JP2000129247A - Surface treatment agent, surface treating agent composition, surface treatment method, and substrate treated therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a treating agent which imparts excellent water repellency and water drop falling-off properties to the surface of a substrate by including a hydrolyzable silane compound and/or a partial hydrolyzate thereof. SOLUTION: This agent comprises a hydrolyzable silane compound represented by formula I and/or a partial hydrolyzate thereof. In the formula, R1 to R5 are each a monovalent organic group (desirably, R1 to R5 is a group of the formula: -Q2-Rf, R2 to R4 are each a monovalent hydrocarbon group, or all of R1 to R5 are CH3 groups); Rf is a monovalent polyfluorohydrocarbon group optionally containing an etheric oxygen atom; Q2 is a divalent organic group; X1 to X3 are each a hydrolyzable group or NCO; and Q1 is a divalent organic group, desirably, dimethylene; and (m) is 0 or greater. The hydrolyzable silane compound of formula I is exemplified by a compound of formula II (wherein (x) and (y) are each 0-3, provided that x+y=3). This agent is incorporated with an organic solvent (e.g. butyl acetate) to obtain a surface treating agent composition for treating the surface of glass.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a surface treating agent comprising a specific compound capable of imparting excellent water repellency and water droplet falling properties to a substrate surface, a surface treating agent composition containing the surface treating agent, The present invention relates to a treatment method using a composition, and a treated substrate obtained by the treatment method.

[0002]

2. Description of the Related Art In various substrates such as glass, plastics, ceramics, and metals, and various substrates having a surface treatment layer, there is a problem that adverse effects of water may occur on the substrate surface.

[0003] For example, exterior members such as outer plates, window glasses and mirrors of transportation equipment such as trains, automobiles, ships, and aircraft;
It is desirable that the surface of the interior members such as the instrument panel surface is always clean.However, if dust or dirt adheres with raindrops or moisture adheres due to atmospheric humidity or temperature,
There is a problem that its appearance is impaired. In addition, if the surface is a surface that can be directly touched by humans or a surface that can be seen visually, it causes discomfort and causes a hygiene problem. In addition, there is a problem that the function of the transportation equipment article is significantly reduced. In particular, when the article for transport equipment is an article that requires transparency and transparency (for example, a window glass, a mirror, and the like), a decrease in transparency and transparency is a problem.

[0004] Means for cleaning the surface of the substrate (for example, wiping, removing means with a wiper, etc.) may cause minute scratches on the surface of the substrate. Further, when foreign particles exist on the surface of the base material, there is a problem that the surface of the base material is significantly damaged by the removing means. Further, when the substrate is a glass substrate, there is a problem that the glass component is eluted in the moisture attached to the surface and the surface is eroded (so-called burning occurs). Then, there is a problem that fine irregularities occur on the glass surface. In addition, glass that is severely burned or glass that has fine irregularities on its surface has a problem in that the see-through performance is reduced and light is scattered on the surface.

In addition, water and dust and dirt accompanying water are
There is also a problem of promoting damage, contamination, coloring, corrosion, and the like, and changing the electrical properties, mechanical properties, optical properties, and the like of the transport equipment articles. This problem has also become a problem in articles for construction and construction, articles for electric and electronic equipment, and the like. For the purpose of solving the above-mentioned problem, there has been conventionally proposed a method of imparting a property of preventing adhesion of water droplets and eliminating its adverse effect (hereinafter, this property is referred to as water repellency) to the surface of the base material. For example, there is a proposal to apply a surface treating agent composed of a silicone wax, an organosiloxane compound, a surfactant or the like directly to a substrate.

Specifically, a surface treating agent comprising an alkyl polysiloxane and an acid (Japanese Patent Publication No. 50-15473)
No.), a surface treating agent comprising an organic solvent and a metal halide (JP-A-55-9652), and a surface-treating agent containing a siloxane compound containing a chlorine atom (JP-A-55-9652).
No. 78080, No. 55-90580), a surface treatment agent containing an amino-modified silicone oil and a surfactant (JP-A-5-301742), and a surface treatment agent containing a compound having a perfluoroalkyl moiety at a terminal (JP-A No. 2-301). -1
38262, JP-A-2-248480), a surface treatment agent comprising a fluoroalkylsilane, an insoluble fine powder, an alcohol solvent, and an acid or an alkali (JP-A-8-27).
7388) and the like.

However, the conventional surface treating agent tends to cause unevenness during application, has poor adhesion to the substrate and is inferior in the effect, and is limited in the type of the substrate and application conditions. And so on. In addition, in the case of a surface treatment agent containing a fluoroalkylsilane, there was a problem that water could not be efficiently removed due to low water-dropping property.

Further, when a surface treatment agent is used to impart water repellency and water droplet falling property to a used article or a base material incorporated in another article, it is effective only to apply directly at normal temperature. Is a practical condition. For example, when processing a commercial automotive windshield,
It is not really possible to replace all the windshields. Further, it is not actually possible to fire the entire automobile after the application. On the other hand, there has been a problem that the treatment agents proposed hitherto do not exhibit sufficient performance when directly applied at normal temperature.

[0009]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks of the conventional water repellent and provides a surface capable of imparting excellent water repellency to various kinds of substrates, particularly excellent water drop-fall properties. Provided are a treating agent, a treating method using the surface treating agent, and a treated substrate.

[0010]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and has been made in consideration of the above-mentioned problems. The present invention provides a hydrolyzable silane compound represented by the following formula 1 and / or a partial hydrolysis of the hydrolyzable silane compound. The present invention relates to a surface treatment agent composed of a decomposition product, a surface treatment agent composition containing the surface treatment agent, a treatment method using the composition, and a treated substrate obtained by the treatment method.

[0011]

Embedded image

However, the symbols in the formula 1 have the following meanings. R ^{1 to} R ⁵ : monovalent organic groups which may be the same or different. Q ¹ : divalent organic group. X ¹ , X ² , X ³ : each may be the same or different, and are a hydrolyzable group or an isocyanate group. m: an integer of 0 or more.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the hydrolyzable silane compound (formula 1) of the present invention will be described. The organic group in the present specification means a group containing a carbon atom.

R ^{1 to} R ⁵ are each a monovalent organic group which may be the same or different. As R ^{1 to} R ⁵ , a hydrocarbon group or a monovalent fluorinated organic group is preferable.

The hydrocarbon group is preferably an alkyl group, particularly preferably an alkyl group having 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and an s-butyl group, and a methyl group is particularly preferable. As the monovalent fluorine-containing organic group, a group represented by the following formula A is preferable.

-Q ² -R ^f ... Formula A where the symbols in the formula A have the following meanings. R ^f : a monovalent polyfluorohydrocarbon group which may contain an etheric oxygen atom. Q ² : divalent organic group.

R ^f in the group (Formula A) represents a monovalent polyfluorohydrocarbon group which may contain an etheric oxygen atom.

A monovalent polyfluorohydrocarbon group not containing an etheric oxygen atom (hereinafter referred to as a monovalent polyfluorohydrocarbon group) means that two or more hydrogen atoms of the monovalent hydrocarbon group are replaced by fluorine atoms. It refers to a substituted group, and is preferably a polyfluoroalkyl group.

