JP6642309B2 - Organosilicon compound and surface treatment composition - Google Patents

Description

  TECHNICAL FIELD The present invention relates to an organosilicon compound and a surface treating agent composition, and more particularly to a water-repellent material which cures at room temperature without heating and has excellent water repellency, water-sliding property (dropping property of water droplets), and durability. The present invention relates to an organosilicon compound that gives a film, a surface treatment agent composition using the same, a substrate with a water-repellent film formed by surface treatment with the composition, and a method for forming a water-repellent film using the composition. .

Conventionally, as a water repellent for glass, a water repellent composition containing a fluoroalkylsilane or an amino-modified polysiloxane has been proposed (see Patent Documents 1 to 6).
The water-repellent films produced from the water-repellent compositions disclosed in these patent documents are excellent in water repellency, but have insufficient water-sliding properties of water droplets on the film surface.
Therefore, when the water-repellent film is applied to a window glass of an automobile, further improvement in water slippage is required in order to secure a good visibility during rainfall.

In this regard, Patent Document 7 discloses a composition containing a linear one-terminal functional polydimethylsiloxane compound and a silane coupling agent as a composition for providing a water-repellent coating film having both good water repellency and good water repellency. Has been proposed.
However, the water-repellent film formed from the composition of Patent Document 7 has a problem that the durability is not sufficient, it is not possible to sufficiently exhibit water resistance and abrasion resistance, and the water-repellent film is maintained for a long time. It was difficult to do.

JP 2012-224668 A JP 2009-137775 A JP 2009-173491 A JP-A-10-102046 JP 2003-160361 A JP-A-09-176622 JP-A-11-315276

  The present invention has been made in view of the above circumstances, an organic silicon compound capable of forming a film having excellent water repellency, water slippage and durability, and a surface treating agent composition containing the same, and surface treatment with the composition. An object of the present invention is to provide a formed substrate having a water-repellent film and a method for forming a water-repellent film using the composition.

  The present inventor has conducted intensive studies to solve the above problems, and as a result, a composition containing a specific linking group, a hydrolyzable group, and an organosilicon compound having a siloxy group, is cured at room temperature without heating, The present inventors have found that a film having excellent water repellency, water slip and durability can be provided, and have completed the present invention.

｛式中、Ｒ¹は、互いに独立して、炭素原子数１〜１２のアルキル基または式（２）で表される基を表し、

〔式中、Ｒ⁴は、互いに独立して、炭素原子数１〜１２のアルキル基または式（３）で表される基を表す。

（式中、Ｒ⁵は、互いに独立して炭素原子数１〜１２のアルキル基を表す。）〕
Ｒ²は、互いに独立して炭素原子数１〜１２のアルキル基を表し、Ｒ³は、互いに独立して炭素原子数１〜４のアルキル基を表し、Ｘは、互いに独立してヒドロキシ基または加水分解性基を表し、Ｙは、アリーレン基またはフッ化アルキレン基を含有する２価連結基を表し、ａは、１〜１００の数を表し、ｂは、０〜２の数を表す。｝
２． 前記Ｙが、式（４）で表される２価連結基である１の有機ケイ素化合物、

〔式中、Ｚは、式（５）〜（７）から選ばれるいずれか１つの２価連結基を表し、Ｒ⁶およびＲ⁷は、互いに独立して、単結合またはＺと異なる２価連結基を表す。

（式（５）中、ｃは、１〜１０の数を表し、式（７）中、Ｒ⁸は、互いに独立して炭素原子数１〜１２のアルキル基を表す。）〕
３． 式（８）または式（９）で表される２の有機ケイ素化合物、

〔式中、Ｚは、式（５）〜（７）から選ばれるいずれか１つの２価連結基を表し、Ｒ³、Ｒ⁶、Ｒ⁷、Ｘ、ａおよびｂは、前記と同じ意味を表す。

（式（５）中、ｃは、前記と同じ意味を表し、式（７）中、Ｒ⁸は、メチル基を表す。）〕
４． 前記Ｒ⁶およびＲ⁷が、互いに独立して式（１０）で表される２または３の有機ケイ素化合物、

