JP2019035077A - Composition - Google Patents

Abstract

To provide a composition for obtaining a coat that allows any water droplets in contact with it, to slip down on satisfactorily, and can easily remove the water droplets from the surface.SOLUTION: A composition contains a silane compound (A) represented by the formula (1), a silane compound (B) represented by the formula (2), and a fluorine-based solvent (C). R-Si(X)(1), Si(R)(X)(2). [In formula (1), Ris a hydrocarbon group having 6 or more carbon atoms, where -CH- contained in the hydrocarbon group is optionally substituted with -O-. Xis a hydrolyzable group. In formula (2), Ris a C1-5 hydrocarbon group. Xis a hydrolyzable group. n is 0 or 1].SELECTED DRAWING: None

Description

  The present invention relates to a composition.

  In various display devices, optical elements, semiconductor elements, building materials, automobile parts, nanoimprint technology, and the like, liquid droplets such as water adhere to the surface of the base material. Problems such as performance degradation may occur due to corrosion. Therefore, it is required that the droplets attached to the surface of the substrate can be easily removed. For example, in Patent Documents 1 and 2, a water / oil repellent coating composition containing an organosilicon compound (A) and a metal compound (B) in a predetermined molar ratio is applied onto a glass substrate and dried. A technique for obtaining a transparent film is disclosed, and it is described that this transparent film is excellent in the sliding speed of water droplets.

International Publication No. 2016/068118 International Publication No. 2016/068103

  There has been a demand for a film having a further improved sliding property as compared with the transparent films described in Patent Documents 1 and 2 above.

  The present invention has been made in view of such circumstances, and an object thereof is to obtain a film that has good sliding properties of water droplets and can easily remove water droplets from the surface even when the droplets come into contact with the film. It is in providing the composition of this.

The present invention that has achieved the above object is as follows.
[1] A composition comprising a silane compound (A) represented by the following formula (1), a silane compound (B) represented by the following formula (2), and a fluorine-based solvent (C).
R ¹ —Si (X ¹ ) ₃ (1)
[In Formula (1), R ¹ represents a hydrocarbon group having 6 or more carbon atoms, and —CH ₂ — contained in the hydrocarbon group may be replaced by —O—. X ¹ represents a hydrolyzable group. ]
Si (R ² ) _n (X ² ) _4-n (2)
[In formula (2), R ² represents a hydrocarbon group having 1 to 5 carbon atoms. X ² represents a hydrolyzable group. n is 0 or 1. ]
[2] The composition according to [1], further comprising a non-fluorinated solvent (D).
[3] The composition according to [2], wherein the non-fluorinated solvent (D) is an alcohol solvent.
[4] The composition according to any one of [1] to [3], wherein the fluorine-based solvent (C) has a vapor pressure at 20 ° C. of 8.0 kPa or more.
[5] The composition according to any one of [1] to [4], wherein the content of the fluorine-based solvent (C) in 100% by mass of the composition is 20% by mass to 85% by mass.
[6] The composition according to any one of [1] to [5], wherein a molar ratio of the silane compound (B) to the silane compound (A) is 0.1 or more and 48 or less.
[7] Any of [1] to [6], wherein the total content of the silane compounds (A) and (B) in 100% by mass of the composition is 0.005% by mass or more and 12% by mass or less. A composition according to 1.
[8] A film obtained by curing the composition according to any one of [1] to [7].
[9] The film according to [8], wherein the sliding speed of 50 μL of water droplets at an inclination of 20 ° is 10.0 mm / second or more.

  Since the composition of the present invention contains predetermined silane compounds (A) and (B) and contains a fluorinated solvent (C) as a solvent, it can form a film with good sliding properties of water droplets.

  The composition of the present invention is characterized in that it contains predetermined silane compounds (A) and (B) as silane compounds and a fluorine-based solvent (C) as a solvent.

  First, (1) the silane compound will be described, and then (2) the solvent will be described.

(1) Silane compound (1-1) Silane compound (A)
The silane compound (A) is represented by the following formula (1).
R ¹ —Si (X ¹ ) ₃ (1)

In the above formula (1), R ¹ represents a hydrocarbon group having 6 or more carbon atoms, and —CH ₂ — contained in the hydrocarbon group may be replaced with —O—. X ¹ represents a hydrolyzable group.

The hydrocarbon group represented by R ¹ is preferably a saturated hydrocarbon group, more preferably a linear or branched alkyl group, and still more preferably a linear alkyl group.

The number of carbon atoms of the hydrocarbon group represented by R ¹ is preferably 7 or more, more preferably 8 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.

As the hydrocarbon group represented by R ¹ , a linear alkyl group having 6 to 30 carbon atoms is preferable, and among them, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group , Tetradecyl group, hexadecyl group and octadecyl group are preferable, and octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group and octadecyl group are particularly preferable.

When —CH ₂ — contained in the hydrocarbon group represented by R ¹ is replaced by —O—, the number of —O— replaced is also counted as the number of carbons.

Examples of the group in which —CH ₂ — contained in the hydrocarbon group represented by R ¹ is replaced by —O— include groups containing one or more alkyleneoxy units. Examples of the alkyleneoxy unit include an ethyleneoxy unit and a propyleneoxy unit, and an ethyleneoxy unit is preferable.

The group in which —CH ₂ — contained in the hydrocarbon group represented by R ¹ is replaced by —O— can be represented by, for example, —R ³ — (R ⁴ —O) _n1 —R ⁵ . R ³ represents a single bond or a divalent hydrocarbon group having 1 to ⁴ carbon atoms, R ⁴ represents a divalent hydrocarbon group having 2 or 3 carbon atoms, and R ⁵ represents a hydrogen atom or 1 to 4 carbon atoms. In which n1 represents an integer of 1 to 10. However, the -R ³ - (R ⁴ -O) the sum of the carbon and the number of oxygen atoms contained in the _n1 -R ⁵ is 6 or more.

R ³ is preferably a divalent hydrocarbon group having 1 to 4 carbon atoms, and the divalent hydrocarbon group represented by R ³ is a divalent group such as a methylene group, an ethylene group, a propylene group, or a butylene group. Of saturated hydrocarbon groups.

Examples of R ⁴ include divalent saturated hydrocarbon groups such as an ethylene group and a propylene group.

R ⁵ is preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms, and the monovalent hydrocarbon group represented by R ⁵ is a monovalent hydrocarbon group such as a methyl group, an ethyl group, a propyl group, or a butyl group. Of saturated hydrocarbon groups.

In the above formula (1), examples of the hydrolyzable group represented by X ¹ include groups that give a hydroxy group (silanol group) by hydrolysis, preferably an alkoxy group having 1 to 6 carbon atoms, a cyano group, Examples include an acetoxy group, a chlorine atom, and an isocyanate group. The three X ^{1 s} may be the same or different and are preferably the same.

