JP2022079889A - Fluorine-containing silane compound, method for producing the same and surface-modifying composition comprising the same - Google Patents

Abstract

To provide a surface modifier that demonstrates statically and kinetically excellent, water- and oil-repellency in surface modification, can easily dissolve in general organic solvents, and has its molecular structure composed of a perfluoroalkyl group having carbon atoms of 6 or less.SOLUTION: A fluorine-containing silane compound is produced that has a plurality of perfluoroalkyl groups and has a binding silyl group at its end. A surface-modifying composition including the fluorine-containing silane compound is used to modify a substrate surface. The fluorine-containing silane compound is produced by, for example, the following formula.SELECTED DRAWING: None

Description

The present invention relates to a novel fluorine-containing silane compound useful as a surface modifier, a method for producing the same, and a surface modification composition containing the same.

Fluoroalkyl-based materials exhibit properties such as heat resistance, chemical resistance, water and oil repellency, low friction, and low refractive index, and are industrially applied as functional materials utilizing these properties. In particular, in surface modification functional products that impart water repellency and oil repellency to a solid surface, a perfluoroalkyl group and a covalent bond group to the solid surface are used in order to strongly introduce a perfluoroalkyl group onto the solid surface. A surface modifier having both of these is used. The effect of the surface modification function of such an agent becomes more remarkable as the perfluoroalkyl chain length in the surface modifier molecule is longer, but the surface modifier having a perfluoroalkyl group having 8 or more carbon atoms Has problems with toxicity due to residue and accumulation in the environment and in vivo, and its industrial use is strongly restricted. Therefore, studies have been conducted to develop good functions for surface modification by using a compound having a perfluoroalkyl group having 6 or less carbon atoms in the molecule.

As a method of improving water repellency and oil repellency by using a material having a perfluoroalkyl group having 6 or less carbon atoms in the molecule, a part of the fluorine atom of the long-chain perfluoroalkyl group is replaced with a hydrogen atom to accumulate in the living body. A method is known in which a plurality of components of a perfluoroalkyl group unit having 6 or less carbon atoms, which are said to have low properties, are used as a modifier (see, for example, Patent Document 1 and Patent Document 2).
In Patent Document 3, a reaction between a diene compound having a perfluoroalkyl group and a perfluoroalkylene group in the molecule and a hydrosilane compound provides good characteristics while being composed of a plurality of perfluoroalkyl group constituents having 6 or less carbon atoms. The synthesis of having a fluoroalkyl substituted silane compound is disclosed.

Since liquid repellency strongly depends on the presence density of fluoroalkyl groups on the solid surface, the use of surface modifiers with multiple perfluoroalkyl groups in the molecule is a surface with a single perfluoroalkyl group in the molecule. It is highly possible that a highly liquid-repellent surface treatment can be achieved at a higher speed than that of a modifier.

In Patent Document 4, a silane-based surface treatment agent having a plurality of perfluoroalkyl groups is produced using tetravinylsilane as a raw material. However, expensive tetravinylsilane is used as a raw material, and the linker structure is ethylene due to the convenience of the raw material. It was limited to the base.

In addition to the static liquid repellency that can be evaluated by the contact angle of the droplets with the substrate, the slipperiness of the droplets adhering to the substrate surface, that is, the dynamic liquid repellency, is also the surface modification of the solid. Important above. This correlates with the self-cleaning ability of droplets and solid powders on the solid surface and the ease with which contamination can be removed, and can be evaluated by the critical angle of water droplets. However, in the case of a solid surface surface-modified with a perfluoroalkyl group, it may be a problem that water droplets are difficult to slide off. This is considered to be the electrostatic interaction between the fluorine atom and the hydrogen of the water molecule. Therefore, there is a demand for a solid surface modifier that easily slips off, but it imparts a surface condition that is soluble in inexpensive general-purpose solvents, has high durability such as wear resistance, and has excellent dynamic liquid repellency. Possible perfluoroalkyl-based surface modifiers are scarce in current materials.

Patent No. 5146455 Japanese Unexamined Patent Publication No. 2014-040373 International Publication No. 2017/119371 International Publication No. 2007/135315

The subject of the present invention is a novel inclusion in which a liquid-repellent partial molecular structure is composed of a perfluoroalkyl group having up to 6 carbon atoms, and a high static and dynamic liquid-repellent effect superior to the conventional one can be imparted to a solid surface. It is an object of the present invention to provide a fluorosilane compound, a method for producing the same, and a surface modification composition containing the same.

As a result of diligent studies to solve the above problems, the inventors have found that they have a plurality of perfluoroalkyl chains having 6 or less carbon atoms and have a functional silyl group at the end that can be chemically bonded to the solid surface. By producing a fluorine-containing silane compound in which a group is bonded with a linker and modifying the solid surface using a surface modification composition containing the compound, high water repellency and oil repellency can be imparted to the solid surface. We found that there was something, and came to complete the present invention.

That is, the present invention has the following configuration.
[1]
General formula (1)

[In the formula, n is an integer from 2 to 6. m is 2 or 3. R ¹ represents an alkyl group having 1 to 4 carbon atoms. A is an alkylene group having 2 to 6 carbon atoms, or the general formula (2).

(In the formula, R ³ and R ⁴ each independently represent an alkyl group having 1 to 4 carbon atoms which may be substituted with a fluorine atom. P is an integer of 1 to 9.)
Represents the siroxanilen group represented by. X ¹ represents a halogen atom, an alkoxy group having 1 to 3 carbon atoms or a dialkylamino group having 2 to 6 carbon atoms, and a plurality of X ^1s may be the same or different from each other. R ² represents an alkyl group having 1 to 4 carbon atoms. r is 0 or 1. However, when n is 6 and m is 3, A cannot be a 1,2-ethylene group. ]
Fluorine-containing silane compound indicated by.
[2]
The fluorine-containing silane compound according to [1], wherein n is 4 or 6 and m is 2.
[3]
The fluorine-containing silane compound according to [1] or [2], wherein A is a 1,2-ethylene group, a 1,3-propylene group or a siloxanilen group in which R3 and ^{R4 are} methyl groups.
[4]
General formula (3)

(In the formula, n is an integer of 2 to 6. m is 2 or 3. R ¹ represents an alkyl group having 1 to 4 carbon atoms. Q is an integer of 2 to 6.)
The olefin compound represented by the above and the general formula (4).

(In the formula, X ¹ represents a halogen atom, an alkoxy group having 1 to 3 carbon atoms or a dialkylamino group having 2 to 6 carbon atoms, and a plurality of X ^1s may be the same or different from each other. R ² may have 1 carbon atom. Represents an alkyl group from 4 to 4. r is 0 or 1.)
The general formula (1a) is characterized in that the hydrosilane compound represented by the above is reacted in the presence of a hydrosilylation catalyst.

(In the formula, n, m, R ¹ , q, X ¹ , R ² and r are synonymous with the above. However, when n is 6 and m is 3, A becomes a 1,2-ethylene group. I don't get it.)
A method for producing a fluorine-containing silane compound shown by.
[5]
General formula (6)

(In the formula, R ³ and R ⁴ each independently represent an alkyl group having 1 to 4 carbon atoms which may be substituted with a fluorine atom. P is an integer of 1 to 9.)
The siloxane diol compound represented by the above formula (5)

(In the formula, n is an integer of 2 to 6. m is 2 or 3. R ¹ represents an alkyl group having 1 to 4 carbon atoms. X ² represents a halogen atom.)
Fluorine-containing halogenated silane compound represented by and the general formula (8).

(In the formula, X ¹ represents a halogen atom, an alkoxy group having 1 to 3 carbon atoms or a dialkylamino group having 2 to 6 carbon atoms, and a plurality of X ^1s may be the same or different from each other. R ² may have 1 carbon atom. Represents an alkyl group from 4 to 4. r is 0 or 1. X ³ represents a halogen atom.)
The general formula (1b) is characterized by reacting with the halogenated silane compound represented by.

(In the formula, n, m, R ¹ , X ¹ , R ³ , R ⁴ , p, R ² and r are synonymous with the above.)
A method for producing a fluorine-containing silane compound shown by.
[6]
General formula (1c)

[In the formula, n is an integer from 2 to 6. m is 2 or 3. R ¹ represents an alkyl group having 1 to 4 carbon atoms. A is an alkylene group having 2 to 6 carbon atoms, or the general formula (2).

(In the formula, R ³ and R ⁴ each independently represent an alkyl group having 1 to 4 carbon atoms which may be substituted with a fluorine atom. P is an integer of 1 to 9.)
Represents the siroxanilen group represented by. ^X4 represents a halogen atom. R ² represents an alkyl group having 1 to 4 carbon atoms. r is 0 or 1. ]
The general formula (1d), which comprises reacting the fluorine-containing silane compound represented by

(In the formula, n, m, R ¹ , A, R ² and r are synonymous with the above. X ⁵ represents an alkoxy group having 1 to 4 carbon atoms or a dialkylamino group having 2 to 6 carbon atoms). The method for producing a fluorine-containing silane compound shown.
[7]
The method for producing a fluorine-containing silane compound according to [6], wherein the alkoxylating agent is an alcohol compound.
[8]
A surface modification composition comprising the fluorine-containing silane compound according to any one of [1] to [3] and an organic solvent.
[9]
The surface modification composition according to [8], which comprises the fluorine-containing silane compound according to any one of [1] to [3], an organic solvent and a polymerization promoting catalyst.
[10]
The surface modification composition according to [9], wherein the polymerization promoting catalyst is an acid catalyst.
[11]
A method for surface modification of a glass substrate, a metal oxide substrate or a metal substrate, which comprises applying the surface modification composition according to any one of [8], [9] or [10].

By using the fluorine-containing silane compound (1) of the present invention or a surface modification composition containing the same as a surface modifier, extremely high liquid repellency can be imparted to the surface of the substrate. In particular, it is suitable for water-repellent, oil-repellent and antifouling surface modification of inorganic glass substrates.

Hereinafter, the present invention will be described in detail.
First, the general formulas (1), (1a), (1b), (1c), (1d), (2), (3), (4), (5), (6), (7) and (8). ) R ¹ , R ² , R ³ , R ⁴ , A, X ¹ , X ² , X ³ , X ⁴ and X ⁵ in the equation will be described.
R ¹ is an alkyl group having 1 to 4 carbon atoms. The alkyl group may be linear, branched or cyclic, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group or a sec-butyl group. , Tert-Butyl group, cyclobutyl group and the like can be exemplified. Of these, a methyl group is preferable from the viewpoint of economic efficiency and surface modification ability.
^R2 is an alkyl group having 1 to 4 carbon atoms. The alkyl group may be linear, branched or cyclic, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group or a sec-butyl group. , Tert-Butyl group, cyclobutyl group and the like can be exemplified. Of these, a methyl group is preferable from the viewpoint of economic efficiency and surface modification ability.
R ³ is an alkyl group having 1 to 4 carbon atoms which may be substituted with a fluorine atom. The alkyl group may be linear, branched or cyclic, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group or a sec-butyl group. , Turt-butyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 1-trifluoromethyl-2,2,2-trifluoroethyl group, Examples thereof include 3,3,4,4,4-pentafluorobutyl groups. Of these, a methyl group or a 3,3,3-trifluoropropyl group is preferable, and a methyl group is more preferable, from the viewpoints of economy, ease of purification, and surface modification ability.
^R4 is an alkyl group having 1 to 4 carbon atoms which may be substituted with a fluorine atom. The alkyl group may be linear, branched or cyclic, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group or a sec-butyl group. , Turt-butyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 1-trifluoromethyl-2,2,2-trifluoroethyl group, Examples thereof include 3,3,4,4,4-pentafluorobutyl groups. Of these, a methyl group or a 3,3,3-trifluoropropyl group is preferable, and a methyl group is more preferable, from the viewpoints of economy, ease of purification, and surface modification ability.
X ¹ is a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or a dialkylamino group having 2 to 6 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a chlorine atom or a bromine atom is preferable, and a chlorine atom is more preferable, from the viewpoints of economy, surface modification ability and storage stability. Moreover, as the alkoxy group, a methoxy group, an ethoxy group, a 1-propyloxy group or a 2-propyloxy group can be exemplified. Of these, a methoxy group or an ethoxy group is preferable, and a methoxy group is more preferable, from the viewpoint of economic efficiency and surface modification ability. Examples of the dialkylamino group include a dimethylamino group, a diethylamino group, an ethylmethylamino group, a dipropylamino group, a diisopropylamino group, a 1-pyrrolidino group, a 1-piperidino group and the like.
The group represented by X ² is a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a chlorine atom or a bromine atom is preferable, and a bromine atom is more preferable, from the viewpoints of economy, surface modification ability and storage stability.
The group represented by X ³ is a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a chlorine atom or a bromine atom is preferable, and a chlorine atom is more preferable, from the viewpoints of economy, surface modification ability and storage stability.
The group represented by ^X4 is a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a chlorine atom or a bromine atom is preferable, and a chlorine atom is more preferable, from the viewpoints of economy, surface modification ability and storage stability.
The group represented by ^X5 is an alkoxy group having 1 to 4 carbon atoms and a dialkylamino group having 2 to 6 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a 1-propyloxy group and a 2-propyloxy group. Of these, a methoxy group or an ethoxy group is preferable, and a methoxy group is more preferable, from the viewpoint of economic efficiency and surface modification ability. Examples of the dialkylamino group include a dimethylamino group, a diethylamino group, an ethylmethylamino group, a dipropylamino group, a diisopropylamino group, a 1-pyrrolidino group, a 1-piperidino group and the like.
The group represented by A is a divalent alkylene group having 1 to 6 carbon atoms or the general formula (2).

