JPH11181412A - Surface treatment agent and base material treated therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a surface treatment agent eliminating adverse effects caused by water, excellent in water repellency, a water-drop falling property and chemical resistance, and suitable for treating the surface of glass and others, by including a specific fluorinated silicone compound (hydrolysate). SOLUTION: This surface treatment agent includes a fluorinated silicone compound (hydrolysate) of formula III [RA is a fluorinated organic group of formula I (see below); RB is a hydrolyzable group-containing organic group of formula II (see below); R<10> is a monovalent organic group except for formulae I and II; (p) and (q) are each an integer of >=1; (r) is an integer of >=0] or the like, essentially having an organosiloxane unit S<1> obtained by directly linking a fluorinated group expressed by formula I (R<1> is a 1-30C alkyl; A<1> is a 1-30C fluorinated divalent organic group; B<1> is a 2-30C divalent organic group containing no fluorine) to a silicon atom forming the organosiloxane unit and an organosiloxane unit S<2> obtained by directly linking a hydrolyzable group- containing organic group expressed by formula II [R<2> is a monovalent organic group; X<1> is a monovalent hydrolyzable group; (a) is an integer of >=1; (b) is 1-3] to the above silicon atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a surface treatment agent capable of imparting excellent water repellency and water droplet falling property to a substrate surface, and a surface-treated substrate.

[0002]

2. Description of the Related Art Various substrates such as glass, plastics, ceramics, and metals, and various substrates having a surface treatment layer are used in various fields, but the adverse effect of water on the substrate surface is problematic. It has become.

[0003] For example, the surfaces of outer panels, windowpanes, mirrors, exterior members such as display device surfaces, interior members such as instrument panel surface materials, and other articles in transportation equipment such as trains, automobiles, ships, and aircraft are always clean. It is preferred that If raindrops, dust, dirt, etc. adhere to the surface of the transportation equipment article, or if moisture condenses due to the influence of humidity and temperature in the atmosphere, there is a problem that its appearance is impaired. In addition, if the surface is in direct contact with the human eyes or the surface is in direct contact with humans, discomfort and hygiene problems occur. Further, there is a problem that the original function of the transport equipment article is significantly reduced. In particular, when an article for transportation equipment is an article that requires transparency and transparency (for example, a window glass, a mirror, etc.), the reduction in transparency and transparency cannot achieve the original purpose of the article. There is.

[0004] Means for removing dust, dirt, water and the like (eg, wiping, removal with a wiper) may cause minute scratches on the surface. In addition, foreign particles associated with dust, dirt, water, etc. may make the scratch more remarkable. Further, it is well known that when moisture adheres to the glass surface, the glass component elutes in the moisture and the surface is eroded (so-called burning occurs). Strong rubbing to remove this burn will cause fine irregularities on the surface. In addition, see-through parts made of glass with severe burns or glass with fine irregularities on the surface deteriorate their original function, and light scattering on the surface is severe, which is inconvenient in securing the visual field. There is a problem that occurs.

[0005] In addition, dust, dirt, and water have a harmful effect on the surface of transport equipment articles, and promote damage, contamination, coloring, corrosion, and the like. There is also a problem that induces changes in characteristics and the like. This type of adverse effects is not limited to transportation equipment goods, but also to building and construction goods,
It is a problem in various fields such as articles for electric and electronic devices.

In order to solve these problems, a silicone-based wax, an organosiloxane compound, or the like is used to impart the property of eliminating adhesion of water droplets and eliminating the adverse effect thereof (hereinafter simply referred to as water repellency) to the substrate surface. There have been proposals for imparting water repellency by directly applying a surfactant or the like.

For example, a water-repellent composition comprising an alkylpolysiloxane and an acid (JP-B-50-15473), a water-repellent treating agent comprising an organic solvent and a metal halide (JP-A-55-9652), a chlorine atom-containing siloxane compound And a water-repellent composition containing the same (JP-A-55-78080;
JP-A-55-90580), a water-repellent containing an amino-modified silicone oil and a surfactant (JP-A-5-301)
742), a water / oil repellent containing a compound having a terminal perfluoroalkyl moiety as an essential component (JP-A-2-1382)
62, JP-A-2-248480), a fluoroalkylsilane, an insoluble fine powder, an alcohol-based solvent and a water-repellent comprising an acid or an alkali (JP-A-8-277388).

However, the conventional water-repellent treatment agent tends to cause unevenness during application or has insufficient adhesion to a substrate, so that its effect is not maintained for a long period of time and its application range is limited. . In particular, conventional water repellents containing a compound having a perfluoroalkyl moiety at the terminal as an essential component exhibit excellent water repellency and durability, but have poor water-dropping properties and lack practicality.

In order to impart water repellency and water droplet falling property to already used articles, it is necessary to impart water repellency and water drop falling property only by directly applying each article at room temperature. For example, if the treatment is to be carried out on already marketed vehicle windshields, it is not possible for economic reasons to replace all the windshields of each vehicle. Further, it is practically impossible to fire the entire automobile after coating. However, with the conventionally proposed treatment agents, there is a problem in terms of performance in the water-repellent treatment in which the treatment is simply applied directly at room temperature.

[0010]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks of the conventional water repellent, and provides a surface treatment capable of imparting excellent water repellency to various kinds of substrates, particularly excellent water drop-fall properties. It is an object of the present invention to provide an agent and a treated substrate treated with the surface treating agent.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the conventional problems, and as a result, have found that a compound having a specific structural unit or a hydrolysis product of the compound is regarded as an essential component. It has been found that by treating the surface of a substrate with a surface treating agent to be used, a substrate excellent in water repellency, water-dropping property, adhesion (durability), abrasion resistance, and chemical resistance can be obtained. That is, the present invention provides the following organosiloxane unit (S ¹ ) and the following organosiloxane unit (S ² )
And / or a hydrolyzate of the fluorine-containing silicone compound, which is essential for the surface treatment agent, and a treated substrate treated with the surface treatment agent.

Organosiloxane unit (S ¹ ): An organosiloxane unit in which a fluorine-containing group represented by the following formula 1 is directly bonded to a silicon atom forming the organosiloxane unit. Organosiloxane unit (S ² ): An organosiloxane unit in which a hydrolyzable group-containing organic group represented by the following formula 2 is directly bonded to a silicon atom forming the organosiloxane unit.