X ¹ is preferably an alkoxy group having 1 to 6 carbon atoms (more preferably 1 to 4) or a cyano group, and an alkoxy group having 1 to 6 carbon atoms (more preferably 1 to 4). More preferably, all X ¹ are more preferably an alkoxy group having 1 to 6 (more preferably 1 to 4) carbon atoms.

Examples of the silane compound (A), R ¹ is a linear alkyl group having 6 to 18 carbon atoms (more preferably 7 to 13), all of X ¹ are the same group, 1 carbon atoms Those having 6 (more preferably 1 to 4, more preferably 1 or 2) alkoxy groups are preferred.

  Specific examples of the silane compound (A) include hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, nonyltrimethoxysilane, and nonyl. Triethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, undecyltrimethoxysilane, undecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tridecyltrimethoxysilane, tridecyltriethoxysilane, tetradecyl Trimethoxysilane, tetradecyltriethoxysilane, pentadecyltrimethoxysilane, pentadecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecylto Examples include ethoxysilane, heptadecyltrimethoxysilane, heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyl. Trimethoxysilane, dodecyltriethoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, and octadecyltriethoxysilane are preferred.

  As for the said silane compound (A), only 1 type may be used and multiple may be used together.

(1-2) Silane compound (B)
The silane compound (B) is represented by the following formula (2).
Si (R ² ) _n (X ² ) _4-n (2)

In the above formula (2), R ² represents a hydrocarbon group having 1 to 5 carbon atoms, X ² represents a hydrolyzable group, n is 0 or 1.

The hydrocarbon group represented by R ² is preferably a saturated hydrocarbon group, more preferably a linear or branched alkyl group, and still more preferably a linear alkyl group.

The hydrocarbon group represented by R ² is preferably a linear alkyl group having 1 to 3 carbon atoms, and specifically, a methyl group, an ethyl group, or a propyl group.

In the above formula (2), examples of the hydrolyzable group represented by X ² include the same groups as the hydrolyzable group represented by X ¹ , preferably an alkoxy group having 1 to 6 carbon atoms, A cyano group, an acetoxy group, a chlorine atom, an isocyanate group, etc. are mentioned. Three or four X ² may be the same or different and are preferably the same.

X ² is preferably an alkoxy group having 1 to 6 carbon atoms (more preferably 1 to 4) or an isocyanate group, and is preferably an alkoxy group having 1 to 6 carbon atoms (more preferably 1 to 4). More preferably, all X ² are more preferably alkoxy groups having 1 to 6 (more preferably 1 to 4) carbon atoms.

  In the above formula (2), n is preferably 0.

Examples of the silane compound (B), n is 0, those X ² is an alkoxy group is 1 to 6 carbon atoms (more preferably 1 to 3) is preferable.

  Specific examples of the silane compound (B) include tetramethoxysilane, tetraethoxysilane (tetraethyl orthosilicate), tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, Examples thereof include methyltributoxysilane, and tetramethoxysilane and tetraethoxysilane are preferable.

  The silane compound (B) may be used alone or in combination.

  The molar ratio (B / A) of the silane compound (B) to the silane compound (A) is usually 0.1 or more and 48 or less. Can be improved more. The molar ratio is more preferably 0.5 or more, further preferably 1 or more, more preferably 2 or more, and particularly preferably 4 or more. The molar ratio is preferably 40 or less, more preferably 25 or less, still more preferably 12 or less, particularly preferably 10 or less, and most preferably 8 or less. The molar ratio is preferably 0.1 or more and 12 or less.

  The total content of the silane compounds (A) and (B) in 100% by mass of the composition is preferably 0.005% by mass or more and 12% by mass or less. When the total content is in the above range, the water droplet sliding on the surface of the film can be improved. The total content is more preferably 0.010% by mass or more, still more preferably 0.05% by mass or more, still more preferably 0.10% by mass or more, and particularly preferably 0.2% by mass or more. The total content is preferably 10.0% by mass or less, and the appearance of the film can be improved. The total content is more preferably 5% by mass or less, still more preferably 3.0% by mass or less, particularly preferably 1% by mass or less, and most preferably 0.65% by mass or less.

  The appearance of the film is preferably good, and the appearance of the film can be evaluated based on, for example, transmitted light that passes through the film. Specifically, a film is placed over a light source in an environment with an illuminance of 1000 lux, and visually observed for coloring, color unevenness, and the presence or absence of foreign matter (hereinafter, these may be collectively referred to as “dirt”). What is necessary is just to evaluate that the appearance is good if the dirt cannot be confirmed.

(2) Solvent The composition of the present invention contains a fluorinated solvent (C) in addition to the silane compounds (A) and (B), and may further contain a non-fluorinated solvent (D).

(2-1) Fluorinated solvent (C)
By using a fluorinated solvent as the solvent, the sliding speed of the water droplets on the surface of the film can be increased, so that the sliding properties of the water droplets can be improved.

  The fluorine-based solvent (C) means a solvent containing a fluorine atom, and examples thereof include an aliphatic hydrocarbon solvent in which part or all of hydrogen is replaced with a fluorine atom.

  The aliphatic hydrocarbon may be a chain hydrocarbon or a cyclic hydrocarbon.

  Examples of chain hydrocarbons in which part or all of hydrogen is replaced with fluorine atoms include 1,1,1,3,3-pentafluorobutane, 2H, 3H-decafluoropentane, and the like.

  Examples of the cyclic hydrocarbon in which part or all of hydrogen is replaced by fluorine atoms include 1,1,2,2,3,3,4-heptafluorocyclopentane, 1,1,2,2,3, Examples include 4,4,5-octafluorocyclopentane. 1,1,2,2,3,3,4-heptafluorocyclopentane can be obtained, for example, as “Zeorolla H (registered trademark)” from ZEON Corporation.

  The fluorine-based solvent (C) preferably has a vapor pressure at 20 ° C. of 8.0 kPa or more. The vapor pressure is more preferably 10 kPa or more, further preferably 15 kPa or more, and still more preferably 20 kPa or more. Although the upper limit of the said vapor pressure is not specifically limited, For example, 50 kPa or less is preferable.

  The content of the fluorinated solvent (C) is preferably 20% by mass or more and 85% by mass or less in 100% by mass of the composition. The content is more preferably 25% by mass or more, and further preferably 30% by mass or more, in 100% by mass of the composition. As for the said content, 80 mass% or less is more preferable in 100 mass% of the said compositions, More preferably, it is 75 mass% or less.

  The mass ratio [(C) / ((A) + (B))] of the content of the fluorinated solvent (C) to the total content of the silane compounds (A) and (B) is, for example, 4 or more. More preferably, it is 10 or more, More preferably, it is 20 or more, 9000 or less is preferable, More preferably, it is 6500 or less, More preferably, it is 5000 or less, More preferably, it is 2000 or less.