(In the formula, R ³ and R ⁴ represent alkyl groups having 1 to 4 carbon atoms, which may be independently substituted with fluorine atoms, respectively. P is an integer of 1 to 9.)
It is a divalent siroxanilene group represented by.
Examples of the alkylene group include a methylene group, a 1,2-ethylene group, a 1,3-propylene group, an isopropylene group, a 1,4-butylene group, an isobutylene group, a 1,5-pentylene group, a 1-methyl-1, 4-butylene group, 2-methyl-1,4-butylene group, 3-methyl-1,4-butylene group, 1,2-dimethyl-1,3-propylene group, 2,2-dimethyl-1,3- Propropylene group, 1-ethyl-1,3-propylene group, 1,6-hexylene group, 1-methyl-1,5-pentylene group, 2-methyl-1,5-pentylene group, 3-methyl-1,5 -Pentylene group, 4-methyl-1,5-pentylene group, 1,2-dimethyl-1,4-butylene group, 1,3-dimethyl-1,4-butylene group, 2,2-dimethyl-1,4 -Butylene group, 2,3-dimethyl-1,4-butylene group, 3,3-dimethyl-1,4-butylene group, 1-ethyl-1,4-butylene group, 2-ethyl-1,4-butylene The group etc. can be mentioned. Of these, 1,3-propylene groups are preferable from the viewpoint of liquid repellency.
The following partial structure can be exemplified as the siroxanilen group.

Of these siroxanilen groups (2), (2-7), (2-12), (2-13), or (2-18) is preferable, and (2) is preferable from the viewpoint of economic efficiency and surface modification ability. -13) or (2-18) is more preferable.

Next, the fluorine-containing silane compound (1) of the present invention will be described. The fluorine-containing silane compound of the present invention has the following general formula (1).

Indicated by. Here, the carbon number n of the perfluoroalkyl group in the general formula (1) is an integer from 1 to 6, and the number m of the perfluoroalkyl groups is 2 or 3. The C _n F _{2n + 1} group is a perfluoroalkyl group. The structure may have a branched structure, but since it is considered that a linear perfluoroalkyl group easily has a self-association structure and easily forms a monomolecular layer on the surface of the substrate, it is linear. Perfluoroalkyl groups are preferred. As for n, the surface modification ability is higher as the chain length of the perfluoroalkyl group is larger. Therefore, n is preferably 4 or 6, and more preferably 6. From the viewpoint of liquid repellency, m is preferably 2 or 3, and more preferably 2. r is the number of alkyl groups substituted with the terminally bonded silyl group, which is 0 or 1. 0 is preferable from the viewpoint of surface modification ability.
Examples of the fluorine-containing silane compound (1) of the present invention include the following compounds. In addition, in this specification, Me, Et, Pr and ⁱ Pr represent a methyl group, an ethyl group, a propyl group and an isopropyl group, respectively.

Of these, (1-2-1), (1-2-3), (1-4-1), (1-4-3) from the viewpoint of economy, surface liquid repellency and storage stability. , (1-9-1), (1-9-3), (1-15-1), (1-15-3) or (1-25-3), preferably (1-4-1). , (1-4-3), (1-9-1), (1-9-3) or (1-25-3) are more preferred, (1-4-3), (1-9-3). ) Or (1-25-3) is particularly preferable.

Next, a method for producing the fluorine-containing silane compound (1) of the present invention will be described. The method for producing the fluorine-containing silane compound (1) of the present invention differs depending on the structure of A as a linker moiety and the structure of the terminal-binding group, and can be produced by three types of production methods represented by the following formulas. Hereinafter, in the present specification, these are referred to as the production method 1 of the present invention, the production method 2 of the present invention, and the production method 3 of the present invention, respectively.

(In the formula, n is an integer of 2 to 6. m is 2 or 3. R ¹ represents an alkyl group having 1 to 4 carbon atoms. Q is an integer of 2 to 6. X ¹ is an integer of 2 to 6. Represents a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or a dialkylamino group having 2 to 6 carbon atoms, and a plurality of X ^1s may be the same or different from each other. R ² is an alkyl group having 1 to 4 carbon atoms. R is 0 or 1. p is an integer from 1 to 9. R ³ and R ⁴ each represent an alkyl group having 1 to 4 carbon atoms which may be independently substituted with a fluorine atom. X ² , X ³ and X ⁴ represent a halogen atom. X ⁵ represents an alkoxy group having 1 to 4 carbon atoms, a dialkylamino group having 2 to 6 carbon atoms, or a halogen atom).

First, the manufacturing method 1 of the present invention will be described. The production method 1 of the present invention is a fluorine-containing silane compound (1a) in which the linker moiety A is an alkylene group.

(In the equation, n is an integer of 2 to 6. m is 2 or 3. R ¹ represents an alkyl group having 1 to 4 carbon atoms. Q is an integer of 2 to 6. X ¹ is an integer of 2 to 6. Represents a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or a dialkylamino group having 2 to 6 carbon atoms, and a plurality of X ^1s may be the same or different from each other. R ² is an alkyl group having 1 to 4 carbon atoms. Represents r is 0 or 1.)
The general formula (3)

(In the formula, n, m, ^R1 and q are synonymous with the above.)
The olefin compound (3) represented by the above and the general formula (4).

(In the formula, X ¹ , R ² and r are synonymous with the above.)
It is characterized by reacting with the hydrosilane compound (4) represented by (1) in the presence of a hydrosilylation catalyst.
Examples of the olefin compound (3) that can be used include the following.

Of these, (3-7), (3-12), (3-22) or (3-27) are preferable, and (3-12) or (3-12) or (3-27) are preferable from the viewpoint of production yield and easy purification. 27) is more preferable.
These olefin compounds (3) can be synthesized with reference to methods known in the literature (for example, Tetrahedron Letters, Vol. 47, pp. 239-243, 2006).
Examples of the hydrosilane compound (4) that can be used in the production method 1 of the present invention include the following.

Of these, (4-1) or (4-2) is preferable, and (4-1) is more preferable, from the viewpoint of cost and production yield. These may be synthesized and used according to a known production method, or commercially available products may be used.
The production method 1 of the present invention is characterized in that it is carried out in the presence of a hydrosilylation catalyst. Examples of the hydrosilylation catalyst include radical-generating hydrosilylation catalysts such as azobis (isobutyronitrile) (AIBN), di-tert-butyl peroxide (DTBP), tert-butylhydroperoxide, and benzoyl peroxide (BPO); Hydrosilylation catalysts of Lewis acid such as aluminum chloride, gallium chloride, indium chloride, boron trifluoride, and tris (pentafluorophenyl) boron; metallic palladium, metallic platinum, palladium activated charcoal, platinum activated charcoal, platinum chloride acid, palladium chloride, palladium acetate. , Tris (triphenylphosphine) rhodium chloride, (1,3-divinyltetramethyldisiloxane) platinum complex, 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane) platinum An example is a platinum group transition metal catalyst such as a complex. Platinum group transition metal catalysts such as platinum chloride are preferred because of their high economic efficiency, production yield and catalytic activity.
In the production method 1 of the present invention, there is no limitation on the amount of the hydrosilylation catalyst used, and it can be carried out using a general molar equivalent when a person skilled in the art carries out the hydrosilylation reaction. As a specific example, the molar equivalent of the hydrosilylation catalyst can be appropriately selected from the range of 0.00001 molar equivalent to 0.5 molar equivalent with respect to the molar equivalent of the olefin compound (3). From the viewpoint of production yield and economic efficiency, the molar equivalent is preferably selected from the range of 0.0001 molar equivalent to 0.2 molar equivalent, and is within the range of 0.001 molar equivalent to 0.1 molar equivalent. It is more preferable that the molar equivalent is appropriately selected from the above.
The production method 1 of the present invention may be carried out under solvent-free conditions, but may be carried out in an organic solvent if necessary. The organic solvent that can be used is not particularly limited as long as it does not inhibit the reaction, but is limited to hydrocarbon solvents such as benzene, toluene and xylene, benzotrifluoride (α, α, α-trifluorotoluene) and 1,3-bis. Fluoroalkyl-substituted aromatic hydrocarbon solvents such as (trifluoromethyl) benzene; fluoroaromatic hydrocarbon solvents such as pentafluorobenzene and hexafluorobenzene; 2H, 3H-decafluoropentane (Bertrel), tetradecafluorohexane, octa Examples thereof include fluoroaliphatic hydrocarbon solvents such as decafluorooctane, dodecafluorocyclohexane, 1,3-bis (trifluoromethyl) decafluorocyclohexane, and perfluorokerocene. Toluene, xylene, 2H, 3H-decafluoropentane, benzotrifluoride, 1,3-bis (trifluoromethyl) benzene or hexafluorobenzene are preferable in terms of economy and yield. As these organic solvents, one kind may be used alone, or a plurality of organic solvents may be mixed and used at an arbitrary ratio. The amount of the organic solvent used is preferably from 1 to 1000% by weight and preferably from 5 to 200% by weight based on the weight of the olefin compound (3) from the viewpoint of yield. It is more preferably the weight% that is appropriately selected.
The equivalent ratio of the olefin compound (3) to the hydrosilane compound (4) in carrying out the production method 1 of the present invention is not particularly limited, but for example, the hydrosilane compound (4) is used with respect to 1 molar equivalent of the olefin compound (3). Equivalents appropriately selected from the range of 0.8 to 100 molar equivalents are preferable in terms of good yield.
The mixing order of the olefin compound (3), the hydrosilane compound (4) and the hydrosilylation catalyst in carrying out the production method 1 of the present invention is not particularly limited, but for example, the olefin compound (3) is mixed with the hydrosilylation catalyst. , The method of adding the hydrosilane compound (4) here is preferable from the viewpoint of safety.
When the production method 1 of the present invention is carried out, it is preferably carried out in an inert gas atmosphere in terms of good yield. Specific examples of the inert gas include nitrogen, helium, neon, and argon. Nitrogen or argon is preferable because of its low cost.
In the production method 1 of the present invention, the reaction temperature and the reaction time are not limited, and general conditions for a person skilled in the art to carry out a hydrosilylation reaction of an olefin can be used. As a specific example, the yield of the fluorine-containing silane compound (1a) is obtained by selecting a reaction time appropriately selected from the range of 1 minute to 120 hours at a reaction temperature appropriately selected from the temperature range of −10 ° C. to 300 ° C. Can be manufactured well.
In the production method 1 of the present invention, the fluorine-containing silane compound (1a) can be suitably produced by appropriately selecting n, m, R ¹ , R ² , A and X ¹ . Examples of the fluorine-containing silane compound (1a) that can be produced by the production method 1 of the present invention include the following compounds.

Of these, (1-2-1), (1-4-1), (1-9.1) or (1-15-1) are preferable in terms of production yield and ease of purification, and (1). 4-1) or (1-9-1) is more preferable.
The fluorine-containing silane compound (1a) produced by the production method 1 of the present invention can be purified by appropriately selecting and using a general purification method when a person skilled in the art purifies an organic silane compound. Specific purification methods include concentration, filtration, extraction, centrifugation, decantation, vacuum distillation, sublimation, crystallization, column chromatography and the like.

Next, the manufacturing method 2 of the present invention will be described. In the production method 2 of the present invention, the fluorine-containing silane compound (1b) in which the linker moiety A is a siloxanilen group.

(In the formula, n is an integer from 2 to 6. m is 2 or 3. R ¹ represents an alkyl group having 1 to 4 carbon atoms. P is an integer from 1 to 9. X ¹ is an integer. Representing a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or a dialkylamino group having 2 to 6 carbon atoms, the plurality of X1s may be the same or different from ^each other. R ³ and R ⁴ are independently fluorines. Represents an alkyl group having 1 to 4 carbon atoms which may be substituted with an atom. P is an integer of 1 to 9. R ² represents an alkyl group having 1 to 4 carbon atoms. R is 0 or 1. .)
The general formula (6).

(In the formula, R ³ , R ⁴ and p are synonymous with the above.)
The siloxane diol compound represented by the above formula (5)

(In the formula, n, m, and R ¹ have the same meaning as above. X ² represents a halogen atom.)
Fluorine-containing halogenated silane compound represented by and the general formula (8).

(In the formula, X ¹ , R ² and r are synonymous with the above. X ³ represents a halogen atom.)
It is characterized by reacting with the halogenated silane compound represented by.
The number of carbon chains of the fluoroalkyl group represented by n in the general formulas (1b) and (5) is an integer of 2 to 6, and may be 4 or 6 in terms of low raw material cost and good production yield. It is preferably 6, and even more preferably 6. Further, the number of fluoroalkyl groups in the molecule represented by m in the general formulas (1b) and (5) is 2 or 3, and is preferably 2 from the viewpoint of facilitating purification.
Examples of the siloxane diol compound (6) that can be used as a raw material in the production method 2 of the present invention include the following.

Of these siloxane diol compounds (6), (6-7) or (6-9) is preferable, and (6-7) is more preferable, from the viewpoint of economy or ease of purification. These siloxane diol compounds (6) can be appropriately synthesized and used according to a known synthesis method (for example, JP-A-2016-150906). Further, a commercially available product may be obtained and used.

Examples of the fluorine-containing halogenated silane compound (5) that can be used as a raw material in the production method 2 include the following.

Of these, (5-4), (5-6), (5-10) or (5-12) are preferable, and (5-6) or (5-12) are preferable in terms of economic efficiency and ease of preparation. ) Is more preferable, and (5-6) is particularly preferable. These are known synthetic methods (eg, Applied Surface Science, Vol. 371, pp. 453-467, 2016.
), And can be appropriately synthesized and used.
Examples of the halogenated silane compound (8) that can be used in the production method 2 include the following.

Of these, (8-1) or (8-6) is preferable, and (8-6) is more preferable, in terms of economy and ease of preparation. These can be appropriately synthesized and used according to a known synthetic method (for example, Angewandte Chemie, International, Edition, Vol. 50, pp. 10708-10711 (2011)). Alternatively, a commercially available product may be obtained and used.
The production method 2 of the present invention comprises the step 1 of dissolving the siloxane diol compound (6) in an organic solvent and adding the fluorine-containing halogenated silane compound (5) to the intermediate (7) to prepare the intermediate (7). The process 2 comprises the step 2 of adding the halogenated silane compound (8) to 7) to prepare the fluorine-containing silane compound (1b). Steps 1 and 2 may be continuously carried out in the same container, or the intermediate (7) may be purified once and used in step 2.
The organic solvent in steps 1 and 2 in the production method 2 of the present invention is not limited as long as it does not inhibit the reaction, and hydrocarbons such as benzene, toluene, xylene, methylene, pentane, hexane, heptane, and octane. , Benzene, chloroform, halogenated hydrocarbons such as carbon tetrachloride, and ethers such as diethyl ether, cyclopentylmethyl ether, tert-butylmethyl ether, tetrahydrofuran, and dioxane can be exemplified. Diethyl ether or tetrahydrofuran is preferable from the viewpoint of economy and production yield.
The production method 2 of the present invention is preferably carried out with an organic base in order to accelerate the reaction or avoid self-condensation of the siloxane diol compound (6) and the intermediate (7). Examples of the organic base include organic amines such as triethylamine, pyridine, quinoline, and aniline. Triethylamine or pyridine is preferable from the viewpoint of production yield, economy and ease of handling. The amount of these substances to be used is not particularly limited, but for example, 1 molar equivalent of the siloxane diol compound (6) should be accompanied by an equivalent amount of an organic base appropriately selected from the range of 1.5 to 100 molar equivalents. However, it is preferable in that the production yield is good.
The equivalent ratio of the three raw materials in the production method 2 of the present invention is not particularly limited, and for example, the fluorine-containing silane compound (5) is 0.8 to 1 with respect to 1 molar equivalent of the siloxane diol compound (6). It is preferable to carry out the halogenated silane compound (8) at an equivalent amount appropriately selected from the range of .5 molar equivalents and an equivalent amount appropriately selected from the range of 0.8 to 10 molar equivalents in terms of good yield.
The fluorine-containing silane compound (1b) produced by the production method 2 of the present invention can be purified by appropriately selecting and using a general purification method when a person skilled in the art purifies an organic silane compound. Specific purification methods include concentration, filtration, extraction, centrifugation, decantation, vacuum distillation, sublimation, crystallization, column chromatography and the like.
In the production method 2 of the present invention, the fluorine-containing silane compound (1b) can be suitably produced by appropriately selecting n, m, R ¹ , R ² , A and X ¹ . Examples of the fluorine-containing silane compound (1b) that can be produced by the production method 2 include the following compounds.

Of these, (1-9-1), (1-9-3) or (1-25-3) are preferable in terms of production yield and ease of purification, and (1-9-3) or (1). -25-3) is more preferable.

Next, the manufacturing method 3 of the present invention will be described. In the production method 3 of the present invention, the general formula (1c)

[In the formula, n is an integer from 2 to 6. m is 2 or 3. R ¹ represents an alkyl group having 1 to 4 carbon atoms. A is an alkylene group having 2 to 6 carbon atoms, or the general formula (2).

(In the formula, R ³ and R ⁴ represent alkyl groups having 1 to 4 carbon atoms, which may be independently substituted with fluorine atoms, respectively. P is an integer of 1 to 9.)
Represents the siroxanilen group represented by. ^X4 represents a halogen atom. R ² represents an alkyl group having 1 to 4 carbon atoms. r is 0 or 1. ]
From the fluorine-containing silane compound (1c) represented by the above, the general formula (1d).

(In the formula, n, m, R ¹ , A, R ² and r are synonymous with the above. X ⁵ is an alkoxy group having 1 to 4 carbon atoms, a dialkylamino group having 2 to 6 carbon atoms, or a halogen atom. show.)
It is a method for producing a fluorine-containing silane compound shown by. This can be done by reacting the fluorine-containing silane compound (1c) with an alkoxy agent or an aminating agent. Examples of the alkoxylating agent include an alcohol compound R ⁵ OH (in the formula, R ⁵ represents an alkyl group having 1 to 4 carbon atoms) and a metal alkoxide R ⁵ OM _s (in the formula, R ⁵ represents 1 to 4 carbon atoms). M is an alkali metal or an alkaline earth metal. S is 1 or 0.5.) Or Trialkyl HC orthogeate HC (OR ⁵ ) ₃ (in the formula, R ⁵ is carbon. (Representing an alkyl group of numbers 1 to 4) can be used. The halogen atom ^X5 in the production method can be exemplified by fluorine, chlorine, bromine or iodine, and is preferably chlorine or bromine from the viewpoint of production yield, and more preferably chlorine atom. The alcohol compound R ⁵ OH is an alkyl alcohol having 1 to 4 carbon atoms, and examples of the alcohol include methanol, ethanol, propanol, isopropyl alcohol, butanol, sec-butanol, isobutyl alcohol, and tert-butyl alcohol. Of these, methanol or ethanol is preferable, and methanol is more preferable, from the viewpoint of economy and production yield. Examples of the metal alkoxide include sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, magnesium methoxide, magnesium ethoxide and the like. Examples of the trialkyl orthoformate include trimethyl orthoformate or triethyl orthoformate.
In the production method 3 of the present invention, when an alcohol compound is used as the alkoxy agent, it may be carried out with an organic base in order to accelerate the reaction and increase the production yield. Examples of the organic base include organic amines such as triethylamine, pyridine, quinoline, and aniline. Triethylamine or pyridine is preferable from the viewpoint of production yield, economy and ease of handling. The amount of these used is not particularly limited, but for example, an amount of an organic base selected from the range of 0.8 to 20 molar equivalents is accompanied by 1 molar equivalent of the halogen atom X4 ^on the fluorine-containing silane compound (1c). It is preferable to carry out this.
Further, in the production method 3 of the present invention, the amino-terminal fluorine-containing silane compound (1d) can be produced by reacting the fluorine-containing silane compound represented by the general formula (1c) with an aminating agent.
Examples of the aminating agent include secondary amines such as dimethylamine, diethylamine, and dipropylamine. When a secondary amine is used as the aminating agent in the production method 3 of the present invention, it may be further accompanied by an organic base in order to accelerate the reaction and increase the production yield. Examples of the organic base include organic amines such as trimethylamine, dimethylamine, diethylamine, triethylamine, pyridine, quinoline and aniline. Triethylamine or pyridine is preferable from the viewpoint of production yield, economy and ease of handling. The amount of these used is not particularly limited, but for example, an amount of an organic base appropriately selected from the range of 0.8 to 20 mol equivalent with respect to ¹ mol equivalent of the halogen atom X 41 in the fluorine-containing silane compound (1c) is used. It is preferable to accompany them.
Examples of the fluorine-containing silane compound (1c) that can be used as a raw material in the production method 3 of the present invention include the following compounds.

Of these, (1-2-1), (1-4-1), (1-15-1) or (1-19-1) are preferable in terms of economy and production yield, and (1). 4-1) or (1-15-1) is more preferable.

Examples of the fluorine-containing silane compound (1d) that can be produced by the production method 3 include the following.

Of these, (1-2-3), (1-4-3), (1-9-3), (1-13-3), in terms of production yield and ease of isolation and purification. (1-15-3), (1-17-3), (1-21-3) or (1-25-3) are preferable, and (1-4-3), (1-9-3), (1-15-3) or (1-17-3) is more preferable.
The fluorine-containing silane compound (1d) produced by the production method 3 of the present invention can be purified by appropriately selecting and using a general purification method when a person skilled in the art purifies an organic silane compound. Specific purification methods include concentration, filtration, extraction, centrifugation, decantation, vacuum distillation, sublimation, crystallization, column chromatography and the like.

Next, a surface modification composition containing the fluorine-containing silane compound (1) of the present invention (hereinafter, referred to as the surface modification composition of the present invention) will be described. The surface modification composition of the present invention comprises the fluorine-containing silane compound (1) of the present invention and an organic solvent. Further, it may contain an acid catalyst, water, a silane additive, other auxiliaries and the like that smoothly promote the surface modification action. The fluorine-containing silane compound (1) in the surface modification composition of the present invention is represented by the general formula (1), and the following compounds can be exemplified.

Of these, (1-2-1), (1-2-3), (1-4-1), and (1-4) are excellent in surface modification properties, stability of the composition, and economy. -3), (1-9-1), (1-9-3), (1-15-1) or (1-15-3) are preferable, and (1-4-1), (1-4). -3), (1-9-1) or (1-9-3) is more preferable. As the fluorine-containing silane compound (1) in these surface modification compositions of the present invention, even if one type is used alone, a plurality of types of fluorine-containing silane compounds (1) are mixed and used in an arbitrary ratio. Is also good.
The concentration of the fluorine-containing silane compound (1) in the surface-modified composition of the present invention is 0.0001% by weight with respect to the total amount of the surface-modified composition of the present invention from the viewpoint of economy and film homogeneity. It is preferable that the concentration is appropriately selected from the range of 50% by weight, and more preferably the concentration is appropriately selected from the range of 0.01% to 20% by weight.
As a component constituting the surface modification composition of the present invention, an organic solvent that partially or completely dissolves the fluorine-containing silane compound (1) is used. The organic solvent is not particularly limited as long as it dissolves the fluorine-containing silane compound (1), and is a lower alcohol solvent such as methanol, ethanol and isopropyl alcohol; acetone, methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK). Ketones such as; ester solvents such as methyl acetate, ethyl acetate, butyl acetate; hydrocarbon solvents such as hexane, heptane, octane, benzene, toluene, xylene; 1,2-dimethoxyethane, digrim, 1,4- Examples of ether solvents such as dioxane, diethyl ether, dibutyl ether, tert-butylmethyl ether, cyclopentylmethyl ether, tetrahydrofuran, and diisopropyl ether can be exemplified. Further, a fluorocarbon-based organic solvent such as hydrofluorocarbons, perfluorocarbons, perfluoroethers or hydrofluoroalkyl ethers can also be used. As specific examples, benzotrifluoride (α, α, α-trifluorotoluene), 1,3-bis (trifluoromethyl) benzene, pentafluorobenzene, hexafluorobenzene, 2H, 3H-decafluoropentane (Bertrel), Examples thereof include tetradecafluorohexane, octadecafluorooctane, dodecafluorocyclohexane, 1,3-bis (trifluoromethyl) decafluorocyclohexane, methylnonafluorobutyl ether (isomer mixture), ethylnonafluorobutyl ether (isomer mixture) and the like. can. Of these, lower alcohol solvents such as ethanol and isopropyl alcohol, hydrocarbon solvents such as heptane, octane and toluene, and fluorine-based solvents such as 1,3-bis (trifluoromethyl) benzene and ethyl nonafluorobutyl ether (isomer mixture). The organic solvent is preferable because it has high solubility of the fluorine-containing silane compound (1) and the acid catalyst, and further, the coatability (easiness of spreading) and the drying time (working time) of the water-repellent liquid become appropriate. As these organic solvents, one kind may be used alone, or a plurality of organic solvents may be mixed and used at an arbitrary ratio.
The amount of the organic solvent added is preferably selected from the range of 50 to 99.999% by weight, preferably from 80 to 99.99% by weight, based on the total amount of the surface-modified composition of the present invention. Is more preferable. If it is less than 80% by weight, the amount of the fluorine-containing silane compound (1) adhered to the substrate becomes too large, and the coatability (easiness of spreading) of the composition is lowered. Further, when it exceeds 99.999% by weight, the amount of the fluorine-containing silane compound (1) adhered to the substrate is reduced, and it becomes difficult to sufficiently develop water repellency.
Water may be contained in the surface modification composition of the present invention. The water used in the surface modification composition of the present invention is a component for partially hydrolyzing the fluorine-containing silane compound (1) and smoothly chemically bonding it to a solid surface. The amount of water added is preferably a number of moles appropriately selected from the range of 0.1 to 200 times the number of moles of the fluorine-containing silane compound (1), and the amount of moles appropriately selected from the range of 1 to 50 times. The number is more preferred. Further, in order to adjust the water content in the surface modification composition of the present invention, a dehydrating agent may be added to the water repellent liquid and dehydration treatment may be performed for a predetermined time. As the dehydrating agent, silica gel, synthetic zeolite, activated alumina and the like can be used.
An acid catalyst that facilitates surface treatment may be added to the surface modification composition of the present invention. As the acid catalyst, either an inorganic acid or an organic acid can be used. Examples of the inorganic acid include hydrohalogenated acids such as hydrochloric acid, hydrobromic acid, and hydroiodic acid; inorganic oxo acids such as sulfuric acid, nitric acid, and perchloric acid; and organic carboxylic acids such as formic acid, acetic acid, propionic acid, and oxalic acid. Acids; methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, 2-propane sulfonic acid, butane sulfonic acid, 2-butane sulfonic acid, pentan sulfonic acid, trifluoromethane sulfonic acid, 2-hydroxyethan-1-sulfonic acid (Isetion). Acid), allylsulfonic acid, 1,3-propanedisulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, m-xylene-4-sulfonic acid, p-xylene-2-sulfonic acid, 2-sulfobenzoic acid, 5 -Organic sulfonic acids such as sulfosalicylic acid and p-phenolsulfonic acid can be exemplified. Of these, acetic acid, methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid or p-toluenesulfonic acid are preferable from the viewpoints of economy, safety, handleability and high-quality surface modification. , Methane sulfonic acid, benzene sulfonic acid or p-toluene sulfonic acid are more preferable.
The concentration of the acid catalyst in the surface modification composition of the present invention is 0.0001 weight by weight with respect to the total amount of the surface modification composition in terms of economy, stability of the composition (pot life) and homogeneity of the film. The concentration is preferably selected from the range of% to 50% by weight, and more preferably the concentration is selected from the range of 0.01% to 20% by weight.
The surface modification composition of the present invention may contain a silane additive having another surface modification action. The silane additive is a functional silane having a binding action on a solid surface and the fluorine-containing silane compound (1) of the present invention. Specific examples of the silane additive include alkylalkoxysilanes such as trimethoxymethylsilane, triethoxymethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, trimethoxyoctylsilane, and triethoxyoctylsilane, and hexamethyldi. Disilazans such as silazane and tetramethyldisilazane, chlorotrimethylsilane, dichlorodimethylsilane, trichlorooctylsilane, chlorodimethyloctylsilane, chlorodimethyloctadecylsilane, trichlorooctadecylsilane, halogenated silanes such as silicon tetrachloride, tetramethoxysilane , Tetraalkoxysilanes such as tetraethoxysilane, and peralkoxyoligosiloxanes such as hexamethoxydisiloxane and hexaethoxydisiloxane can be exemplified. These can be appropriately selected from the range of about 0.001 to 1000% by weight with respect to the weight of the fluorine-containing silane compound (1) in the surface modification composition of the present invention.

The surface-modified composition of the present invention contains, if necessary, an amine-based neutralizing agent such as triethylamine, triethanolamine, tris (2-hydroxyethyl) amine, and morpholin, and an ionic system for improving the wettability of the composition. , Various surfactants such as non-ionic surfactants, silicone oils that further improve lubricity, silicone varnishes, and the like can also be added. These can be used in a ratio of about 0.001 to 300% by weight with respect to the weight of the fluorine-containing silane compound (1) in the surface modification composition of the present invention.
The method for formulating the composition is carried out by mixing an appropriately determined amount of each component and an organic solvent. This may be stored after mixing and used as appropriate, or may be mixed immediately before coating and used for coating.
The surface modification composition of the present invention may be applied to a substrate by a dipping method, a dip coating method, a spraying method, a pouring method, a spin coating method, an aerosol injection method, a brush coating method, a coating method using an impregnated cloth, or the like. It can be carried out by any method usually used for surface modification of fluoroalkyl-based surface modifiers. From the viewpoint of uniformity of surface modification, high liquid repellency and economy, a dipping method, a dip coating method, a spin coating method, a brush coating method or a coating method using an impregnated cloth is preferable, and a dip coating method or an impregnated cloth is used. The coating method is more preferable. Further, after coating, a film curing (annealing) and cleaning step under heating or non-heating conditions may be added as needed.
The base material that can be surface-modified by the surface-modifying composition of the present invention has a hydroxyl group to which the fluorine-containing silane compound (1) can be bonded to the solid surface. The shape may be a flat surface or a three-dimensional object. Further, it may be a powder or a molded body. The material of the base material may be an inorganic base material or an organic polymer base material. Examples of the inorganic base material include inorganic glass material base materials such as quartz glass, soda glass, lead glass, borosilicate glass, and phosphate glass; silicon dioxide material base materials such as single crystal quartz, polycrystalline quartz, and silica gel; zeolite. , Mulite, mica, aluminosilicate material base material such as clay minerals; metal oxide material base material such as alumina (aluminum oxide), titania (titanium oxide), zirconia (zinc oxide); double oxidation of spinel, iron ferrite, etc. A material material base material can be exemplified. Examples of the organic polymer base material include cellulose and the like.
Further, since the metal surface has a hydroxyl group structure, it can also be used for surface modification treatment of the metal surface. Examples of the metal material include aluminum, titanium, iron, manganese, vanadium, nickel, chromium, copper, zinc, silicon, germanium and alloys thereof.

The fluorine-containing silane compound (1) of the present invention is useful for surface modification to glass, metal or metal oxide-based materials as a surface modifier capable of imparting transparent and high water and oil repellency to a solid surface. .. Such surface-modified materials can be used as contact-type devices such as touch panels, optical window materials, water-repellent / stain-resistant materials, or mold release molds. In particular, it can be suitably used for windowpanes and mirrors for aircraft and automobiles, and for water-repellent and antifouling treatment of vehicle bodies.
Further, since the fluorine-containing silane compound (1) has a reactive functional group at one end, it can be used as an amphipathic molecule and as a fluorous phase surfactant. Furthermore, by converting a reactive functional group and converting it to another group, it can be used as a raw material for a surface modifier having a new molecular structure, such as a completely condensed type or an incompletely condensed type silsesquioxane. You can expect to use it.

Hereinafter, the present invention will be described in more detail with reference to Examples, Evaluation Examples and Comparative Examples, but the scope of the present invention should not be construed as being limited by the specific examples shown below.
All the productions described in the examples were carried out in an argon atmosphere. Instrumental analysis includes ¹ H-NMR (proton nuclear magnetic resonance spectrum), ¹³ C-NMR (carbon 13 nuclear magnetic resonance spectrum), ¹⁹ F-NMR (fluoronuclear magnetic resonance spectrum) and ²⁹ Si-NMR (silicon 29 nuclear magnetic resonance). (Resonance spectrum) The measurement was performed using an Ascend 400 nuclear magnetic resonance spectrometer manufactured by Bruker-Avance. Heavy chloroform is used as the solvent for measuring the nuclear magnetic resonance spectrum, tetramethylsilane is used as the internal standard material in ¹ H-NMR and ²⁹ Si-NMR, and hexafluorobenzene is used as the secondary external standard material in ¹⁹ F-NMR. I asked. The IR (infrared absorption) spectrum was measured using an FT-720 spectrophotometer manufactured by HORIBA, Ltd. and a DuraSamplIRII (reflection type) measuring cell manufactured by SensIR technologies.