（式中、ｄは、０〜１０の数を表す。）
５． 前記Ｘが、ヒドロキシ基、アルコキシ基、ハロゲン原子またはイソシアネート基である１〜４のいずれかの有機ケイ素化合物、
６． １〜５のいずれかの有機ケイ素化合物の加水分解縮合物、
７． １〜５のいずれかの有機ケイ素化合物、その加水分解縮合物、またはそれらの混合物と、有機溶剤とを含む表面処理剤組成物、
８． メタンスルホン酸、ｐ−トルエンスルホン酸および硫酸から選ばれる少なくとも１種の加水分解触媒を含有する７の表面処理剤組成物、
９． １〜５のいずれかの有機ケイ素化合物以外の、その他の加水分解性基を有する有機ケイ素化合物、その加水分解縮合物、またはそれらの混合物を含有する７または８の表面処理剤組成物、
１０． 輸送機用ガラスの撥水処理用である７〜９のいずれかの表面処理剤組成物、
１１． 輸送機用ボディーの撥水処理用である７〜９のいずれかの表面処理剤組成物、
１２． 基材と、この基材上に設けられた、７〜９のいずれかの表面処理剤組成物を用いてなる撥水膜とを有する撥水膜付き基材、
１３． 前記基材と撥水膜との間に介在する下地層を備え、前記下地層が、１〜５のいずれかの有機ケイ素化合物以外の、その他の加水分解性基を有する有機ケイ素化合物の加水分解生成物からなる１１の撥水膜付き基材、
１４． 前記基材が、ガラス、金属、セラミックまたは樹脂である１２または１３の撥水膜付き基材、
１５． 基材上に、７〜９のいずれかの表面処理剤組成物を塗布して塗膜を形成し、この塗膜表面を水で拭き上げ処理した後、５〜３５℃で硬化皮膜を形成する撥水膜の形成方法
を提供する。 That is, the present invention
1. An organosilicon compound represented by the general formula (1),

In the formula, R ¹ independently represents an alkyl group having 1 to 12 carbon atoms or a group represented by the formula (2),

[In the formula, R ⁴ independently represents an alkyl group having 1 to 12 carbon atoms or a group represented by the formula (3).

(In the formula, R ⁵ independently represents an alkyl group having 1 to 12 carbon atoms.)]
R ² independently represents an alkyl group having 1 to 12 carbon atoms, R ³ independently represents an alkyl group having 1 to 4 carbon atoms, X represents a hydroxy group or Represents a hydrolyzable group, Y represents a divalent linking group containing an arylene group or a fluorinated alkylene group, a represents a number of 1 to 100, and b represents a number of 0 to 2. ｝
2. 1 is an organosilicon compound in which Y is a divalent linking group represented by the formula (4),

[In the formula, Z represents any one divalent linking group selected from formulas (5) to (7), and R ⁶ and R ⁷ are each independently a single bond or a divalent link different from Z. Represents a group.

(In the formula (5), c represents a number of 1 to 10, and in the formula (7), R ⁸ independently represents an alkyl group having 1 to 12 carbon atoms.)]
3. 2 organosilicon compounds represented by the formula (8) or the formula (9),

[Wherein, Z represents any one divalent linking group selected from the formulas (5) to (7), and R ³ , R ⁶ , R ⁷ , X, a and b have the same meanings as described above. Represent.

(In the formula (5), c has the same meaning as described above, and in the formula (7), R ⁸ represents a methyl group.)
4. R ⁶ and R ⁷ independently of one another, 2 or 3 organosilicon compounds represented by formula (10):

(In the formula, d represents a number from 0 to 10.)
5. Wherein X is a hydroxy group, an alkoxy group, a halogen atom or an isocyanate group;
6. A hydrolyzed condensate of the organosilicon compound of any of 1 to 5,
7. A surface treatment agent composition comprising any one of the organosilicon compounds of 1 to 5, a hydrolyzed condensate thereof, or a mixture thereof, and an organic solvent;
8. 7, a surface treating agent composition containing at least one hydrolysis catalyst selected from methanesulfonic acid, p-toluenesulfonic acid and sulfuric acid,
9. Other than the organosilicon compound of any one of 1 to 5, an organosilicon compound having another hydrolyzable group, a hydrolysis condensate thereof, or a surface treatment agent composition of 7 or 8 containing a mixture thereof,
10. The surface treatment agent composition according to any one of 7 to 9, which is for water-repellent treatment of glass for a transport machine,
11. The surface treatment agent composition according to any one of 7 to 9, which is for water-repellent treatment of a body for a transport machine,
12. A substrate having a water-repellent film, comprising: a substrate;
13. An underlayer interposed between the base material and the water-repellent film, wherein the underlayer is a compound other than the organosilicon compound of any of 1 to 5, and hydrolyzes an organosilicon compound having another hydrolyzable group. 11 substrates with a water-repellent film comprising a product,
14． The substrate is a substrate with a water-repellent film of 12 or 13, which is glass, metal, ceramic or resin,
15. A coating film is formed by applying any one of the surface treatment agent compositions 7 to 9 on a substrate, and after wiping the surface of the coating film with water, a cured film is formed at 5 to 35 ° C. Provided is a method for forming a water-repellent film.