(2-2) Non-fluorinated solvent (D)
The non-fluorinated solvent (D) means a solvent not containing a fluorine atom, and examples thereof include hydrophilic organic solvents such as alcohol solvents, ether solvents, ketone solvents, ester solvents, amide solvents. These non-fluorinated solvents (D) may be used alone or in combination of two or more.

  Examples of the alcohol solvent include ethanol, 1-propanol, 2-propanol (isopropanol), butanol, ethylene glycol, propylene glycol, diethylene glycol and the like. Examples of the ether solvent include dimethoxyethane and dioxane. Examples of the ketone solvent include methyl isobutyl ketone. Examples of the ester solvent include ethyl acetate and butyl acetate. Examples of the amide solvent include dimethylformamide. Among these, alcohol solvents (particularly 1-propanol or 2-propanol) and ketone solvents (particularly methyl isobutyl ketone) are preferably used, and alcohol solvents are more preferred.

  The non-fluorinated solvent (D) can be adjusted in accordance with the material of the base material to be described later. For example, when using an organic material, it is preferable to use a ketone solvent, and when using an inorganic material, an alcohol solvent. Is preferably used.

  The non-fluorinated solvent (D) preferably has a vapor pressure at 20 ° C. of less than 8.0 kPa. The vapor pressure is more preferably 7.0 kPa or less, still more preferably 6.0 kPa or less, and particularly preferably 5.0 kPa or less. Although the minimum of the said vapor pressure is not specifically limited, For example, 0.0001 kPa or more is preferable.

  The mass ratio [(D) / ((A) + (B))] of the content of the non-fluorinated solvent (D) to the total content of the silane compounds (A) and (B) is, for example, 2 or more More preferably, it is 5.0 or more, More preferably, it is 7 or more, 4000 or less is preferable, More preferably, it is 2500 or less, More preferably, it is 1000 or less, More preferably, it is 600 or less.

  The total of the fluorinated solvent (C) and the non-fluorinated solvent (D) is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more, in 100% by mass of the composition. is there. Although the upper limit of the said sum total is not specifically limited, For example, 99.99 mass% or less is preferable.

  When both the fluorinated solvent (C) and the non-fluorinated solvent (D) are included, the mass ratio [(C) / (D)] of the fluorinated solvent (C) and the non-fluorinated solvent (D) is, for example, 5/95 or more is preferable, more preferably 20/80 or more, still more preferably 25/75 or more, particularly preferably 30/70 or more, 99/1 or less is preferable, more preferably 85/15 or less, and further Preferably it is 80/20 or less, Most preferably, it is 75/25 or less.

  Preferred combinations of the fluorinated solvent (C) and the non-fluorinated solvent (D) include, for example, 1,1,1,3,3-pentafluorobutane and 1,1 as the fluorinated solvent (C). , 2, 2, 3, 3, 4-heptafluorocyclopentane, and a combination using at least one of ethanol, 1-propanol, and 2-propanol as the non-fluorinated solvent (D) Can be illustrated.

  The composition of the present invention may include a catalyst (E) for hydrolyzing and polycondensing the silane compound (A) and the silane compound (B).

  As the catalyst (E), hydrogen chloride (but usually used as hydrochloric acid), acidic compounds such as nitric acid and acetic acid, basic compounds such as ammonia and amine, organometallic compounds such as aluminum ethyl acetoacetate compound and the like are used. be able to.

  The content of the catalyst (E) is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and still more preferably with respect to 100 parts by mass in total of the silane compound (A) and the silane compound (B). Is 0.01 parts by mass or more, preferably 3 parts by mass or less, more preferably 1 part by mass or less, and still more preferably 0.1 parts by mass or less.

  The mass ratio [(E) / ((A) + (B))] of the content of the catalyst (E) to the total content of the silane compounds (A) and (B) is, for example, 0.1 or more. More preferably, it is 0.5 or more, More preferably, it is 1.0 or more, 2 or less is preferable, More preferably, it is 1.5 or less.

  The composition of the present invention is within the range not inhibiting the effects of the present invention, for example, an antioxidant, a rust inhibitor, a UV absorber, a light stabilizer, a fungicide, an antibacterial agent, a bioadhesion inhibitor, and a deodorant. Other components such as various additives such as pigments, flame retardants and antistatic agents may be contained.

  After the composition of the present invention is brought into contact with a substrate, a film can be formed by curing the composition on the substrate. The formed film can easily remove water droplets from the surface since the sliding speed of the water droplets is large even when the water droplets come into contact with the film.

  Examples of the method of bringing the composition of the present invention into contact with the substrate include spin coating, dip coating, spray coating, roll coating, bar coating, die coating, and hand coating (soaking a cloth into a liquid or the like). , A method of applying to the base material, preferably reciprocating on the substrate a plurality of times), pouring (a method of applying the liquid as it is to the base material using a dropper or the like), spraying (base material using spraying) And a combination of these methods. Among these, hand coating, pouring or spraying is preferable, and hand coating or spraying is particularly preferable.

  The film is allowed to stand in the air at room temperature (for example, 10 hours to 48 hours) in a state where the composition of the present invention is in contact with the base material, so that moisture in the air is taken in and the hydrolyzable group. Hydrolysis and polycondensation are accelerated, and the composition is cured to form on the substrate. It is also preferable to further dry the obtained film.

  The film thickness of the film is, for example, preferably 1 nm or more, more preferably 1.5 nm or more, and the upper limit is, for example, preferably 150 nm or less, more preferably 100 nm or less, still more preferably 60 nm or less, particularly preferably 15 nm. It is as follows. It is preferable that the film thickness of the film is equal to or greater than a certain value because stable water repellency can be expected. Moreover, since it can anticipate that an external appearance will become favorable when the film thickness of a film is below fixed, it is preferable.

  Examples of the material of the base material with which the composition of the present invention is brought into contact include organic materials and inorganic materials. Examples of the organic material include thermoplastic resins such as acrylic resins, polycarbonate resins, polyester resins, styrene resins, acrylic-styrene copolymer resins, cellulose resins, and polyolefin resins; phenol resins, urea resins, melamine resins, and epoxy resins. , Thermosetting resins such as unsaturated polyester, silicone resin, and urethane resin. Examples of the inorganic material include ceramics; glass; metals such as iron, silicon, copper, zinc, and aluminum; alloys containing the metals.

  The shape of the base material is not particularly limited, and may be a flat surface or a curved surface, or may be a three-dimensional structure in which a large number of surfaces are combined.

  The base material may be subjected to an easy adhesion treatment in advance to improve the adhesion between the base material and the film.

  Examples of the easy adhesion treatment include hydrophilization treatment such as corona treatment, plasma treatment, and ultraviolet treatment. In addition, a primer treatment with a resin, a silane coupling agent, tetraalkoxysilane, or the like may be performed, or a glass film such as polysilazane may be applied to the substrate in advance.

