JP2003206477A - Super water-repellent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a super water-repellent composition capable of readily imparting super water repellency to a coated surface, preventing waterdrops from sticking and forming a transparent film having durability, a method for a super water-repellent treatment of a surface of an article and the article having the surface subjected to the super water repellent treatment. <P>SOLUTION: This super water-repellent composition comprises (A) inorganic fine particles subjected to a hydrophobizing treatment and having ≤100 nm average particle diameter, (B) an organosilicon compound and (C) an organic solvent dissolving the organosilicon compound and having 50-150°C boiling point under 1.013×10<SP>2</SP>kPa and 0.2-1.3 kJ/g evaporation latent heat. The method for super water-repellent treatment of the surface of the article comprises using the super water-repellent composition. The article has the surface subjected to the super water-repellent treatment with the super water-repellent composition. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a super water repellent composition. More specifically, the present invention is applied to a hard surface such as a painted surface of an automobile or the like, a glass surface, a side mirror, a mirror placed outdoors, a building, or the surface of the glass, thereby super-repelling the surface. When water is applied and the contact angle with water is 140 ° or more, water droplets do not adhere to the coating surface, the coating surface does not whiten when applied, and a transparent film is formed, which has excellent durability, and The present invention relates to a super water repellent composition that can easily obtain super water repellency. The present invention further relates to a method for treating an article surface with a super water repellent composition using the super water repellent composition, and an article treated with a super water repellent agent by the super water repellent composition.

[0002]

2. Description of the Related Art Conventionally, when a surface of a material having a contact angle of water of 90 ° or more is made uneven, the surface area becomes large and the contact angle becomes large. It is known. It is also known that when this surface has a fractal structure, an extremely large water-repellent surface having a contact angle of more than 160 °, that is, a super-water-repellent surface can be obtained. On this super water repellent surface, water drops will fall on the lotus leaf.

In order to obtain such super water repellency, there is known a technique of applying hydrophobic fine particles. However, the durability of the coating cannot be obtained only by coating the fine particles, and it is difficult to uniformly attach the fine particles.

As a conventional technique for imparting durability and imparting superhydrophobicity, JP-A-6-16455 discloses two or more compounds selected from metal alkoxide compounds and metal acetylacetonate compounds. Select and mix two or more compounds with a solvent to form a coating solution,
A technique is disclosed in which an underlayer of a sol-gel film having a micropit-shaped, uneven or convex-shaped surface layer formed by heating film is treated to be water-repellent to obtain super water repellency. In addition, JP 20
No. 01-144116 discloses a method of forming unevenness by heat treatment after applying a treatment liquid containing a polycondensate of trialkoxysilane or trialkoxysilane or its oligomer and a metal alkoxide or its oligomer to a glass surface. There is. These methods require heat treatment and are difficult to process on already equipped mirrors, glass surfaces, painted surfaces or buildings. Also,
In addition to this, there is a method of corrugating the surface of the substrate by corona discharge, plasma treatment disclosed in Japanese Patent Laid-Open No. 2001-254030, or the like to perform water repellent treatment, but these are not easily treated in the same manner as above. Have difficulty.

Further, Japanese Unexamined Patent Publication No. 11-116945 discloses a technique for obtaining super-water repellency by spraying fine particles of water-repellent ceramic or metal oxide on the surface to form irregularities. However, although this method can be used for soft materials such as plastic, it cannot be used for hard materials such as glass, and it requires a machine such as a blast machine for spraying, so it is easy to process. It is difficult.

Further, Japanese Unexamined Patent Publication No. 10-273617 discloses a method of using a polyvinylidene fluoride polymer as a binder for adhering the hydrophobized inorganic fine particles to the surface. However, in this method, it is difficult to form a transparent coating because a polymer is used, and it is difficult to use it on a surface such as a glass surface or a mirror, which requires transparency. Further, JP-A-10-316
Japanese Patent No. 820 discloses a method of adhering fine particles of fluororesin on the surface by using a resin or the like as a binder, but it is difficult to form a transparent film as in the above.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to easily impart super water repellency to a coated surface, prevent water droplets from adhering, and form a durable transparent film. It is to provide a super water repellent composition that can be used. Another object of the present invention is to provide a method for superhydrophobicizing a surface of an article using the superhydrophobic agent composition, and an article whose surface is superhydrophobicized by the superhydrophobic agent composition. That is.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventor has found that a super water repellent composition containing specific components can achieve the above object. The present invention has been made based on the above findings, in which (A) hydrophobically treated inorganic fine particles having a primary average particle diameter of 100 nm or less, (B) an organosilicon compound, and (C) the organosilicon compound are dissolved, 1.
Boiling point at 013 × 10 ² kPa is 50 to 150 ° C.,
Further, the present invention provides a super water repellent composition containing an organic solvent having a latent heat of vaporization of 0.2 to 1.3 kJ / g. The present invention also provides a method for imparting superhydrophobicity to an article surface, which comprises applying the above superhydrophobic agent composition to the surface of the article. The present invention further provides an article that has been treated to be super water repellent with the above super water repellent composition.

