 5 minutes later to obtain a coating liquid. (4) On a washed glass substrate, 1 ml of the above coating solution was applied to a cotton cloth and applied. (5) Excess coating liquid was wiped off with a fresh cotton cloth to obtain a treated glass. The water contact angle of the obtained water repellent glass was 109 degrees, and the water contact angle after the weather resistance test was 94 degrees.

The above solution a and solution b were mixed at room temperature for 1 hour.
Left for months. In this case, the solution a was cloudy. The solution a and the solution b were mixed and treated similarly. Regarding the water repellency, the initial contact angle was 109 degrees, and
It did not change compared to. However, the contact angle after the weather resistance test showed a low value of 75 degrees.

[0120]

As described in detail above, the present invention is characterized in that, when storing a silane compound containing a fluoroalkyl group, the silane compound is first stored in a state free of an acid and a solvent. Storing in this manner has the effect of preventing the water-repellent, oil-repellent, antifouling treatment liquid from becoming cloudy as described above.

Further, in the water-repellent, oil-repellent, antifouling treatment liquid of the present invention, even when the proportion of the fluoroalkyl group-containing silane compound in the treatment liquid is 1% by mass or less, a good water-repellent, oil-repellent, antifouling effect can be obtained. . Therefore, there is an effect that surplus hydroalkyl silane hydrolyzate hardly remains on the treated surface. For this reason, there is also a ripple effect that the work of wiping this is unnecessary or reduced.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 83/04 C08L 83/04 C09K 3/00 112 C09K 3/00 112F (72) Inventor Kazutaka Kamiya Osaka Prefecture Mitsuhiro Asai, Nippon Sheet Glass Co., Ltd. (72) Inventor Mitsuhiro Kawazu 3-5-11 Doshomachi, Chuo-ku, Osaka City, Osaka Prefecture 1-10 Hitomi, Matsuida-machi, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory

Claims (30)