  The film obtained by curing the composition of the present invention is excellent in water droplet sliding. The sliding property of the water droplet can be evaluated by calculating the sliding velocity by dropping 50 μL of the water droplet on the film on the substrate inclined at 20 °, measuring the time from the initial dropping position until the water droplet slides 15 mm. The sliding speed is, for example, 10.0 mm / second or more, preferably 20 mm / second or more, more preferably 30 mm / second or more, and further preferably 40 mm / second or more. The upper limit of the sliding speed is, for example, 100 mm / second.

  The film obtained by curing the composition of the present invention preferably has a haze (cloudiness) of, for example, 0.50% or less, more preferably 0.17% or less, still more preferably 0.15%. Hereinafter, it is particularly preferably 0.12% or less. The lower limit of haze is, for example, 0.01%.

  It is preferable that the film obtained by curing the composition of the present invention has no stain even when visually observed and has a good appearance.

  By using the composition of the present invention, it is possible to provide a film having excellent water drop sliding properties. The coating is useful, for example, for building materials, automobile parts, factory equipment, and the like.

  Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited by the following examples, and can of course be implemented with appropriate modifications within a range that can be adapted to the above-described gist. Included in the range.

Example 1
9.4 × 10 ⁻⁴ mol of n-decyltrimethoxysilane as the silane compound (A) and 3.8 × 10 ⁻³ mol of tetraethyl orthosilicate as the silane compound (B) are dissolved in 2.63 ml of isopropyl alcohol, and room temperature is obtained. For 20 minutes. To the resulting solution, 1.27 ml of 0.01M aqueous hydrochloric acid solution was added dropwise as a catalyst (E), and the mixture was stirred for 24 hours to prepare Sample Solution 1.
The sample solution 1 was mixed with 1,1,1,3,3-pentafluorobutane (vapor pressure 43.4 kPa at 20 ° C.) and isopropyl alcohol (vapor pressure 4.4 kPa at 20 ° C.) in a volume ratio of 10 The coating solution 1 was prepared by diluting twice. The volume ratio of 1,1,1,3,3-pentafluorobutane to the total of 1,1,1,3,3-pentafluorobutane and isopropyl alcohol contained in the coating solution 1 was 50%.
Incorporate Asahi Kasei Co., Ltd. Bencot (registered trademark) with 1.5 ml of the coating solution 1 and continuously apply it to a 5 cm × 5 cm glass substrate (EAGLE XG, Corning) without placing time in the same place. The film was repeatedly applied, allowed to stand at room temperature for 24 hours and dried to form a film on the glass substrate.

(Example 2)
9.4 × 10 ⁻⁴ mol of n-decyltrimethoxysilane as the silane compound (A) and 3.8 × 10 ⁻³ mol of tetraethyl orthosilicate as the silane compound (B) are dissolved in 2.63 ml of isopropyl alcohol, and room temperature is obtained. For 20 minutes. After adding 1.27 ml of 0.01M aqueous hydrochloric acid solution as a catalyst (E) dropwise to the obtained solution, the solution was stirred for 24 hours to prepare Sample Solution 2.
The sample solution 2 is a mixed solution of 1,1,1,3,3-pentafluorobutane (vapor pressure 43.4 kPa at 20 ° C.) and isopropyl alcohol (vapor pressure 4.4 kPa at 20 ° C.) with a volume ratio of 30. The coating solution 2 was prepared by diluting twice. The volume ratio of 1,1,1,3,3-pentafluorobutane to the total of 1,1,1,3,3-pentafluorobutane and isopropyl alcohol contained in the coating solution 2 was 50%.
A film was formed on the glass substrate in the same manner as in Example 1 except that the coating solution 2 was used.

(Example 3)
9.4 × 10 ⁻⁴ mol of n-decyltrimethoxysilane as the silane compound (A) and 3.8 × 10 ⁻³ mol of tetraethyl orthosilicate as the silane compound (B) are dissolved in 2.63 ml of isopropyl alcohol, and room temperature is obtained. For 20 minutes. To the resulting solution, 1.27 ml of 0.01M aqueous hydrochloric acid solution was added dropwise as a catalyst (E), and the mixture was stirred for 24 hours to prepare Sample Solution 3.
The sample solution 3 is a mixed solution of 1,1,1,3,3-pentafluorobutane (vapor pressure 43.4 kPa at 20 ° C.) and isopropyl alcohol (vapor pressure 4.4 kPa at 20 ° C.) with a volume ratio of 50. The coating solution 3 was prepared by diluting it twice. The volume ratio of 1,1,1,3,3-pentafluorobutane to the total of 1,1,1,3,3-pentafluorobutane and isopropyl alcohol contained in the coating solution 3 was 50%.
A film was formed on the glass substrate in the same manner as in Example 1 except that the coating solution 3 was used.

Example 4
9.4 × 10 ⁻⁴ mol of n-decyltrimethoxysilane as the silane compound (A) and 3.8 × 10 ⁻³ mol of tetraethyl orthosilicate as the silane compound (B) are dissolved in 2.63 ml of isopropyl alcohol, and room temperature is obtained. For 20 minutes. To the obtained solution, 1.27 ml of 0.01M aqueous hydrochloric acid solution was added dropwise as a catalyst (E), and the mixture was stirred for 24 hours to prepare Sample Solution 4.
The sample solution 4 was diluted to 50 times volume ratio with a mixed solution of ZEOLOR H manufactured by Nippon Zeon Co., Ltd. (vapor pressure at 8.3 kPa at 20 ° C) and isopropyl alcohol (vapor pressure at 20 ° C of 4.4 kPa), A coating solution 4 was prepared. The volume ratio of Zeolora H to the total of Zeolola H and isopropyl alcohol contained in the coating solution 4 was 50%.
A film was formed on the glass substrate in the same manner as in Example 1 except that the coating solution 4 was used.

(Example 5)
9.4 × 10 ⁻⁴ mol of n-decyltrimethoxysilane as the silane compound (A) and 3.8 × 10 ⁻³ mol of tetraethyl orthosilicate as the silane compound (B) are dissolved in 2.63 ml of isopropyl alcohol, and room temperature is obtained. For 20 minutes. After adding 1.27 ml of 0.01 M hydrochloric acid aqueous solution as a catalyst (E) dropwise to the resulting solution, the solution was stirred for 24 hours to prepare Sample Solution 5.
The sample solution 5 is a mixed solution of 1,1,1,3,3-pentafluorobutane (vapor pressure 43.4 kPa at 20 ° C.) and isopropyl alcohol (vapor pressure 4.4 kPa at 20 ° C.) with a volume ratio of 100. The coating solution 5 was prepared by diluting it twice. The volume ratio of 1,1,1,3,3-pentafluorobutane to the total of 1,1,1,3,3-pentafluorobutane and isopropyl alcohol contained in the coating solution 5 was 50%.
A film was formed on the glass substrate in the same manner as in Example 1 except that the coating solution 5 was used.