The ratio of fluorine atoms in the monovalent polyfluorohydrocarbon group is (the number of fluorine atoms in the monovalent polyfluorohydrocarbon group) / (the number of carbon atoms having the same number of carbon atoms corresponding to the monovalent polyfluorohydrocarbon group). Number of hydrogen atoms in hydrogen group) × 100
When expressed as (%), it is preferably at least 60%, particularly preferably at least 80%, and more preferably substantially 1%.
When it is 00%, that is, it is preferably a “monovalent perfluorohydrocarbon group” in which substantially all of the hydrogen atoms of the monovalent hydrocarbon group have been substituted with fluorine atoms.

The monovalent polyfluorohydrocarbon group may have a linear structure or a branched structure, and a linear structure is particularly preferable. In the case of a branched structure, the branched portion is preferably a short chain having about 1 to 3 carbon atoms, and a structure in which the branched portion is present at the terminal of a monovalent polyfluorohydrocarbon group is preferred. The carbon number of the monovalent polyfluorohydrocarbon group is preferably from 1 to 18, and particularly preferably from 4 to 12.

Further, the monovalent polyfluorohydrocarbon group is
Polyfluoroalkyl groups are preferred, and perfluoroalkyl groups are preferred. The carbon number of the polyfluoroalkyl group is preferably from 1 to 18, and particularly preferably from 4 to 12.

Specific examples of the monovalent polyfluorohydrocarbon group include the following. In addition, in the following specific examples, groups corresponding to respective structurally isomer groups are also included. C ₄ F ₉ - _{[However, F (CF 2) 4 -} , (CF
₃ ) ₂ CFCF _2- , (CF ₃ ) ₃ C-, CF ₃ CF ₂
CF (CF ₃ ) — etc.], C ₅ F ₁₁
− ｛However, F (CF ₂ ) ₅ −, (CF ₃ ) ₂ CF (C
F ₂ ) _2- , (CF ₃ ) ₃ CCF _2- , F (CF ₂ ) ₃
Including a group of structural isomers such as CF (CF ₃ ) —, C ₆ F ₁₃
- _{{However, F (CF 2) 3 C} (CF 3) 2 - including structural isomers groups _{such}, C 8 F 17 -,} C 10 F 21 -, C 12 F 25
_{-, C 14 F 29 -,} C 16 F 33 -, C 18 F 37 -, C 20 F
_{41 -, (CF 3) 2} CF (CF 2) s - (s is 0 or an integer of 1 or _{more), HC t F 2t - (} t is 0 or an integer of 1 or more).

The monovalent polyfluorohydrocarbon group containing an etheric oxygen atom refers to a carbon-carbon bond in the above-mentioned monovalent polyfluorohydrocarbon group or the above-mentioned monovalent polyfluorohydrocarbon group. It refers to a group having an etheric oxygen atom inserted between itself and Q ^2, and is preferably a group having an etheric oxygen atom inserted between carbon-carbon bonds in a monovalent polyfluorohydrocarbon group.

The monovalent polyfluorohydrocarbon group containing an etheric oxygen atom is preferably a group containing a polyfluorooxyalkylene moiety, particularly preferably a group containing a perfluorooxyalkylene moiety, and particularly preferably containing a perfluorooxyalkylene moiety. Further, a group whose terminal is a perfluoroalkyl group is preferable. Examples of the perfluorooxyalkylene include perfluorooxymethylene, perfluorooxyethylene, perfluorooxypropylene, and perfluorooxybutylene.

Specific examples of the monovalent polyfluorohydrocarbon group containing an etheric oxygen atom include the following.

[0026]

Embedded image CF ₃ (CF ₂ ) ₄ OCF (CF ₃ ) —, F
[CF (CF ₃ ) CF ₂ O] _u CF (CF ₃ ) CF ₂ C
F _2- (u is an integer of 1 or more), F [CF (CF ₃ ) CF
₂ O] _y CF (CF ₃ )-(y is an integer of 1 or more), F
(CF ₂ CF ₂ CF ₂ O) _v CF ₂ CF _2- (v is an integer of 1 or more), (CF ₂ CF ₂ O) _w CF ₂ CF _2- (w
Is an integer of 1 or more).

As the hydrolyzable silane compound (formula 1), R ¹ is preferred because the water-dropping property of the surface treating agent is improved.
Or a hydrolyzable silane compound wherein all of R ⁵ are methyl groups (Formula 1); or R ¹ or R ⁵ is a group represented by the following formula A, and all of R ^{2 to} R ⁴ are hydrocarbon groups. The hydrolyzable silane compound (formula 1) when it is (preferably a methyl group) is preferred.

Q ² in the formula A is a divalent organic group, and is preferably a divalent hydrocarbon group or a group having an etheric oxygen atom inserted between carbon-carbon bonds of the divalent hydrocarbon group. As the divalent hydrocarbon group, an alkylene group is preferable, and it may have any of a linear or branched structure, and — (CH ₂ )
_i- (where i is an integer of 1 to 20, preferably 4 to 8
Is an integer. )) Is preferred. In the case of a branched structure, it is preferable that the branched portion is a short chain having about 1 to 3 carbon atoms.

The group in which an etheric oxygen atom is inserted between the carbon-carbon bonds of the divalent hydrocarbon group includes the group in which an etheric oxygen atom is inserted at one position between the carbon-carbon bonds of the above-mentioned alkylene group. Is preferred.

The group (formula A) includes the following formulas A ¹ and A
² or a group represented by the following formula A ^3, are preferred. However,
The symbols in the formulas A ¹ , A ² and A ³ have the following meanings. R ^f1 and R ^f3 each independently represent a monovalent polyfluorohydrocarbon group. R ^f2 : a monovalent polyfluorohydrocarbon group containing an etheric oxygen atom. X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a divalent hydrocarbon group.

[0031]

Embedded image R ^f1 -X ¹ - ··· formula ^{A 1 R f2 -X 2 -O-} X 3 - ··· formula ^{A 2 R f3 -X 4 -O-} X 5 - ··· formula A ³

Each of R ^f1 , R ^f2 and R ^f3 is preferably a group described as a preferable embodiment of the above-mentioned monovalent polyfluorohydrocarbon group which may contain an etheric oxygen atom. X ¹ , X ² , X ³ , X ⁴ , and X ⁵ are each independently — (CH ₂ ) _h — (where h is an integer of 1 to 10, preferably 2 to 4). )) Is preferable.

Further, the group (formula A) is represented by the following formula A ¹⁰ ,
²⁰ or is preferably a group represented by the following formula A ^30,.
However, the symbols in the formulas A ¹⁰ , A ²⁰ and A ³⁰ have the following meanings.

D: an integer of 1 to 18, preferably an integer of 6 to 12. e: an integer of 0 to 10, preferably an integer of 1 to 5. g: an integer of 1 to 18, preferably 4 to 12. X ¹ , X ² , X ³ , X ⁴ , X ⁵ : each independently represents a divalent hydrocarbon group, preferably a linear alkylene group.

