JPH09137117A - Method for forming silane compound coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of forming a silane compd. coating film which enables a silane compd. coating film having an excellent antifouling property to be durably and easily formed by subjecting a resin surface to particular treatment, coating the treated surface with a predetermined silane compd., and curing the coating. SOLUTION: The surface of a resin (e.g. an acrylic film) is coated with a compsn. comprising 100 pts.wt. polymerizable compd. having two or more (meth)acryloyloxy groups in its molecule (e.g. a urethane acrylate hard coating agent) and 1 to 50 pts.wt. fine particles of an inorg. compd. (e.g. silica), and the coating is then cured to form a cured film. The surface of the coating is then subjected to corona treatment or plasma treatment. The treated surface is then coated with a silane compd. having in its molecule at least one group hydrolyzable to produce a silanol group, pref. a fluorosilane compd. having represented by the formula (wherein Rf represents a 1-16C perfluoroalkyl; R<1> represents a divalent org. compd.; R<2> represents a hydrolyzable group; R<3> represents H or an inactive monovalent org. compd.; and (n) is 0 to 2), and the coating is cured.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for forming a silane compound film on a resin surface. Specifically, it relates to a method for forming a silane compound coating film on a resin surface with good durability.

[0002]

2. Description of the Related Art By subjecting a vapor-deposited film of an inorganic compound formed on a glass or resin surface to a treatment with a silane compound, a chemical bond is formed between the surface of the base material and the silane compound to semipermanently achieve various performances. It has been widely known that it can be given, and it is also widely used industrially.
As an example of the treatment with the silane compound, there is a treatment on a front plate of a display screen used for OA equipment, an eyeglass lens, or the like. When used by a person, the front plate of the display screen, the spectacle lens, and the like adhere to hand marks, fingerprints, sweat, cosmetics, and the like. Therefore, by treating the surface of the silane compound with a certain kind of silane compound, it has been devised to make it hard to adhere to such dirt or to easily wipe off the dirt.

For example, JP-A-2-248480 and JP-A-6-184527 propose an article in which a stain-resistant coating composed of a fluoroalkylsilane compound layer is formed on the surface of a glass plate. In addition, JP-A-6-256
Japanese Patent No. 756 proposes an article in which a stain-resistant coating film made of a fluoroalkylsilane compound and a polysiloxane compound is formed on the surface of a glass plate.

Further, since the windows for construction use have a problem that dirt due to rain, mud, exhaust gas, etc. adheres and the transparency of the base material is lost, a stain resistant treatment is desired. . In order to impart stain resistance to the resin surface, generally, there is a method of coating the surface with a fluorine resin such as polytetrafluoroethylene or polyvinylidene fluoride.

[0005]

The conventional silane compound coating can be formed only on the glass surface, and even if a coating is formed on a general resin surface, it does not have a bond with the substrate. It had the drawback of being easily peeled off. A method of forming a silane compound film on a resin substrate has also been proposed, but even in that case, a vapor deposition film or the like made of an inorganic compound such as silicon dioxide must be formed on the resin surface, and the process is complicated. However, there is a problem that the cost becomes high.

On the other hand, in the method of coating the surface of the resin with the fluororesin, some chemical bonding is necessary because the fluororesin has poor adhesion to the base resin. Although the silane compound has a functional group for forming a chemical bond with the base material, a general resin surface often does not have a functional group for reacting with the silane compound.

Therefore, as a result of extensive studies on a method for forming a coating film made of a silane compound on the surface of a general resin, the present inventor applied a composition containing a polymerizable compound and inorganic compound fine particles to form a coating film. Then, the surface of the coating is subjected to a corona treatment or a plasma treatment, and the treated surface is coated with a silane compound having a group to be a silanol group by hydrolysis, and cured to give a silane compound coating having excellent durability on the resin surface. The present invention has been completed by finding out that the above can be formed.