(Example 6)
9.4 × 10 ⁻⁴ mol of n-decyltrimethoxysilane as the silane compound (A) and 3.8 × 10 ⁻³ mol of tetraethyl orthosilicate as the silane compound (B) are dissolved in 2.63 ml of isopropyl alcohol, and room temperature is obtained. For 20 minutes. To the obtained solution, 1.27 ml of 0.01M aqueous hydrochloric acid solution was added dropwise as a catalyst (E), followed by stirring for 24 hours to prepare a sample solution 6.
The sample solution 6 is a mixed solution of 1,1,1,3,3-pentafluorobutane (vapor pressure 43.4 kPa at 20 ° C.) and isopropyl alcohol (vapor pressure 4.4 kPa at 20 ° C.) with a volume ratio of 2 The coating solution 6 was prepared by diluting it twice. The volume ratio of 1,1,1,3,3-pentafluorobutane to the total of 1,1,1,3,3-pentafluorobutane and isopropyl alcohol contained in the coating solution 6 was 40%.
Soak a 1.5 ml coating solution 6 into Bencot (registered trademark) manufactured by Asahi Kasei Co., Ltd. and apply once to a 5 cm × 5 cm glass substrate (EAGLE XG, Corning) by hand, and leave at room temperature for 24 hours. And dried to form a film on the glass substrate.

(Example 7)
9.4 × 10 ⁻⁴ mol of n-decyltrimethoxysilane as the silane compound (A) and 3.8 × 10 ⁻³ mol of tetraethyl orthosilicate as the silane compound (B) are dissolved in 2.63 ml of isopropyl alcohol, and room temperature is obtained. For 20 minutes. To the obtained solution, 1.27 ml of 0.01M aqueous hydrochloric acid solution was added dropwise as a catalyst (E), and the mixture was stirred for 24 hours to prepare Sample Solution 7.
The sample solution 7 is a mixed solution of 1,1,1,3,3-pentafluorobutane (vapor pressure 43.4 kPa at 20 ° C.) and isopropyl alcohol (vapor pressure 4.4 kPa at 20 ° C.) with a volume ratio of 3 The coating solution 7 was prepared by diluting twice. The volume ratio of 1,1,1,3,3-pentafluorobutane to the total of 1,1,1,3,3-pentafluorobutane and isopropyl alcohol contained in the coating solution 7 was 40%.
A film was formed on the glass substrate in the same manner as in Example 6 except that the coating solution 7 was used.

(Example 8)
9.4 × 10 ⁻⁴ mol of n-decyltrimethoxysilane as the silane compound (A) and 3.8 × 10 ⁻³ mol of tetraethyl orthosilicate as the silane compound (B) are dissolved in 2.63 ml of isopropyl alcohol, and room temperature is obtained. For 20 minutes. To the resulting solution, 1.27 ml of 0.01M aqueous hydrochloric acid solution was added dropwise as a catalyst (E), and the mixture was stirred for 24 hours to prepare Sample Solution 8.
The sample solution 8 is a mixed solution of 1,1,1,3,3-pentafluorobutane (vapor pressure 43.4 kPa at 20 ° C.) and isopropyl alcohol (vapor pressure 4.4 kPa at 20 ° C.) with a volume ratio of 5 The coating solution 8 was prepared by diluting twice. The volume ratio of 1,1,1,3,3-pentafluorobutane to the total of 1,1,1,3,3-pentafluorobutane and isopropyl alcohol contained in the coating solution 8 was 50%.
A film was formed on the glass substrate in the same manner as in Example 6 except that the coating solution 8 was used.

Example 9
9.4 × 10 ⁻⁴ mol of n-decyltrimethoxysilane as the silane compound (A) and 3.8 × 10 ⁻³ mol of tetraethyl orthosilicate as the silane compound (B) are dissolved in 2.63 ml of isopropyl alcohol, and room temperature is obtained. For 20 minutes. To the obtained solution, 1.27 ml of 0.01M aqueous hydrochloric acid solution was added dropwise as a catalyst (E), and the mixture was stirred for 24 hours to prepare a sample solution 9.
The sample solution 9 is a mixed solution of 1,1,1,3,3-pentafluorobutane (vapor pressure 43.4 kPa at 20 ° C.) and isopropyl alcohol (vapor pressure 4.4 kPa at 20 ° C.) with a volume ratio of 10 The coating solution 9 was prepared by diluting twice. The volume ratio of 1,1,1,3,3-pentafluorobutane to the total of 1,1,1,3,3-pentafluorobutane and isopropyl alcohol contained in the coating solution 9 was 50%.
A film was formed on the glass substrate in the same manner as in Example 6 except that the coating solution 9 was used.

(Example 10)
9.4 × 10 ⁻⁴ mol of n-decyltrimethoxysilane as the silane compound (A) and 3.8 × 10 ⁻³ mol of tetraethyl orthosilicate as the silane compound (B) are dissolved in 2.63 ml of isopropyl alcohol, and room temperature is obtained. For 20 minutes. To the obtained solution, 1.27 ml of 0.01M aqueous hydrochloric acid solution was added dropwise as a catalyst (E), followed by stirring for 24 hours to prepare a sample solution 10.
The sample solution 10 is a mixed solution of 1,1,1,3,3-pentafluorobutane (vapor pressure 43.4 kPa at 20 ° C.) and isopropyl alcohol (vapor pressure 4.4 kPa at 20 ° C.) with a volume ratio of 30. The coating solution 10 was prepared by diluting it twice. The volume ratio of 1,1,1,3,3-pentafluorobutane to the total of 1,1,1,3,3-pentafluorobutane and isopropyl alcohol contained in the coating solution 10 was 50%.
A film was formed on the glass substrate in the same manner as in Example 6 except that the coating solution 10 was used.

(Example 11)
9.4 × 10 ⁻⁴ mol of n-decyltrimethoxysilane as the silane compound (A) and 3.8 × 10 ⁻³ mol of tetraethyl orthosilicate as the silane compound (B) are dissolved in 2.63 ml of isopropyl alcohol, and room temperature is obtained. For 20 minutes. After adding 1.27 ml of 0.01M aqueous hydrochloric acid solution as a catalyst (E) dropwise to the obtained solution, the solution was stirred for 24 hours to prepare a sample solution 11.
The sample solution 11 is a mixed solution of 1,1,1,3,3-pentafluorobutane (vapor pressure 43.4 kPa at 20 ° C.) and isopropyl alcohol (vapor pressure 4.4 kPa at 20 ° C.) with a volume ratio of 50. The coating solution 11 was prepared by diluting it twice. The volume ratio of 1,1,1,3,3-pentafluorobutane to the total of 1,1,1,3,3-pentafluorobutane and isopropyl alcohol contained in the coating solution 11 was 50%.
A film was formed on the glass substrate in the same manner as in Example 6 except that the coating solution 11 was used.