[0035]

_{Embedded image} C _d F _{2d + 1} -X ^1- ··· Formula A ¹⁰ F [CF (CF ₃ ) CF ₂ O] _e CF (CF ₃ ) -X ² -OX ^3- ··· A ²⁰ C _g F _{2g + 1} -X ⁴ -OX ⁵ -... Formula A ³⁰

[0036] Specific examples of the type A ^10. The perfluoroalkyl group in the following formula preferably has a linear structure. C
_{4 F 9 - (CH 2)} 2 -, C 4 F 9 - (CH 2) 3 -,
_{C 4 F 9 - (CH 2} ) 4 -, C 5 F 11 - (CH 2) 2
_{-, C 5 F 11 - (} CH 2) 3 -, C 6 F 13 - (CH 2)
_{2 -, C 8 F 17 -} (CH 2) 2 -, C 8 F 17 - (CH
_{2) 3 -, C 8 F} 17 - (CH 2) 4 -, C 9 F 19 - (C
_{H 2) 2 -, C 9} F 19 - (CH 2) 3 -, C 10 F 21 -
(CH _{2) 2} -.

[0037] Specific examples of the type A ^20.

[0038]

## STR5 ## F [CF (CF ₃ ) CF ₂ O] ₂ CF (CF
_{3) CH 2 O (CH 2} ) 3 -, F [CF (CF 3) CF
₂ O] ₄ CF (CF ₃ ) CH ₂ O (CH ₂ ) ₃ —, F
_{(CF 2 CF 2 CF 2 O} ) 2 CF 2 CF 2 CH 2 O (C
H ₂ ) _3- .

[0039] Specific examples of the type A ^30. However, the perfluoroalkyl group in the following formula preferably has a linear structure.

[0040]

Embedded image C ₄ F ₉ — (CH ₂ ) ₂ —O— (CH ₂ ) _{3
-, C 6 F 13 - (} CH 2) 2 -O- (CH 2) 3 -, C
_{8 F 17 - (CH 2)} 2 -O- (CH 2) 3 -, C 8 F 17
— (CH ₂ ) ₃ —O— (CH ₂ ) ₃ —.

Q ¹ is a divalent organic group, which means a group having a heteroatom or a heteroatom-containing group between carbon-carbon bonds or at the terminal of the divalent hydrocarbon group or divalent hydrocarbon group. The hetero atom is preferably an etheric oxygen atom or a thioetheric sulfur atom. The hetero atom-containing groups, -NH -, - CO -, - SO 2 -, - CONH- groups such like.

As Q ¹ , -CH ₂ CH ₂ --CH _{2
OCH 2 CH 2 CH 2 -,} - CONHCH 2 CH 2 CH
_{2 -, - CONHCH 2 CH 2} NHCH 2 CH 2 CH 2
_{-, - SO 2 NHCH 2 CH} 2 CH 2 -, or -CH
_{2 CH 2 OCONHCH 2 CH 2 CH} 2 - groups such like.

X ^{1 of} the hydrolyzable silane compound (formula 1)
X ² and X ³ each represent a hydrolyzable group or an isocyanate group. In the present specification, a distinction is made between an isocyanate group and a hydrolyzable group.

The following are examples of the hydrolyzable group. Halogen atom such as chlorine atom and bromine atom. Alkoxy groups such as methoxy, ethoxy and butoxy groups; -O-
N = C (R ²⁰ ) (R ²¹ ) (however, R ²⁰ and R ²¹ are each independently an alkyl group having 1 to 7 carbon atoms, preferably a methyl group, an ethyl group, or a propyl group). Examples of the ketoxime group include a dimethyl ketoxime group and a methyl ethyl ketoxime group. An acyloxy group such as an acetoxy group; Amino groups such as an N-butylamino group and an N, N-diethylamino group; N-
Amide group such as methylacetamide group. Aminooxy groups such as N, N-dimethylaminooxy group; Propenyloxy group, isopropenyloxy group, isobutenyloxy group,
An alkenyloxy group such as a cyclohexenyloxy group;

X ¹ , X ² , and X ³ are each preferably a chlorine atom, a lower alkoxy group having 1 to 3 carbon atoms, or an isocyanate group, respectively, from the viewpoints of water-dropping property, workability, and economy. Particularly, a chlorine atom, a methoxy group, an ethoxy group, or an isocyanate group is preferred. X ¹ , X ² and X ³ may be the same or different, and are preferably the same.

M is an integer of 0 or more, and is preferably an integer of 1 or more, particularly preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 4 from the viewpoint of water droplet falling property. The surface treating agent of the present invention may contain two or more compounds having different numbers of m.

Further, even if three groups represented by the following formula 1A in formula 1 are composed of three groups having the same structure,
Alternatively, it may be composed of three kinds of groups, and is preferably composed of one kind or two kinds of groups, or a mixture thereof.

[0048]

Embedded image

Specific examples of the hydrolyzable silane compound (formula 1) include the following compounds. However, m in the following formula has the same meaning as described above, x is an integer of 0 to 3, y is an integer of 0 to 3, and (x + y) is 3.

[0050]

[(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _m ] ₃ Si (CH ₂ ) ₂ SiCl ₃ , [(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _m ] _x [ (F (CF ₂ ) ₈ (CH ₂ ) ₃ ) (CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO] _m ] _y Si--(CH ₂ ) ₂ SiCl ₃ , [(F (CF ₂ ) ₈ ( _{CH 2) 3) (CH 3} ) 2 SiO [(CH 3) 2 SiO] m] 3 Si (CH 2) 2 SiCl 3, [(CH 3) 3 SiO [(CH 3) 2 SiO] m] x [ (H (CH ₂ ) ₈ ) (CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO] _m ] _y Si--(CH ₂ ) ₂ SiCl ₃ , ((CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO ] _m ] ₃ Si (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , [(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _m ] _x [(F (CF ₂ ) ₈ (CH ₂ ) ₃ ) ( CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO] _m ] _y Si--(CH ₂ ) ₂ Si (OCH ₃ ) ₃ , [F (CF ₂ ) ₈ (CH ₂ ) ₃ (CH ₃ ) ₂ SiO [ (CH ₃ ) ₂ SiO] _m ] ₃ Si (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , [(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _m ] _x [(H (CH ₂ ) ₈ ) (CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO] _m ] _y Si--(CH ₂ ) ₂ Si (OCH ₃ ) ₃ , [(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _m ] ₃ Si (CH ₂ ) ₂ Si (OCH ₂ CH ₃ ) ₃ , [(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _m ] _x [(F (CF ₂ ) ₈ (CH ₂ ) ₃ ) (CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO] _m ] _y Si--(CH ₂ ) ₂ Si (OCH ₂ CH ₃ ) ₃ , [(F (CF ₂ ) ₈ (CH ₂ ) ₃ ) (CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO] _m ] ₃ Si (CH ₂ ) ₂ Si (OCH ₂ CH ₃ ) ₃ , ((CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO ] _m ] _x [(H (CH ₂ ) ₈ ) (CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO] _m ] _y Si--(CH ₂ ) ₂ Si (OCH ₂ CH ₃ ) ₃ , [(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _m ] _x [(F (CF ₂ ) ₄ (CH ₂ ) ₃ ) (CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO] _m ] _y Si--( CH ₂ ) ₂ SiCl ₃ , [(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _m ] _x [(F (CF ₂ ) ₄ (CH ₂ ) ₃ ) (CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO] _m ] _y Si--(CH ₂ ) ₂ Si (OCH ₃ ) ₃ , [(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _m ] ₃ Si (CH ₂ ) ₂ Si (NCO) ₃ .