-B ¹ -A ¹ -R ¹ Formula 1-(CH ₂ ) _a Si (R ² ) _3-b (X ¹ ) _b Formula 2 where the symbols in the formula have the following meanings: Show. R ¹ : an alkyl group having 1 to 30 carbon atoms. A ¹ : a fluorine-containing divalent organic group having 1 to 30 carbon atoms. B ¹ : a fluorine-free divalent organic group having 2 to 30 carbon atoms. R ² : a monovalent organic group. X ¹ : a monovalent hydrolyzable group. a: an integer of 1 or more. b: 1, 2 or 3.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The silicone compound in the present invention is a compound having a basic skeleton having a structure in which two or more organosiloxane units in which one or more organic groups are bonded to a siloxane unit. Further, the organic group refers to a group containing a carbon atom.

The surface treating agent of the present invention contains a specific fluorine-containing silicone compound as an essential component. The fluorinated silicone compound essentially contains an organosiloxane unit (S ¹ ) and an organosiloxane unit (S ² ). The organosiloxane unit (S ¹ ) is an organosiloxane unit in which a fluorine-containing group represented by the formula 1 is directly bonded to a silicon atom forming the organosiloxane unit.

The fluorine-containing group (formula 1) in the organosiloxane unit (S ¹ ) is a structural unit indispensable for exhibiting excellent water repellency and water drop resistance. The fluorinated group (Formula 1)
A compound having an alkyl terminal, a fluorine-containing divalent organic group and a divalent organic group as constituents, and a compound having an alkyl group conventionally proposed as a water-repellent material, It is a group different from the group in the compound having an alkyl moiety.

The terminal alkyl group (R ¹ ) present in the formula 1
Is an alkyl group having 1 to 30 carbon atoms, and is a group that exhibits good water-dropping property. R ¹ is preferably a methyl group or an ethyl group from the viewpoint of water repellency and durability.

The fluorine-containing divalent organic group (A)
¹ ) is a fluorine-containing divalent organic group having 1 to 30 carbon atoms, and is a group that exhibits good water repellency, falling property of water droplets, and durability. The fluorine-containing divalent organic group means a divalent organic group containing a fluorine atom, a divalent hydrocarbon group containing a divalent hetero atom, a substituted divalent hydrocarbon group, or an unsubstituted divalent hydrocarbon group, A group in which one or more of the hydrogen atoms therein has been replaced with a fluorine atom is preferred.

The divalent hydrocarbon group containing a divalent hetero atom includes an etheric oxygen atom (—O
-) Or a divalent hydrocarbon group containing a thioetheric sulfur atom (-S-) is preferred. The divalent hetero atom may be inserted between the carbon-carbon bonds of the hydrocarbon group, or may be bonded to a carbon atom at the terminal of the hydrocarbon group. Further, as the substituted divalent hydrocarbon group, at least one hydrogen atom of the divalent hydrocarbon group is selected from a carbonyl group, an epoxy group, a carbamoyl group, an N-alkylcarbamoyl group, an alkoxycarbonyl group, and a hydroxyl group. A divalent hydrocarbon group substituted with a group is preferred.

The structure of the fluorine-containing divalent organic group (A ¹ ) may be any of a straight-chain structure, a structure having a cyclic portion or a branched portion, and is preferably a straight-chain structure. In the case of a structure having a branched portion, the branched portion preferably has 4 or less carbon atoms.

As the fluorine-containing divalent organic group (A ¹ ), 2
A group in which two or more hydrogen atoms in a divalent hydrocarbon group or a divalent hydrocarbon group containing a divalent hetero atom are substituted with fluorine atoms is preferable. Further, A ¹ is a “polyfluoroalkylene group optionally containing a divalent hetero atom”, which is a group in which two or more hydrogen atoms in an alkylene group or an alkylene group containing a hetero atom are substituted with fluorine atoms. preferable.

The number of fluorine atoms in the polyfluoroalkylene group which may contain a divalent hetero atom is [(the number of fluorine atoms present in the polyfluoroalkylene group which may contain a divalent hetero atom) / ( Represented by the number of hydrogen atoms contained in the alkylene group optionally having the same carbon number and corresponding to the polyfluoroalkylene group optionally having a divalent hetero atom) × 100 (%)] In this case, it is preferably at least 60%, particularly preferably at least 80%.

Further, as the fluorine-containing divalent organic group (A ¹ ), from the viewpoints of water repellency, water drop resistance and durability,
A “perfluoroalkylene group optionally containing a divalent hetero atom”, which is a group in which all hydrogen atoms in an alkylene group or an alkylene group containing a hetero atom are substituted with fluorine atoms, is preferred.

The divalent good perfluoroalkylene group which may contain a hetero atom, -CF ₂ - preferably a group containing, in particular, _{- (CF 2) n - (} . N is an integer of 1 to 30) consists of groups, A group having the group as a partial structure, or a group in which an etheric oxygen atom or a thioetheric sulfur atom is bonded between carbon-carbon bonds or one terminal of-(CF ₂ ) _n-wherein n is 2 or more, is preferable. especially - (CF _{2) n}
-(N is an integer of 1 to 30, preferably 4 to 8)
The group consisting of is preferred.

[0025] B ¹ of formula 1, (not including fluorine) fluorine-free C2-30 represents a divalent organic group, good water repellency, waterdrop rolling property, structural units capable of expressing the durability It is. The fluorine-free divalent organic group (B ¹ ) may have either a straight-chain structure or a structure having a cyclic portion or a branched portion, and a straight-chain structure is preferred. In the case of a structure having a branched portion, the branched portion preferably has 4 or less carbon atoms.

As the fluorine-free divalent organic group (B ¹ ),
In addition to the divalent hydrocarbon group containing a divalent hetero atom, the substituted divalent hydrocarbon group, the unsubstituted divalent hydrocarbon group, and the carbon of the divalent hydrocarbon group described in the description of the above formula 1, -Between carbon atoms or at terminal carbon atoms -CONH-, -COO-,
A group having a group such as -NH- is preferable.

The fluorine-free divalent organic group (B ¹ ) is-(CH ₂ ) _m- from the viewpoints of water repellency, water droplet falling property and durability.
(Where m is an integer of 1 to 16, and preferably 2 to 4).
A group consisting of (CH ₂ ) _m- (where m is as defined above) is preferable.