The mechanism by which the super water repellent composition of the present invention imparts the super water repellent effect to the surface is not fully clear, but it is presumed as follows. When the super water repellent composition of the present invention is applied to a hard surface, the inorganic fine particles and the organosilicon compound which have been hydrophobized are thinly applied by the action of the organic solvent. Inorganic fine particles form an uneven surface by volatilization of the organic solvent,
It is considered to impart super water repellency. Further, a thin film of an organic silicon compound covers the inorganic fine particles, and durability is obtained. Furthermore, the primary average particle diameter of the inorganic fine particles is 100 nm.
It is considered that a transparent film can be obtained by the following.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The super water repellent composition of the present invention will be described in detail below. In the super water repellent composition of the present invention, (A) the hydrophobically treated inorganic fine particles having a primary average particle diameter of 100 nm or less, (B) an organosilicon compound, and (C) the organosilicon compound are dissolved to give 1.013. The boiling point at × 10 ² kPa is 50 to 150 ° C, and the latent heat of vaporization is 0.2 to 1.3 kJ.
/ G of organic solvent.

First, the hydrophobized inorganic fine particles as the component (A) will be described. As inorganic fine particles,
Although not limited, oxides of Si, Ti, Al and Zr can be used. The oxides of Si, Ti, Al and Zr may be those obtained by a known method. For example, Si oxide can be obtained by flame hydrolysis of silanes such as silicon tetrachloride, methyltrichlorosilane, and trichlorosilane. It can also be obtained by dropping ammonia into an aqueous solution of silanes such as tetrachlorosilane and tetramethoxysilane. Oxides of Ti, Al and Zr
It can be obtained by flame hydrolysis of titanium tetrachloride, aluminum trichloride and zirconium tetrachloride.

The primary average particle diameter of the inorganic fine particles is 10
It must be 0 nm or less. This is because when the primary average particle diameter is larger than 100 nm, light is diffusely reflected and a transparent film cannot be obtained.

The inorganic fine particles obtained above are treated with hydrocarbon-based silanes such as dimethyldimethoxysilane and trimethylmethoxysilane, fluorine-based silanes such as heptadecatrifluorodecyltrimethoxysilane, and silicone such as dimethylpolysiloxane. By subjecting the compound to a hydrophobic treatment, the inorganic fine particles of the component (A) of the present invention can be obtained.

In order to promote the reaction between the silanes or silicone compounds and the inorganic fine particles, 100 parts by mass of silanes or silicone compounds are added with organic acids such as formic acid and acetic acid, and inorganic acids such as nitric acid, hydrochloric acid, phosphoric acid and sulfuric acid. It is preferable to add 1 to 10 parts by mass. This reaction is from room temperature to 100
It progresses sufficiently at 0.5 ° C. for 0.5 to 2 hours.

The organosilicon compound as the component (B) is at least one compound represented by the following general formula (1) or general formula (2). General formula (1)

[Chemical 2] In the formula, R ¹ and R ² may be the same or different and each is hydrogen, alkyl, aryl, aminoalkyl, aminoalkylaminoalkyl, glycidoxyalkyl, epoxycycloalkyl, alkylcarbonyloxy, fluoroalkyl, mercaptoalkyl. Or indicates hydroxy,
When two or more R _1's are present, they may be the same or different. n and m are 0 or an integer of 1 or more, and n + m is 0 to 3.
It is 000. Specific examples of R ¹ and R ² include H and C.
_{H 3, C 6 H 5,} (CH 2) p CH 3 (p = 1 or 17 or _{less), C 3 H 6 NH 2} , C 3 H 6 NHC 2 H 4 NH 2, C 3 H 6 O
CH ₂ CHCH ₂ O, C ₂ H ₄ C ₆ H ₉ O, OCO (CH ₂ ) _q
CH ₃ (q = 6 to 16), CH ₂ CH ₂ CF ₃ , C ₃ H ₆ S
H, OH, etc. may be mentioned.