[Claims] 1. A water-repellent, oil-repellent and antifouling treatment liquid which is used by mixing a liquid A containing a silane compound having a fluoroalkyl group and a liquid B containing an acid and a solvent. 2. The water-repellent, oil-repellent and antifouling treatment liquid according to claim 1, wherein the acid contains at least one of hydrochloric acid, methanesulfonic acid, and paratoluenesulfonic acid. Processing liquid. 3. The water-repellent, oil-repellent and antifouling treatment liquid according to claim 1, wherein the solvent contains an organic solvent compatible with water. 4. The water-repellent, oil-repellent and antifouling treatment liquid according to claim 1, wherein the solvent contains at least one kind of alcohol having 1 to 10 carbon atoms. 5. The water-repellent, oil-repellent and antifouling treatment liquid according to claim 1, wherein the solvent contains at least one kind of alkane having 4 to 14 carbon atoms. 6. The water-repellent, oil-repellent and antifouling treatment liquid according to claim 3, wherein the solvent further contains water. 7. The water-repellent, oil-repellent and antifouling treatment liquid according to claim 1, wherein the fluoroalkyl group-containing silane compound is represented by the following chemical formula 1. ## STR1 ## _{CF 3 - (CF 2) n} -R-SiX p Y 3-p ·· (1) ( wherein, n represents 0 to 12 integer, preferably 3 to 12 integer, R represents a carbon atom X is H or a monovalent hydrocarbon group having 1 to 4 carbon atoms (eg, an alkyl group), wherein X is a divalent organic group having 1 to 10 groups (eg, a methylene group or an ethylene group) or a group containing a silicon atom and an oxygen atom. , Cycloalkyl group, allyl group) or a substituent selected from derivatives of these groups, or hydrogen, p is 0, 1 or 2, Y is an alkoxyl group having 1 to 4 carbon atoms, an acyloxy group, or a halogen atom. ) 8. The water / oil repellent / antifouling treatment liquid according to claim 1, wherein the fluoroalkyl group-containing silane compound is contained at a rate of 0.01 to 5% by mass of the treatment liquid. Oil repellent and antifouling treatment liquid. 9. The water / oil repellent / antifouling treatment liquid according to claim 1, wherein the acid is contained such that the acid concentration of the treatment liquid is 0.0001 to 1N. Soil treatment liquid. 10. The water-repellent, oil-repellent and antifouling treatment liquid according to claim 4, wherein the alcohol is contained at a ratio of 1 to 99% by mass of the treatment liquid. 11. The water-repellent, oil-repellent and antifouling treatment liquid according to claim 5, wherein the alkane is contained at a ratio of 1 to 99% by mass of the treatment liquid. 12. The water-repellent, oil-repellent, and antifouling treatment liquid according to claim 6, wherein the water is contained at a ratio of 0.1 to 5% by mass of the treatment liquid. liquid. 13. The water-repellent, oil-repellent and antifouling treatment liquid according to claim 1, wherein the liquid A further comprises a polysiloxane compound or Si.
R _n X _(4-n) in water-repellent, oil-repellent antifouling treatment solution hydrolyzable silane compound is contained represented. (However, R: an alkyl group having 1 to 5 carbon atoms, n = 0 to 3, X; an alkoxyl group, a halogen, an acetoxyl group, or an isocyanate group) 14. A step of preparing (A) a liquid A containing a fluoroalkyl group-containing silane compound, (2) a step of preparing a liquid B comprising an acid and a solvent, (3) the liquid A and the liquid B Mixing to prepare a water- and oil-repellent antifouling treatment liquid,
(4) a step of applying the water-repellent, oil-repellent, and soil-repellent treatment liquid to the surface of the article. 15. The water-repellent, oil-repellent, antifouling treatment method according to claim 14, wherein the acid includes at least one of hydrochloric acid, methanesulfonic acid, and paratoluenesulfonic acid. . 16. The water / oil repellent / antifouling treatment method according to claim 14, wherein the solvent includes an organic solvent having water compatibility. 17. The water / oil repellent / antifouling treatment method according to claim 14, wherein the solvent contains at least one kind of alcohol having 1 to 10 carbon atoms. 18. The water / oil / oil repellent / antifouling treatment method according to claim 14, wherein the solvent contains at least one kind of alkane having 4 to 14 carbon atoms. 19. The water-repellent, oil-repellent and antifouling treatment method according to claim 16, wherein the solvent further contains water. 20. The water / oil repellent / antifouling treatment method according to claim 14, wherein the fluoroalkyl group-containing silane compound is represented by the following chemical formula 1. ## STR1 ## _{CF 3 - (CF 2) n} -R-SiX p Y 3-p ·· (1) ( wherein, n represents 0 to 12 integer, preferably 3 to 12 integer, R represents a carbon atom X represents H or a monovalent hydrocarbon group having 1 to 4 carbon atoms (eg, an alkyl group); , Cycloalkyl group, allyl group) or a substituent selected from these derivatives,
Or hydrogen, p is 0, 1 or 2, and Y is 1 carbon atom.
To 4 alkoxyl groups, acyloxy groups, or halogen atoms) 21. The water-repellent, oil-repellent, antifouling treatment method according to claim 14, wherein the fluoroalkyl group-containing silane compound is used in the treatment liquid such that the ratio thereof is 0.01 to 5% by mass. A water-repellent, oil-repellent, antifouling treatment method contained in the liquid. 22. The water / oil repellent / antifouling treatment method according to claim 14, wherein the acid is contained in the B liquid such that the acid concentration of the treatment liquid is 0.0001 to 1N. Water and oil repellent antifouling treatment method. 23. The water / oil repellent / antifouling treatment method according to claim 17, wherein the alcohol is used in an amount of 1 to 99% by mass in the treatment liquid.
The water-repellent, oil-repellent, antifouling treatment method contained in the liquid B so that the ratio becomes as follows. 24. The water / oil repellent / antifouling treatment method according to claim 18, wherein the alkane is contained in the B liquid such that the alkane is contained in the treatment liquid at a ratio of 1 to 99% by mass. Water and oil repellent antifouling treatment method. 25. The water-repellent, oil-repellent, antifouling treatment method according to claim 19, wherein the water is contained in the solution B so as to be in a ratio of 0.1 to 5% by mass in the treatment solution. Water and oil repellent anti-fouling treatment method. 26. The water / oil repellent / antifouling treatment method according to claim 14, wherein the article is one of glass, ceramics, plastic, and metal. 27. The water / oil repellent / antifouling treatment method according to claim 14, wherein the application method is a hand coating method, a dip coating method,
Water-repellent, oil-repellent and antifouling treatment methods such as flow coating method, curtain coating method, spin coating method, spray coating method, bar coating method, roll coating method, and brush coating method. 28. A water-repellent, oil-repellent, anti-fouling treated article treated by the method of claim 14. 29. A two-part mixed water / oil / oil repellent / antifouling treatment liquid comprising a liquid A containing a fluoroalkyl group-containing silane compound and a liquid B containing an acid and a solvent. 30. The two-liquid mixed water / oil repellent / antifouling treatment liquid according to claim 29, wherein the liquid A contains substantially no acid and / or solvent, and the liquid B is substantially a fluoroalkyl. A two-component mixed water / oil / oil repellent / antifouling treatment liquid containing no group-containing silane compound.