(Example 12)
9.4 × 10 ⁻⁴ mol of n-decyltrimethoxysilane as the silane compound (A) and 3.8 × 10 ⁻³ mol of tetraethyl orthosilicate as the silane compound (B) are dissolved in 2.63 ml of isopropyl alcohol, and room temperature is obtained. For 20 minutes. To the obtained solution, 1.27 ml of 0.01M aqueous hydrochloric acid solution was added dropwise as a catalyst (E), followed by stirring for 24 hours to prepare a sample solution 12.
The sample solution 12 is a mixed solution of 1,1,1,3,3-pentafluorobutane (vapor pressure 43.4 kPa at 20 ° C.) and isopropyl alcohol (vapor pressure 4.4 kPa at 20 ° C.) with a volume ratio of 300. The coating solution 12 was prepared by diluting it twice. The volume ratio of 1,1,1,3,3-pentafluorobutane to the total of 1,1,1,3,3-pentafluorobutane and isopropyl alcohol contained in the coating solution 12 was 20%.
A 5 cm × 5 cm glass substrate (EAGLE XG, manufactured by Corning) was installed at an elevation angle of 80 °, sprayed with 1.5 ml of the coating solution 12 using a spray, and then allowed to stand at room temperature for 24 hours to dry, A film was formed on a glass substrate.

(Example 13)
9.4 × 10 ⁻⁴ mol of n-decyltrimethoxysilane as the silane compound (A) and 3.8 × 10 ⁻³ mol of tetraethyl orthosilicate as the silane compound (B) are dissolved in 2.63 ml of isopropyl alcohol, and room temperature is obtained. For 20 minutes. To the obtained solution, 1.27 ml of 0.01M aqueous hydrochloric acid solution was added dropwise as a catalyst (E), and the mixture was stirred for 24 hours to prepare a sample solution 13.
The sample solution 13 is a mixed solution of 1,1,1,3,3-pentafluorobutane (vapor pressure 43.4 kPa at 20 ° C.) and isopropyl alcohol (vapor pressure 4.4 kPa at 20 ° C.) with a volume ratio of 300. The coating solution 13 was prepared by diluting twice. The volume ratio of 1,1,1,3,3-pentafluorobutane to the total of 1,1,1,3,3-pentafluorobutane and isopropyl alcohol contained in the coating solution 13 was 50%.
A film was formed on the glass substrate in the same manner as in Example 12 except that the coating solution 13 was used.

(Example 14)
9.4 × 10 ⁻⁴ mol of n-decyltrimethoxysilane as the silane compound (A) and 3.8 × 10 ⁻³ mol of tetraethyl orthosilicate as the silane compound (B) are dissolved in 2.63 ml of isopropyl alcohol, and room temperature is obtained. For 20 minutes. To the obtained solution, 1.27 ml of 0.01M aqueous hydrochloric acid solution was added dropwise as a catalyst (E), followed by stirring for 24 hours to prepare a sample solution 14.
The sample solution 14 is a mixed solution of 1,1,1,3,3-pentafluorobutane (vapor pressure 43.4 kPa at 20 ° C.) and isopropyl alcohol (vapor pressure 4.4 kPa at 20 ° C.) with a volume ratio of 300. The coating solution 14 was prepared by diluting twice. The volume ratio of 1,1,1,3,3-pentafluorobutane to the total of 1,1,1,3,3-pentafluorobutane and isopropyl alcohol contained in the coating solution 14 was 70%.
A film was formed on the glass substrate in the same manner as in Example 12 except that the coating solution 14 was used.

(Example 15)
9.4 × 10 ⁻⁴ mol of n-decyltrimethoxysilane as the silane compound (A) and 3.8 × 10 ⁻³ mol of tetraethyl orthosilicate as the silane compound (B) are dissolved in 2.63 ml of isopropyl alcohol, and room temperature is obtained. For 20 minutes. After adding 1.27 ml of 0.01 M hydrochloric acid aqueous solution as a catalyst (E) dropwise to the obtained solution, the solution was stirred for 24 hours to prepare a sample solution 15.
The sample solution 15 is a mixed solution of 1,1,1,3,3-pentafluorobutane (vapor pressure 43.4 kPa at 20 ° C.) and isopropyl alcohol (vapor pressure 4.4 kPa at 20 ° C.) with a volume ratio of 2000. The coating solution 15 was prepared by diluting it twice. The volume ratio of 1,1,1,3,3-pentafluorobutane to the total of 1,1,1,3,3-pentafluorobutane and isopropyl alcohol contained in the coating solution 15 was 70%.
A film was formed on the glass substrate in the same manner as in Example 12 except that the coating solution 15 was used.

(Example 16)
N-decyltrimethoxysilane 2.8 × 10 ⁻³ mol as silane compound (A) and tetraethyl orthosilicate 1.4 × 10 ⁻³ mol as silane compound (B) were dissolved in 2.90 ml of isopropyl alcohol, and room temperature. For 20 minutes. To the obtained solution, 0.98 ml of 0.01M hydrochloric acid aqueous solution was added dropwise as a catalyst (E), followed by stirring for 24 hours to prepare a sample solution 16.
The sample solution 16 was a mixed solution of 1,1,1,3,3-pentafluorobutane (vapor pressure 43.4 kPa at 20 ° C.) and isopropyl alcohol (vapor pressure 4.4 kPa at 20 ° C.), and the volume ratio was 300 times. The coating solution 16 was prepared. The volume ratio of 1,1,1,3,3-pentafluorobutane to the total of 1,1,1,3,3-pentafluorobutane and isopropyl alcohol contained in the coating solution 16 was 50%.
A film was formed on the glass substrate in the same manner as in Example 12 except that the coating solution 16 was used.

(Example 17)
As the silane compound (A), 1.5 × 10 ⁻³ mol of n-decyltrimethoxysilane and 3.0 × 10 ⁻³ mol of tetraethyl orthosilicate as the silane compound (B) were dissolved in 2.70 ml of isopropyl alcohol, For 20 minutes. To the obtained solution, 1.18 ml of 0.01M aqueous hydrochloric acid solution was added dropwise as a catalyst (E), followed by stirring for 24 hours to prepare a sample solution 17.
The sample solution 17 is a mixed solution of 1,1,1,3,3-pentafluorobutane (vapor pressure 43.4 kPa at 20 ° C.) and isopropyl alcohol (vapor pressure 4.4 kPa at 20 ° C.) with a volume ratio of 300. The coating solution 17 was prepared by diluting it twice. The volume ratio of 1,1,1,3,3-pentafluorobutane to the total of 1,1,1,3,3-pentafluorobutane and isopropyl alcohol contained in the coating solution 17 was 50%.
A film was formed on the glass substrate in the same manner as in Example 12 except that the coating solution 17 was used.