General formula (2) R_aSiX_4-a In the formula, R is alkyl, aryl or fluoroalkyl
X is halogen or alkoxy, and a is 1
Indicates an integer of ˜3. As a specific example of R, CH₃, C₆H
_Five, (CH₂)_tCH₃(T = 1 to 17), C ₂H_FourCF₃,
C₂H_FourC₈F₁₇Etc., specific examples of X include Cl, OC
H₃, OC₂H _FiveEtc.

Examples of the organosilicon compound of the general formula (1) used in the present invention include the following compounds.
Dimethylpolysiloxane in which R ₁ and R ₂ are CH ₃ . It is commonly called silicone oil or dimethyl silicone. Compounds in which R ₁ and R ₂ are other than CH ₃ , commonly referred to as modified silicones or modified silicone oils. For example, R ₂ is CH ₃ , R ₁ is C ₆ H ₅ phenyl-modified silicone, R ₂ is CH ₃ , and R ₁ is (CH ₂ ) _p CH ₃ (p = 1 or more and 1
7 or less) alkyl-modified silicone.

R ₂ is CH ₃ or OH, R ₁ is C ₃ H ₆ NH ₂
Or a compound of C ₃ H ₆ NHC ₂ H ₄ NH ₂ , or R ₂ is C
₃ H ₆ NH ₂ or C ₃ H ₆ NHC ₂ H ₄ NH ₂ , amino-modified silicone in which R ₁ is CH ₃ . R ₂ is CH ₃ , R ₁ is C ₃ H ₆ OC
A compound of H ₂ CHCH ₂ O or C ₂ H ₄ C ₆ H ₉ O, or R ₂ is C ₃ H ₆ OCH ₂ CHCH ₂ O or C ₂ H ₄ C ₆ H
₉ O, R ₁ is CH ₃ epoxy modified silicone.

R ₂ is CH ₃ , R ₁ is OCO (CH ₂ ) _q CH ₃
(Q = 6 or more and 16 or less) higher fatty acid ester-modified silicone, fluorine-modified silicone in which R ₂ is CH ₃ , and R ₁ is CH ₂ CH ₂ CF ₃ . R ₂ is CH ₃ , R ₁ is C ₃ H ₆ SH or R ₂
Is C ₃ H ₆ SH and R ₁ is CH ₃ mercapto-modified silicone. R ₂ is CH ₃ , R ₁ is OH or R ₂ is OH, and R ₁ is C
H ₃ silanol modified silicone. R ₂ is CH ₃ , R ₁ is H
Methyl hydrogen polysiloxane, commonly known as methyl hydrogen silicone.

The compound of the general formula (2) used in the super water repellent composition of the present invention is a compound commonly called silane. Specific examples of preferable silanes include the following compounds. Methyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, hexatrichlorosilane, decyltrichlorosilane, trifluoropropyltrichlorosilane, heptadecatrifluorodecyltrichlorosilane, methyltrimethoxysilane, Methyldimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, hexatrimethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, heptadecatrifluorodecyltrimethoxysilane, methyltriethoxy Silane, methyldiethoxysilane, dimethyldiethoxysilane, trimethyleth Shishiran, phenyltriethoxysilane, diphenyl diethoxy silane, hexa triethoxysilane, decyl triethoxysilane, trifluoropropyl triethoxysilane, heptadecafluoro-trifluoro-decyl triethoxysilane.

The mass ratio B / A of the inorganic fine particles as the component (A) and the organosilicon compound as the component (B) in the super water repellent composition of the present invention is such that the durability of the super water repellent performance and the film It affects transparency and the mass ratio B / A is preferably 0.025 to 0.5. If it is less than 0.025, the inorganic fine particles are likely to be peeled off and durability may not be obtained, and if it exceeds 0.5, a transparent coating film may not be obtained due to the influence of the organosilicon compound.

Further, (A) in the super water repellent composition of the present invention
The total amount of the inorganic fine particles as the component and the organosilicon compound as the component (B) also affects the durability of the super water-repellent performance and the transparency of the coating. The sum of the components (A) and (B) is 0.5 to
5 mass% is preferable. If it is less than 0.5% by mass, super water repellency may not be obtained, and if it exceeds 5% by mass, the film may become thick and a transparent film may not be obtained, or wavy during coating and drying. In some cases, a non-uniform coating cannot be obtained and a transparent coating cannot be obtained. The organic acid such as formic acid and acetic acid, nitric acid, hydrochloric acid, as an auxiliary agent for accelerating the film formation and for dissolving the organosilicon compound in an organic solvent,
An inorganic acid such as phosphoric acid or sulfuric acid may be added. The addition amount is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the organosilicon compound.

The organic solvent which is the component (C) is (B)
1.013 × 10 ²
The boiling point at kPa is 50 to 150 ° C., and the latent heat of vaporization is 0.2 to 1.3 kJ / g. When an organic solvent in which the organosilicon compound as the component (B) is not dissolved is used, a non-uniform coating film is formed and a super water-repellent, transparent coating film cannot be obtained. Boiling point less than 50 ° C, latent heat of vaporization 0.2 kJ / g
If it is less than the above range, a uniform coating cannot be obtained when applied because the evaporation rate is too fast, and superhydrophobicity is not exhibited. Also, the boiling point is 1
If it exceeds 50 ° C. or the latent heat of vaporization exceeds 1.3 kJ / g, it takes a long time to dry because the evaporation rate is slow, and there is a problem in workability.

As the organic solvent of the component (C), hydrocarbons, halogenated hydrocarbons, alcohols, ethers,
Ketones, esters and glycol ethers are preferred. Specific examples thereof include hydrocarbons such as toluene, xylene, n-hexane and n-heptane, halogenated hydrocarbons such as chloroform, ethylene chloride, 1,1,1-trichloroethane and butyl chloride, methanol, ethanol and n-.
Alcohols such as propanol, isopropanol and n-butanol, ethers such as isopropyl ether and n-butyl ether, ketones such as acetone and methyl ethyl ketone, esters such as ethyl formate, ethyl acetate, butyl acetate, methyl propionate and ethyl butyrate. And glycol ethers such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether.

The super water repellent composition of the present invention is preferably stored in a bottle, a spray can, an aerosol can or the like for storage and use. A super water repellent surface can be obtained by uniformly applying this to a hard surface and then drying it. The coating method is not particularly limited, and examples thereof include spray coating, brush coating, dipping and the like. The coating amount is usually 0.2 to 3 g / dry weight.
About m ² is preferable. The article which is subjected to water repellent treatment using the above super water repellent composition is not particularly limited, for example, glass products such as mirrors and window glass, outer walls such as concrete and mortar, building materials, iron, aluminum, copper and the like. Metal products, plastic products, painted products, wood products, etc.

[0026]

EXAMPLES The present invention will now be described in more detail with reference to examples. However, the present invention is not limited to the embodiment. The obtained super water repellent composition was evaluated by the following test methods.

Water Repellent Test A preparation (2.5 cm × 7.5 cm × 0.2 cm) which has been washed with an oil film remover containing an abrasive and dried in advance is immersed in a super water repellent, and the preparation is pulled up vertically. Air-dry to obtain a test piece. The test piece is set on a S-150 type contact angle measuring instrument manufactured by Kyowa Interface Science Co., Ltd., and 10 μl of pure water is dropped on the test piece to measure the contact angle.

Durability test A 500 ml beaker containing 500 ml of tap water is charged with a stirrer having a diameter of 7.5 mm and a length of 35 mm, and stirred at 1,500 rpm with a magnetic stirrer. While continuing stirring, the test piece used in the water repellency test is dipped and held for 2 minutes. Then, the test piece is taken out and the peeled state of the film is visually observed. In addition, the test piece is placed on a table tilted at 10 °, 20 μl of pure water is added dropwise, and it is confirmed whether the water drop slips off. The evaluation criteria are as follows. ◯: Does not peel or slides off ×: Does not peel or slides

Transparency of the coating The preparation prepared in the same manner as in the water repellency test was overlaid, and JI
SK 0102 Measure the number of sheets where the cross of the indicator plate of the fluorometer used in the perspective of the drainage test method can be clearly confirmed.

Examples 1 to 14 Heptadecatrifluorodecyltrimethoxysilane (K
BM7803: manufactured by Shin-Etsu Chemical Co., Ltd.) 10 g 400
g dissolved in methanol. Add 2% by weight nitric acid to this.
0 g was added and stirred for 30 minutes. To this solution, 50 g of fine particle silica (primary average particle diameter 12 nm) obtained by reacting silicon tetrachloride by a flame hydrolysis method was added little by little, and stirred for 1 hour for hydrophobic treatment. Methanol was dried and removed at 100 ° C. to complete the hydrophobization to obtain hydrophobized fine particle silica.
Using this hydrophobized fine particle silica, the components shown in Tables 1 and 2 were mixed at the ratios shown in Tables 1 and 2 to obtain a super water repellent composition. The numbers in the table indicate g.

Examples 15 to 16 Dimethyldimethoxysilane (KBM22: manufactured by Shin-Etsu Chemical Co., Ltd.) (10 g) was dissolved in 400 g of methanol.
10 g of 2 mass% nitric acid was added to this, and it stirred for 30 minutes.
Fine aluminum oxide particles obtained by reacting this solution with aluminum trichloride by a flame hydrolysis method (first average particle diameter 1
(3 nm) (50 g) was added little by little and stirred for 1 hour for hydrophobic treatment. Methanol was dried and removed at 100 ° C. to complete the hydrophobization to obtain hydrophobized particulate aluminum oxide.
Using the hydrophobized particulate aluminum oxide, the components shown in Table 3 were mixed in the proportions shown in Table 3 to obtain a super water repellent composition. The numbers in the table indicate g.

Examples 17 to 18 15 g of dimethyl silicone (KF96-10: manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 400 g of isopropanol. 1 g of sulfuric acid was added thereto, and the mixture was stirred for 30 minutes. To this solution, 50 g of fine particle titanium oxide (primary average particle diameter 21 nm) obtained by reacting titanium tetrachloride by a flame hydrolysis method was added little by little, and stirred for 1 hour for hydrophobic treatment. Isopropanol was removed by drying at 100 ° C. to complete the hydrophobization to obtain hydrophobized particulate titanium oxide. Using the hydrophobized particulate titanium oxide, the components shown in Table 3 were mixed in the proportions shown in Table 3 to obtain a super water repellent composition. The numbers in the table indicate g.

Examples 19 to 20 Diphenyldimethoxysilane (KBM202SS: manufactured by Shin-Etsu Chemical Co., Ltd.) (10 g) was dissolved in 400 g of methanol. 10 g of 2 mass% nitric acid was added to this, and it stirred for 30 minutes. To this solution, 50 g of fine particle zirconium oxide (primary average particle diameter 25 nm) obtained by reacting zirconium tetrachloride by the flame hydrolysis method was added little by little, and stirred for 1 hour for hydrophobic treatment. Methanol was removed by drying at 100 ° C. to complete the hydrophobization to obtain hydrophobized particulate zirconium oxide. Using this hydrophobized zirconium oxide,
The components shown in Table 3 were mixed in the proportions shown in Table 3 to obtain a super water repellent composition. The numbers in the table indicate g.

Comparative Examples 1 to 6 The components shown in Table 4 were mixed in the proportions shown in Table 4 to prepare Comparative Examples 1 to 1.
6 compositions were prepared. Comparative Example 1 primary average particle size 15
The 0 nm hydrophobized silica is obtained by reacting silicon tetrachloride by a flame hydrolysis method and hydrophobized in the same manner as the hydrophobized silica of Examples 1 to 14. The hydrophobized silica of Comparative Examples 3 to 5 is the same as the hydrophobized silica used in Examples 1 to 14. The silica (SiO ₂ ) of Example 6 is the same as those of Examples 1-14.
The silica prepared in 1. is not subjected to a hydrophobic treatment.
The numbers in the table indicate g. Table 5 shows the evaluation results of the compositions of the above Examples and Comparative Examples.

[0035]

[Table 1]

(1) to (7): manufactured by Shin-Etsu Chemical Co., Ltd. * 1 Boiling point: 111 ° C. Latent heat of vaporization: 0.36 kJ /
g * 2 Boiling point: 78.5 ° C Latent heat of vaporization: 0.84 kJ /
g

[0037]

[Table 2]

(8) (9) (11) to (14): manufactured by Shin-Etsu Chemical Co., Ltd. (10): manufactured by Nippon Unicar Co., Ltd. * 1 Boiling point: 111 ° C. Latent heat of vaporization: 0.36 kJ /
g * 2 Boiling point: 78.5 ° C Latent heat of vaporization: 0.84 kJ /
g * 3: Heptadecatrifluorodecyltrimethoxysilane

[0039]

[Table 3]

(3) (13): manufactured by Shin-Etsu Chemical Co., Ltd. * 2 Boiling point: 78.5 ° C Latent heat of vaporization: 0.84 kJ /
g

[0041]

[Table 4]

(3) (13): The hydrophobic silica of Comparative Example 1 manufactured by Shin-Etsu Chemical Co., Ltd. has a primary average particle diameter of 150 nm * 2 Boiling point: 78.5 ° C Latent heat of vaporization: 0.84 kJ /
g * 4 Boiling point: 76.7 ° C Latent heat of vaporization: 0.19 kJ /
g * 5 Boiling point: 197 ° C Latent heat of vaporization: 0.85 kJ /
g * 6 Boiling point: 34.6 ° C Latent heat of vaporization: 0.38 kJ /
g

[0043]

[Table 5] Judgment Criteria ○: Does not peel and slides off ×: Peels does not slide-: Unknown because it is almost transparent

As is clear from the description in Table 5, the super water repellent composition of the present invention easily imparts super water repellency to form a durable transparent film. On the other hand, in Comparative Example 1, since the hydrophobized silica having a primary average particle diameter of 150 nm is used, the transparency of the coating film is poor.
Since Comparative Example 2 does not contain inorganic fine particles, it does not exhibit super water repellency and water drops do not slide off. Comparative Example 3 has a boiling point of 1
Since an organic solvent higher than 50 ° C is used, the solvent does not evaporate. In Comparative Example 4, since the solvent having a boiling point lower than 50 ° C. is used, the evaporation rate is high, the coating is non-uniform, the contact angle with water is small, the water repellency is not exhibited, and the water droplets do not slip off. In Comparative Example 5, since the fluororesin is used without using the organosilicon compound, the transparency of the coating film is poor.
Comparative Example 6 is not a hydrophobicized inorganic fine particle and thus has a small contact angle with water and does not exhibit super water repellency. Further, since it is not hydrophobicized, a water resistant coating cannot be obtained and durability is poor.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hiromitsu Saito             3075-11 Shimasu, Itako-shi, Ibaraki Sanai Oil Co., Ltd.             In the company F-term (reference) 4H020 BA32                 4J038 DL031 DL051 DL071 DL081                       HA216 HA446 KA06 KA08                       KA15 MA07 NA07 PB07 PC02                       PC03 PC04 PC06 PC08

Claims (7)

[Claims] 1. (A) Hydrophobized inorganic fine particles having an average primary particle size of 100 nm or less, (B) an organosilicon compound, (C) the organosilicon compound are dissolved, and 1.013 ×
A super water repellent composition containing an organic solvent having a boiling point at 10 ² kPa of 50 to 150 ° C. and a latent heat of vaporization of 0.2 to 1.3 kJ / g. 2. The mass ratio B / A of (A) the hydrophobically treated inorganic fine particles having an average primary particle size of 100 nm or less and (B) the organosilicon compound is 0.025 to 0.5. The described super water repellent composition. 3. The total amount of (A) inorganic fine particles having a primary average particle diameter of 100 nm or less subjected to a hydrophobization treatment and (B) an organosilicon compound is 0.5 to 5% by mass. The super water repellent composition according to item 1. 4. A hydrophobized primary average particle diameter of 100.
The super-water repellent composition according to any one of claims 1 to 4, wherein the inorganic fine particles having a size of nm or less are oxides of Si, Ti, Al or Zr. 5. The organosilicon compound has the following general formula (1):
Alternatively, the super water repellent composition according to any one of claims 1 to 4, which is a compound represented by the general formula (2) or a mixture of two or more kinds thereof. General formula (1) In the formula, R ¹ and R ² may be the same or different and each is hydrogen, alkyl, aryl, aminoalkyl, aminoalkylaminoalkyl, glycidoxyalkyl, epoxycycloalkyl, alkylcarbonyloxy, fluoroalkyl, mercaptoalkyl. Or indicates hydroxy,
When two or more R _1's are present, they may be the same or different. n and m are 0 or an integer of 1 or more, and n + m is 0 to 3.
It is 000. In the general formula (2) R _a SiX _4-a , R represents alkyl, aryl or fluoroalkyl, X represents halogen or alkoxy, and a represents 1 to 1
Indicates an integer of 3. 6. A superhydrophobic treatment method for an article surface, which comprises applying the superhydrophobic agent composition according to any one of claims 1 to 5 to the article surface. 7. An article whose surface is treated to be super water repellent by the super water repellent composition according to any one of claims 1 to 5.