The 1H, 1H, 2H, 2H-nonafluorohexyl bromide and 1H, 1H, 2H, 2H-tridecafluorooctyl bromide used in the production contained an excess amount of the corresponding iodine (manufactured by Tokyo Kasei Co., Ltd.) in acetone. It was synthesized and used by heating with tetraethylammonium bromide. 1,3-bis (trifluoromethyl) benzene (reagent manufactured by Tokyo Kasei Kogyo Co., Ltd.), trichlorosilane (reagent manufactured by Tokyo Kasei Kogyo Co., Ltd.), p-toluenesulfonic acid (reagent manufactured by Tokyo Kasei Kogyo Co., Ltd.), triethoxy (reagent manufactured by Tokyo Kasei Kogyo Co., Ltd.) 1H, 1H, 2H, 2H-Tridecafluorooctyl) silane (reagent manufactured by Tokyo Kasei Kogyo Co., Ltd.), bromine (reagent manufactured by Fujifilm Wako Junyaku Co., Ltd.), magnesium (reagent manufactured by Fujifilm Wako Junyaku Co., Ltd.), Triethylamine (reagent manufactured by Fujifilm Wako Junyaku Co., Ltd.), toluene (reagent manufactured by Fujifilm Wako Junyaku Co., Ltd.), dehydrated tetrahydrofuran (reagent manufactured by Fujifilm Wako Junyaku Co., Ltd.), dehydrated methanol (Fujifilm Wako Junyaku Co., Ltd.) Reagents manufactured by Fujifilm Wako Junyaku Co., Ltd., Isopropyl alcohol (Reagent manufactured by Fujifilm Wako Junyaku Co., Ltd.), Dehydrated diethyl ether (Reagent manufactured by Kanto Chemical Co., Ltd.), chloroform (Reagent manufactured by Kanto Chemical Co., Ltd.) (Reagent manufactured), allylmagnesium chloride tetrahydrofuran solution (reagent manufactured by Sigma Aldrich Japan Co., Ltd.) and dichloromethylsilane (reagent manufactured by Sigma Aldrich Japan Co., Ltd.) were purchased as commercial products and used as they were. For chloroplatinic acid hexahydrate, a product of Tanaka Kikinzoku Co., Ltd. was purchased and dried under reduced pressure immediately before use. As ethyl nonafluorobutyl ethyl ether, an isomer mixed product of a reagent manufactured by Tokyo Chemical Industry Co., Ltd. was used as it was.
In the surface modification test, a soda glass plate (short side 26 mm, long side 76 mm) that had been thoroughly cleaned and cleaned was used as a base material, and after surface modification, the surface was cleaned, which was visually confirmed, and surface contamination was observed. .. For the contact angle in the liquid repellency test, 10 μL droplets dispensed from a microsyringe were placed on the surface-modified substrate at five locations for water and n-hexadecane, and the droplets were placed in horizontal light with an xyzφ stage. Photographed from the side of the surface-modified substrate with a 10x axis macrophotographer (objective lens: Microtal 30 mm manufactured by Karl Zeis Jena, flange back 220 mm), and the contact angle by the θ / 2 method from the aspect ratio of the droplet. Was obtained, and the average value and standard deviation were calculated from the measured values at five locations. For the water slip angle, 50 μL of water droplets dispensed from a microsyringe are placed on a surface-modified substrate, the tilt stage is slowly tilted, and the critical angle at which the water droplets start to move is obtained five times at five locations, and the average value and standard deviation are obtained. Was calculated.

(Synthesis Example 1) Synthesis of bis (1H, 1H, 2H, 2H-nonafluorohexyl) methylsilane

A 300 mL three-necked flask equipped with a magnetic stir bar, a 100 mL dropping funnel and a gym funnel was replaced with argon to contain 2.95 g (121 mmol) of metallic magnesium. 10 mL of dehydrated diethyl ether was added to this flask, and magnesium was activated with a small amount of dibromoethane. 80 mL of 1H, 1H, 2H, 2H-nonafluorohexyl bromide 32.7 g (100 mmol) of dehydrated diethyl ether was added dropwise from the dropping funnel over 60 minutes. After the dropping, the mixture was heated to 50 ° C. and stirred for 60 minutes. The solution was returned to 25 ° C., 5.17 g (44.9 mmol) of dichlormethylsilane was slowly added from the syringe, and the mixture was stirred at 60 ° C. for 1 hour. Dilute hydrochloric acid was added to the reaction mixture, and the solution was filtered using Celite. The organic layer was separated and extracted, and the organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off with a rotary evaporator, and the obtained crude product was distilled under Kugelrohr (distillation temperature 65 ° C./40 Pa) under reduced pressure to obtain bis (1H, 1H, 2H, 2H-nonafluorohexyl) methylsilane. 22.98 g (yield 95.0%) was obtained as a colorless and transparent liquid.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ0.19 to 0.20 (m, 3H), 0.87 to 0.94 (m, 4H), 2.03 to 2.17 (m, 4H), 3.93 (s, 1H).
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126.0, -124.3, -116.2, -81.0.
²⁹ Si-NMR (80 MHz, CDCl ₃ ): δ4.37.
IR (neat, cm ^-1 ): 1442, 1354, 1207, 1130, 918, 877, 845, 744.

(Synthesis Example 2) Synthesis of tris (1H, 1H, 2H, 2H-nonafluorohexyl) silane

A 300 mL three-necked flask equipped with a magnetic stir bar, a 100 mL dropping funnel and a gym funnel was replaced with argon to contain 2.95 g (121 mmol) of metallic magnesium. 10 mL of dehydrated diethyl ether was added to this flask, and magnesium was activated with a small amount of dibromoethane. 80 mL of 1H, 1H, 2H, 2H-nonafluorohexyl bromide 32.7 g (100 mmol) of dehydrated diethyl ether was added dropwise from the dropping funnel over 60 minutes. After the dropping, the mixture was heated to 50 ° C. and stirred for 60 minutes. The solution was returned to 25 ° C., 4.04 g (29.8 mmol) of trichlorosilane was slowly added from the syringe, and the mixture was stirred at 50 ° C. for 1 hour. Dilute hydrochloric acid was added to the reaction mixture, and the solution was filtered using Celite. The organic layer was separated and extracted, and the organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off with a rotary evaporator, and the obtained crude product was distilled under Kugelrohr (distillation temperature 100 ° C./40 Pa) under reduced pressure to obtain Tris (1H, 1H, 2H, 2H-nonafluorohexyl) silane. 22.81 g (yield 99.2%) was obtained as a colorless and transparent liquid.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ0.95-1.00 (m, 6H), 2.06-2.19 (m, 6H), 3.95 (s, 1H).
²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ2.52.
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126, 124, -116, -81.1.
IR (neat, cm ^-1 ): 1442, 1354, 1207, 1130, 918, 877, 847, 744.

(Synthesis Example 3) Synthesis of bis (1H, 1H, 2H, 2H-tridecafluorooctyl) methylsilane

A 300 mL three-necked flask equipped with a magnetic stir bar, a 200 mL dropping funnel and a gym funnel was replaced with argon to contain 3.10 g (123 mmol) of metallic magnesium. 10 mL of dehydrated diethyl ether was added to this flask, and magnesium was activated with a small amount of dibromoethane. A solution of 50.8 g (119 mmol) of 1H, 1H, 2H, 2H-tridecafluorooctyl bromide in 100 mL of dehydrated diethyl ether was added dropwise from the dropping funnel over 45 minutes. After the dropping, the mixture was heated to 50 ° C. and stirred for 1 hour. The solution was returned to 25 ° C., 6.41 g (55.7 mmol) of dichlormethylsilane was slowly added from the syringe, and the mixture was stirred at 50 ° C. for 1 hour. Saturated saline and diethyl ether were added to the reaction mixture, and the solution was filtered through Celite. The organic layer was separated and extracted, and the organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off with a rotary evaporator, and the obtained crude product was distilled under reduced pressure (boiling point 81 ° C./13 Pa) to make bis (1H, 1H, 2H, 2H-tridecafluorooctyl) methylsilane colorless. 34.9 g (yield 85.0%) was obtained as a transparent liquid.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ0.19 to 0.20 (m, 3H), 0.83 to 0.98 (m, 4H), 2.03 to 2.16 (m, 4H), 3.93 (s, 1H).
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126.2,-123.4, -122.9, -122.0, -116.0, -80.9.
²⁹ Si-NMR (79.5 MHz, CDCl ₃ ): δ6.78.
IR (neat, cm ^-1 ): 2940, 2130, 1442, 1234, 1188, 1142, 1120, 1066, 914,705.

(Synthesis Example 4) Synthesis of Tris (1H, 1H, 2H, 2H-Tridecafluorooctyl) silane

A 300 mL three-necked flask equipped with a magnetic stir bar, a 200 mL dropping funnel and a gym funnel was replaced with argon to contain 3.09 g (123 mmol) of metallic magnesium. 10 mL of dehydrated diethyl ether was added to this flask, and magnesium was activated with a small amount of dibromoethane. From the dropping funnel, 100 mL of 51.5 g (121 mmol) of 1H, 1H, 2H, 2H-tridecafluorooctyl bromide dehydrated diethyl ether was added dropwise over 60 minutes. After the dropping, the mixture was heated to 60 ° C. and stirred for 30 minutes. The solution was returned to 25 ° C., 5.29 g (39.1 mmol) of trichlorosilane was slowly added from the syringe, and the mixture was stirred at 50 ° C. for 1 hour. Dilute hydrochloric acid was added to the reaction mixture, and the solution was filtered using Celite. The organic layer was separated and extracted, and the organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off with a rotary evaporator, and the obtained crude product was distilled by Kugelrohr (distillation temperature 165 ° C./130 Pa) under reduced pressure to tris (1H, 1H, 2H, 2H-tridecafluorooctyl) silane. Was obtained as a colorless and transparent liquid in an amount of 23.7 g (yield 56.6%).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ0.95 to 1.00 (m, 6H), 2.06 to 2.19 (m, 6H), 3.94 (s, 1H).
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126.3, 123.4, -123.0, -122.0, -116.0, -80.9.
²⁹ Si-NMR (79.5 MHz, CDCl ₃ ): δ2.70.
IR (neat, cm ^-1 ): 1442,1362,1234,1186,1142,1120,916,705.

(Synthesis Example 5) Synthesis of allyl (bis (1H, 1H, 2H, 2H-nonafluorohexyl)) methylsilane

A 50 mL two-necked eggplant flask equipped with a magnetic stirrer, a 30 mL dropping funnel and a Dimroth was replaced with argon and bis (1H, 1H, 2H, 2H-nonafluorohexyl) methylsilane 11.18 g (20.8 mmol) and dehydrated dichloromethane. 10 ml was contained, and a solution of 3.62 g (22.7 mmol) of bromine in 10 mL of dehydrated dichloromethane was added dropwise from the dropping funnel over 2 hours. The solvent was distilled off under reduced pressure, 20.0 ml (40.0 mmol) of a THF solution of allylmagnesium chloride (2.0 M) was added thereto, and the mixture was stirred at 25 ° C. for 36 hours. Chloroform and saturated brine were added thereto, and the mixture was filtered through Celite and then separated. After drying the organic layer with magnesium sulfate, the solvent was distilled off by a rotary evaporator. By subjecting the obtained crude product to Kugelrohr distillation (distillation temperature 95 ° C./40 Pa), 11.6 g of allylbis (1H, 1H, 2H, 2H-nonafluorohexyl) methylsilane as a colorless and transparent liquid (yield 96. 3%) Obtained.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ0.11 (s, 3H), 0.81 to 0.86 (m, 2H), 1.62 to 1.64 (m, 2H), 1.98 to 2.14 (m, 4H), 4.90 to 4.92 (m, 1H), 4.94 to 4.96 (m, 1H), 5.69 to 5.80 (m, 1H).
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126.1, -124.3, -116.4, -81.1.
²⁹ Si-NMR (79.5 MHz, CDCl ₃ ): δ4.00.
IR (neat, cm ^-1 ): 2964, 2910, 1633, 1442, 1354, 1209, 1130, 877, 844, 690.

(Synthesis Example 6) Synthesis of allyl (tris (1H, 1H, 2H, 2H-nonafluorohexyl)) silane

A 100 mL two-necked eggplant flask equipped with a magnetic stir bar, a 30 mL dropping funnel and a Dimroth was replaced with argon to remove 22.6 g (29.3 mmol) of Tris (1H, 1H, 2H, 2H-nonafluorohexyl) silane and dehydrated dichloromethane. A 20 mL solution of 4.67 g (30.4 mmol) of bromine in dehydrated dichloromethane was added dropwise from the dropping funnel over 90 minutes. After the dropping, the mixture was stirred at 25 ° C. for 4 hours. The low boiling point fraction was removed under reduced pressure to obtain 23.6 g (yield 94.8%) of bromotris (1H, 1H, 2H, 2H-nonafluorohexyl) silane as a pale yellow liquid.
Separately, a 50 mL two-necked eggplant flask equipped with a Dimroth condenser and a magnetic stir bar was replaced with argon, and 10.0 g (11.8 mmol) of the previously prepared bromotris (1H, 1H, 2H, 2H-nonafluorohexyl) silane was used. ), 2.0 ml (0.403 g, 4.0 mmol) of a THF solution of allylmagnesium chloride (2.0 M) was added thereto, and the mixture was stirred at 25 ° C. for 3 hours. Diethyl ether and saturated brine were added thereto, and the mixture was filtered through Celite and then separated. After drying the organic layer with magnesium sulfate, the solvent was distilled off by a rotary evaporator. The obtained crude product was distilled by Kugelrohr (distillation temperature 115 ° C./40 Pa) to make allyltris (1H, 1H, 2H, 2H-nonafluorohexyl) silane a colorless and transparent liquid in an amount of 8.37 g (yield 84.). 7%) Obtained.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ0.89 to 0.93 (m, 6H), 1.69 to 1.71 (m, 2H), 1.99 to 2.12 (m, 6H), 4.97 to 4.99 (m, 1H), 5.01 (s, 1H), 5.67 to 5.79 (m, 1H).
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126.0, -124.2, -116.4, -81.0.
²⁹ Si-NMR (79.5 MHz, CDCl ₃ ): δ4.71.
IR (neat, cm ^-1 ): 163,1442,1353,1209,1130,877,843,741,690.