(Example 18)
5.4 × 10 ⁻⁴ mol of n-decyltrimethoxysilane as the silane compound (A) and 4.3 × 10 ⁻³ mol of tetraethyl orthosilicate as the silane compound (B) are dissolved in 2.55 ml of isopropyl alcohol, and room temperature is obtained. For 20 minutes. To the obtained solution, 1.34 ml of 0.01M hydrochloric acid aqueous solution was dropped as a catalyst (E), and then stirred for 24 hours to prepare a sample solution 18.
The sample solution 18 is a mixed solution of 1,1,1,3,3-pentafluorobutane (vapor pressure 43.4 kPa at 20 ° C.) and isopropyl alcohol (vapor pressure 4.4 kPa at 20 ° C.) in a volume ratio of 2000. The coating solution 18 was prepared by diluting it twice. The volume ratio of 1,1,1,3,3-pentafluorobutane to the total of 1,1,1,3,3-pentafluorobutane and isopropyl alcohol contained in the coating solution 18 was 50%.
A film was formed on the glass substrate in the same manner as in Example 12 except that the coating solution 18 was used.

(Example 19)
N-decyltrimethoxysilane 3.8 × 10 ⁻⁴ mol as the silane compound (A) and tetraethyl orthosilicate 4.5 × 10 ⁻³ mol as the silane compound (B) were dissolved in 2.52 ml of isopropyl alcohol, For 20 minutes. To the obtained solution, 1.36 ml of 0.01 M hydrochloric acid aqueous solution as a catalyst (E) was dropped, and then stirred for 24 hours to prepare a sample solution 19.
The sample solution 19 is a mixed solution of 1,1,1,3,3-pentafluorobutane (vapor pressure 43.4 kPa at 20 ° C.) and isopropyl alcohol (vapor pressure 4.4 kPa at 20 ° C.) with a volume ratio of 2000. The coating solution 19 was prepared by diluting it twice. The volume ratio of 1,1,1,3,3-pentafluorobutane to the total of 1,1,1,3,3-pentafluorobutane and isopropyl alcohol contained in the coating solution 19 was 50%.
A film was formed on the glass substrate in the same manner as in Example 12 except that the coating solution 19 was used.

(Example 20)
As the silane compound (A), 1.0 × 10 ⁻⁴ mol of n-decyltrimethoxysilane and 4.9 × 10 ⁻³ mol of tetraethyl orthosilicate as the silane compound (B) were dissolved in 2.47 ml of isopropyl alcohol, and room temperature. For 20 minutes. To the obtained solution, 1.41 ml of 0.01M hydrochloric acid aqueous solution was dropped as a catalyst (E), and then stirred for 24 hours to prepare a sample solution 20.
The sample solution 20 is a mixed solution of 1,1,1,3,3-pentafluorobutane (vapor pressure 43.4 kPa at 20 ° C.) and isopropyl alcohol (vapor pressure 4.4 kPa at 20 ° C.) with a volume ratio of 2000. The coating solution 20 was prepared by diluting it twice. The volume ratio of 1,1,1,3,3-pentafluorobutane to the total of 1,1,1,3,3-pentafluorobutane and isopropyl alcohol contained in the coating solution 20 was 50%.
A film was formed on the glass substrate in the same manner as in Example 12 except that the coating solution 20 was used.

(Example 21)
Hexyltrimethoxysilane 1.0 × 10 ⁻³ mol as the silane compound (A) and tetraethyl orthosilicate 4.0 × 10 ⁻³ mol as the silane compound (B) are dissolved in 2.54 ml of isopropyl alcohol, and 20 at room temperature. Stir for minutes. To the obtained solution, 1.34 ml of 0.01M hydrochloric acid aqueous solution was dropped as a catalyst (E), and then stirred for 24 hours to prepare a sample solution 21.
The sample solution 21 is a mixed solution of 1,1,1,3,3-pentafluorobutane (vapor pressure 43.4 kPa at 20 ° C.) and isopropyl alcohol (vapor pressure 4.4 kPa at 20 ° C.) with a volume ratio of 2000. The coating solution 21 was prepared by diluting it twice. The volume ratio of 1,1,1,3,3-pentafluorobutane to the total of 1,1,1,3,3-pentafluorobutane and isopropyl alcohol contained in the coating solution 21 was 50%.
A film was formed on the glass substrate in the same manner as in Example 12 except that the coating solution 21 was used.

(Example 22)
9.6 × 10 ⁻⁴ mol of n-octyltrimethoxysilane as the silane compound (A) and 3.9 × 10 ⁻³ mol of tetraethyl orthosilicate as the silane compound (B) were dissolved in 2.58 ml of isopropyl alcohol, and room temperature. For 20 minutes. To the obtained solution, 1.30 ml of 0.01M hydrochloric acid aqueous solution as a catalyst (E) was dropped, and then stirred for 24 hours to prepare a sample solution 22.
The sample solution 22 is a mixed solution of 1,1,1,3,3-pentafluorobutane (vapor pressure 43.4 kPa at 20 ° C.) and isopropyl alcohol (vapor pressure 4.4 kPa at 20 ° C.) with a volume ratio of 2000. The coating solution 22 was prepared by diluting twice. The volume ratio of 1,1,1,3,3-pentafluorobutane to the total of 1,1,1,3,3-pentafluorobutane and isopropyl alcohol contained in the coating solution 22 was 50%.
A film was formed on the glass substrate in the same manner as in Example 12 except that the coating solution 22 was used.

(Example 23)
9.1 × 10 ⁻⁴ mol of dodecyltrimethoxysilane as the silane compound (A) and 3.6 × 10 ⁻³ mol of tetraethyl orthosilicate as the silane compound (B) are dissolved in 2.66 ml of isopropyl alcohol, and 20 at room temperature. Stir for minutes. To the obtained solution, 1.22 ml of 0.01M aqueous hydrochloric acid solution was added dropwise as a catalyst (E), and the mixture was stirred for 24 hours to prepare a sample solution 23.
The sample solution 23 is a mixed solution of 1,1,1,3,3-pentafluorobutane (vapor pressure 43.4 kPa at 20 ° C.) and isopropyl alcohol (vapor pressure 4.4 kPa at 20 ° C.) with a volume ratio of 2000. The coating solution 23 was prepared by diluting twice. The volume ratio of 1,1,1,3,3-pentafluorobutane to the total of 1,1,1,3,3-pentafluorobutane and isopropyl alcohol contained in the coating solution 23 was 50%.
A film was formed on the glass substrate in the same manner as in Example 12 except that the coating solution 23 was used.