[0008]

That is, the present invention provides 1 to 50 parts by weight of fine particles of an inorganic compound with respect to 100 parts by weight of a polymerizable compound having at least two (meth) acryloyloxy groups in the molecule on the resin surface. After forming a coating film by coating a composition containing, the surface of the cured coating film is subjected to corona treatment or plasma treatment, and then the treated surface is treated with at least a group that produces a silanol group by hydrolysis in the molecule. A method for forming a silane compound film, which comprises applying and curing a silane compound having one of them. Hereinafter, the present invention will be described in detail.

[0009]

The shape of the resin used in the present invention is not particularly limited, but a film or sheet-like material is preferably used. Examples of the resin include acrylic resins, polycarbonate resins, polyester resins such as polyethylene terephthalate, cellulose resins such as triacetyl cellulose and diacetyl cellulose, styrene resins, vinyl chloride resins and the like. Among these resins, rubber for impact resistance improvement,
An ultraviolet absorber for improving weather resistance and other additives such as an antioxidant, a colorant, and a flame retardant for modification may be contained.

Further, an optical film or sheet provided with polarization characteristics and the like as these resins is also mentioned. The film or sheet may be a single layer or a laminate of a plurality of resins. The thickness can be arbitrarily selected depending on the purpose of use, but is about 0.01 to 5 mm.

As the polymerizable compound having at least two (meth) acryloyloxy groups in the molecule, an esterified product of polyhydric alcohol and (meth) acrylic acid, a compound having an isocyanate group at the terminal and a hydroxyl group ( Examples thereof include urethane-modified (meth) acrylic oligomer obtained from a (meth) acrylic acid derivative.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, propanediol, butanediol, pentanediol, hexanediol, neopentyl glycol, 2-ethyl-1,3-hexane. Diol, 2,2 '
-Dihydric alcohols such as thiodiethanol and 1,4-cyclohexanedimethanol, and trihydric or higher alcohols such as trimethylolpropane, pentaglycerol, glycerol, pentaerythritol, diglycerol and dipentaglycerol.

In order to impart flexibility to a film formed by curing the polymerizable compound and prevent cracking, a polyunsaturated carboxylic acid is further added to the (meth) acrylic acid that esterifies the polyhydric alcohol. A small amount may be added to form a mixed ester. Examples of the polyunsaturated carboxylic acid include succinic acid, tetrahydrophthalic acid, phthalic acid, maleic acid, fumaric acid, itaconic acid and the like.

The urethane-modified (meth) acrylic oligomer is produced by reacting a polyisocyanate such as hexamethylene diisocyanate or isophorone diisocyanate with an oligomer having a plurality of hydroxyl groups such as polycaprolactone diol or polytetramethylene diol. For terminal isocyanate polyurethane,
Furthermore, it can be obtained by a urethanization reaction with a (meth) acrylic acid derivative having a hydroxyl group, for example, 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate.

The fine particles of the inorganic compound are for enhancing the reactivity with the silane compound described later. Examples of the inorganic compound used include inorganic oxides such as silicon dioxide, aluminum oxide, magnesium oxide, tin oxide, silicon monoxide, zirconium oxide, and titanium oxide. Among them, silica fine particles mainly composed of silicon dioxide are preferable from the viewpoints of cost, ease of controlling the particle size, and adhesion to the silane compound layer.

Commercially available silica fine particles can be used. For example, Syloid 72 (manufactured by Fuji Davisson Chemical Co., Ltd.),
Examples include Cyloid 244 (manufactured by Fuji Davison Chemical), Mizukasil P527 (manufactured by Mizusawa Chemical Co., Ltd.) and Aerosil TT600 (manufactured by Degussa). Further, an aggregate of colloidal silica may be used as the silica fine particles. Examples of commercially available colloidal silica include Ludox AM (manufactured by DuPont), Xesol A200 (manufactured by Bayer AG),
Snowtex-C (manufactured by Nissan Chemical Industries) and the like can be mentioned.