The surface treating agent of the present invention includes at least one hydrolyzable silane compound (formula 1), at least one hydrolyzable silane compound (formula 1) and a hydrolyzable silane compound (formula 1).
Or a hydrolysis product of a hydrolyzable silane compound (Formula 1). The hydrolysis product of the hydrolyzable silane compound (Formula 1) is usually 1
A mixture of more than one compound.

The partial hydrolysis product of the hydrolyzable silane compound (formula 1) means a compound in which the hydrolyzable silane compound (formula 1) is partially hydrolyzed and condensed by reacting with water. For example, a product obtained by dehydrating and condensing two or more molecules of a compound in which a part or all of a hydrolyzable group or an isocyanate group in a hydrolyzable silane compound (Formula 1) is converted to an OH group or the like by reaction with water is exemplified. Can be done.

As a method for hydrolyzing the hydrolyzable silane compound (formula 1), a conventionally known method can be employed.
For example, (method 1): a method of simply mixing a hydrolyzable silane compound (formula 1) and water, (method 2): a method of reacting a hydrolyzable silane compound (formula 1) and water in the presence of an acid, (Method 3): A method in which a hydrolyzable silane compound (Formula 1) is reacted with water in the presence of an alkali. The hydrolyzable silane compound (Formula 1) in these methods 1 to 3 may be one type or two or more types.

In the surface treating agent of the present invention, the liquid life,
From the viewpoint of film physical properties and the like, it is preferable to carry out hydrolysis by Method 2. The amount of water to be added to the hydrolyzable silane compound (formula 1) is not limited, but may be 1 to 50 times the molar amount of X ^{1 to} X ³ present in the hydrolyzable silane compound (formula 1). It is preferably 1 to 10 moles in terms of water dropping property and liquid life. As the acid in the method 2,
Preferred are nitric acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, acetic acid and the like. The amount of acid is 0.005 to 10 with respect to the amount of water.
% By weight is preferred. If the amount of the acid is too large, a problem in handling may occur during the operation.

The hydrolysis reaction is preferably carried out in the presence of an organic solvent. Perform the hydrolysis reaction in the presence of the organic solvent. It is preferable to use it as it is as a surface treatment composition containing a partial hydrolysis product and an organic solvent. The amount of the organic solvent is such that the hydrolyzable silane compound (formula 1) is 0.05 to 10% by weight in the surface treatment agent composition.
Preferably, the amount is such that Further, even in the case of a surface treatment agent composition, it is preferable that the amount of the partial hydrolysis product is adjusted to 0.05 to 10% by weight in the surface treatment agent composition.

Even when the hydrolyzable silane compound (formula 1) is not hydrolyzed, it is preferable to use a surface treating agent composition containing an organic solvent and the hydrolyzable silane compound (formula 1). In this case, the amount of the organic solvent may be such that the hydrolyzable silane compound (Formula 1) is contained in the surface treatment agent composition in an amount of 0.05 to 0.05%.
The amount is preferably 10% by weight.

The surface treating agent of the present invention may be directly applied to a substrate, but by forming a surface treating agent composition together with an organic solvent, the workability during the treatment is improved, and an excellent substrate surface treating agent is obtained. Become. The organic solvent can be appropriately changed in consideration of the solvent resistance of the base material, the size of the base material (evaporation rate of the solvent), economy, and the like. For example, alcohol solvents, cellosolve solvents, carbitol solvents, acetate solvents, ketone solvents, ester solvents, halogenated hydrocarbon solvents,
Hydrocarbon solvents and the like are preferable, especially alcohol solvents,
Acetate solvents or hydrocarbon solvents are preferred. The organic solvent may be one kind or two or more kinds. When two or more solvents are used, a mixed solvent of a hydrocarbon solvent and an alcohol solvent or a mixed solvent of a hydrocarbon solvent and an acetate solvent is preferable.

Other additives may be added to the surface treatment composition according to the purpose. Other additives include a hydrolyzable silane compound (formula 1) and a hydrolyzable silane compound (formula 1)
May be selected in consideration of the reactivity with the hydrolysis product of, for example, silica, alumina, zirconia,
Examples include ultrafine particles of metal oxides such as titania and tin, and various resins. When coloring is required, dyes, pigments, and the like can be used. Further, an antioxidant, an ultraviolet absorber and the like may be added. When it is desired to impart conductivity, antistatic property, or the like, a material (for example, tin oxide, ITO (In ₂ O ₃ —SnO ₂ ), zinc oxide, or the like) capable of obtaining a resistance value according to the purpose is used. The amount of other additives can be appropriately changed depending on the purpose, and is preferably 0.01 to 20% by weight in the surface treatment agent. Excessive addition of other additives is not preferred because it lowers the water-dropping property and abrasion resistance of the coating of the present invention.

It is also possible to add another conventionally known water repellent material as another additive. Conventionally known water-repellent materials include siloxane compounds such as dimethylpolysiloxane and reactive silicone oil;
And a silane compound represented by the formula:

[0060]

(R ⁸ ) _a (R ⁹ ) _b (R ¹⁰ ) _c Si (X ²⁰ ) _4-abc Formula 5

However, the symbols in the formula 5 have the following meanings. R ^{8 to} R ¹⁰ : each may be the same or different and each represents a monovalent organic group having 1 to 16 carbon atoms;
It is preferably an alkyl group having 6 to 12 carbon atoms or a group represented by the above formula A. a, b, c: each independently 0, 1, 2 or 3 and (a + b + c) is 0, 1, 2 or 3; (A + b
+ C) is preferably 0 or 1. X ²⁰ : a reactive group, preferably a hydrolyzable group or an isocyanate group. As the silane compound (Formula 5), the following Formula 5a, the following Formula 5b,
Alternatively, a compound represented by the following formula 5c is preferable.

[0062]

Formula 5a: F (CF ₂ ) _n (CH ₂ ) ₂ Si (X ²⁰ ) ₃

(Where n is an integer of 1 to 16;
An integer of from 16 to 16 is preferable, and an integer of from 6 to 12 is particularly preferable. ), Formula 5b: H (CH ₂ ) ₈ Si (X ²⁰ ) ₃ , Formula 5c: Si (X ²⁰ ) ₄ .

The surface treatment composition of the present invention is usually applied by applying it to a substrate and drying it. In this treatment, no special pretreatment is necessary, but it may be carried out according to the purpose. Pretreatment includes sodium hydroxide,
Alkaline treatment with aqueous potassium hydroxide solution, hydrofluoric acid,
Examples include acid treatment with an aqueous hydrochloric acid solution, discharge treatment by plasma irradiation, corona discharge, and the like, polishing treatment with various abrasives such as cerium oxide and alumina, and blast treatment.

The surface treatment composition of the present invention may be brushed,
The surface of the substrate is preferably treated by a method such as flow coating, spin coating, dip coating, spray coating, squeegee coating, or print coating. The surface treatment composition of the present invention is only dried in the air at normal temperature (about 10 to 35 ° C.),
It is excellent in economics to exhibit excellent performance. Heating treatment may be performed when it is desired to dry the material quickly or to increase the durability of the effect. The heating conditions are selected in consideration of the heat resistance of the base material, and are preferably about 36 to 400 ° C, and particularly preferably about 60 to 400 ° C.
About 400 ° C. is preferable. The heating time is 1 to 60.
Of the order of minutes.