(Example 24)
9.4 × 10 ⁻⁴ mol of n-decyltrimethoxysilane as the silane compound (A) and 3.8 × 10 ⁻³ mol of tetraethyl orthosilicate as the silane compound (B) are dissolved in 2.61 ml of ethanol at room temperature. Stir for 20 minutes. To the obtained solution, 1.27 ml of 0.01M aqueous hydrochloric acid solution was added dropwise as a catalyst (E), followed by stirring for 24 hours to prepare a sample solution 24.
The sample solution 24 is a mixed solution of 1,1,1,3,3-pentafluorobutane (vapor pressure 43.4 kPa at 20 ° C.) and ethanol (vapor pressure 5.7 kPa at 20 ° C.) with a volume ratio of 2000 times. The coating solution 24 was prepared. The volume ratio of 1,1,1,3,3-pentafluorobutane to the total of 1,1,1,3,3-pentafluorobutane and ethanol contained in the coating solution 24 was 50%.
A film was formed on the glass substrate in the same manner as in Example 12 except that the coating solution 24 was used.

(Comparative Example 1)
9.4 × 10 ⁻⁴ mol of n-decyltrimethoxysilane as the silane compound (A) and 3.8 × 10 ⁻³ mol of tetraethyl orthosilicate as the silane compound (B) are dissolved in 2.63 ml of isopropyl alcohol, and room temperature is obtained. For 20 minutes. To the obtained solution, 1.27 ml of 0.01M aqueous hydrochloric acid solution was added dropwise as a catalyst (E), followed by stirring for 24 hours to prepare a sample solution 16.
The sample solution 16 was diluted with isopropyl alcohol to a volume ratio of 2000 to prepare a coating solution 16.
A film was formed on the glass substrate in the same manner as in Example 12 except that the coating solution 16 was used.

  The contents of each component in 100% by mass of the coating solution are shown in Tables 1 to 3 below.

  Next, the physical properties of the films on the glass substrates formed in Examples 1 to 24 and Comparative Example 1 were evaluated by the following methods.

(Evaluation of sliding down)
The slidability of the water droplets was evaluated by the sliding speed when the water droplets were dropped on the surface of the film. Specifically, using a contact angle measuring device (DM700) manufactured by Kyowa Interface Science Co., Ltd., 50 μL of water droplets were dropped on the film on the glass substrate inclined at 20 °, and the water droplets were 15 mm from the initial dropping position. The time until sliding down was measured, and the sliding speed (mm / sec) of water droplets on the film surface was calculated. The calculation results are shown in Tables 1 to 3 below.

  Examples 1 to 24 are examples using compositions that satisfy the requirements defined in the present invention, and contain silane compound (A), silane compound (B), and fluorine-based solvent (C). A film with good sliding properties could be formed. On the other hand, Comparative Example 1 is an example using a composition that does not satisfy the requirements defined in the present invention, and does not contain the fluorine-based solvent (C), so that the formed film had poor water drop sliding properties.

  Next, haze (cloudiness) was measured for the films obtained in Examples 1, 3, 4, 5, 7, 11, 14-18, 20, 21, and 23. Haze was measured on the coating surface with a D65 light source (average daylight) using a haze meter (HZ-2) manufactured by Suga Test Instruments Co., Ltd. As a result, the haze value was 0.12% in Example 1, 0.07% in Example 3, 0.08% in Example 4, 0.05% in Example 5, and 0.07 in Example 7. 07%, Example 11 0.04%, Example 14 0.05%, Example 15 0.15%, Example 16 0.20%, Example 17 0.17%, Example 18 was 0.09%, Example 20 was 0.16%, Example 21 was 0.08%, and Example 23 was 0.15%.

  Further, the films obtained in Examples 16 to 24 were held over a light source in an environment with an illuminance of 1000 lux, and the presence or absence of coloring, color unevenness, and foreign matter was visually confirmed. As a result, none of the films had coloration, color unevenness, and the presence or absence of foreign matter, and had a good appearance.

  Next, the film thicknesses of the films obtained in Examples 1, 5, 6, 7, 11, 14 to 18, 20, 21, 23, and Comparative Example 1 were measured. For measurement of the film thickness, an X-ray reflectivity measuring device (SmartLab) manufactured by Rigaku Corporation was used. As the X-ray source, a 45 kW X-ray generator, a CuKα ray wavelength λ = 0.15418 nm or a CuKα1 ray wavelength λ = 0.15406 nm by a Cu target, and a monochromator were not used. As setting conditions, the sampling width was 0.01 °, and the scanning range was 0.0 to 2.5 °. And it measured on the said setting conditions, and obtained the reflectance measured value. The obtained measured values were analyzed using company analysis software (GlobalFit). In addition, a scanning white interference microscope (VertScan) manufactured by Hitachi High-Tech Science Co., Ltd. was used for the measurement of the film thickness of the films obtained in Examples 6 and 7. As a result, the film thicknesses were 8.2 nm in Example 1, 1.7 nm in Example 5, 116 nm in Example 6, 54 nm in Example 7, 2.7 nm in Example 11, and 2 in Example 14. .4 nm, Example 15 is 1.5 nm, Example 16 is 2.4 nm, Example 17 is 2.0 nm, Example 18 is 5.5 nm, Example 20 is 6.6 nm, and Example 21 is 2.4 nm. Example 23 was 2.3 nm, and Comparative Example 1 was 0.3 nm.

Claims (9)

Silane compound (A) represented by the following formula (1),
The composition characterized by including the silane compound (B) represented by following formula (2), and a fluorine-type solvent (C).
R ¹ —Si (X ¹ ) ₃ (1)
[In Formula (1),
R ¹ represents a hydrocarbon group having 6 or more carbon atoms, and —CH ₂ — contained in the hydrocarbon group may be replaced with —O—.
X ¹ represents a hydrolyzable group. ]
Si (R ² ) _n (X ² ) _4-n (2)
[In Formula (2),
R ² represents a hydrocarbon group having 1 to 5 carbon atoms.
X ² represents a hydrolyzable group.
n is 0 or 1. ]   The composition according to claim 1, further comprising a non-fluorinated solvent (D).   The composition according to claim 2, wherein the non-fluorine solvent (D) is an alcohol solvent.   The composition according to claim 1, wherein the fluorine-based solvent (C) has a vapor pressure at 20 ° C. of 8.0 kPa or more.   5. The composition according to claim 1, wherein the content of the fluorine-based solvent (C) in 100% by mass of the composition is 20% by mass or more and 85% by mass or less.   The composition according to claim 1, wherein a molar ratio of the silane compound (B) to the silane compound (A) is 0.1 or more and 48 or less.   7. The composition according to claim 1, wherein the total content of the silane compounds (A) and (B) in 100% by mass of the composition is 0.005% by mass to 12% by mass. .   A film obtained by curing the composition according to claim 1.   The film according to claim 8, wherein the sliding speed of a 50 μL water droplet at a 20 ° inclination is 10.0 mm / second or more.