ADVANTAGE OF THE INVENTION According to this invention, the organosilicon compound which can be hardened | cured at room temperature, and can form a film excellent in water repellency, water lubricity and durability, and a surface treating agent composition containing the same can be provided.
By using the surface treatment agent composition of the present invention, a substrate with a water-repellent film having excellent water repellency, water slippage and durability can be produced by a simple method.
In particular, by applying the water-repellent film of the present invention to a transparent substrate used as a window glass, a mirror, or the like for vehicles, ships, and aircraft, it is possible to impart excellent water repellency and water slip, Good visibility can be ensured even during rainfall.

Hereinafter, the present invention will be described specifically.
The organosilicon compound according to the present invention is represented by the formula (1).

In the formula (1), R ¹ independently represents an alkyl group having 1 to 12 carbon atoms or a group represented by the formula (2), and R ² independently represents a C 1 to C 1 atom. 12 represents an alkyl group, and R ³ independently represents an alkyl group having 1 to 4 carbon atoms.
A is a number of 1 to 100, and a is preferably a number of 5 to 50 from the viewpoint of improving the lubricity of the cured film. When a exceeds 100, the durability of the obtained cured film decreases.
b is a number of 0 to 2, preferably 0 or 1, and more preferably 0. When b exceeds 2, the durability of the obtained cured film becomes insufficient.

（Ｒ⁴は、互いに独立して、炭素原子数１〜１２のアルキル基または式（３）で表される基を表す。）

(R ⁴ independently represents an alkyl group having 1 to 12 carbon atoms or a group represented by the formula (3).)

（Ｒ⁵は、互いに独立して炭素原子数１〜１２のアルキル基を表す。）

(R ⁵ independently represents an alkyl group having 1 to 12 carbon atoms.)

The alkyl group having 1 to 12 carbon atoms in R ¹ , R ² , R ⁴ and R ⁵ may be linear, cyclic, or branched, and specific examples thereof include methyl, ethyl, n -Propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl , Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like.
The alkyl group having 1 to 4 carbon atoms in R ³ may be linear, cyclic, or branched, and specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n- Butyl, s-butyl, t-butyl, cyclopropyl, cyclobutyl and the like.

In the present invention, the above R ¹ , R ² , R ⁴ and R ⁵ are preferably an alkyl group having 8 or less carbon atoms, particularly preferably a methyl group, from the viewpoints of water repellency, water slippage and availability of raw materials. preferable. If the number of these carbon atoms exceeds 12, the water repellency and the water slippage may decrease.
R ³ is preferably a methyl or ethyl group, particularly preferably a methyl group.

X represents a hydroxy group or a hydrolyzable group independently of each other, and when X is a hydrolyzable group, the organosilicon compound of the present invention has a hydrolyzable group bonded to a Si atom at a molecular terminal. A durable film is formed by the silanol group (≡Si—OH) formed by the heat treatment.
Specific examples of such a hydrolyzable group include methoxy, ethoxy, n-propoxy, an alkoxy group such as n-butoxy group, a halogen atom such as a chlorine atom, and an isocyanate group. A methoxy group and a chlorine atom are preferred.

Y is a group for improving the orientation of molecules in the obtained coating film, and for promoting the densification and uniformity of the cured film, and particularly, a functional group having an interactive property such as a π-π stack or a hydrogen bond. A divalent linking group containing a group or an atomic group having a rigid structure can be suitably used. By introducing these divalent linking groups at specific positions in the molecule, the durability of the cured film can be improved while maintaining good water repellency and water slippage.
In the present invention, a divalent linking group containing an arylene group or a fluorinated alkylene group is employed as such a divalent linking group.

Specific examples of the arylene group include a phenylene, biphenylene, and naphthylene group.
Specific examples of the fluorinated alkylene group include-(CHF) _c -,-(CF ₂ ) _c- (c represents a number of 1 to 100), and the like.

  In the present invention, considering that the orientation of the molecules in the film is further increased and the densification and uniformity of the cured film are further promoted, the above-mentioned Y is particularly a divalent compound represented by the formula (4). Linking groups are preferred.

Here, Z represents any one divalent linking group selected from the formulas (5) to (7), improves the orientation of molecules on the substrate, and makes the cured film dense and uniform. It is a group that promotes. By introducing these linking groups at specific positions in the molecule, the durability can be improved while maintaining the water repellency and the lubricity of the cured film satisfactorily.
Among them, a perfluoroalkylene group represented by the formula (5) is preferable. In the formula (5), c is a number of 1 to 10, preferably 1 to 8, and more preferably 1 to 6.
In the formula (7), examples of the alkyl group having 1 to 12 carbon atoms of R ⁸ include the same as described above, and a methyl group is particularly preferable.