The thickness of the film obtained by the surface treatment composition of the present invention is not particularly limited, and is preferably as thin as possible. The thickness is preferably a monomolecular film to 2 μm,
In particular, a monomolecular film to 0.1 μm is preferable. The film thickness can be appropriately controlled by the concentration of components contained in the surface treatment agent composition, application conditions, heating conditions, and the like.

The substrate to be treated with the surface treating agent composition of the present invention is not particularly limited, and examples thereof include glass, plastics, metals, ceramics, other inorganic and organic materials, and combinations thereof (composite materials, laminated materials). Etc.).

The surface of the base material may be the surface of the base material itself, and may be the surface of a coating film of a coating metal or the like, or the surface of a surface-treated layer of surface-treated glass (for example, a sol-gel film, a sputter film, a CVD film, For example, the surface may be made of a material different from the substrate existing on the substrate surface, such as a surface provided with a film or the like. The substrate may have any shape, such as a flat surface, a surface having a curvature over the entire surface, or a surface having a partial curvature.

Since the surface treating composition of the present invention exhibits excellent performance even at room temperature, it is applied to a substrate already used for some purpose, and the surface of the substrate is treated with water repellent or water droplets. Falling properties can also be imparted. Further, depending on processing conditions, functions such as oil repellency, lubricity, mold release properties, low reflectivity, and electrical insulation properties can be imparted. The film formed from the hydrolyzable silane compound (Formula 1) has excellent transparency and therefore has an advantage that the appearance of the substrate itself is not impaired. In addition, the coating is excellent in chemical resistance and abrasion resistance, and can be applied in a wide range of fields that have not been achieved before.

Examples of the substrate on which the surface treatment composition of the present invention can be treated include the following substrates.

Windows, mirrors, bodies of automobiles, ships, aircrafts, etc.
Architectural windows, various mirrors, optical lenses, eyeglass lenses, glass containers, TV CRTs, LCD screens, solar cell cover glasses, touch panels, hot plates, electronic and electrical products such as microwave ovens and rice cookers, cosmetic powders, Textile products, fabric products, leather products, wood products, stone products, paper products, printing press plates and nozzles, paint ingredients, sanitary ware, tableware, vases, aquariums, sashes, or agricultural sheets.

The substrate to be treated with the surface treating agent composition of the present invention is preferably a substrate made of a transparent material, particularly preferably glass. Further, the treated substrate may be mounted in the article. The article provided with the treated substrate of the present invention is preferably an article for transportation equipment, or a building / building article.

Examples of articles for transportation equipment include exterior members such as outer plates, window glasses, mirrors, visibility (CCD) lenses, and display equipment surface materials in transportation equipment such as trains, buses, trucks, automobiles, ships, and aircraft. , Interior materials such as instrument panel surface materials,
Or other transportation equipment articles.

Examples of articles for transportation equipment include those composed only of a surface-treated base material such as a window glass for an automobile treated with the surface treatment agent composition of the present invention, and the surface treatment agent composition of the present invention. Consisting of a rearview mirror member for an automobile in which a glass mirror treated in the above is incorporated. Further, as the articles for transportation equipment, there are bodies of trains, windows, pantographs, etc., bodies of automobiles, buses, trucks, etc., windshields, side glasses, rear glasses, mirrors, bumpers, etc., bodies of ships, aircrafts, etc., or window glasses. Etc. can be exemplified.

In the treated base material or treated article treated with the surface treating agent composition of the present invention, water droplets adhering to the surface are repelled by water repellency, and interaction with wind pressure received during traveling causes It can quickly move over the surface and stay out of water droplets, eliminating the adverse effects of moisture. In particular, when processing is performed on a transparent viewing portion such as a window glass, there is an advantage that the visual field can be easily secured by scattering of water droplets. Further, the film formed from the surface treating agent composition of the present invention is excellent in water droplet falling property, and has an advantage that water droplets move even at low speed running or even when stopped. In addition, even at a low temperature at which water droplets on the surface of the treated base material freeze, freezing hardly occurs, and even if it freezes, thawing is remarkably fast. Furthermore, since there is almost no adhesion of water droplets, the number of regular cleaning operations can be reduced,
There is an advantage that cleaning is easy.

Examples of the building / building article to which the treated base material of the present invention is mounted include window materials such as window glass plates and window glasses, roof glass plates and roofs such as glass roofs, glass plates for doors and the like. Attached doors, glass panes for partitions, glass panes for greenhouses, greenhouses, transparent plastic boards and architectural articles containing them (windows, roofing materials, etc.), wall materials made of ceramics, cement, metal, etc., mirrors and so on And articles attached to a building such as glass for display shelves and showcases. Further, there may be mentioned architectural articles such as furniture and fixtures, and substrates such as glass windows constituting the architectural articles.

In the architectural / building article treated with the surface treating agent composition of the present invention, the water in contact with the surface is repelled due to water repellency and hardly adheres. It is also easy to remove adhering water droplets. Further, even in an environment where water droplets freeze, the water does not freeze, and even if it freezes, thawing is extremely easy. Furthermore, since there is almost no adhesion of water droplets, the number of regular cleaning operations can be reduced, and cleaning is easy, which is advantageous from the viewpoint of aesthetic protection.

[0078]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Various evaluation methods in the examples are as follows. [Water repellency] The contact angle of water (unit: degree) was measured. [Water drop falling property] After dropping 50 μl of water drops on a flat sample base material held horizontally (at an angle of 0 °), the sample base material is tilted, and the angle between the base material and the horizontal plane when the water drops start to roll (Unit: degree) was read.

[Water Drop Survival] Water was sprayed over the entire surface from a nozzle held at a distance of 20 cm to a vertically-standing sample.
After spraying for a time, water droplets remaining on the sample surface were visually observed and evaluated according to the following criteria. A: no water droplets remain on the sample surface; B: small water droplets on the sample surface; C: considerable water droplets on the sample surface; D: water droplets spread on the sample surface.

[Evaluation of Water Repellency Durability] After immersion in boiling water for 6 hours, the water repellency, the falling property of water drops, and the remaining property of water drops were evaluated.

[Synthesis Example 1] 20 equipped with a stirrer and a thermometer
A 0 cc four-necked flask was sufficiently purged with nitrogen, and a compound represented by the following formula (the average value of m was 2.5) was added to 100 flasks.
g.

[0082]

Embedded image [(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _m ] ₃ SiCH 2CH ₂

After the temperature was raised to 90 ° C., HSiCl ₃
A mixture of 15.4 g and chloroplatinic acid (dissolved to be 2 ppm in terms of platinum) was dropped from a dropping funnel into a four-necked flask. As the reaction proceeds, the internal temperature becomes 100 ° C
Was observed. After stirring for 1 hour, HSi was measured by gas chromatography (hereinafter, referred to as GC).
After confirming disappearance of Cl ₃ by an ultraviolet absorption spectrum (IR), the reaction was stopped after 4 hours. The obtained product was analyzed by nuclear magnetic resonance spectrum (NMR) and IR. As a result, a structure represented by the following formula (the average value of m was 2.5)
Was confirmed.