(Synthesis Example 7) Synthesis of allyl (bis (1H, 1H, 2H, 2H-tridecafluorooctyl)) methylsilane

A 100 mL two-necked eggplant flask equipped with a magnetic stir bar, a 50 mL dropping funnel and a Dimroth was replaced with argon to contain 39.8 g (54.4 mmol) of bis (1H, 1H, 2H, 2H-tridecafluorooctyl) methylsilane. , 9.43 g (57.1 mmol) of bromine was added dropwise from the dropping funnel over 40 minutes. After the dropping, the mixture was stirred at 50 ° C. for 15 minutes. The volatile components were removed under reduced pressure to give bromo (bis (1H, 1H, 2H, 2H-tridecafluorooctyl)) methylsilane as a pale yellow liquid.
Separately, a 50 mL two-necked flask equipped with a Dimroth condenser and a three-way cock was replaced with argon, containing 24.0 mL (50.0 mmоl, 2 equivalents) of a THF solution of allylmagnesium chloride 2.0 M and 24 mL of dehydrated THF. Was added. 21.3 g (26.1 mmоl) of the previously prepared bromo (bis (1H, 1H, 2H, 2H-tridecafluorooctyl)) methylsilane was added dropwise thereto over 30 minutes. This was heated to reflux for 90 minutes and stirred at room temperature for 14 hours. Dilute hydrochloric acid and chloroform were added to the solution, and the mixture was allowed to stand after filtration, and the organic layer was dried over magnesium sulfate. This is concentrated using a rotary evaporator and then distilled under reduced pressure by Kugelrohr (distillation temperature 130 ° C./60 Pa) to obtain allyl (bis (1H, 1H, 2H, 2H-tridecafluorooctyl)) methylsilane. 9 g (yield 88.0%) was obtained.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ0.11 (s, 3H), 0.82 to 0.86 (m, 4H), 1.62 to 1.64 (m, 2H), 1.98 to 2.11 (m, 4H), 4.92 (s, 1H), 4.95 (s, 1H), 5.69-5.80 (m, 1H).
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126.2,-123.3, -122.9, -122.0, -116.1, -80.8.
²⁹ Si-NMR (79.5 MHz, CDCl ₃ ): δ4.03.
IR (neat, cm ^-1 ): 1633, 1442, 1362, 1234, 1188, 1141,706.

(Synthesis Example 8) Synthesis of allyl (tris (1H, 1H, 2H, 2H-tridecafluorooctyl)) silane

A 50 mL two-necked eggplant flask equipped with a magnetic stir bar, a 50 mL dropping funnel and a Dimroth was replaced with argon to 23.6 g (22.0 mmol) of Tris (1H, 1H, 2H, 2H-tridecafluorooctyl) silane and dehydration. 44 ml of dichloromethane was contained, and 3.53 g (22.1 mmol) of bromine was added dropwise from the dropping funnel over 5 minutes, and the mixture was stirred for 80 minutes after the addition. The solvent was distilled off under reduced pressure to obtain tris (1H, 1H, 2H, 2H-tridecafluorooctyl) silyl bromide.

Take 10.6 g (9.25 mmоl) of Tris (1H, 1H, 2H, 2H-tridecafluorooctyl) silyl bromide obtained by the above operation, and place this in a separate flask in a THF solution of allylmagnesium chloride (2. 8.7 mL (17.4 mmol) of (0MTHF solution) was added, and the mixture was stirred at 25 ° C. for 2 hours under heating under reflux for 70 minutes. Chloroform and saturated brine were added thereto, and the mixture was filtered through Celite and then separated. After drying the organic layer with magnesium sulfate, the solvent was distilled off by a rotary evaporator. By distilling the obtained crude product under reduced pressure (boiling point 155 ° C. / 12Pa), 9.46 g (yield 92.1) of allyltris (1H, 1H, 2H, 2H-tridecafluorooctyl) silane as a colorless and transparent liquid was obtained. %)Obtained.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ0.89 to 0.94 (m, 6H), 1.69 to 1.72 (m, 2H), 2.00 to 2.13 (m, 6H), 4.97-4.99 (m, 1H), 5.01 (s, 1H), 5.68-5.79 (m, 1H).
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126.2,-123.3, -122.9, -116.1, -80.8.
²⁹ Si-NMR (79.5 MHz, CDCl ₃ ): δ4.67.
IR (neat, cm ^-1 ): 163,1442,1362,1234,1186,1142,706.

(Example 1) Synthesis of trichloro (3- (bis (1H, 1H, 2H, 2H-nonafluorohexyl) methylsilyl) propyl) silane (exemplified compound number (1-2-1))

A capped screw cap test tube equipped with a magnetic stir bar was replaced with argon to contain 11.4 g (19.7 mmol) of allyl (bis (1H, 1H, 2H, 2H-nonafluorohexyl)) methylsilane. To this, 270 mg (2.6 mol%) of hexachloroplatinic acid (IV) acid hydrate and 8.06 g (59.5 mmol) of trichlorosilane were added, and the mixture was heated and stirred at 40 ° C. for 14 hours. The low boiling point component was distilled off under reduced pressure, and the obtained crude product was distilled under Kugelrohr (distillation temperature 110 ° C./40 Pa) under reduced pressure to trichloro (3- (bis (1H, 1H, 2H, 2H)). 10.3 g (yield 73.2%) of -nonafluorohexyl) methylsilyl) propyl) silane (exemplified compound number (1-2-1)) was obtained as a colorless and transparent liquid.
^{1 1} H-NMR (400MHz, CDCl ₃ ): δ0.12 (s, 3H), 0.76 to 0.80 (m, 2H), 0.81 to 0.86 (m, 4H), 1.48 to 1.50 (m, 2H), 1.59 to 1.66 (m, 2H), 1.96 to 2.09 (m, 4H).
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126.1, -124.3, -116.3, -81.1.
²⁹ Si-NMR (79.5 MHz, CDCl ₃ ): δ-5.35, 6.50.
IR (neat, cm ^-1 ): 1354, 1209, 1130, 1070, 877, 736, 692.

(Example 2) Synthesis of trimethoxy (3- (bis (1H, 1H, 2H, 2H-nonafluorohexyl) methylsilyl) propyl) silane (exemplified compound number (1-2-3))

A 100 mL two-necked eggplant flask equipped with a magnetic stir bar and a gym funnel was replaced with argon, which contained 50 mL of dehydrated diethyl ether, 1.00 g (31.2 mmol) of dehydrated methanol and 2.09 g (20.6 mmol) of triethylamine. .. With a syringe, 3.03 g (4.24 mmol) of trichloro (3- (bis (1H, 1H, 2H, 2H-nonafluorohexyl) methylsilyl) propyl) silane was slowly added, and the mixture was stirred at room temperature for 3 hours. The precipitate was filtered off with a Schlenk tube equipped with a sintered glass filter. After distilling off the solvent under reduced pressure, the obtained crude product was subjected to Kugelrohr distillation (distillation temperature 135 ° C./40 Pa) under reduced pressure to obtain trimethoxy (3- (bis (1H, 1H, 2H,). 2.23 g (yield 75.3%) of 2H-nonafluorohexyl) methylsilyl) propyl) silane (exemplified compound number (1-2-3)) was obtained as a colorless liquid.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ0.67 to 0.75 (m, 4H), 0.78 to 0.82 (m, 4H), 1.42 to 1.50 (m, 2H), 1.95 to 2.08 (m, 4H), 3.56 (s, 9H).
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126.1, -124.3, -116.3, -81.1.
²⁹ Si-NMR (79.5 MHz, CDCl ₃ ): δ-42.6, 5.05.
IR (neat, cm ^-1 ): 2497, 2844, 1209, 1130, 1086, 877, 808, 739.

(Example 3) Synthesis of trichloro (3- (tris (1H, 1H, 2H, 2H-nonafluorohexyl) silyl) propyl) silane (exemplified compound number (1-15-1))

A test tube with a stopcock equipped with a magnetic stir bar and a three-way cock was replaced with argon to contain 1.98 g (2.45 mmol) of allyl (Tris (1H, 1H, 2H, 2H-nonafluorohexyl)) silane. To this, 0.032 g (2.5 mol%) of hexachloroplatinic acid (IV) acid hydrate and 0.700 g (5.17 mmol) of trichlorosilane were added, and the mixture was heated and stirred at 40 ° C. for 3 hours. The low boiling point component was distilled off under reduced pressure, and the obtained crude product was distilled under Kugelrohr (distillation temperature 135 ° C./50 Pa) under reduced pressure to trichloro (3- (Tris (1H, 1H, 2H, 2H)). -Nonafluorohexyl)) propyl) silane (Exemplified Compound No. (1-15-1)) was obtained as a colorless and transparent liquid in an amount of 2.05 g (yield 88.3%).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ0.83 to 0.88 (m, 2H), 0.88 to 0.93 (m, 6H), 1.50 to 1.52 (m, 2H), 1.61 to 1.69 (m, 2H), 1.98 to 2.11 (m, 6H).
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126.0, -124.2, -116.3, -81.0.
²⁹ Si-NMR (79.5 MHz, CDCl ₃ ): δ-6.38, 5.25.
IR (neat, cm ^-1 ): 1442, 1353, 1209, 1130, 877, 744,690.

(Example 4) Synthesis of trimethoxy (3- (tris (1H, 1H, 2H, 2H-nonafluorohexyl) silyl) propyl) silane (exemplified compound number (1-15-3))

A 50 mL two-necked eggplant flask equipped with a magnetic stir bar and a gym funnel was replaced with argon, in which 9.0 mL of dehydrated diethyl ether, 0.480 g (15.0 mmol) of dehydrated methanol and 0.936 g (9.24 mmol) of triethylamine were added. I put it in. With a syringe, 1.66 g (1.75 mmol) of trichloro (3-tris (1H, 1H, 2H, 2H-nonafluorohexyl) silyl) propyl) silane and 18.0 mL of dehydrated diethyl ether were slowly added, and the mixture was stirred at room temperature for 15 hours. .. 10 mL of hexane was added to the mixture and the precipitate was removed by filtration through a Schlenk tube equipped with a sintered glass filter. After distilling off the solvent under reduced pressure, the obtained crude product is distilled by Kugelrohr (distillation temperature 135 ° C./40 Pa) under reduced pressure to trimethoxy (3-tris (1H, 1H, 2H, 2H). -Nonafluorohexyl) Cyril) propyl) Silane (Exemplified Compound No. (1-15-3)) was obtained as a colorless liquid in an amount of 1.04 g (yield 63.4%).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ0.73 to 0.78 (m, 4H), 0.85 to 0.89 (m, 6H), 1.43 to 1.51 (m, 2H), 1.97-2.10 (m, 6H), 3.56 (s, 9H).
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126.1, -124.2, -116.3, -81.1.
IR (neat, cm ^-1 ): 2949, 2846, 1442, 1209, 1130, 1088, 1074, 877, 746.