The amount of the inorganic compound fine particles added is 1 to 50 parts by weight, preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, based on 100 parts by weight of the polymerizable compound. If the amount is less than 1 part by weight, sufficient reactivity with the silane compound cannot be obtained. On the other hand, if the amount is more than 50 parts by weight, not only the strength of the cured film is lowered but also the adhesion to the resin substrate is lowered, which is not preferable.

The composition containing the polymerizable compound and the fine particles of the inorganic compound of the present invention includes a known polymerization initiator or polymerization accelerator compatible with the below-mentioned polymerization and curing method, such as an azo compound or a radical of an organic peroxide. Generating agent; carbonyl compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, acetoin, benzyl, benzophenone and p-methoxybenzophenone, and photosensitizers such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide It is desirable to let it. The addition amount of these agents is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polymerizable compound.

Further, additives such as an ultraviolet absorber and a light stabilizer may be contained to the extent that the physical properties of the cured film are not impaired. Examples of the ultraviolet absorber include commercially available benzotriazole type and benzophenone type, and examples of the light stabilizer include hindered amine type.

The method of applying the composition containing the polymerizable compound and the fine particles of the inorganic compound onto the substrate may be a conventional coating operation such as spin coating, dip coating, roll coating, gravure coating or curtain flow coating. The method used may be mentioned. At this time, the raw material composition may be diluted with various solvents in order to facilitate the coating or to adjust the film thickness of the coating film.

To cure the coated composition, there are a method of heat-polymerizing by heating and heating, and a method of photopolymerizing by irradiating active energy rays such as ultraviolet rays and electron rays. Of these, the method of photopolymerization is preferable because it is simple.

The thickness of the cured film is not particularly limited, but is preferably 1 to 20 μm. If it is 1 μm or less, it is difficult to obtain a sufficient effect of increasing the reactivity with the silane compound, and if it is 20 μm or more, it is not preferable in terms of film strength such as cracking of the film. In addition, a film on which a cured coating containing the above-mentioned inorganic compound fine particles is formed is often used as an antiglare film.

In order to improve the adhesion between the cured coating containing the inorganic compound and the silane compound coating, the surface of the cured coating containing the inorganic compound is activated by corona treatment, plasma treatment or the like before providing the silane compound coating. . Of these, the corona treatment is preferable because of the simplicity of the operation.

Examples of the silane compound having a group which becomes a silanol group by hydrolysis include chlorosilane compounds, alkoxysilane compounds, acyloxysilane compounds, silazane compounds and the like.

Examples of the silane compound having at least one such group in the molecule include dimethyldimethoxysilane, tetramethoxysilane, phenyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, γ-chloropropyltrimethoxy. Silane, γ
-Aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyl Examples thereof include dimethoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, dimethyltrimethylsilylamine, N-trimethylsilylacetamide and hexamethyldisilazane.

Further, a copolymer of a polymerizable compound such as γ-methacryloxypropyltrimethoxysilane and another polymerizable compound as disclosed in JP-A No. 7-16940 is also exemplified. be able to. Silicon oil composed of polydimethylsiloxane in which the terminal of the molecule is silanol-modified is also mentioned as an example.

Further, in order to impart water repellency, stain resistance and the like to the resin surface, the general formula 4

Embedded image (In the formula, Rf is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, R ¹ is a divalent organic group, R ² is a hydrolyzable group, R ³ is hydrogen or an inert group. A fluorinated silane compound represented by a valent organic group and n represents an integer of 0 to 2 is preferably used.

Rf in the formula is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms. R ¹ is a divalent organic group, specifically, —CH ₂ CH ₂ —, —CH
_{2 OCH 2 CH 2 CH 2 -} , - CONHCH 2 CH 2 C
_{H 2 -, - CONHCH 2 CH} 2 NHCH 2 CH 2 CH
_{2 -, - SO 2 NHCH 2} CH 2 CH 2 -, - CH 2 C
_{H 2 OCONHCH 2 CH 2 CH 2} - and the like.
R ² is a hydrolyzable group, and is halogen, —OR ⁴ ,
^{-OCOR 4, -OC (R 4)} = C (R 5) 2, -ON = C
(R ⁴ ) ₂ and -ON = CR ⁶ are preferable (provided that R ⁴ is an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R ⁵ is hydrogen or a lower aliphatic hydrocarbon group, and R ⁶ has 3 to 3 carbon atoms). A divalent aliphatic hydrocarbon group of 6), and more preferably
Chlorine, -OCH _3, is -OC ₂ H _5. R ³ is hydrogen or an inactive monovalent organic group, but is preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms. n is an integer of 0 to 2, but is preferably 0.