（式（７）中、Ｒ⁸は、互いに独立して炭素原子数１〜１２のアルキル基を表し、ｃは、１〜１０の数を表す。）

(In the formula (7), R ⁸ independently represents an alkyl group having 1 to 12 carbon atoms, and c represents a number of 1 to 10.)

R ⁶ and R ⁷ independently represent a single bond or a divalent linking group different from Z, and such a divalent linking group is not particularly limited as long as it is different from Z described above. However, specific examples thereof include an alkylene group which may include a hetero atom such as an ether bond (-O-), a thioether bond (-S-), and an imino group (-NH-).
Among these, a group represented by the formula (10) is preferable as R ⁶ and R ⁷ .
In the formula (10), d is a number from 0 to 10, preferably from 0 to 5, more preferably from 0 to 3, and still more preferably from 1 to 3. Ease of production and availability of the organosilicon compound Considering the low cost of ethylene, ethylene and trimethylene groups are preferred.

（式中、ｄは、０〜１０の数を表す。）

(In the formula, d represents a number from 0 to 10.)

  Therefore, the organosilicon compound of the present invention is preferably represented by the general formula (1 ′), and more preferably represented by the formulas (8), (9) and (11).

（式中、Ｒ¹〜Ｒ³、Ｒ⁶、Ｒ⁷、Ｘ、Ｚ、ａおよびｂは、上記と同じ意味を表す。）

(In the formula, R ^{1 to} R ³ , R ⁶ , R ⁷ , X, Z, a and b represent the same meaning as described above.)

In the formula, Z represents any one divalent linking group selected from the formulas (5) to (7), and R ³ , R ⁶ , R ⁷ , X, a and b represent the same meaning as described above. .

（式（５）中、ｃは、上記と同じ意味を表し、式（７）中、Ｒ⁸は、メチル基を表す。）〕

(In the formula (5), c represents the same meaning as described above, and in the formula (7), R ⁸ represents a methyl group.)]

  Suitable organosilicon compounds include, for example, the following compounds, but are not limited thereto.

  The organosilicon compound of the present invention can be synthesized by a known method. For example, the organosilicon compound represented by the above formula (1 ') can be synthesized by a known hydrosilylation reaction as shown in the following schemes (A) and (B).

The platinum compound-containing catalyst used in the hydrosilylation reaction is not particularly limited, and specific examples thereof include chloroplatinic acid, an alcohol solution of chloroplatinic acid, platinum-1,3-divinyl-1,1 , 3,3-tetramethyldisiloxane complex in toluene or xylene, tetrakistriphenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobisacetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadiene platinum, platinum-carbon , Platinum-alumina, supported catalysts such as platinum-silica, and the like.
From the viewpoint of selectivity in hydrosilylation, a zero-valent platinum complex is preferred, and a toluene or xylene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex is more preferred.
The amount of the platinum compound-containing catalyst used is not particularly limited, but from the viewpoint of reactivity, productivity and the like, the platinum atom contained is 1 × 10 5 per mol of the organosilicon compound having a Si—H group. ^The amount is preferably ^-7 to 1 × 10 ^-2 mol, more preferably 1 × 10 ^-7 to 1 × 10 ^-3 mol.

Note that the above reaction proceeds even without solvent, but a solvent can also be used.
Specific examples of usable solvents include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene and xylene; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; ethyl acetate, butyl acetate and the like. Ester solvents; aprotic polar solvents such as N, N-dimethylformamide; chlorinated hydrocarbon solvents such as dichloromethane, chloroform and the like. Mixtures of more than one species may be used.

The reaction temperature in the above hydrosilylation reaction is not particularly limited, and the reaction can be carried out under heating from 0 ° C, but is preferably 0 to 200 ° C.
In order to obtain an appropriate reaction rate, it is preferable to carry out the reaction under heating, and from such a viewpoint, the reaction temperature is more preferably from 40 to 110 ° C, and still more preferably from 60 to 100 ° C.
The reaction time is not particularly limited, and is usually about 1 to 60 hours, preferably 1 to 30 hours, more preferably 1 to 20 hours.

The surface treatment composition of the present invention comprises the above-mentioned organosilicon compound, its hydrolytic condensate, or a mixture thereof, and an organic solvent.
Specific examples of usable organic solvents include esters such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate and isobutyl acetate; hydrocarbons such as hexane, cyclohexane, heptane, octane, decane, dodecane, toluene and xylene. Halogenated hydrocarbons such as dichloromethane, 1,1-dichloroethane and 1,2-dichloroethane; ketones such as methyl ethyl ketone, 2-pentanone and methyl isobutyl ketone; ethers such as diethylene glycol monomethyl ether and dipropylene glycol monomethyl ether; Examples include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and isobutyl alcohol, and these may be used alone or in combination of two or more. Good.