(Example 5) Synthesis of trichloro (3- (bis (1H, 1H, 2H, 2H-tridecafluorooctyl) methylsilyl) propyl) silane (exemplified compound number (1-4-1))

A capped screw cap test tube equipped with a magnetic stir bar was replaced with argon to contain 14.5 g (18.6 mmol) of allyl (bis (1H, 1H, 2H, 2H-tridecafluorooctyl)) methylsilane. To this, 48 mg (1 mol%) of hexachloroplatinic acid (IV) acid hydrate and 7.88 g (57.8 mmol) of trichlorosilane were added, and after sealing, the mixture was heated and stirred at 50 ° C. for 1 hour, and then stirred at room temperature for 14 hours. The low boiling point component was distilled off from the mixture under reduced pressure, and the obtained crude product was distilled by Kugelrohr (distillation temperature 150 ° C./18 Pa) under reduced pressure to trichloro (3- (bis (1H, 1H, 2H)). , 2H-Tridecafluorooctyl) methylsilyl) propyl) silane (Exemplified Compound No. (1-4-1)) was obtained as a colorless and transparent liquid in an amount of 15.8 g (yield 92.7%).
^{1 1} H-NMR (400MHz, CDCl ₃ ): δ0.12 (s, 3H), 0.76 to 0.90 (m, 2H), 1.48 to 1.52 (m, 2H), 1.60 to 1.68 (m, 2H), 1.96 to 2.09 (m, 4H).
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126.1, -123.3, -122.9, -121.9, -116.0, -80.8.
IR (neat, cm ^-1 ): 1234, 1190, 1142, 1068, 906, 706.

(Example 6) Synthesis of trimethoxy (3- (bis (1H, 1H, 2H, 2H-tridecafluorooctyl) methylsilyl) propyl) silane (exemplified compound number (1-4-3))

A 50 mL two-necked eggplant flask equipped with a magnetic stir bar and a gym funnel was replaced with argon, which contained 10 mL of dehydrated THF, 0.831 g (25.9 mmol) of dehydrated methanol and 1.55 g (15.3 mmol) of triethylamine. 3.99 g (4.37 mmol) of trichloro (3- (bis (1H, 1H, 2H, 2H-tridecafluorooctyl) methylsilyl) propyl) silane was slowly added with a syringe and stirred at room temperature for 18 hours. 10 mL of hexane was added to the mixture and the precipitate was removed by filtration through a Schlenk tube equipped with a sintered glass filter. After distilling off the solvent under reduced pressure, the obtained crude product was subjected to Kugelrohr distillation (distillation temperature 115 ° C./25 Pa) under reduced pressure to obtain trimethoxy (3- (bis (1H, 1H, 2H,). 2H-Tridecafluorooctyl) methylsilyl) propyl) silane (Exemplified Compound No. (1-4-3)) was obtained as a colorless liquid in an amount of 3.03 g (yield 76.9%).
^{1 1} H-NMR (400MHz, CDCl ₃ ): δ0.08 (s, 3H), 0.68 to 0.78 (m, 4H), 0.80 to 0.83 (m, 4H), 1.43 to 1.51 (m, 2H), 1.96 to 2.09 (m, 4H), 3.57 (s, 9H).
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126.5, 123.6, -123.2-2-122.2, -116.4-81.2.
²⁹ Si-NMR (80MHz, CDCl ₃ ): δ-42.58, 5.07.
IR (neat, cm ^-1 ) 2946, 2844, 1234, 1188, 1142, 1090, 906, 810, 706.

(Example 7) Synthesis of trichloro (3- (tris (1H, 1H, 2H, 2H-tridecafluorooctyl) silyl) propyl) silane (exemplified compound number (1-16-1))

A test tube with a stopcock equipped with a magnetic stir bar and a three-way cock was replaced with argon to contain 3.00 g (2.70 mmol) of allyl (Tris (1H, 1H, 2H, 2H-tridecafluorooctyl)) silane. .. To this, 20 mg (0.1 mol%) of hexachloroplatinic acid (IV) acid hydrate (7.3 wt% solution) dissolved in isopropyl alcohol and 1.11 g (8.20 mmol) of trichlorosilane were added, and the temperature was 60 ° C. The mixture was heated and stirred for 15 hours. The low boiling point component was distilled off under reduced pressure, and the obtained crude product was distilled under Kugelrohr (distillation temperature 175 ° C./50 Pa) under reduced pressure to trichloro (3- (Tris (1H, 1H, 2H, 2H)). -Tridecafluorooctyl) silyl) propyl) silane (Exemplified Compound No. (1-16-1)) was obtained as a colorless and transparent liquid in an amount of 3.14 g (yield 93.2%).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ0.83 to 0.93 (m, 8H), 1.50 to 1.52 (m, 2H), 1.63 to 1.65 (m, 2H), 1.98-2.11 (m, 6H).
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126.2,-123.3, -122.9, -116.1, -80.8.
²⁹ Si-NMR (79.5 MHz, CDCl ₃ ): δ-6.40, 5.23
IR (neat, cm ^-1 ): 1442, 1360, 1186, 1142, 1072,706.

(Example 8) Synthesis of trimethoxy (3- (tris (1H, 1H, 2H, 2H-tridecafluorooctyl) silyl) propyl) silane (exemplified compound number (1-16-3))

A 50 mL two-necked eggplant flask equipped with a magnetic stir bar and a gym funnel was replaced with argon, which contained 13 mL of dehydrated diethyl ether, 0.331 g (10.3 mmol) of dehydrated methanol and 0.650 g (6.42 mmol) of triethylamine. .. With a syringe, 1.35 g (1.08 mmol) of trichloro (3- (tris (1H, 1H, 2H, 2H-tridecafluorooctyl) silyl) propyl) silane and 20 mL of dehydrated diethyl ether were added, and the mixture was stirred at room temperature for 18 hours. The precipitate was filtered off with a Schlenk tube equipped with a sintered glass filter. After distilling off the solvent under reduced pressure, the obtained crude product was subjected to Kugelrohr distillation (distillation temperature 135 ° C./40 Pa) under reduced pressure to obtain trimethoxy (3- (Tris (1H, 1H, 2H,). 2H-Tridecafluorooctyl) silyl) propyl) silane (Exemplified Compound No. (1-16-3)) was obtained as a colorless liquid in 923 mg (yield 69.4%).

^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ0.73 to 0.79 (m, 4H), 0.85 to 0.90 (m, 6H), 1.43 to 1.49 (m, 2H), 1.97-2.10 (m, 6H), 3.56 (s, 9H).
¹⁹ F-NMR (376 MHz, CDCl ₃ ): δ-126.1, -123.3, -122.9, -122.0, -116.1, -80.8.

(Example 9) 9,9,9-Tris ((1H, 1H, 2H, 2H-tridecafluorooctyl) -3,3,5,5,7,7-hexamethyl-1,1,1-trimethoxy) Synthesis of pentasiloxane (exemplified compound number (1-21-3)).

A 50 mL three-necked flask equipped with a magnetic stirrer, a dropping rotor, a gym rotor condenser and a three-way cock was replaced with argon. The flask contained 20 mL of diethyl ether and 1.68 g (6.98 mmol) of hexamethyltrisiloxane-1,5-diol. A 10 mL solution of dehydrated diethyl ether of Tris ((1H, 1H, 2H, 2H-tridecafluorooctyl) bromosilane 7.64 g (6.65 mmol) and pyridine 1.93 g (24.5 mmol) from the dropping rotor at 0 ° C. The mixture was added dropwise over 7 hours and then stirred for 1 hour. 1.92 g (12.3 mmol) of chlorotrimethoxysilane was added to the reaction vessel over 3 minutes from the injector, and then the mixture was stirred for 18 hours. Was removed, hexane was added, and the mixture was filtered under an argon atmosphere using a Schlenk tube with a glass filter. 9,9-Tris ((1H, 1H, 2H, 2H-tridecafluorooctyl) -3,3,5,5,7,7-hexamethyl-1,1,1-trimethoxypentasiloxane (exemplified compound number (exemplified compound number) 1-21-3)) was obtained as a colorless liquid in an amount of 4.95 g (yield: 52.0%).
^{1 1} H-NMR (400MHz, CDCl ₃ ) δ (ppm): 0.09 (s, 6H), 0.12 (s, 6H), 0.14 (s, 6H), 0.88-0.93 ( m, 6H), 2.03-2.18 (m, 6H), 3.55 (s, 9H)
¹⁹ F-NMR (376MHz, CDCl ₃ ) δ (ppm): -126.42, -123.50, -123.11, -122.14, -116.26, -81.16
²⁹ Si-NMR (79MHz, CDCl ₃ ) δ (ppm): -85.42, -20.17, -19.40, -18.46, 5.389
IR (net, cm ^-1 ): 2964, 2914, 848, 1442, 1423, 1362, 1317, 1236, 1192, 114, 1093, 1072, 1032, 949, 904, 843, 802, 773, 737, 706, 644 , 621.

(Example 10) 9,9,9-Tris ((1H, 1H, 2H, 2H-tridecafluorooctyl) -3,5,7- (3,3,3-trifluoropropyl) -3,5, Synthesis of 7-trimethyl-1,1,1-trimethoxypentasiloxane (exemplified compound number (1-25-3))

A 50 mL three-necked flask equipped with a magnetic stirrer, a dropping roto, a gym rote cooling tube and a three-way cock was replaced with argon and diethyl ether 15 mL and 1,3,5- (3,3,3-trifluoro). It contained 1.11 g (2.50 mmol) of propyl) -1,3,5-trimethylsiloxane-1,5-diol. A 5 mL solution of dehydrated diethyl ether of Tris ((1H, 1H, 2H, 2H-tridecafluorooctyl) bromosilane 2.11 g (1.84 mmol) and pyridine 0.810 g (10.2 mmol) from the dropping rotor at 0 ° C. After 2 hours, the mixture was stirred at room temperature for 1.5 hours. To this solution, 0.823 g (5.25 mmol) of chlorotrimethoxysilane was added over 3 minutes at 0 ° C. with a syringe, and 18 at room temperature. The mixture was stirred for hours. The low boiling point component was removed under reduced pressure, hexane was added, and the mixture was filtered under an argon atmosphere using a Schlenk tube with a glass filter. By vacuum distillation (distillation temperature 170 ° C./20Pa), 9,9,9-tris 9,9,9-tris ((1H, 1H, 2H, 2H-tridecafluorooctyl) -3,5,7 -(3,3,3-trifluoropropyl) -3,5,7-trimethyl-1,1,1-trimethoxypentasiloxane (exemplified compound number (1-25-3)) as a colorless liquid 1.38 g (Yield: 46.0%) was obtained.
^{1 1} H-NMR (400MHz, CDCl ₃ ) δ (ppm): 0.17-0.18 (m, 9H), 0.77-0.80 (m, 6H), 0.91-0.96 (m) , 6H), 2.03-2.15 (m, 12H), 3.55 (s, 9H)
¹⁹ F-NMR (376MHz, CDCl ₃ ) δ (ppm): -126.54, -123.67, -123.22, -122.23, -116.49, -81.30, -69.33
²⁹ Si-NMR (79MHz, CDCl ₃ ) δ (ppm): -85.60, -21.59, -20.98 to -20.86 (m), 7.237
IR (net, cm ^-1 ): 2951,210,2852,1444,1423,1367,1135,1265, 1236,1205,1140,1092,1068,1020,949,899,839,810,773,746,706 , 644.

(Evaluation example 1)
Exemplified compound No. (1-4-1) 50 mg was taken, and this was dissolved in 24.8 g of ethyl ethyl nonafluorobutyl ether (isomer mixture) (concentration: 0.2% by weight), and the soda glass was cleaned in this solution. The substrate was immersed for 2 hours. The soda glass substrate was pulled out of the solution, washed thoroughly with ethyl nonafluorobutyl ether and distilled water in this order, immersed in chloroform, and ultrasonically washed for 10 minutes. This was dried in a dryer at 70 ° C. for 30 minutes and then dried in a desiccator.
Water and 1 μL of hexadecane were placed on the treated substrate with a microsyringe, and the contact angle was determined by the θ / 2 method. When the five measurements were averaged, the water contact angle was 106 (2) degrees and the hexadecane contact angle was 68 (1). ) Degree. Further, when 50 μL of distilled water was placed on the glass substrate, the glass substrate was gradually tilted, the critical angles when the water droplets started to move were measured at 5 points, and the average was calculated, it was 10.7 (7) degrees. ..