Further, in the formula (1) in the present invention, the total number of carbon atoms is preferably from 3 to 60, particularly preferably from 6 to 18. Also, the total number of fluorine atoms present in the formula 1, A ¹ is formula A ¹ assuming that a fluorine-containing divalent same number of carbon atoms of which corresponds to the organic radical fluorine-free divalent hydrocarbon radical When expressed as a ratio (%) to the hydrogen atoms present therein, it is preferably at least 40%, particularly preferably at least 60%.

The following are specific examples of the formula 1, but are not limited thereto. In the following formula, R ¹ is an alkyl group having 1 to 30 carbon atoms, and is preferably a methyl group or an ethyl group. c is an integer of 1 to 20, d is an integer of 1 to 20,
(C + d) is an integer of 1 to 30. e is an integer of 2 to 20, f is an integer of 0 to 20, g is an integer of 0 to 20,
(F + g) is an integer of 2 to 30, and h is an integer of 1 to 29.

[0030]

Embedded image R ¹ (CF ₂ ) _c (CH ₂ ) _e −, R ¹ (CF
_{2) c O (CF 2)} d (CH 2) e -, R 1 (CF 2)
_{c S (CF 2) d (} CH 2) e -, R 1 (CF 2) c
_{(CH 2) f O (CH} 2) g -, R 1 (CF 2) c (C
_{H 2) f S (CH 2} ) g -, R 1 (CF 2) c (CH
_{2) f NH (CH 2)} g -, R 1 (CF 2) c CONH
_{(CH 2) e -, R} 1 (CF 2) c CONH (CH 2)
_{f NH (CH 2) g -} , R 1 (CF 2) c (CH 2) 2
_{OCO (CH 2) f S (} CH 2) g -, R 1 (CF 2)
_{2 O [CF (CF 3)} CF 2 O] 3 --CF (CF 3)
CONH (CH _{2) h} -.

The organosiloxane unit (S ¹ ) in the fluorinated silicone compound is an organosiloxane unit in which a fluorinated group represented by the formula 1 is directly bonded to a silicon atom forming the organosiloxane unit.

The following are specific examples of the organosiloxane unit (S ¹ ). (R ^A ) ₃ SiO
_1/2 , (R ^A ) ₂ (R ¹⁰ ) SiO _1/2 , (R ^A )
(R ¹⁰ ) ₂ SiO _1/2 , (R ^A ) (R ¹⁰ ) SiO _2/2 ,
And (R ^A ) ₂ SiO _2/2 , (R ^A ) SiO _{3/2 and the} like.

[0033] However, the group R ^A of the formula 1, R ¹⁰
Represents a monovalent organic group, and when two or more are present in the same siloxane unit, they may be the same or different. R ¹⁰ represents a group represented by the above formula 1, and
Groups other than the group represented by the following formula 2 (hereinafter, referred to as other monovalent organic groups) are preferable, and an alkyl group or a polyfluoroalkyl group having a perfluoroalkyl group at a terminal is preferable. Here, a polyfluoroalkyl group refers to a group in which two or more hydrogen atoms of an alkyl group have been substituted with fluorine atoms, and a perfluoroalkyl group has substantially all of the hydrogen atoms of an alkyl group substituted with fluorine atoms. Refers to the group

Specific examples of other monovalent organic groups (R ¹⁰ ) include the following groups, and organosiloxane units (S
The R ^{10 1),} a methyl group is preferable from the easiness of availability or synthetic. _{-CH 3, -CH 2 CH 3,} - (CH
₂ ) ₂ (CF ₂ ) ₃ CF ₃ ,-(CH ₂ ) ₃ (CF ₂ ) ₃
CF ₃ , — (CH ₂ ) ₂ (CF ₂ ) ₇ CF ₃ , — (C
_{H 2) 3 (CF 2)} 7 CF 3.

Fluorine-containing silicone compound of the present invention
Represents an organosiloxane unit (S ¹ ) With Olga
Siloxane unit (S^Two ) Is required. Organoshiro
Kisane unit (S^Two ) Forms organosiloxane units
A hydrolyzable group-containing group represented by Formula 2
It is an organosiloxane unit directly bonded. Organo
Siloxane unit (S^Two ) Can develop adhesion to the substrate
Is a unit.

Examples of the R ² in the formula 2, a methyl group is preferable from the easiness of availability. X ^{1 in} Formula 2 is preferably an alkoxy group, a halogen atom, an isocyanate group, or a carbamoyl group. Particularly, when it is desired to exhibit performance when the surface treating agent is treated at room temperature, a halogen atom or an isocyanate group is preferred. When a heat treatment is performed after the treatment, an alkoxy group is desirable from the viewpoint of the working environment and the like. A halogen atom is preferably a chlorine atom, and an alkoxy group is preferably a methoxy group or an ethoxy group.

In the present specification, regardless of whether the isocyanate group exhibits the property as a hydrolyzable group,
The isocyanate group is described as being included in the hydrolyzable group. A in Formula 2 is preferably an integer of 1 to 5, and b is preferably 3. Specific examples of Formula 2 include the following groups.

[0038]

Embedded image-(CH ₂ ) ₂ Si (OCH ₃ ) ₃ ,-(CH
₂ ) ₂ Si (OCH ₂ CH ₃ ) ₃ ,-(CH ₂ ) ₂ Si
_{(CH 3) (OCH 2 CH} 3) 2, - (CH 2) 2 Si
_{(CH 3) 2 (OCH 2} CH 3), - (CH 2) 2 Si
_{Cl 3, - (CH 2)} 2 Si (CH 3) Cl 2, - (C
_{H 2) 2 Si (CH 3} ) 2 Cl, - (CH 2) 2 Si
_{(NCO) 3, - (CH} 2) 2 Si (CH 3) (NC
_{O) 2, - (CH 2} ) 2 Si (CH 3) 2 (NCO).

The organosiloxane unit (S ² ) is a unit in which a hydrolyzable group-containing group represented by Formula 2 is directly bonded to a silicon atom forming the organosiloxane unit, and examples thereof include the following. (R ^B ) ₃ SiO _1/2 , (R ^B )
₂ (R ¹⁰ ) SiO _1/2 , (R ^B ) (R ¹⁰ ) ₂ SiO
_1/2 , (R ^B ) (R ¹⁰ ) SiO _2/2 , and (R ^B ) ₂
SiO _2/2 , (R ^B ) SiO _{3/2 and the} like. However, R ^B represents a group represented by the formula 2, R ¹⁰ represents a monovalent organic group, and other monovalent organic groups are preferable. R ¹⁰ in the organosiloxane unit (S ² ) is preferably a methyl group.