[0084]

Embedded image [(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _m ] ₃ Si (CH ₂ ) ₂ SiCl ₃

[Synthesis Example 2] 20 equipped with a stirrer and a thermometer
A 0 cc four-necked flask was sufficiently purged with nitrogen, and 100 g of a compound represented by the following formula (where the average value of m was 8) was charged.

[0086]

Embedded image [(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _m ] ₃ SiCH = CH ₂

After the temperature was raised to 90 ° C., HSiCl ₃
A mixture of 6.5 g and chloroplatinic acid (dissolved to 2 ppm in terms of platinum) was dropped from a dropping funnel into a four-necked flask. It was observed that the internal temperature rose to 100 ° C. as the reaction proceeded. After stirring for 1 hour, disappearance of HSiCl ₃ was confirmed by GC by IR, and the reaction was stopped after 4 hours. The obtained product was analyzed by NMR and IR. As a result, it was confirmed that the product had a structure represented by the following formula (however, the average value of m was 8).

[0088]

Embedded image [(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _m ] ₃ Si (CH ₂ ) ₂ SiCl ₃

[Synthesis Example 3] 20 equipped with a stirrer and a thermometer
A 0 cc four-necked flask was sufficiently purged with nitrogen, and 100 g of a compound represented by the following formula (where the average value of m was 2.5, the average value of x was 2, and the average value of y was 1) were charged. .

[0090]

Embedded image [(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _m ] _x [(F (CF ₂ ) ₈ ) (CH ₂ ) ₃
(CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO] _m ] _y SiCH = CH ₂

After the temperature was raised to 90 ° C., HSiCl ₃
A mixture of 10.2 g and chloroplatinic acid (dissolved to be 2 ppm in terms of platinum) was dropped from a dropping funnel into a four-necked flask. As the reaction proceeds, the internal temperature becomes 100 ° C
Was observed. After stirring for 1 hour, disappearance of HSiCl ₃ was confirmed by GC by IR, and the reaction was stopped after 4 hours. As a result of analyzing the obtained product by NMR and IR, it was confirmed that the product had a structure represented by the following formula (where the average value of m was 2.5, the average value of x was 2, and the average value of y was 1). confirmed.

[0092]

Embedded image [(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _m ] _× [(F (CF ₂ ) ₈ (CH ₂ ) ₃ ) (CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO] _{m] y Si- - (CH 2} ) 2 Si
Cl ₃

[Synthesis Example 4] 20 equipped with a stirrer and a thermometer
A 0 cc four-necked flask was sufficiently purged with nitrogen, and a compound represented by the following formula (the average value of m was 2.5) was added to 100 flasks.
g.

[0094]

Embedded image [(F (CF ₂ ) ₈ (CH ₂ ) ₃ ) (CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO] _m ] ₃ SiCH = CH ₂

After the temperature was raised to 90 ° C., HSiCl ₃
A mixture of 6.1 g and chloroplatinic acid (dissolved to 2 ppm in terms of platinum) was dropped from a dropping funnel into a four-necked flask. It was observed that the internal temperature rose to 100 ° C. as the reaction proceeded. After stirring for 1 hour, disappearance of HSiCl ₃ was confirmed by GC by IR, and the reaction was stopped after 4 hours. As a result of analyzing the obtained product by NMR and IR, it was confirmed that the product had a structure represented by the following formula (however, the average value of m was 2.5).

[0096]

Embedded image [(F (CF ₂ ) ₈ (CH ₂ ) ₃ ) (CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO] _m ] ₃ S
i (CH ₂ ) ₂ SiCl ₃

Synthesis Example 5 20 equipped with a stirrer and a thermometer
A 0 cc four-necked flask was sufficiently purged with nitrogen, and 100 g of a compound represented by the following formula (where the average value of m was 2.5, the average value of x was 2, and the average value of y was 1) were charged. .

[0098]

[(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _m ] _x [(H (CH ₂ ) ₈ (C
H ₃ ) ₂ ) SiO [(CH ₃ ) ₂ SiO] _m ] _y SiCH = CH ₂

After the temperature was raised to 90 ° C., HSiCl ₃
A mixture of 13.8 g and chloroplatinic acid (dissolved to 2 ppm in terms of platinum) was dropped from a dropping funnel into a four-necked flask. As the reaction proceeds, the internal temperature becomes 100 ° C
Was observed. After stirring for 1 hour, disappearance of HSiCl ₃ was confirmed by GC by IR, and the reaction was stopped after 4 hours. As a result of analyzing the obtained product by NMR and IR, it was confirmed that the product had a structure represented by the following formula (where the average value of m was 2.5, the average value of x was 2, and the average value of y was 1). confirmed.

[0100]

Embedded image [(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _m ] _x [(H (CH ₂ ) ₈ ) (CH ₃ ) ₂
SiO [(CH ₃ ) ₂ SiO] _m ] _y Si (CH ₂ ) ₂ SiCl ₃

[Synthesis Example 6] 20 equipped with a stirrer and a thermometer
A 0 cc four-necked flask was sufficiently purged with nitrogen, and a compound represented by the following formula (the average value of m was 2.5) was added to 100 flasks.
g.

[0102]

Embedded image [(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _m ] ₃ SiCH 2CH ₂

After the temperature was raised to 90 ° C., HSiCl ₃
A mixture of 17.2 g and chloroplatinic acid (dissolved to 2 ppm in terms of platinum) was dropped into a four-necked flask from a dropping funnel. As the reaction proceeds, the internal temperature becomes 100 ° C
Was observed. After stirring for 1 hour, the disappearance of HSi (OC ₂ H ₅ ) ₃ was confirmed by IR by GC, and the reaction was stopped after 4 hours. The product obtained is NM
As a result of analysis by R and IR, it was confirmed that the structure was represented by the following formula (however, the average value of m was 2.5).

[0104]

Embedded image [(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _m ] ₃ Si (CH ₂ ) ₂ Si (OCH ₂ CH ₃ ) ₃

[Example 1] (Example) 97.00 g of butyl acetate was placed in a glass reaction vessel equipped with a thermometer and a stirrer, and the compound obtained in Synthesis Example 1 was 3.00.
g and stirred at 25 ° C. for one day to prepare a surface treating agent composition. Polished and cleaned size 10cm
1 cc of the prepared surface treating agent composition was dropped on a surface of soda lime glass having a size of 10 cm (3.5 mm in thickness), spread with a tissue paper in the manner of car waxing, dried in the air, and dried in air. 1 was obtained. Table 1 shows the evaluation results of the sample substrate 1.

Example 2 (Example) 97.00 g of butyl acetate was placed in a glass reaction vessel equipped with a thermometer and a stirrer, and the compound obtained in Synthesis Example 2 was 3.00.
g and stirred at 25 ° C. for one day to prepare a surface treating agent composition. Size 10cm x 10 which has been previously polished and cleaned
1 cc of the prepared surface treating agent composition was dropped onto a soda lime glass surface of 3.5 cm (thickness: 3.5 mm), spread with a tissue paper in the manner of car waxing, dried in the air, and the sample substrate 2 was dried. Obtained. Table 1 shows the evaluation results of the sample substrate 2.