  The concentration of the organosilicon compound of the present invention contained in the surface treating agent composition is not particularly limited, but is preferably 0.1 to 20% by mass, and 0.5 to 10% by mass based on the whole composition. % Is more preferable, and 0.5 to 5.0% by mass is even more preferable. When the content is within this range, uniform and excellent water repellency and water slip can be imparted to the coating film itself.

Further, the surface treating agent composition of the present invention may contain a hydrolysis catalyst for the purpose of promoting the reaction between the hydrolyzable group of the organosilicon compound and water and promoting the production of a silanol group. .
Specific examples of the hydrolysis catalyst include organic acids such as acetic acid, formic acid, methanesulfonic acid, and p-toluenesulfonic acid; and inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid. These may be used in combination.
Among these, methanesulfonic acid, p-toluenesulfonic acid, and sulfuric acid are preferred, and sulfuric acid is particularly preferred.
The concentration of the catalyst is preferably from 0.1 to 15.0% by mass, more preferably from 1.0 to 10.0% by mass, based on the organosilicon compound.

Further, the surface treating agent composition of the present invention may contain a curing catalyst.
Specific examples of the curing catalyst include titanium catalysts such as titanium tetraisopropoxide, titanium tetranormal butoxide, titanium tetra-2-ethylhexoxide, and titanium tetraacetylacetonate; dibutyltin dilaurate, dibutyltin diacetate, and dioctyltin. Tin catalysts such as diacetate; aluminum catalysts such as aluminum secondary butoxide, aluminum trisacetylacetonate, aluminum bisethylacetoacetate, monoacetylacetonate, aluminum trisethylacetoacetate; normal propyl zirconate, normal butyl zirconate, zirconium tetra Acetylacetonate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium tetraacetylacetonate And zirconium catalysts such Toneto like.
The concentration of the catalyst is preferably from 0.1 to 15.0% by mass, more preferably from 1.0 to 10.0% by mass, based on the organosilicon compound.

The surface treating agent composition of the present invention, other than the above-described organosilicon compound of the present invention, other organosilicon compounds having a hydroxy group or a hydrolyzable group bonded to a Si atom, a hydrolysis condensate thereof, or a condensate thereof It may further comprise a mixture.
Examples of the hydrolyzable group include an alkoxy group, a halogen atom, an acyloxy group, and an isocyanate group.
Specific examples of other organosilicon compounds include silane compounds having an alkoxysilyl group, such as tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and phenyltrimethoxysilane. Silane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, diphenyldimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, hexamethyldi Silazane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (triethoxysilylpropyl) Tetrasulfide, 3-isocyanatopropyltriethoxysilane, and the like.Examples of the silane compound having a silyl halide group include methyltrichlorosilane, ethyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, and trifluorosilane. Ethyltrichlorosila and the like can be mentioned.
The addition amount of the other organosilicon compound is not particularly limited as long as it does not affect the water repellency and lubricity of the obtained cured film, but is preferably 20% by mass or less based on the organosilicon compound of the present invention. .

The surface treatment composition of the present invention may contain various additives in addition to the components described above.
Examples of the additives include metal oxides, resins, dyes, pigments, ultraviolet absorbers, antioxidants, and the like, and specific examples include silica sol, titania sol, and alumina sol.
The amount of the additive is not particularly limited as long as it does not affect the water repellency and the lubricity of the obtained cured film, but is preferably 30% by mass or less based on the organosilicon compound of the present invention.

A water-repellent film can be formed on a substrate by applying the surface treating agent composition of the present invention described above to a substrate and drying it.
As the substrate, glass, metal, ceramic, resin, or the like can be preferably used. Examples of the metal include iron and stainless steel, and examples of the ceramic include titania, alumina and zirconia, and examples of the resin include polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, vinyl chloride, polystyrene, ABS resin, and phenol resin. Epoxy resins, acrylics and the like can be mentioned.

As a coating method, a conventionally known method such as wiping coating, spin coating, bar coating, dip coating, squeegee coating, or spray coating can be appropriately adopted.
Drying after application may be either natural drying or heat drying, but is preferably performed in the range of 5 to 150 ° C. If the temperature is lower than 5 ° C., the reaction rate of the organosilicon compound of the present invention on the base material becomes low, the reaction requires a long time, and sufficient durability may not be obtained. If it exceeds 150 ° C., denaturation and thermal decomposition of the applied surface treating agent composition tend to occur, and sufficient water repellency and lubricity may not be obtained.
In particular, it is preferable that the surface of the coating film is wiped up with water after the surface treatment agent composition is applied on the substrate, and the temperature at which a cured film is formed is preferably around room temperature (5 to 35 ° C.).

The thickness of the water-repellent film is not particularly limited, but is preferably 100 nm or less in consideration of transparency, mechanical strength of the film, and the like.
The water-repellent film preferably has a water contact angle of 100 ° or more and a falling angle of 30 ° or less in a 2 μl water droplet, and has a haze value (cloudiness value) of preferably 5 or less, more preferably 1 or less. More preferably, it has a transparency of 0.5 or less.

  The surface treating agent composition of the present invention can be applied directly to the surface of a substrate to form a water-repellent film (cured film). It is preferable to interpose an underlayer formed from a hydrolysis product of a silicon compound having a hydrolyzable group other than the compound. By providing such an underlayer, the bond between the water-repellent film and the substrate becomes stronger, and the durability of the water-repellent film of the present invention is improved.

  The organosilicon compound used for forming the underlayer has high hydrolyzability and is represented by the following general formula (12) in consideration of forming a thin film on a substrate at around room temperature (5 to 35 ° C.). Isocyanate silane compounds are preferred.

（式中、ｋは、０または１を表す。）

(In the formula, k represents 0 or 1.)

  The film comprising the surface treating agent composition of the present invention described above is excellent in water repellency, water slippage, and transparency, and thus can be suitably used for water repellent treatment of glass for a transport machine or a vehicle body. In particular, when the present invention is applied to a window glass or a mirror, it is possible to efficiently prevent a decrease in visibility due to adhesion of water droplets in rainy weather.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[1] Synthesis of organosilicon compound [Example 1-1] Synthesis of organosilicon compound (13)

In a 1-liter three-necked flask equipped with a stirrer, thermometer, ester adapter and Dimroth condenser, 23.8 g of toluene, 5.05 g (0.0225 mol) of compound (14), and toluene of vinylsiloxane coordinated Pt were placed. 0.3 g of a solution (Pt concentration: 0.5% by mass) was added, the temperature was raised to 80 ° C., and 50.0 g (0.0225 mol) of compound (15) was added dropwise while maintaining the temperature at 80 to 90 ° C. Then, the reaction was further performed at 90 ° C. for 5 hours. Measurement of the amount of hydrogen gas generated by addition of alkaline water and IR measurement were performed to confirm the completion of the reaction of the ≡Si-H group.
Subsequently, the Dimroth cooling pipe was connected to the exhaust gas pipe, and the system was heated at 150 ° C. for 3 hours under an internal pressure of 10 mmHg under nitrogen gas bubbling, then cooled to 25 ° C., and the pressure was restored to normal pressure. The resulting liquid was purified by filtration to obtain 49.5 g of an organosilicon compound (13).

[Example 1-2] Synthesis of organosilicon compound (16)

In a 1 liter three-necked flask equipped with a stirrer, thermometer, ester adapter and Dimroth condenser, 17.1 g of toluene, 31.7 g (0.0146 mol) of compound (18), and toluene of vinylsiloxane coordinated Pt were placed. 0.3 g of a solution (Pt concentration: 0.5% by mass) was added, the temperature was raised to 80 ° C, and then 5.0 g (0.0146 mol) of compound (17) was added dropwise while maintaining the temperature at 80 to 90 ° C. Then, the reaction was further performed at 90 ° C. for 5 hours. Here, the completion of the reaction of the Si—H group was confirmed in the same manner as in Synthesis Example 1.
After connecting the Dimroth cooling pipe to the exhaust gas pipe and heating at 150 ° C. for 3 hours under a system pressure of 10 mmHg under nitrogen gas bubbling, it was cooled to 25 ° C., and the pressure was restored to normal pressure. After filtration and purification, 33.0 g of organosilicon compound (16) was obtained.

[Example 1-3] Synthesis of organosilicon compound (19)

In a 1-liter three-necked flask equipped with a stirrer, thermometer, ester adapter and Dimroth condenser, 29.6 g of toluene, 10.0 g (0.0266 mol) of compound (20), and toluene of vinylsiloxane coordinated Pt were placed. 0.3 g of a solution (Pt concentration: 0.5% by mass) was added, the temperature was raised to 80 ° C, and 59.1 g (0.0266 mol) of compound (15) was added dropwise while maintaining the temperature at 80 to 90 ° C. The reaction was performed at 90 ° C. for 5 hours. Here, the completion of the reaction of the Si—H group was confirmed in the same manner as in Synthesis Example 1.
After connecting the Dimroth cooling pipe to the exhaust gas pipe and heating at 150 ° C. for 3 hours under a system pressure of 10 mmHg under nitrogen gas bubbling, it was cooled to 25 ° C., and the pressure was restored to normal pressure. After filtration and purification, 62.2 g of an organosilicon compound (29) was obtained.

[Example 1-4] Synthesis of organosilicon compound (21)

In a 1 liter three-necked flask equipped with a stirrer, thermometer, ester adapter and Dimroth condenser, 22.4 g of toluene, 8.57 g (0.0228 mol) of compound (20), and toluene of vinylsiloxane coordinated Pt were placed. 0.3 g of a solution (Pt concentration: 0.5% by mass) was added, the temperature was raised to 80 ° C, and 54.0 g (0.0228 mol) of compound (22) was added dropwise while maintaining the temperature at 80 to 90 ° C. The reaction was performed at 90 ° C. for 5 hours. Here, the completion of the reaction of the Si—H group was confirmed in the same manner as in Synthesis Example 1.
After connecting the Dimroth cooling pipe to the exhaust gas pipe and heating at 150 ° C. for 3 hours under a system pressure of 10 mmHg under nitrogen gas bubbling, it was cooled to 25 ° C., and the pressure was restored to normal pressure. After filtration and purification, 56.7 g of an organosilicon compound (21) was obtained.

[Example 1-5] Synthesis of organosilicon compound (23)

In a 1-liter three-necked flask equipped with a stirrer, thermometer, ester adapter and Dimroth condenser, 30.1 g of toluene, 10.0 g (0.0266 mol) of compound (20), and toluene of vinylsiloxane coordinated Pt were placed. 0.3 g of a solution (Pt concentration: 0.5% by mass) was added, the temperature was raised to 80 ° C, and 60.2 g (0.0266 mol) of compound (24) was added dropwise while maintaining the temperature at 80 to 90 ° C. The reaction was performed at 90 ° C. for 5 hours. Here, the completion of the reaction of the Si—H group was confirmed in the same manner as in Synthesis Example 1.
After connecting the Dimroth cooling pipe to the exhaust gas pipe and heating at 150 ° C. for 3 hours under a system pressure of 10 mmHg under nitrogen gas bubbling, it was cooled to 25 ° C., and the pressure was restored to normal pressure. After filtration and purification, 63.1 g of an organosilicon compound (23) was obtained.

[2] Preparation of surface treatment agent composition [Example 2-1]
0.920 g of the organosilicon compound (13) obtained in Example 1-1 and 0.080 g of 98% by mass sulfuric acid were added to 19.0 g of ethyl acetate and mixed to obtain a surface treating agent composition.

[Example 2-2]
A surface treating agent composition was obtained in the same manner as in Example 2-1 except that the organosilicon compound (13) was changed to the organosilicon compound (16) obtained in Example 1-2.

[Example 2-3]
A surface treating agent composition was obtained in the same manner as in Example 2-1 except that the organosilicon compound (13) was changed to the organosilicon compound (19) obtained in Example 1-3.

[Example 2-4]
A surface treating agent composition was obtained in the same manner as in Example 2-1 except that the organosilicon compound (13) was changed to the organosilicon compound (21) obtained in Example 1-4.

[Example 2-5]
A surface treating agent composition was obtained in the same manner as in Example 2-1 except that the organosilicon compound (13) was changed to the organosilicon compound (23) obtained in Example 1-5.

[Comparative Example 2-1]
A surface treating agent composition was obtained in the same manner as in Example 2-1 except that the organosilicon compound (13) was changed to an organosilicon compound represented by the following formula.

[Comparative Example 2-2]
A surface treating agent composition was obtained in the same manner as in Example 2-1 except that the organosilicon compound (13) was changed to an organosilicon compound represented by the following formula.

Each surface treating agent composition prepared in Examples 2-1 to 2-5 and Comparative Examples 2-1 and 2-2 was impregnated in tissue paper, and wiped and applied to a glass substrate. After air-drying for 1 minute, the tissue paper was impregnated with water, and the coated surface of the glass substrate was wiped off. Air drying was performed at 25 ° C. for 1 hour to obtain a glass substrate with a water-repellent film.
Using the obtained glass substrate with a water-repellent film, the following evaluation tests (1) to (4) were performed. Table 1 shows the results.
The water contact angle and the water drop sliding angle (fall angle) were measured by a contact angle meter (Drop Master DM-701, manufactured by Kyowa Interface Science Co., Ltd.) equipped with a sliding unit.
(1) Water repellency 2 μl of water was dropped on the surface to be treated of the glass substrate with a water repellent film, and the water contact angle was measured.
(2) Water Slidability A water droplet having a volume of 2 μl was dropped on the surface to be treated of the glass substrate having a water-repellent film, and the falling angle was measured.
(3) Water resistance test A glass substrate with a water-repellent film was immersed in an aqueous solution of 1% by mass of a surfactant (Lipon F, manufactured by Lion Hygene Co., Ltd.) and irradiated with ultrasonic waves (100 W, 42 kHz) for 30 minutes. The water repellency and the water slip were evaluated for the glass substrate with the water repellent film before and after the test.
(4) Abrasion resistance test A wear test was performed on the surface of the glass substrate with a water-repellent film under the conditions of 2 cm × 2 cm flannel cloth, 1.2 kg load, and 1,200 reciprocations. The water repellency and the water slip were evaluated for the glass substrate with the water repellent film before and after the test.