The ratio of the organosiloxane unit (S ¹ ) and the organosiloxane unit (S ² ) contained in the fluorinated silicone compound is based on the ratio of the organosiloxane unit (S
Against total amount of ¹⁾ and the organosiloxane units (S ^2), organosiloxane units (S ¹⁾ is 5 to 99 wt%
And particularly preferably 80 to 95% by weight.

The fluorine-containing silicone compound in the present invention may contain an organosiloxane unit (S ³ ) other than the organosiloxane unit (S ¹ ) and the organosiloxane unit (S ² ).

The organosiloxane unit (S ³ ) is preferably an organosiloxane unit in which the organo group bonded to the silicon atom forming the organosiloxane unit is only another monovalent organic group. Examples of the organosiloxane unit (S ³ ) include the following. (R ¹⁰ ) ₃ SiO _1/2 , (R ¹⁰ ) ₂ SiO _2/2 ,
(R ¹⁰⁾ SiO _3/2. Here, R ¹⁰ represents another monovalent organic group, and 2 in the same unit.
When there are more than one, they may be the same or different, and are preferably the same. As R ¹⁰ in the organosiloxane unit (S ³ ), an alkyl group or a polyfluoroalkyl group having a perfluoroalkyl group at a terminal is preferable.

When the fluorine-containing silicone compound contains an organosiloxane unit (S ³ ), 10 to 10
Preferably it is 90% by weight, especially 20-80% by weight
It is preferred that

The fluorinated silicone compound contains at least one of the organosiloxane units (S ¹ ) and at least one of the organosiloxane units (S ² ) and, if necessary, at least one of the organosiloxane units (S ³ ). , A linear or branched structure is preferable, and a linear structure is particularly preferable.
Preferably, the compound is represented by

[0045]

Embedded image

However, the symbols in the formula have the following meanings. ^RA : a fluorine-containing organic group represented by the formula 1. R ^B : a hydrolyzable group-containing organic group represented by Formula 2. R ^10: R ¹⁰ in the formula may be the same or different and each independently other monovalent organic group. p: an integer greater than or equal to one. q: an integer of 1 or more. r: an integer of 0 or more.

In the formula (3), the sequence of the respective organosiloxane units may be block-shaped or random. The same applies to other silicone compounds described below.

In the formula 3, p is preferably an integer of 1 to 1000, q is preferably an integer of 1 to 100, and r is 1 to 1
An integer of 000 is preferred. The ratio of each of p, q, and r [p: q: r (molar ratio)] is [1: (0.
5-3): (0.01-0.1)], and particularly preferably [1: (1-2) :( 0.02-0.05)]. Further, the molecular weight of the compound (Formula 3) is preferably such that the viscosity of the compound is 10 to 10000 cSt, and particularly preferably 20 to 1000 cSt.

Specific examples of the fluorine-containing silicone compound in the present invention include the following compounds. However,
P and q in the following formula each represent an integer of 1 or more;
r represents an integer of 0 or more. When two r are present in the same compound, they may be the same or different.

[0050]

Embedded image (CH ₃ ) ₃ SiO · {Si (CH ₃ ) [(CH ₂ ) ₂ (CF ₂ ) ₆ CH ₃ ] O} _p ·· {S
i (CH ₃ ) [(CH ₂ ) ₂ SiCl ₃ ] O} _q・ Si (CH ₃ ) ₃ , (CH ₃ ) ₃ SiO ・ {Si (C
H ₃ ) [(CH ₂ ) ₂ (CF ₂ ) ₆ CH ₃ ] O} _p・ ・ {Si (CH ₃ ) [(CH ₂ ) ₂ Si (OCH ₂ C
H ₃ ) ₃ ] O} _q • Si (CH ₃ ) ₃ , (CH ₃ ) ₃ SiO • {Si (CH ₃ ) [(CH ₂ ) ₂ (CF ₂ )
₆ CH ₃ ] O} _p ·· {Si (CH ₃ ) [(CH ₂ ) ₂ Si (NCO) ₃ ] O} _q · Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO ・ {Si (CH ₃ ) [(CH ₂ ) ₂ (CF ₂ ) ₆ CH ₂ CH ₃ ] O} _p・ ・ {Si (C
H ₃ ) [(CH ₂ ) ₂ SiCl ₃ ] O} _q • Si (CH ₃ ) ₃ , (CH ₃ ) ₃ SiO • {Si (CH ₃ )
[(CH ₂ ) ₃ (CF ₂ ) ₇ CF ₃ ] O} _r・ ・ {Si (CH ₃ ) [(CH ₂ ) ₂ (CF ₂ ) ₆ CH ₃ ] O} _p
・ {Si (CH ₃ ) [(CH ₂ ) ₂ SiCl ₃ ] O} _q・ Si (CH ₃ ) ₃ , (CH ₃ ) ₃ SiO ・ {Si
(CH ₃ ) [(CH ₂ ) ₄ (CF ₂ ) ₇ CF ₃ ] O} _r・ ・ {Si (CH ₃ ) [(CH ₂ ) ₂ (CF ₂ ) ₆ CH
₃ ] O} _p • {Si (CH ₃ ) [(CH ₂ ) ₂ SiCl ₃ ] O} _q • Si (CH ₃ ) ₃ , (CH ₃ ) ₃ Si
O ・ {Si (CH ₃ ) [(CH ₂ ) ₃ (CF ₂ ) ₇ CF ₃ ] O} _r・ {Si (CH ₃ ) [(CH ₂ ) ₂ (C
F ₂ ) ₆ CH ₃ ] O} _p ·· {Si (CH ₃ ) [(CH ₂ ) ₂ SiCl ₃ ] O} _q · {Si (CH ₃ ) ₂ O} _r
・ Si (CH ₃ ) ₃ , (CH ₃ ) ₃ SiO ・ {Si (CH ₃ ) [(CH ₂ ) ₃ NHCO (CF ₂ ) ₇ C
F ₃ ] O} _r・ ・ {Si (CH ₃ ) [(CH ₂ ) ₂ (CF ₂ ) ₆ CH ₃ ] O} _p・ {Si (CH ₃ ) [(C
H ₂ ) ₂ SiCl ₃ ] O} _q · Si (CH ₃ ) ₃ .