Example 3 (Example) 97.00 g of butyl acetate was placed in a glass reaction vessel equipped with a thermometer and a stirrer, and the compound obtained in Synthesis Example 3 was 3.00.
g and stirred at 25 ° C. for one day to prepare a surface treating agent composition. Size 10cm x 10 which has been previously polished and cleaned
1 cc of the surface treating agent composition prepared on a soda lime glass surface of 3.5 cm (thickness: 3.5 mm) was dropped, spread with a tissue paper in the manner of car waxing, and dried in air to dry the sample substrate 3. Obtained. Table 1 shows the evaluation results of the sample base material 3.

Example 4 (Example) In a glass reaction vessel equipped with a thermometer and a stirrer, 97.00 g of butyl acetate, 3.00 g of the compound obtained in Synthesis Example 4, were prepared.
g and stirred at 25 ° C. for one day to prepare a surface treating agent composition. Size 10cm x 10 which has been previously polished and cleaned
cm (3.5mm thick) soda lime glass surface,
1 cc of the prepared surface treatment agent composition was dropped, spread on a tissue paper in a manner similar to automobile waxing, and dried in the air to obtain a sample substrate 4. Sample substrate 4
Table 1 shows the evaluation results.

Example 5 (Example) In a glass reaction vessel equipped with a thermometer and a stirrer, 97.00 g of butyl acetate, 3.00 g of the compound obtained in Synthesis Example 5, were prepared.
g and stirred at 25 ° C. for one day to prepare a surface treating agent composition. Size 10cm x 10 which has been previously polished and cleaned
cm (3.5mm thick) soda lime glass surface,
1 cc of the prepared surface treating agent composition was dropped, applied in a manner similar to automobile waxing with a tissue paper, and dried in the air to obtain a sample substrate 5. Sample substrate 5
Table 1 shows the evaluation results.

Example 6 (Example) In a glass reaction vessel equipped with a thermometer and a stirrer, 2-
93.00 g of propanol and 3.41 g of the compound obtained in Synthesis Example 6 were added, and the mixture was stirred at 25 ° C. for 10 minutes. Next, 3.59 g of a 0.6% by weight nitric acid aqueous solution was gradually added dropwise.
After completion of the dropwise addition, stirring was continued at 25 ° C. for three days and nights to prepare a surface treatment composition. Size 10 previously polished and cleaned
1 cc of the prepared surface treating agent composition was dropped on a soda lime glass surface of cm × 10 cm (3.5 mm thick), spread with a tissue paper in the manner of car waxing, dried in the air, and dried in air. Material 6 was obtained. Table 1 shows the evaluation results of the sample substrates 6.

[Comparative Example 1] 97.00 g of butyl acetate was placed in a glass reaction vessel equipped with a thermometer and a stirrer.
3.00 g of polydimethylsiloxane (terminal trimethyl) having a viscosity of centistokes was added and stirred at 25 ° C. for one day to prepare a surface treating agent composition. 10cm × 10cm (3.5m thick)
1 cc of the prepared surface treating agent composition A was dropped on the surface of the soda-lime glass of m), spread with a tissue paper in the manner of car waxing, and dried in the atmosphere to obtain a sample base material A. Table 1 shows the evaluation results of sample substrate A.
Shown in

Comparative Example 2 A glass reaction vessel equipped with a thermometer and a stirrer was charged with 97.00 g of butyl acetate and H (C
3.00 g of H ₂ ) ₈ SiCl ₃ was added and stirred at 25 ° C. for 24 hours to prepare a surface treatment composition. 10cm × 10cm (3.5m thick)
1 cc of the prepared surface treating agent composition was dropped on the surface of the soda lime glass of m), spread with a tissue paper in the manner of car waxing, and dried in air to obtain a sample base material B. Table 1 shows the evaluation results of the sample base material B.

Comparative Example 3 97.00 g of butyl acetate and C ₈ F were placed in a glass reaction vessel equipped with a thermometer and a stirrer.
3.00 g of ₁₇ C ₂ H ₄ SiCl ₃ was added, and the mixture was stirred at 25 ° C. for 24 hours to prepare a surface treating agent composition. 10cm × 10cm (3.5m thick)
To 1 m of the soda lime glass surface of m), 1 cc of the prepared surface treating agent composition was dropped, applied in a manner of car waxing with a tissue paper, and dried in air to obtain a sample base material C. Table 1 shows the evaluation results of the sample base material C.

[0114]

[Table 1]

[Examples 7 to 12] (Examples) Sample base materials 1 to 6 were added to the chemicals shown in Table 2, respectively.
It was immersed for a period of time, and the water repellency and the water droplet falling property after immersion were evaluated.
The results are shown in Tables 2 and 3.

[0116]

[Table 2]

[0117]

[Table 3]

[Examples 13 to 18] (Examples) Each of the sample substrates 1 to 6 was loaded with a load of 1 kg.
, And was reciprocated abrasion 1500 times with a flannel cloth. Table 4 shows the results of evaluating the water repellency and the water droplet falling property after the abrasion test.

[0119]

[Table 4]

[Examples 19 to 24] (Examples) Tables 5 show the results of evaluating the water repellency and water droplet falling property after heating each of the sample base materials 1 to 6 at 250 ° C for 30 minutes.

[0121]

[Table 5]

[Example 25] (Example) A glass reaction vessel equipped with a thermometer and a stirrer was placed in a glass reactor.
99.00 g of butyl acetate, 1.00 g of Si (NCO) ₄
Was added, and stirring was continued at 25 ° C. for one day to prepare a pretreatment liquid 1. Polished and cleaned size 10cm x 1
1 cc of the prepared pretreatment liquid 1 was dropped on a 0 cm (3.5 mm thick) soda lime glass surface, spread with a tissue paper in the manner of car waxing, and further dried under an environment of 25 ° C. and 50% humidity. Left for hours. next,
Using the substrate treated with the pretreatment liquid 1, a sample substrate 7 was prepared in the same manner as in Example 1. Table 6 shows the evaluation results of the sample base material 7.

[Example 26] (Example) A glass reaction vessel equipped with a thermometer and a stirrer was used.
78.80 g of ethyl alcohol, Si (OC ₂ H ₅ ) ₄
10.40 g was added and stirred at 25 ° C. for 10 minutes. Next, 10.80 g of a 0.6% by weight aqueous nitric acid solution was gradually added dropwise. After completion of the dropwise addition, stirring was continued at 25 ° C. for 24 hours to synthesize a pretreatment liquid 2. Polished and cleaned size 10c
1 cc of the pretreatment liquid 2 was dropped on the surface of soda lime glass having a size of mx 10 cm (thickness: 3.5 mm), spread with a tissue paper in the manner of car waxing, and then heated to 250 ° C.
For 30 minutes. Next, a sample substrate 8 was prepared in the same manner as in Example 1 using the substrate treated with the pretreatment liquid 2. Table 6 shows the evaluation results of the sample base materials 8.

[0124]

[Table 6]

[Example 27] (Example) A glass reaction vessel equipped with a thermometer and a stirrer was used.
93.00 g of 2-propanol, 2.39 g of the compound obtained in Synthesis Example 6, and 1.02 g of tetraethoxysilane
And stirred at 25 ° C. for 10 minutes. Next, 3.58 g of a 0.6% by weight nitric acid aqueous solution was gradually added dropwise. After dropping, 2
Stirring was continued at 5 ° C. for three days to prepare a surface treatment composition. Size 10cm x 10c, previously polished and cleaned
1 cc of the prepared surface treatment composition was dropped on a soda lime glass surface having a thickness of 3.5 m (thickness: 3.5 mm), spread with a tissue paper in the manner of car waxing, dried in air, and dried in air. I got Table 7 shows the evaluation results of the sample base material 9.