## EQU3 ## Such a fluorine-containing compound represented by the general formula 4
CF as the elemental silane compound_ThreeCH_TwoCH_TwoSi (O
CH_Three)_Three , C_FourF₉CH_TwoCH_TwoSi (CH_Three) (OCH
_Three)_Two, C₈F₁₇ CH_TwoCH_TwoSi (OCH_Three)_Three , C₈
F₁₇CH_TwoCH_TwoSi (OC _TwoH_Five)_Three , C₈F₁₇CH_Two
CH_TwoSiCl_3,, (CF_Three)_TwoCF (CF_Two)₈CH_TwoC
H_TwoSi (OCH_Three)_Three, C_TenF_{twenty one}CH_TwoCH_TwoSi (O
CH_Three)_Three, C_TenF_{twenty one}CH_TwoCH_TwoSiCl_ThreeEtc.
It is.

In order to form a more excellent antifouling film, a fluorine-containing silane compound represented by the following general formula 5 is used.

Embedded image (In the formula, Rf is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, X is iodine or hydrogen, Y is hydrogen or a lower alkyl group, Z is a fluorine or trifluoromethyl group, and R ² is hydrolyzed. A decomposable group, R ³ is hydrogen or an inert monovalent organic group, and a, b, c and d are 0 to 200.
, E is 0 or 1, m and n are integers from 0 to 2,
p represents an integer of 1 to 10. )

[0031] Rf in the formula is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, preferably _{CF 3 -, C 2 F 5} -, C 3 F 7 - a. R ² is a hydrolyzable group, and is halogen, —OR ⁴ , or —OCOR.
^{4, -OC (R 4) =} C (R 5) 2, -ON = C (R 4) 2,
—ON = CR ⁶ is preferable (provided that R ⁴ is an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R ⁵ is hydrogen or a lower aliphatic hydrocarbon group, and R ⁶ is a divalent aliphatic group having 3 to ⁶ carbon atoms). Group hydrocarbon group), and more preferably chlorine or -O.
CH _3, is -OC ₂ H _5. R ³ is hydrogen or an inactive monovalent organic group, but is preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms. a, b, c, d are 0 to 200
Is an integer but is preferably 1 to 50, and e is 0 or 1. m and n are integers of 0 to 2, preferably 0. p is an integer of 1 or more, preferably an integer of 1-10. The molecular weight is 5 × 10 ² -1
× 10 ⁵ , but preferably 5 × 10 ² to 1 × 10 ^4.
It is.

Further, a preferable example of the fluorine-containing silane compound represented by the above general formula 5 is a fluorine-containing compound represented by the following general formula 6.

[Chemical 6] (In the formula, Y is hydrogen or a lower alkyl group, R ² is a hydrolyzable group, r is an integer of 1 to 10 or more, and q is 1 to 50.
, And m is an integer of 0 to 2. )

These fluorine-containing silane compounds can be obtained by silane treatment of commercially available perfluoropolyether. This means that, for example, Japanese Patent Laid-Open No. 1-2-2
It is disclosed in Japanese Patent Publication No. 94709.

These silane compounds described above are hydrolyzed in the solvent described below or after coating with water in the air to form silanol groups, which firmly form a cured coating containing corona-treated or plasma-treated inorganic compound fine particles. It is considered that they bond to form a highly durable film.