The surface treating agent of the present invention contains the above-mentioned fluorine-containing silicone compound and / or a hydrolysis product of the fluorine-containing silicone compound as essential components. The hydrolysis product of the fluorinated silicone compound refers to a compound formed by a reaction between the fluorinated silicone compound and water. Specifically, the monovalent hydrolyzable group (X ¹ ) in the organosiloxane unit (S ² ) reacts with water, and a part or all of the hydrolyzable group (X ¹ ) becomes an OH group. A compound formed by forming a -Si-O-Si- bond by dehydration condensation of two or more kinds of changed compounds or compounds changed to the OH group is given.

As a method for hydrolyzing the fluorine-containing silicone compound, a known method can be adopted. For example,
There are a method of simply mixing the fluorine-containing silicone compound and water, a method of mixing the fluorine-containing silicone compound and water in the presence of an acid, and a method of mixing the fluorine-containing silicone compound and water in the presence of an alkali. Among these, a method of mixing a fluorine-containing silicone compound and water in the presence of an acid is preferred from the viewpoint of the liquid life as a surface treatment agent, film properties, and the like.

When the method of mixing the fluorinated silicone compound and water in the presence of an acid is employed, the amount of water may be an equimolar amount of the monovalent hydrolyzable group (X ¹ ) present in the fluorinated silicone compound. The molar ratio is preferably up to 500 times. As the acid, nitric acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, acetic acid and the like are preferable. The acid amount is 0.005 to 10 with respect to water.
% By weight is preferred. If the amount of the acid is too large, there is a possibility that a problem occurs in safety at the time of work. Further, at the time of the hydrolysis, it is preferable that an organic solvent is present. The amount of the organic solvent is such that the concentration of the fluorine-containing silicone compound is 0.1 in the reaction system.
It is preferable that the amount is from 0.05 to 10% by weight.
It is preferable that the organic solvent is not removed after the hydrolysis but is contained in the surface treatment agent as it is.

Even when the fluorinated silicone compound is included in the surface treatment agent as it is, that is, without being hydrolyzed, the surface treatment agent may contain an organic solvent to reduce the concentration of the fluorinated silicone compound to 0. It is preferable that the content be 0.05 to 10% by weight.

Examples of the organic solvent that can be contained in the surface treating agent include alcohol solvents, cellosolve solvents, carbitol solvents, ketone solvents, ester solvents, and halogenated hydrocarbon solvents. These organic solvents may be used alone or in combination of two or more. It is preferable that the organic solvent is appropriately selected in consideration of the solvent resistance of the substrate to which the surface treatment agent is applied, the size of the substrate (evaporation rate of the solvent), economy, and the like.

In the surface treating agent of the present invention, other organosilicon compounds and additives may be added according to the purpose. The following examples are given as additives. Ultrafine particles of a metal oxide such as silica, alumina, zirconia, titania, or tin. Various resins. If coloring is required, dyes,
Pigment. Antioxidants, UV absorbers. When it is desired to impart conductivity, antistatic property, and the like, tin oxide, ITO (In ₂ O ₃ —SnO)
₂ ), zinc oxide and so on.

Further, as other organosilicon compounds which can be contained in the surface treating agent of the present invention, conventionally known organosilicon compounds having water repellency can be mentioned. Examples of the water-repellent organosilicon compound include a silicon compound represented by the following formula 4.

(R ³ ) _a Si (X ² ) _4-a ( ₄ ) where the symbols in the formula have the following meanings. R ³ is a monovalent organic group having 1 to 20 carbon atoms, and when two or more are present in the formula, they may be the same or different. a: 0, 1, 2 or 3. X ² : a reactive group.

R ^{3 in} Formula 4 is preferably the other monovalent organic group described above, a is preferably 0, 1, or 2, X ² is preferably a hydrolyzable group, and particularly preferably is the same as X ¹ described above. Are preferred. Specific examples of the silicon compound represented by the formula 4 include the following compounds.

[0060]

Embedded image CF ₃ (CH ₂ ) ₂ Si (X ² ) ₃ , CF ₃
(CF ₂ ) ₃ (CH ₂ ) ₂ Si (X ² ) ₃ , CF ₃ (C
F ₂ ) ₅ (CH ₂ ) ₂ Si (X ² ) ₃ , CF ₃ (CF
₂ ) ₇ (CH ₂ ) ₂ Si (X ² ) ₃ , CF ₃ (CF ₂ )
₃ (CH ₂ ) ₃ Si (X ² ) ₃ , CF ₃ (CF ₂ ) ₅
(CH ₂ ) ₃ Si (X ² ) ₃ , CF ₃ (CF ₂ ) ₇ (C
H ₂ ) ₃ Si (X ² ) ₃ , CF ₃ (CF ₂ ) ₇ (CH
^{_{2) 4 Si (X 2)}} 3, CF 3 (CF 2) 4 O (CF
₂ ) ₂ (CH ₂ ) ₂ Si (X ² ) ₃ , CF ₃ (CF ₂ )
₄ O (CF ₂ ) ₂ (CH ₂ ) ₃ Si (X ² ) ₃ , CF ₃
(CF ₂ ) ₇ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (X ² )
₃ , CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ Si (X
² ) ₃ , CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₃ Si
(X ² ) ₃ , CF ₃ (CF ₂ ) ₃ O [CF (CF ₃ ) C
_{F (CF 3) O] 2} --CF 2 CONH (CH 2) 3 S
i (X ² ) ₃ .

[0061]

Embedded image CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ Si (CH
₃ ) (X ² ) ₂ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si
(CH ₃ ) (X ² ) ₂ , CF ₃ (CH ₂ ) ₂ Si (CH
₃ ) (X ² ) ₂ , CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₃ Si
(CH ₃ ) (X ² ) ₂ , CF ₃ (CF ₂ ) ₅ (CH ₂ )
₃ Si (CH ₃ ) (X ² ) ₂ , CF ₃ (CF ₂ ) ₇ (C
H ₂ ) ₃ Si (CH ₃ ) (X ² ) ₂ , CF ₃ (CF ₂ )
₇ (CH ₂ ) ₄ Si (CH ₃ ) (X ² ) ₂ , CF ₃ (C
F ₂ ) ₄ (CF ₂ ) ₂ (CH ₂ ) ₂ Si (CH ₃ ) (X
^{_{2) 2, CF 3 (CF}} 2) 4 (CF 2) 2 (CH 2) 3
Si (CH ₃ ) (X ² ) ₂ , CF ₃ (CF ₂ ) ₄ (CH
₂ ) ₂ O (CH ₂ ) ₃ Si (CH ₃ ) (X ² ) ₂ , CF
₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ Si (CH ₃ )
(X ² ) ₂ , CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₃
Si (CH ₃ ) (X ² ) ₂ , CF ₃ (CF ₂ ) ₃ O [C
_{F (CF 3) CF (CF} 3) O] 2 --CF 2 CONH
(CH ₂ ) ₃ Si (CH ₃ ) (X ² ) ₂ , CH ₃ (CH
^{_{2) 7 Si (X 2)}} 3, Si (X 2) 4.