As shown in Table 1, the glass substrates with a water-repellent film obtained in Examples 2-1 to 2-5 had good water repellency and water slip in the initial stage, after the water resistance test and after the abrasion resistance test. You can see that there is.
On the other hand, it can be seen that the glass substrates with water-repellent films obtained in Comparative Examples 2-1 and 2-2 have remarkably reduced particularly the water slip after the water resistance test or the abrasion resistance test.

Claims (15)

An organosilicon compound represented by the general formula (1).

In the formula, R ¹ independently represents an alkyl group having 1 to 12 carbon atoms or a group represented by the formula (2),

[In the formula, R ⁴ independently represents an alkyl group having 1 to 12 carbon atoms or a group represented by the formula (3).

(In the formula, R ⁵ independently represents an alkyl group having 1 to 12 carbon atoms.)]
R ² independently represents an alkyl group having 1 to 12 carbon atoms,
R ³ independently represents an alkyl group having 1 to 4 carbon atoms,
X independently represents a hydroxy group or a hydrolyzable group,
Y represents a divalent linking group containing an arylene group or a fluorinated alkylene group,
a represents a number of 1 to 100, and b represents a number of 0 to 2. ｝ The organosilicon compound according to claim 1, wherein Y is a divalent linking group represented by the formula (4).

[In the formula, Z represents any one divalent linking group selected from formulas (5) to (7), and R ⁶ and R ⁷ are each independently a single bond or a divalent link different from Z. Represents a group.

(In the formula (5), c represents a number of 1 to 10, and in the formula (7), R ⁸ independently represents an alkyl group having 1 to 12 carbon atoms.)] The organosilicon compound according to claim 2, represented by formula (8) or (9).

[Wherein, Z represents any one divalent linking group selected from the formulas (5) to (7), and R ³ , R ⁶ , R ⁷ , X, a and b have the same meanings as described above. Represent.

(In the formula (5), c has the same meaning as described above, and in the formula (7), R ⁸ represents a methyl group.) 4. The organosilicon compound according to claim 2, wherein R ⁶ and R ⁷ are independently represented by the formula (10).

(In the formula, d represents a number from 0 to 10.)   5. The organosilicon compound according to claim 1, wherein X is a hydroxy group, an alkoxy group, a halogen atom, or an isocyanate group. 6.   A hydrolyzed condensate of the organosilicon compound according to claim 1.   A surface treating agent composition comprising the organosilicon compound according to any one of claims 1 to 5, its hydrolytic condensate, or a mixture thereof, and an organic solvent.   The surface treatment composition according to claim 7, comprising at least one hydrolysis catalyst selected from methanesulfonic acid, p-toluenesulfonic acid and sulfuric acid.   The organic silicon compound having another hydrolyzable group other than the organic silicon compound according to any one of claims 1 to 5, a hydrolysis condensate thereof, or a mixture thereof. Surface treatment composition.   The surface treating agent composition according to any one of claims 7 to 9, which is used for water repellent treatment of glass for a transport machine.   The surface treating agent composition according to any one of claims 7 to 9, which is used for water repellent treatment of a body for a transport machine.   A substrate with a water-repellent film, comprising: a substrate; and a water-repellent film formed on the substrate using the surface treatment agent composition according to any one of claims 7 to 9. A base layer interposed between the base material and the water-repellent film,
The water-repellent film according to claim 12 , wherein the underlayer comprises a hydrolysis product of an organosilicon compound having another hydrolyzable group, other than the organosilicon compound according to any one of claims 1 to 5. Base material.   14. The substrate with a water-repellent film according to claim 12, wherein the substrate is glass, metal, ceramic or resin.   A substrate is coated with the surface treating agent composition according to any one of claims 7 to 9 to form a coating film, and after wiping the coating film surface with water, the coating solution is heated at 5 to 35 ° C. A method for forming a water-repellent film for forming a cured film.