(Evaluation example 2)
Exemplified compound No. (1-4-3) 50 mg (concentration: 0.2% by weight) was taken, this was dissolved in 24.8 g of ethyl nononafluorobutyl ether (isomer mixture), and the soda glass substrate was cleaned in this solution. Was immersed for 10 seconds. The soda glass substrate was pulled out of the solution and left at room temperature for a day. The soda glass substrate was thoroughly washed with ethyl nonafluorobutyl ether and distilled water in this order, immersed in chloroform, and ultrasonically washed for 10 minutes. This was dried in a dryer at 70 ° C. for 30 minutes and then dried in a desiccator.
Water and 1 μL of hexadecane were placed on the treated substrate with a microsyringe, and the contact angle was determined by the θ / 2 method. When the five measurements were averaged, the water contact angle was 107 (1) degrees and the hexadecane contact angle was 68 (1). ) Degree. Further, when 50 μL of distilled water was placed on the glass substrate, the glass substrate was gradually tilted, the critical angles when the water droplets started to move were measured at 5 points, and the average was calculated, it was 10.5 (7) degrees. ..

(Evaluation example 3)
After mixing 1 g of the 5 wt% isopropyl alcohol solution of Exemplified Compound No. (1-4-3) and 60 mg of the 10 wt% isopropyl alcohol solution of p-toluenesulfonic acid monohydrate, immediately take 0.5 mL and use cellulose tissue paper. The surface of a clean soda glass substrate was wiped and coated. This was allowed to stand at room temperature for 16 hours. It was flushed with chloroform and then flushed with distilled water for washing. This was immersed in 100 mL of chloroform and washed for 10 minutes while irradiating with ultrasonic waves (28 kHz + 38 kHz, 340 W) to obtain a homogeneous and transparent surface-modified glass substrate. The contact angle of this treated glass substrate with water and hexadecane was determined by the θ / 2 method. The contact angle with water was 112.0 (7) degrees, the contact angle with hexadecane was 71 (2) degrees, and the water sliding angle was 9.4 (6) degrees.

(Evaluation example 4)
Exemplified compound number (1-21-3) was taken at 50 mg (concentration: 0.2% by weight), dissolved in 24.8 g of ethyl nonafluorobutyl ether, and a clean soda glass substrate was immersed in this solution for 10 seconds. .. The soda glass substrate was pulled out of the solution and left at room temperature for a day. The soda glass substrate was thoroughly washed with ethyl nonafluorobutyl ether and distilled water in this order, immersed in chloroform, and ultrasonically washed for 10 minutes. This was dried in a dryer at 70 ° C. for 30 minutes and then dried in a desiccator.
Water and 1 μL of hexadecane were placed on the treated substrate with a microsyringe, and the contact angle was determined by the θ / 2 method. When the five measurements were averaged, the water contact angle was 105 (1) degrees and the hexadecane contact angle was 59 (2). ) Degree. Further, when 50 μL of distilled water was placed on the glass substrate, the glass substrate was gradually tilted, the critical angles when the water droplets started to move were measured at 5 points, and the average was calculated, it was 8.2 (8) degrees. ..

(Evaluation example 5)
Exemplified compound number (1-25-3) was taken at 50 mg (concentration: 0.2% by weight), dissolved in 24.8 g of ethyl nonafluorobutyl ether, and a clean soda glass substrate was immersed in this solution for 10 seconds. .. The soda glass substrate was pulled out of the solution and left at room temperature for a day. The soda glass substrate was thoroughly washed with ethyl nonafluorobutyl ether and distilled water in this order, immersed in chloroform, and ultrasonically washed for 10 minutes. This was dried in a dryer at 70 ° C. for 30 minutes and then dried in a desiccator.
Water and 1 μL of hexadecane were placed on the treated substrate with a microsyringe, and the contact angle was determined by the θ / 2 method. When the five measurements were averaged, the water contact angle was 104.7 (9) degrees and the hexadecane contact angle was 52. It was (4) degrees. Further, when 50 μL of distilled water was placed on the glass substrate, the glass substrate was gradually tilted, the critical angles when the water droplets started to move were measured at 5 points, and the average was calculated, it was 9.8 (5) degrees. ..

(Comparative Example 1)
Take 50 mg (concentration: 0.2% by weight) of trimethoxy (1H, 1H, 2H, 2H-tridecafluorooctyl) silane _{(C6 F 13 CH 2} CH ₂ Si (OMe) ₃ ) (comparative compound (1)). , This was dissolved in 24.8 g of ethyl nonafluorobutyl ether, and the cleaned soda glass substrate was immersed in this solution for 10 seconds. The soda glass substrate was pulled out of the solution and left at room temperature for a day. The soda glass substrate was thoroughly washed with ethyl nonafluorobutyl ether and distilled water in this order, immersed in chloroform, and ultrasonically washed for 10 minutes. This was dried in a dryer at 70 ° C. for 30 minutes and then dried in a desiccator.
Water and 1 μL of hexadecane were placed on the treated substrate with a microsyringe, and the contact angle was determined by the θ / 2 method. When the five measurements were averaged, the water contact angle was 105 (2) degrees and the hexadecane contact angle was 62 (4). ) Degree. In addition, 50 μL of distilled water was placed on the glass substrate, the glass substrate was gradually tilted, the critical angles when the water droplets started to move were measured at five points, and the average was calculated. As a result, a large value of 15.5 (8) degrees was obtained. The result was that the dynamic liquid repellency was slightly inferior.

(Comparative Example 2)
_{10 g of a 5 wt% isopropyl alcohol solution of the comparative compound (triethoxy (1H, 1H, 2H, 2H-tridecafluorooctyl) silane (C6 F 13 CH 2} CH ₂ Si (OEt) ₃ )) (comparative compound (2)). After mixing 600 mg of a 10 wt% isopropyl alcohol solution of p-toluenesulfonic acid monohydrate, 0.5 mL was immediately taken and wiped onto a clean soda glass substrate surface with cellulose tissue paper. This was allowed to stand at room temperature for 16 hours. Hexafluorobenzene / chloroform 1: 3 solution was flushed, and then distilled water was flushed and washed. This was immersed in 100 mL of chloroform and washed for 10 minutes while irradiating with ultrasonic waves (28 kHz + 38 kHz, 340 W) to obtain a surface-modified glass substrate having a large haze and cloudiness. The contact angle of this treated glass substrate with water and hexadecane was determined by the θ / 2 method. The contact angle with water was 106 (2) degrees, and the contact angle with hexadecane was 65 (2) degrees. The water sliding angle showed a large value of 19 (4) degrees, and the result that the dynamic liquid repellency was inferior was obtained.

(Comparative Example 3)
1 g of a 5 wt% isopropyl alcohol solution of a comparative compound (trimethoxy (1H, 1H, 2H, 2H-tridecafluorooctyl) silane (C ₆ F ₁₃ CH ₂ CH ₂ Si (OMe) ₃ )) (comparative compound (1)). After mixing 60 mg of a 10 wt% isopropyl alcohol solution of p-toluenesulfonic acid monohydrate, 0.5 mL was immediately taken and wiped onto a clean soda glass substrate surface with cellulose tissue paper. This was allowed to stand at room temperature for 16 hours. Hexafluorobenzene / chloroform 1: 3 solution was flushed, and then distilled water was flushed and washed. This was immersed in 100 mL of chloroform and washed for 10 minutes while irradiating with ultrasonic waves (28 kHz + 38 kHz, 340 W) to obtain a surface-modified glass substrate having a large haze and cloudiness. The contact angle of this treated glass substrate with water and hexadecane was determined by the θ / 2 method. The contact angle with water was 109 (5) degrees, and the contact angle with hexadecane was 71 (3) degrees. The water sliding angle showed a large value of 19 (2) degrees, and the result that the dynamic liquid repellency was inferior was obtained.

Claims (11)

General formula (1)

[In the formula, n is an integer from 2 to 6. m is 2 or 3. R ¹ represents an alkyl group having 1 to 4 carbon atoms. A is an alkylene group having 2 to 6 carbon atoms, or the general formula (2).

(In the formula, R ³ and R ⁴ each independently represent an alkyl group having 1 to 4 carbon atoms which may be substituted with a fluorine atom. P is an integer of 1 to 9.)
Represents the siroxanilen group represented by. X ¹ represents a halogen atom, an alkoxy group having 1 to 3 carbon atoms or a dialkylamino group having 2 to 6 carbon atoms, and a plurality of X ^1s may be the same or different from each other. R ² represents an alkyl group having 1 to 4 carbon atoms. r is 0 or 1. However, when n is 6 and m is 3, A cannot be a 1,2-ethylene group. ]
Fluorine-containing silane compound indicated by. The fluorine-containing silane compound according to claim 1, wherein n is 4 or 6 and m is 2. The fluorine-containing silane compound according to claim 1 or 2, wherein A is a 1,2-ethylene group, a 1,3-propylene group or a siloxanilen group in which R3 and ^{R4 are} methyl groups. General formula (3)

(In the formula, n is an integer of 2 to 6. m is 2 or 3. R ¹ represents an alkyl group having 1 to 4 carbon atoms. Q is an integer of 2 to 6.)
The olefin compound represented by the above and the general formula (4).

(In the formula, X ¹ represents a halogen atom, an alkoxy group having 1 to 3 carbon atoms or a dialkylamino group having 2 to 6 carbon atoms, and a plurality of X ^1s may be the same or different from each other. R ² may have 1 carbon atom. Represents an alkyl group from 4 to 4. r is 0 or 1.)
The general formula (1a) is characterized in that the hydrosilane compound represented by the above is reacted in the presence of a hydrosilylation catalyst.

(In the formula, n, m, R ¹ , q, X ¹ , R ² and r are synonymous with the above. However, when n is 6 and m is 3, A becomes a 1,2-ethylene group. I don't get it.)
A method for producing a fluorine-containing silane compound shown by. General formula (6)

(In the formula, R ³ and R ⁴ each independently represent an alkyl group having 1 to 4 carbon atoms which may be substituted with a fluorine atom. P is an integer of 1 to 9.)
The siloxane diol compound represented by the above formula (5)

(In the formula, n is an integer of 2 to 6. m is 2 or 3. R ¹ represents an alkyl group having 1 to 4 carbon atoms. X ² represents a halogen atom.)
Fluorine-containing halogenated silane compound represented by and the general formula (8).

(In the formula, X ¹ represents a halogen atom, an alkoxy group having 1 to 3 carbon atoms or a dialkylamino group having 2 to 6 carbon atoms, and a plurality of X ^1s may be the same or different from each other. R ² may have 1 carbon atom. Represents an alkyl group from 4 to 4. r is 0 or 1. X ³ represents a halogen atom.)
The general formula (1b) is characterized by reacting with the halogenated silane compound represented by.

(In the formula, n, m, R ¹ , X ¹ , R ³ , R ⁴ , p, R ² and r are synonymous with the above.)
A method for producing a fluorine-containing silane compound shown by. General formula (1c)

[In the formula, n is an integer from 2 to 6. m is 2 or 3. R ¹ represents an alkyl group having 1 to 4 carbon atoms. A is an alkylene group having 2 to 6 carbon atoms, or the general formula (2).

(In the formula, R ³ and R ⁴ each independently represent an alkyl group having 1 to 4 carbon atoms which may be substituted with a fluorine atom. P is an integer of 1 to 9.)
Represents the siroxanilen group represented by. ^X4 represents a halogen atom. R ² represents an alkyl group having 1 to 4 carbon atoms. r is 0 or 1. ]
The general formula (1d), which comprises reacting the fluorine-containing silane compound represented by

(In the formula, n, m, R ¹ , A, R ² and r are synonymous with the above. X ⁵ represents an alkoxy group having 1 to 4 carbon atoms or a dialkylamino group having 2 to 6 carbon atoms). The method for producing a fluorine-containing silane compound shown. The method for producing a fluorine-containing silane compound according to claim 6, wherein the alkoxylating agent is an alcohol compound. A surface modification composition comprising the fluorine-containing silane compound according to any one of claims 1 to 3 and an organic solvent. The surface modification composition according to claim 8, which comprises the fluorine-containing silane compound according to any one of claims 1 to 3, an organic solvent and a polymerization promoting catalyst. The surface modification composition according to claim 9, wherein the polymerization promoting catalyst is an acid catalyst. A method for surface modification of a glass substrate, a metal oxide substrate or a metal substrate, which comprises applying the surface modification composition according to any one of claims 8, 9 or 10.