The surface treating agent of the present invention may contain dimethylpolysiloxane, silicone oil having a reactive group such as a hydrolyzable group, and the like. Other organosilicon compounds and additives that can be included in the surface treatment agent can be selected in consideration of the reactivity and compatibility with the fluorine-containing silicone compound or the hydrolysis product of the fluorine-containing silicone compound. The amount of the other organosilicon compound or additive is preferably 0.01 to 20% by weight in the surface treatment agent. If this amount is too large, there is a possibility that the water-dropping property and abrasion resistance of the film formed from the surface treatment agent may be reduced.

The surface treating agent of the present invention can impart excellent properties to the surface of the substrate by treating the surface of the substrate. As a method of treating the surface of the substrate, it can be usually carried out by coating the surface of the substrate and drying.

The substrate surface does not need to be subjected to any special pretreatment, but may be subjected to a pretreatment depending on the purpose. Pretreatment includes alkali treatment with an aqueous solution of sodium hydroxide or potassium hydroxide, acid treatment with an aqueous solution of hydrofluoric acid or hydrochloric acid, discharge treatment by plasma irradiation or corona discharge, polishing with various abrasives such as cerium oxide or alumina. Treatment or blast treatment.

As a method of applying the surface treatment agent, a method such as brushing, flow coating, spin coating, dip coating, spray coating, squeegee coating, or various printing coatings can be adopted. As the drying conditions after the application, drying in the air at room temperature is sufficient, and it is an economical advantage that such conditions can be adopted. Heat drying may be performed for the purpose of increasing the drying speed or increasing the durability of the effect.
In the case of drying by heating, the heating temperature may be selected in consideration of the heat resistance of the substrate, and is preferably about 60 to 400 ° C. The heating time is preferably about 1 to 60 minutes.

The thickness of the film formed by the treatment with the surface treating agent is not particularly limited, and is preferably as thin as possible.
The specific thickness is preferably from a monomolecular film to 2 μm, particularly preferably from a monomolecular film to 0.1 μm. The film thickness can be controlled by the component concentration of the surface treatment agent, application conditions, heating conditions, and the like.

Examples of the substrate which can be treated with the surface treating agent include a substrate composed of an inorganic material and a substrate composed of an organic material. Glass, plastics, metals, ceramics and the like are preferable. Further, examples of the substrate include a powder made of an inorganic material and a powder made of an organic material.

The base material may be a composite material or a laminate material in which an inorganic material and an organic material are combined. The surface of the substrate may be the substrate itself, a coating of a coated metal, or a surface treatment layer (eg, a sol-gel film, a sputtered film, a CV film).
D film, vapor-deposited film, etc.). The shape of the base material may be any shape according to the purpose, may be a flat shape, or may be a shape having a curvature over the entire surface or a part thereof.

Since the surface treating agent of the present invention exhibits its performance even at room temperature, it can be applied to the surface of a substrate which has already been used to impart water repellency and water droplet falling property to the surface of the substrate. Further, by changing the processing conditions, it is possible to impart functions such as oil repellency, lubricity, mold release properties, low reflection properties, and electrical insulation properties to the substrate surface. In addition, the fluorine-containing silicone compound contained in the surface treatment agent has excellent transparency,
There is also an advantage that the appearance of the substrate itself is not impaired. The coating formed on the surface of the substrate has excellent chemical resistance and abrasion resistance.

The use of the treated substrate obtained by treating the substrate surface with the surface treating agent of the present invention includes the following applications. Automobile windows, ship windows, aircraft windows, mirrors, car bodies, architectural windows, mirrors, optical lenses, spectacle lenses, glass containers, TV CRTs, LCD screens, hot plates, microwaves, and rice cookers・ Electric appliances, powder for cosmetics, textile products, textile products, leather products, wood products, stone products, paper products, printing press plates and nozzles, paint additives, sanitary ware, tableware, vases, aquariums, sashes , Agricultural sheets.

The substrate to be treated with the surface treating agent of the present invention is preferably a transparent substrate, and particularly preferably glass. Further, the treated glass obtained by treating the surface treating agent into glass is preferably used as an article for transportation equipment, an article for construction, or an article for exterior.

As the articles for transportation equipment, articles used for transportation equipment such as trains, buses, trucks, automobiles, ships, and aircrafts are preferable. Goods include outer panels, window glasses, mirrors, visibility (CCD) lenses, display device surfaces,
Instrument panel surface and the like. The transport equipment item may be an already used item.

As the article for transport equipment, an article made of treated glass or an article incorporating the treated glass is preferable. Examples of the article made of the treated glass include a window glass for an automobile. Examples of the article incorporating the treated glass include an automobile rearview mirror incorporating a mirror using the treated glass.

The following are specific examples of the article made of the treated glass or the article incorporating the treated glass. In trains, body, window glass, pantograph. In a car, bus or truck, body, windshield, side glass, rear glass, mirror, bumper. In ships and aircraft, body or window glass.

An article for transport equipment using the treated substrate of the present invention has an advantage that water droplets are repelled by the water repellency of the treated substrate surface. Further, when the transport equipment travels, the water drops move on the surface due to the wind pressure, so that it is possible to prevent the water drops from stopping on the surface of the processing base material. When the processing base material is a transparent field of view such as a window glass, there is an advantage that water droplets are scattered to secure a visual field, and that the safety of transport equipment is improved. Furthermore, since the surface of the treated base material obtained is particularly excellent in water droplet falling properties, there is also an advantage that the visibility can be ensured even when the transportation device runs at a low speed or stops. In addition, since the adhesion of water droplets can be prevented, dirt does not easily adhere, the number of cleaning operations can be reduced, and cleaning is easy. That is, the aesthetic protection of the substrate surface can be easily performed. Further, water droplets hardly freeze on the surface of the treated base material, and are easily thawed even if the water droplets freeze.

Examples of the building article or exterior article using the treated substrate of the present invention include an article attached to a building and an article used together with a building. Examples of these articles include articles made of only a processing base material such as a glass plate for a window, and articles incorporating a processing base material such as furniture with a glass mirror.