When the silane compound is applied, it may be diluted with a solvent. As the solvent, water is generally used, but due to the solubility of the silane compound, aromatic hydrocarbons such as benzene, toluene, xylene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, acetic acid. Common organic solvents such as esters such as isobutyl, chlorinated hydrocarbons such as methylene chloride, trichloroethylene and chloroform, alcohols such as ethanol, 1-propanol, 2-propanol and 1-butanol may be used. . Further, with respect to the fluorine-containing silane compounds represented by the general formulas 5 and 6, perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane and the like can be used as a diluent solvent.

In order to accelerate the reaction between the resin surface and the silane compound, the silane compound solution may contain a catalyst such as a dilute hydrochloric acid aqueous solution, a dilute sulfuric acid aqueous solution, a phosphoric acid aqueous solution, a fatty acid metal salt or a metal alkoxide. .

Examples of the method for forming the silane compound coating on the resin surface include methods used in ordinary coating operations such as spin coating, dip coating, roll coating, gravure coating and curtain flow coating. Also, if necessary, it is heated and dried after coating.

The thickness of the silane compound film is not particularly limited, but is preferably 0.001 to 20 μm.
When the thickness is 0.001 μm or less, the effects such as antifouling property are poor, and when the thickness is 20 μm or more, the strength of the coating is lowered, which is not preferable. Further, in the case of the fluorine-containing silane compounds represented by the above general formulas 5 and 6, the surface is sticky, so 0.5
μm or less is preferred.

[0039]

According to the present invention, a silane compound film having excellent durability can be easily formed on the resin surface.
In particular, it is suitable for forming a silane compound film having excellent antifouling property on the resin surface with good durability.

[0040]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. In the examples, various physical property evaluation test methods are as follows. (1) Contact angle: A contact angle meter (CA-A type: manufactured by Kyowa Interface Science Co., Ltd.) is used to make a water drop having a diameter of 1.0 mm at the needle tip at room temperature, and the water is brought into contact with the surface of the measurement sample to make the liquid Made a drop. The angle between the droplet and the surface generated at this time was measured and defined as the contact angle. (2) Durability: After wiping the surface of the base material 20 times with a cellulose nonwoven fabric (Bencott: manufactured by Asahi Kasei),
A durability test was performed by measuring the contact angle with water by the method described above. (3) Adhesiveness of fingerprint: The right thumb was pressed against the surface for 3 seconds to attach the fingerprint, and its stickiness or conspicuousness was visually determined. The criteria were as follows. ◯: The amount of fingerprints attached is small and the attached fingerprints are inconspicuous. ×: Fingerprint adhesion can be clearly recognized. (4) Fingerprint wiping property: The attached fingerprint was wiped off with a cellulose nonwoven fabric, and the ease of removing the fingerprint was visually determined. The criteria were as follows. ：: The fingerprint can be completely wiped off. Δ: A fingerprint is wiped off. ×: Fingerprint wiping marks remain, making it difficult to remove.

Reference Example (1) Preparation of Polymerizable Composition Solution (I) Urethane acrylate-based hard coating agent (UNIDIC 17-) diluted with toluene so that the solid content was 30%.
806: 6 parts by weight of silica fine particles (Cyroid 244: manufactured by Fuji Davisson Chemical Co., Ltd.) was added to 100 parts by weight of the hard coat solid content in a stirrer (Bio-).
Mixer: manufactured by Nippon Seiki Seisakusho, Ltd.) and stirred for 5 minutes to disperse. (2) Preparation of Polymerizable Composition Solution (II) The above (1) except that the amount of silica fine particles was changed to 20 parts by weight.
A polymerizable composition solution was prepared in the same manner as. (3) Preparation of silane compound solution (I) Perfluorooctylethyltrimethoxysilane [C ₈ F
₁₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ] was diluted with isopropyl alcohol to give a 2.0 g / L solution. To 100 parts of this solution, 3 parts of a 0.1 N hydrochloric acid aqueous solution was added, and the mixture was stirred for 1 hour or more. (4) Preparation of silane compound solution (II) Perfluoropolyether silane compound represented by the following formula (7) (molecular weight: about 5000, manufactured by Daikin Industries, Ltd.)
Was diluted with perfluorohexane to give a 2.0 g / L solution.