[Example 28] (Example) A glass reaction vessel equipped with a thermometer and a stirrer was used.
93.00 g of 2-propanol, 2.39 g of the compound obtained in Synthesis Example 6, and 1.02 g of tetraethoxysilane
And stirred at 25 ° C. for 10 minutes. Next, 3.58 g of a 0.6% by weight nitric acid aqueous solution was gradually added dropwise. After dropping, 2
Stirring was continued at 5 ° C. for 3 days to prepare a surface treating agent composition. Size 10cm x 10c, previously polished and cleaned
1 cc of the prepared surface treating agent composition was dropped on a soda lime glass surface having a thickness of 3.5 m (thickness: 3.5 mm).
The sample was heated at 0 ° C. for 30 minutes to obtain a sample substrate 10. Table 7 shows the evaluation results of the sample substrates 10.

[Example 29] (Example) A glass reaction vessel equipped with a thermometer and a stirrer was prepared as follows.
93.00 g of 2-propanol, 1.71 g of the compound obtained in Synthesis Example 6, and F (CF ₂ ) ₈ (CH ₂ ) ₂ Si
1.71 g of (OCH ₃ ) ₃ was added and stirred at 25 ° C. for 10 minutes. Next, 3.58 g of a 0.6% by weight nitric acid aqueous solution was gradually added dropwise. After completion of the dropwise addition, stirring was continued at 25 ° C. for three days and nights to prepare a surface treatment composition. The prepared surface treatment composition was applied to a surface of soda lime glass of 10 cm × 10 cm (thickness: 3.5 mm) which had been polished and cleaned in advance.
The sample base material 1 was dropped by dropping cc, spread with a tissue paper in the manner of car waxing, and dried in air.
1 was obtained. Table 7 shows the evaluation results of the sample base material 11.

[Example 30] (Example) A glass reaction vessel equipped with a thermometer and a stirrer was used.
97.00 g of butyl acetate, 0.1% of the compound obtained in Synthesis Example 1.
68 g and F (CF ₂ ) ₈ (CH ₂ ) ₂ Si (NC
O) ₃ (2.73 g) was added and stirred at 25 ° C. for 24 hours to prepare a surface treating agent composition. 1 cc of the prepared surface treating agent composition is dropped on a 10 cm × 10 cm (3.5 mm thick) soda lime glass surface which has been polished and cleaned in advance, and is spread with a tissue paper in the manner of car waxing. Then, the sample substrate 12 was obtained. Table 7 shows the evaluation results of the sample base materials 12.

[Example 31] (Example) A glass reaction vessel equipped with a thermometer and a stirrer was prepared as follows.
The compound obtained in Synthesis Example 1 was 97.00 g of butyl acetate.
73 g and 0.68 g of Si (NCO) ₄ were added, and 25
The mixture was stirred at ℃ for one day to prepare a surface treatment composition. 1 cc of the prepared surface treating agent composition is dropped on a 10 cm × 10 cm (3.5 mm thick) soda lime glass surface which has been polished and cleaned in advance, and is spread with a tissue paper in the manner of car waxing. To obtain a sample substrate 13. Table 7 shows the evaluation results of the sample base material 13.

[0130]

[Table 7]

Example 32 (Example) After the surface of a front laminated glass for an automobile was treated by the method of Example 1, the laminated glass was mounted on an automobile. The automobile was actually used for three months, and the state of adhesion of dirt and dust on the front surface and the state of adhesion of water droplets in rainy weather were visually observed. As a result, no generation of stains due to adhesion of dirt, dust, or water droplets was observed, and even in the rare case of such generation, they could be easily removed by gently wiping with a tissue paper. Also, in rainy weather, water droplets were repelled on the surface, and the water droplets moved quickly due to interaction with wind pressure caused by traveling, so that the field of view was secured without using a wiper. In addition, even when the vehicle was stopped, the water droplets rolled well because of their own weight, so that the visual field could be secured without using a wiper. Further, in a running test at 0 ° C., water droplets adhering to the untreated front laminated glass were frozen, whereas no freezing was observed on the treated windshield.

Example 33 (Example) In Example 32, the front laminated glass was replaced with a side glass.
When the rear glass and the side mirror were changed, the same effect as in Example 32 was confirmed.

Example 34 (Example) The surface of an automobile windshield, which has been used for three years, was polished with an aqueous cerium oxide solution, washed with water and dried. The washed front laminated glass was treated in the same manner as in Example 1 as a substrate. When a running test similar to that of Example 32 was performed on this vehicle, the same effect was confirmed.

[0134]

The surface treating agent composition containing the surface treating agent of the present invention imparts the following excellent effects to the substrate surface. (1) Since the substrate surface is provided with excellent water repellency and excellent water-dropping properties, the adverse effects of water can be eliminated.
In addition, the cleaning can be simplified. (2) It has excellent water repellency and durability of water droplet falling, and can be used semipermanently. (3) Excellent in chemical resistance. Therefore, the effect is exerted also in the see-through portion of a ship that is directly in contact with seawater. (4) Since no special pretreatment is required, the economic effect is high. (5) Since the characteristics are exhibited even at ordinary temperature treatment, it is excellent in versatility and economy, and can be used for repair. Also, the types of substrates to be applied are wide-ranging.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Mami Kodera 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture F-term in Asahi Glass Co., Ltd. 4H020 BA36

Claims (10)

[Claims] A surface treating agent comprising a hydrolyzable silane compound represented by the following formula 1 and / or a partial hydrolysis product of the hydrolyzable silane compound. Embedded image However, the symbols in Formula 1 have the following meanings. R ^{1 to} R ⁵ : monovalent organic groups which may be the same or different. Q ¹ : divalent organic group. X ¹ , X ² , X ³ : each may be the same or different, and are a hydrolyzable group or an isocyanate group. m: an integer of 0 or more. 2. R ¹ or R ⁵ is a group represented by the following formula A, and R ² , R ³ and R ⁴ are monovalent hydrocarbon groups, or all of R ^{1 to} R ⁵ are The surface treating agent according to claim 1, which is a methyl group. -Q ² -R ^f Formula A where the symbols in the formula A have the following meanings. R ^f : a monovalent polyfluorohydrocarbon group which may contain an etheric oxygen atom. Q ² : divalent organic group. 3. The surface treating agent according to claim 1, wherein Q ¹ is a dimethylene group. 4. A surface treating agent composition comprising the surface treating agent according to claim 1, and an organic solvent. 5. A method for treating a substrate, comprising treating the surface of a substrate with the surface treating agent composition according to claim 4. 6. The method according to claim 5, wherein the surface of the substrate is treated and then dried.
The method for treating a base material according to item 1. 7. The method according to claim 5, wherein the surface of the substrate is a glass surface. 8. The method for treating a base material according to claim 5, wherein the surface of the base material has been previously treated with a hydrolyzable silane compound other than the compound represented by the formula 1. 9. A treated substrate obtained by the method for treating a substrate according to claim 5. 10. A member on which the treated substrate according to claim 9 is mounted.