The following examples are given as the articles to be attached to the building. Window glass sheet, window glass, mirror, roof glass sheet, door glass sheet, door with glass sheet
Window or roofing materials consisting of glass sheets for partitions, glass sheets for greenhouses, and transparent plastic sheets. Ceramics, cement, or metals, including treated glass.

Articles used with buildings include:
The following examples are given. Mirrors, mirrored furniture, display shelves with windowpanes, showcases, furniture, furniture, etc.

Also in an architectural article or an exterior article using the treated substrate of the present invention, the surface has water repellency,
Water droplets are difficult to adhere, even if they adhere, the amount is small, and the adhered water droplets are easily removed. In addition, it does not freeze even in an environment where water droplets freeze, and thawing is easy even if it freezes. Further, since the attachment of water droplets can be prevented, the number of cleaning operations can be reduced, and cleaning is easy. That is, aesthetic protection can be easily performed. In addition, it does not impair the appearance of the surface treatment agent and the substrate itself, and has excellent chemical resistance and abrasion resistance.

[0080]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but the present invention is not limited thereto. Various evaluations in the examples were performed by the following methods. [Water repellency] The contact angle of water [unit: degree (°)] was measured.

[Water Dropping Property] After dropping 50 μl of water droplets onto a sample substrate held horizontally (at an angle of 0 °), the sample substrate was tilted, and the angle between the substrate and the horizontal plane when the water droplets began to roll [unit: Degree (°)] was read.

[Water Drop Residue] Water was sprayed on the entire surface of the sample substrate for 1 hour from a nozzle held at a distance of 20 cm to the sample substrate set upright, and then water droplets remaining on the surface of the sample substrate were visually observed. Evaluation was based on criteria. A: No water droplet remains on the sample substrate surface, B: A small amount of water droplet remains on the sample substrate surface, C: A considerable amount of water droplet remains on the sample substrate surface, D: Water droplets spread on the sample substrate surface.

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

Example 1 (Synthesis Example) A 200-cc four-necked flask equipped with a stirrer and a thermometer was sufficiently purged with nitrogen.
An oily hydrosilicone compound represented by the following formula 5 [where the hydrosilicone compound (formula 5) is a random polymer. ) Was placed in an amount of 100 g. After the temperature was raised to _{90 ℃, CF 3 (CF 2} ) 7 CH 2 CH = CH 2 7
A solution obtained by dissolving chloroplatinic acid as platinum at 2 ppm in 5.4 g was dropped from a dropping funnel. With the progress of the reaction, an increase in the internal temperature of about 5 ° C. was observed.

Next, CH ₃ (CF ₂ ) ₇ CH ₂ CH = C
When 66.6 g of H ₂ was dropped from the dropping funnel, an increase in the internal temperature of about 5 ° C. was observed. Next, CH ₂ = CHS
13.2 g of iCl ₃ was added dropwise from a dropping funnel. HS
After confirming the disappearance of i (2150 cm ^-1 ) by IR spectrum, the reaction was stopped after 4 hours. After adding 0.5 g of activated carbon and stirring at room temperature for 1 hour, the mixture was filtered to obtain a clear oil.
The obtained product was analyzed by NMR and IR.
[Where the compound (Formula 6) is a random polymer. ] Was confirmed.

[0086]

Embedded image (CH ₃ ) ₃ SiO · [SiH (CH ₃ ) O] ₁₅ · [Si (CH ₃ ) ₂ O] ₃₅ · Si (CH ₃ ) ₃ ··· Formula 5 (CH ₃ ) ₃ SiO · { Si [(CH ₂ ) ₃ (CF ₂ ) ₇ CF ₃ ] (CH ₃ ) O} ₆・ {Si [(CH ₂ ) ₃ (CF ₂ ) ₇ CH ₃ ] (CH ₃ ) O} ₆・ ・ {Si [CH ₂ CH ₂ SiCl ₃ ] (CH ₃ ) O} ₃ · [Si (CH ₃ ) ₂ O] ₃₅ · Si (CH ₃ ) ₃ ··· Formula 6

Example 2 (Example) 97.00 g of butyl acetate and 3.00 g of the compound (formula 6) obtained in Example 1 were placed in a glass reaction vessel equipped with a thermometer and a stirrer, and were placed at 25 ° C. The mixture was stirred day and night, and the product was designated as surface treatment agent 1. 10cm × 10cm × 3.5m thick, which has been polished and cleaned in advance
1 cc of the surface treating agent 1 was dropped on the surface of soda lime glass having a thickness of m, and the resulting solution was spread with a tissue paper in the manner of car waxing, and dried at 23 ° C. and 45% humidity to obtain a sample substrate 1. Table 1 shows the evaluation results of the sample substrate 1 and the evaluation results of the durability of the sample substrate 1.

Example 3 (Comparative Example) 97.00 g of butyl acetate was placed in a glass reaction vessel equipped with a thermometer and a stirrer.
3.00 g of F ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCl ₃
Was added and stirred at 25 ° C. for one day and night, and the product was used as a surface treatment agent 2. The surface treating agent 2 was treated in the same manner as in Example 2 to obtain a sample substrate 2. Table 1 shows the evaluation results of the sample substrate 2.

Example 4 (Comparative Example) 97.00 g of butyl acetate was placed in a glass reaction vessel equipped with a thermometer and a stirrer.
25. Charge 3.00 g of CH ₃ (CH ₂ ) ₇ SiCl ₃
The mixture was stirred at ℃ for one day and night, and the product was designated as surface treatment agent 3. The surface treating agent 3 was treated in the same manner as in Example 2 to obtain a sample substrate 3.
Table 1 shows the evaluation results of the sample substrate 3.

[0090]

[Table 1]

Example 5 (Example) The sample substrate 1 obtained in Example 2 was immersed in the chemicals shown in Table 2 for 24 hours, and the water repellency, water droplet falling property and water droplet remaining property after immersion were evaluated. Table 2 shows the results.

Example 6 (Example) The sample substrate 1 obtained in Example 2 was reciprocated 1500 times with a flannel cloth under a load of 1 kg. Table 2 shows the results of evaluation of the water repellency, water droplet falling properties, and water droplet remaining properties after the abrasion test.

[0093]

[Table 2]

Example 7 (Example) The sample substrate 1 obtained in Example 2 was heated at 200 ° C. for 30 minutes. Table 3 shows the evaluation results of the water repellency, water droplet falling property, and water droplet remaining property of the sample substrate 1 after heating.

Example 8 (Example) 99.00 g of butyl acetate was placed in a glass reaction vessel equipped with a thermometer and a stirrer.
1.00 g of Si (NCO) ₄ was added thereto, and stirring was continued at 25 ° C. for 24 hours, and the obtained product was used as pretreatment liquid 1. Pretreatment liquid 1 is applied to the surface of soda lime glass of size 10 cm × 10 cm × 3.5 mm, which has been previously polished and cleaned.
Then, cc was dripped and spread with a tissue paper in the manner of car waxing to obtain a pre-treated substrate 1. The pre-processed substrate 1 was left for 1 hour in an environment of 25 ° C. and 50% humidity. Furthermore, the same processing as in Example 2 was performed using the pre-processed substrate 1 in place of the soda lime glass in Example 2, and the sample substrate 4
It was created. Table 3 shows the evaluation results of the sample substrate 4.

Example 9 (Example) 78.8 of ethyl alcohol was placed in a glass reaction vessel equipped with a thermometer and a stirrer.
0 g and 10.40 g of Si (OCH ₂ CH ₃ ) ₄ were 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 dropping, 25 ° C
The stirring was continued for one day, and the obtained product was used as pretreatment liquid 2. The same treatment was performed using the pretreatment liquid 2 in place of the pretreatment liquid 1 in Example 8 to obtain a pretreatment substrate 2. Example 2
In the same manner as in Example 2 except that the pre-processed substrate 2 was used in place of the soda lime glass in Example 2, a sample substrate 5 was prepared. Table 3 shows the evaluation results of the sample substrate 5.

[0097]

[Table 3]

Example 10 (Example) After treating the surface of the front laminated glass for a vehicle with the surface treating agent 1 in the same manner as in Example 2 in place of the soda lime glass, the laminated glass was mounted on a vehicle. 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 dirt, dust, or water droplets were formed due to the adhesion of water droplets. In rare cases, these were easily removed by gently wiping with a tissue paper. Further, in rainy weather, water droplets were repelled on the surface, and the water droplets moved promptly due to interaction with wind pressure caused by traveling, so that the field of view was secured without using a wiper. Also, even when the vehicle is stopped, the water droplets fall off well,
Water droplets fell due to their own weight, and it was easy to secure a visual field without using a wiper. Further, in an environment where water drops adhering to the untreated front laminated glass freeze (0 ° C.
-5 ° C.), no freezing on the windshield was observed.

Example 11 (Example) When the front laminated glass in Example 10 was changed to a side glass, a rear glass, and a side mirror, the same effect as in Example 10 was confirmed.

Example 12 (Example) The surface of a windshield for an automobile, which has been used for three years, has been polished with an aqueous cerium oxide solution, washed with water and dried to obtain a washed laminated glass. The same process as in Example 2 was performed using the front laminated glass as a substrate instead of the soda lime glass in Example 2. A running test similar to that of Example 10 was performed using this automobile, and the same effect was confirmed.

[0102]

The surface treating agent of the present invention imparts the following excellent properties to the substrate surface, and excellent effects are recognized. (1) It is excellent in water repellency and water-dropping property, can eliminate the adverse effect of water, and can save labor for cleaning. (2) It has excellent water repellency and long lasting effect, and can be used semi-permanently. (3) It is excellent in chemical resistance, and for example, the treated substrate can be used in the see-through portion of a ship that is directly in contact with seawater.

(4) It is economically advantageous because the effect is exhibited without special pretreatment of the substrate. (5) In order to exhibit the effect by application and drying at room temperature,
It can also be used as a repair agent. Further, it can be applied to various uses. (6) Since the film formed from the surface treatment agent is transparent, the treated substrate can be used for a transparent field of view of a vehicle, a ship, an aircraft, a building or the like.

Claims (8)

[Claims] ( ¹ ) An organosiloxane unit (S ¹ ) and a fluorine-containing silicone compound having the following organosiloxane unit (S ² ) as essential components and / or a hydrolysis product of the fluorine-containing silicone compound. Surface treatment agent. Organosiloxane unit (S ¹ ): an organosiloxane unit in which a fluorine-containing group represented by the following formula 1 is directly bonded to a silicon atom forming the organosiloxane unit. Organosiloxane unit (S ² ): An organosiloxane unit in which a hydrolyzable group-containing organic group represented by the following formula 2 is directly bonded to a silicon atom forming the organosiloxane unit. -B ¹ -A ¹ -R ¹ Formula 1- (CH ₂ ) _a Si (R ² ) _3-b (X ¹ ) _b Formula 2 where the symbols in the formula have the following meanings. R ¹ : an alkyl group having 1 to 30 carbon atoms. A ¹ : a fluorine-containing divalent organic group having 1 to 30 carbon atoms. B ¹ : a fluorine-free divalent organic group having 2 to 30 carbon atoms. R ² : a monovalent organic group. X ¹ : a monovalent hydrolyzable group. a: an integer of 1 or more. b: 1, 2 or 3. 2. The surface treating agent according to claim 1, wherein R ¹ is a methyl group or an ethyl group. 3. A ¹ is-(CF ₂ ) _n- (where n is 1
Integer of ~ 30. The surface treating agent according to claim 1 or 2, which is a group consisting of: Wherein B ¹ is - (CH _{2) m} - (where m is 1
An integer of 16. The surface treating agent according to claim 1, 2, or 3, which is a group consisting of: 5. The method according to claim 1, wherein X ¹ is an alkoxy group, a halogen atom, an isocyanate group, or a carbamoyl group.
The surface treatment agent according to 2, 3, or 4. 6. The surface treating agent according to claim 1, wherein the fluorine-containing silicone compound is represented by the following formula 3. However, the sequence of the organosiloxane units in Formula 3 may be block or random. Embedded image However, the symbols in the formula have the following meanings. ^RA : a fluorine-containing organic group represented by the formula 1. R ^B : a hydrolyzable group-containing organic group represented by Formula 2. R ^10: R ¹⁰ in the formula may be the same or different and each independently, a monovalent organic group other than the formula 1 and formula 2. p: an integer greater than or equal to one. q: an integer of 1 or more. r: an integer of 0 or more. 7. A treated substrate obtained by applying the surface treating agent according to claim 1, 2, 3, 4, 5, or 6 to a substrate surface and drying. 8. The treated substrate according to claim 7, wherein the substrate surface is a glass surface.