[0042]

Embedded image

Example 1 A 200 × 300 × 0.25 mm impact-resistant acrylic film (Technoloy: manufactured by Sumitomo Chemical Co., Ltd.) was dipped in the polymerizable composition solution (I) prepared in Reference Example and pulled up by 30 cm / min. Applied at speed. After volatilizing the solvent, 120
A cured coating was formed by irradiating a W metal halide lamp (UB0451: manufactured by Eye Graphic Co., Ltd.) from a distance of 20 cm for 10 seconds. The obtained film on which the cured coating was formed was treated with a corona treatment machine (3005DW-SL
The surface of the cured coating was corona-treated with R: Sophthal made in Japan) at an energy of 400 W · min / m 2. The corona-treated film was dipped in the silane compound solution (I) prepared in Reference Example and applied at a pulling rate of 15 cm / min. After the application, the solvent was volatilized by standing at room temperature for 24 hours to obtain a film on which a silane compound film was formed. Table 1 shows the evaluation results.

Example 2 The procedure of Example 1 was repeated except that the polymerizable composition solution (II) prepared in Reference Example was used. Table 1 shows the evaluation results.

Example 3 The procedure of Example 1 was repeated except that the polymerizable composition solution (I) and the silane compound solution (II) prepared in Reference Example were used. Table 1 shows the evaluation results.

Example 4 The procedure of Example 3 was repeated except that the polymerizable composition solution (II) prepared in Reference Example was used. Table 1 shows the evaluation results.

Comparative Example 1 A polymerizable composition solution was prepared and used in the same manner as in the polymerizable composition solution (I) without adding silica fine particles.
Performed in the same manner as in Example 3. Table 1 shows the evaluation results.

Comparative Example 2 The procedure of Example 3 was repeated except that the silane compound solution was applied without corona treatment. Table 1 shows the evaluation results.

Comparative Example 3 The procedure of Example 1 was repeated except that the silane compound film was not formed. Table 1 shows the evaluation results.

[0050]

[Table 1] _{* Si-I: C 8 F} 17 CH 2 CH 2 Si (OCH 3) 3 Si-II: C 3 F 7 - (OCF 2 CF 2 CF 2) 24 -O (CF 2) 2 - [CH 2 CH ( -Si (OCH ₃ ) ₃ )] _1-10 -H

Claims (4)

[Claims] 1. A polymerizable compound 1 having at least two (meth) acryloyloxy groups in the molecule on the surface of a resin.
After applying a composition containing 1 to 50 parts by weight of the inorganic compound fine particles to 00 parts by weight and curing the composition to form a film,
A corona treatment or plasma treatment is performed on the surface of the cured coating, and then the treated surface is coated with a silane compound having at least one group capable of generating a silanol group by hydrolysis in the molecule and cured. Method of forming coating film. 2. A silane compound is represented by the general formula: (In the formula, Rf is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, R ¹ is a divalent organic group, R ² is a hydrolyzable group, R ³ is hydrogen or an inert group. 2. The method according to claim 1, which is a fluorinated silane compound represented by a valent organic group, and n represents an integer of 0 to 2.). 3. A silane compound is represented by the general formula: (In the formula, Rf is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, X is iodine or hydrogen, Y is hydrogen or a lower alkyl group, Z is a fluorine or trifluoromethyl group, and R ² is hydrolyzed. A decomposable group, R ³ is hydrogen or an inert monovalent organic group, and a, b, c and d are 0 to 200.
, E is 0 or 1, m and n are integers from 0 to 2,
p represents an integer of 1 to 10. The forming method according to claim 1, which is a fluorine-containing silane compound represented by the formula (1). 4. A silane compound is represented by the general formula: (In the formula, Y is hydrogen or a lower alkyl group, R ² is a hydrolyzable group, r is an integer of 1 to 10, q is an integer of 1 to 50, and m is an integer of 0 to 2.) The method according to claim 1, which is a fluorine-containing silane compound represented by: