TWI784014B - The composition and the film formed by hardening it - Google Patents

Abstract

An object of the present invention is to provide a composition for obtaining a film with a good appearance from which droplets can be easily removed by a simple coating method. 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 solvent (C), and the composition is characterized in that the The total content of the silane compound (A) and the silane compound (B) in 100% by mass of the composition is 0.015% by mass or more and 0.70% by mass or less.

R ¹ -Si(X ¹ ) ₃ (1)

Si(R ² ) _n (X ² ) _4-n (2)

[R ¹ represents a hydrocarbon group having 6 or more carbon atoms, and -CH ₂ - contained in the hydrocarbon group may be substituted with -O-. X ¹ represents a hydrolyzable group. R ² represents a hydrocarbon group having 1 to 5 carbon atoms. X ² represents a hydrolyzable group. n is 0 or 1]

Description

The composition and the film formed by hardening it

The present invention relates to a composition.

In various display devices, optical elements, semiconductor elements, building materials, automotive parts, nanoimprinting technology, etc., there is contamination or corrosion of the substrate due to the attachment of liquid droplets to the surface of the substrate, and the resulting contamination In the case of problems such as degradation of corrosion performance, it is required that the attached liquid droplets can be easily removed.

For example, Patent Document 1 and Patent Document 2 disclose that a water-repellent and oil-repellent coating composition comprising an organosilicon compound (A) and a metal compound (B) at a predetermined molar ratio is applied to a glass substrate by spin coating and drying it to obtain a transparent film, and it is described that the water droplet sliding speed of the transparent film is excellent.

[Prior art literature]

[Patent Document]

[Patent Document 1] International Publication No. 2016/068118

[Patent Document 2] International Publication No. 2016/068103

In the above-mentioned Patent Document 1 and Patent Document 2, the transparent film is formed by spin coating, but even if a machine such as a spin coater is not used, it can be coated by hand, A simple method such as spraying has not yet been studied to form a composition capable of easily removing droplets (good water droplet sliding properties) and having a good appearance (transparency, etc.).

Therefore, an object of the present invention is to provide a composition for obtaining a film with a good appearance from which droplets can be easily removed by a simple coating method.

The present invention that achieves the above-mentioned problems 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 solvent (C), and the composition is characterized by In that, the total content of the silane compound (A) and the silane compound (B) in 100% by mass of the composition is not less than 0.015% by mass and not more than 0.70% by mass.

[Chem] 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 substituted with -O-.

X ¹ represents a hydrolyzable group]

[Chem.2]Si(R ² ) _n (X ² ) _4-n (2)

[In the formula (2), R ² represents a hydrocarbon group with 1 to 5 carbon atoms.

X ² represents a hydrolyzable group.

n is 0 or 1]

[2] The composition according to [1], wherein the molar ratio of the silane compound (B) to the silane compound (A) is 0.1 to 48.

[3] The composition according to [2], wherein the molar ratio of the silane compound (B) to the silane compound (A) is 0.1 to 12.

[4] The composition according to any one of [1] to [3], wherein the solvent (C) is an alcoholic solvent.

[5] The composition according to [4], further comprising a solvent (D) having a higher vapor pressure at 20° C. than the solvent (C).

[6] The composition according to [5], wherein the solvent (D) has a vapor pressure at 20° C. of 8.0 kPa or more.

[7] A film obtained by curing the composition according to any one of [1] to [6].

The composition of the present invention contains a small amount of the predetermined silane compound (A) and silane compound (B) in a total of 0.015% by mass or more and 0.70% by mass or less, so that water droplets can be formed by a simple method such as manual coating or spraying Film with good slip properties and appearance.

The composition of the present invention is characterized in that it contains silane compound (A) represented by the following formula (1) and the following formula ( 2) The silane compound (B) shown. When the total amount of the silane compound (A) and the silane compound (B) is 0.015% by mass or more, water droplet sliding properties can be improved, and when the total amount is 0.70% by mass or less, the appearance of the film can be improved. The total amount of the silane compound (A) and the silane compound (B) is preferably at least 0.05% by mass, more preferably at least 0.1% by mass, still more preferably at least 0.2% by mass, further preferably at most 0.65% by mass, more preferably at most 0.60% by mass or less.

Hereinafter, the silane compound (A) and the silane compound (B) are demonstrated respectively.

1. Silane compound (A)

The silane compound (A) is represented by the following formula (1).

[Chemical 3]R ¹ -Si(X ¹ ) ₃ (1)

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

R ¹ is preferably a saturated hydrocarbon group, more preferably a straight-chain or branched-chain alkyl group, and still more preferably a straight-chain alkyl group. In addition, the carbon number of the hydrocarbon group represented by R ¹ is preferably 7 or more, more preferably 8 or more, further preferably 30 or less, more preferably 20 or less, further preferably 15 or less. Furthermore, when -CH ₂ - contained in the hydrocarbon group represented by R ¹ is substituted with -O-, the number of substituted -O- is also counted as the number of carbon atoms.

Examples of the group in which —CH ₂ — contained in the hydrocarbon group represented by R ¹ is substituted with —O— include groups containing one or more alkyleneoxy units. As an alkoxyl unit, an ethoxyl unit, a propoxyl unit, etc. are mentioned, Preferably it is an ethoxyl unit.

A group in which -CH ₂ - contained in the hydrocarbon group represented by R ¹ is substituted with -O- can be expressed, for example, as -R ³ -(R ⁴ -O) _n1 -R ⁵ , where R ³ represents a single bond or A divalent hydrocarbon group with 1 to 4 carbons, R ⁴ represents a divalent hydrocarbon group with 2 to 3 carbons, R ⁵ represents a hydrogen atom or a monovalent hydrocarbon group with 1 to 4 carbons, n1 represents an integer of 1 to 10. However, the total number of atoms of carbon and oxygen contained in -R ³ -(R ⁴ -O) _n1 -R ⁵ is 6 or more. R ³ is preferably a divalent hydrocarbon group. As the divalent hydrocarbon group represented by R ³ , divalent saturated hydrocarbon groups such as methylene, ethylidene, propylidene, and butylene can be mentioned. As R ⁴ , it can be Examples include divalent saturated hydrocarbon groups such as ethylidene and propylidene, and R ⁵ is preferably a monovalent hydrocarbon group with 1 to 4 carbon atoms. As the monovalent hydrocarbon group represented by R ⁵ , methyl, ethyl Monovalent saturated hydrocarbon groups such as radicals, propyl groups, and butyl groups.

The hydrocarbon group represented by R is preferably ^a straight-chain alkyl group having 6 to 30 carbon atoms, among which hexyl, heptyl, octyl, nonyl, decyl, undecyl, Dodecyl, tetradecyl, hexadecyl, octadecyl, particularly preferably octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl.

In the above-mentioned formula (1), as the hydrolyzable group represented by X ¹ , a group to which a hydroxyl group (silanol group) is given by hydrolysis is mentioned, preferably an alkoxy group having 1 to 6 carbon atoms, cyano group, acetyloxy group, chlorine atom and isocyanate group, etc. The three X ¹ may be the same or different, preferably the same. As X ¹ , it is preferably an alkoxy group or cyano group with 1 to 6 carbons (more preferably 1 to 4), more preferably an alkoxy group with 1 to 6 carbons (more preferably 1 to 4), and Preferably, all X ¹ are alkoxy groups having 1 to 6 carbon atoms (more preferably 1 to 4 carbon atoms).

As the silane compound (A), it is preferable that R ¹ is a linear alkyl group with 6 to 18 carbon atoms (more preferably 7 to 13), and all X ¹ are the same group with 1 to 6 carbon atoms (more preferably 1 to 4, more preferably 1 to 2) alkoxyl.

As the silane compound (A), specifically, hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltrimethoxysilane, Triethoxysilane, nonyltrimethoxysilane, nonyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, undecyltrimethoxysilane, undecyltrimethoxysilane Triethoxysilane, Dodecyltrimethoxysilane, Dodecyltriethoxysilane, Tridecyltrimethoxysilane, Tridecyltriethoxysilane, Tetradecyltrimethoxysilane tetradecyltriethoxysilane, tetradecyltriethoxysilane, pentadecyltrimethoxysilane, pentadecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane , Heptadecyltrimethoxysilane, Heptadecyltriethoxysilane, Octadecyltrimethoxysilane, Octadecyltriethoxysilane, etc. Among these, octyltrimethoxysilane, octyltrimethoxysilane and octyltrimethoxysilane are preferred Ethoxysilane, Decyltrimethoxysilane, Decyltriethoxysilane, Dodecyltrimethoxysilane, Dodecyltriethoxysilane, Tetradecyltrimethoxysilane, Tetradecyltrimethoxysilane Alkyltriethoxysilane, Hexadecyltrimethoxysilane, Hexadecyltriethoxysilane, Octadecyltrimethoxysilane, Octadecyltriethoxysilane.

Silane compound (A) may use only 1 type, and may use multiple types together.

2. Silane compound (B)

The silane compound (B) is represented by the following formula (2).

[Chemical 4] Si(R ² ) _n (X ² ) _4-n (2)

In the formula (2), R ² represents a hydrocarbon group with 1 to 5 carbons, X ² represents a hydrolyzable group, and n is 0 or 1.

R ² is preferably a saturated hydrocarbon group, more preferably a straight-chain or branched-chain alkyl group, further preferably a straight-chain alkyl group, preferably a methyl group, an ethyl group, or a propyl group.

The hydrolyzable group represented by X2 in the formula ( ² ) can include the same groups as the hydrolyzable group represented by X1, preferably an alkoxy group and a cyano group having ¹ to 6 carbon atoms. , acetyloxy group, chlorine atom and isocyanate group, etc. The three X ² can be the same or different, preferably the same. X ² is preferably an alkoxy group or an isocyanate group with 1 to 6 carbons (more preferably 1 to 4), more preferably an alkoxy group with 1 to 6 carbons (more preferably 1 to 4), and Preferably, all X ² are alkoxy groups having 1 to 6 carbon atoms (more preferably 1 to 4 carbon atoms).

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

As the silane compound (B), n is preferably 0, and X ² is an alkoxy group having 1 to 6 carbon atoms (more preferably 1 to 4 carbon atoms).

Examples of the silane compound (B) include: tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, Tripropoxysilane, Methyltributoxysilane, etc. Among these, tetramethoxysilane and tetraethoxysilane are preferable.

A silane compound (B) may use only 1 type, and may use multiple types together.

The molar ratio (B/A) of the silane compound (B) to the silane compound (A) is usually not less than 0.1 and not more than 48. If the molar ratio is in the above range, the slipperiness of water droplets on the film surface can be further improved . The molar ratio is more preferably at least 0.5, still more preferably at least 1, still more preferably at least 2, and most preferably at least 4. In addition, the molar ratio is preferably 40 or less, more preferably 25 or less, still more preferably 12 or less, particularly preferably 10 or less, most preferably 8 or less. The molar ratio is also preferably not less than 0.1 and not more than 12.

The composition of the present invention further includes a solvent (C) in addition to the silane compound (A) and the silane compound (B).

Examples of the solvent (C) include hydrophilic organic solvents such as alcohol-based solvents, ether-based solvents, ketone-based solvents, ester-based solvents, and amide-based solvents. These solvents may be used alone or in combination of two or more.

Examples of alcohol-based solvents include ethanol, 1-propanol, 2-propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, and the like. Dimethoxyethane, dioxane, etc. are mentioned as an ether solvent. As a ketone solvent, methyl isobutyl ketone etc. are mentioned. Ethyl acetate, butyl acetate, etc. are mentioned as an ester type solvent. As an amide-based solvent, it can Dimethylformamide etc. are mentioned. Among them, the solvent (C) is preferably an alcohol-based solvent (especially 1-propanol or 2-propanol), a ketone-based solvent (especially methyl isobutyl ketone), more preferably an alcohol-based solvent. The solvent can be adjusted according to the material of the base material described later. For example, in the case of a base material using an organic material, it is preferable to use a ketone-based solvent, and in the case of a base material using an inorganic material, it is preferable to use an alcohol-based solvent. solvent.

In addition, it is preferable to use an alcohol-based solvent as the solvent (C), and further include a solvent (D) having a higher vapor pressure at 20° C. than the solvent (C). When the composition of the present invention contains a solvent (C) and a solvent (D), especially when a film is formed from the composition of the present invention by hand coating, a film with a good appearance can also be formed, which is preferable. The vapor pressure of the solvent (D) at 20° C. is preferably, for example, 8.0 kPa or higher, more preferably 10.0 kPa or higher, further preferably 12.0 kPa or higher, further preferably 14.0 kPa or higher, and the upper limit is not particularly limited, for example, 50 kPa the following. In addition, when both the solvent (C) and the solvent (D) are contained, the alcohol-based solvent as the solvent (C) preferably has a vapor pressure of less than 8.0 kPa at 20° C., more preferably 6.0 kPa or less, and further Preferably, it is 5.0 kPa or less. The lower limit is not particularly limited, and is, for example, 0.0001 kPa or more. For example, it is preferable to use at least one of 1-propanol and 2-propanol as the solvent (C), and use at least one of tetrahydrofuran, acetone, and methyl ethyl ketone as the solvent (D).

When the solvent (D) is included, the solvent (D) is preferably at least 30% by mass, more preferably at least 40% by mass, in a total of 100% by mass of the solvent (C) and the solvent (D), and , preferably at most 99.7% by mass, more preferably at most 99% by mass.

The composition of the present invention may also include a catalyst (E) for promoting the hydrolysis and polycondensation of the silane compound (A) and the silane compound (B). As the catalyst (E), acidic compounds such as hydrogen chloride (among them, usually used as hydrochloric acid), nitric acid, and acetic acid; basic compounds such as ammonia and amine; organometallic compounds such as acetoethyl acetate aluminum compounds, etc. can be used. The content of the catalyst (E) is preferably at least 0.001 parts by mass, more preferably at least 0.005 parts by mass, and still more preferably at least 0.01 parts by mass, based on 100 parts by mass of the total of the silane compound (A) and the silane compound (B), It is preferably at most 3 parts by mass, more preferably at most 1 part by mass, and still more preferably at most 0.1 part by mass.

The composition of the present invention may contain antioxidants, antirust agents, ultraviolet absorbers, light stabilizers, antifungal agents, antibacterial agents, antifouling agents, deodorants, and pigments within the range that does not inhibit the effects of the present invention. , flame retardants, antistatic agents and other additives and other ingredients.

As the method of bringing the composition of the present invention into contact with the base material, there may be mentioned: dip coating method, hand coating (a method of impregnating a liquid into a cloth etc. and applying it to the base material. It is preferable to reciprocate and reciprocate the base material several times) , pouring (a method of directly injecting a liquid onto a base material using a dropper, etc., and applying it), spraying (a method of applying a liquid to a base material using a spray), or a method combining these, and the like.

In the state where the composition of the present invention is in contact with the substrate, let it stand in the air at room temperature (for example, 10 minutes to 48 hours, preferably 10 hours to 48 hours), thereby introducing moisture in the air , and promote the hydrolysis and polycondensation of the hydrolyzable group, and harden the composition to form a film on the substrate. It is also preferable to further dry the obtained film. The thickness of the film is preferably at least 1 nm, more preferably at least 1.5 nm. The limit is, for example, 15 nm or less, and may be 10 nm or less. By making the film thickness of the film more than a certain value, it can be expected to stably express favorable water repellency, which is preferable. Moreover, since the external appearance can be expected to become favorable when the film thickness of a film is below a certain value, it is preferable.

The shape of the base material to be brought into contact with the composition of the present invention may be either a flat surface or a curved surface, or may be a three-dimensional structure composed of a plurality of surfaces. In addition, examples of the material of the substrate 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, Thermosetting resins such as melamine resin, epoxy resin, unsaturated polyester, silicone resin, urethane resin, etc. Examples of the inorganic material include: ceramics; glass; metals such as iron, silicon, copper, zinc, and aluminum; alloys containing these metals, and the like.

It is also possible to perform an easy-adhesive treatment on the base material in advance. Examples of the easy-adhesive treatment include hydrophilization treatments such as corona treatment, plasma treatment, and ultraviolet treatment. In addition, primer treatment using resin, silane coupling agent, tetraalkoxysilane, etc. can be performed, and a glass film such as polysilazane can be pre-coated on the substrate.

The film obtained by curing the composition of the present invention is excellent in slipperiness and appearance. The sliding property was evaluated by dropping 50 μL of water droplets on the film of the substrate inclined at 20°, and evaluating the sliding speed at which the water droplets fell 1.5 cm from the initial drop position. The sliding speed is, for example, not less than 8 mm/sec, preferably not less than 10 mm/sec, more preferably not less than 20 mm/sec, and still more preferably not less than 30 mm/sec. The upper limit of the sliding speed is, for example, 100 mm/sec. In addition, the mist of the film obtained by hardening the composition of the present invention The content is, for example, 0.17% or less, preferably 0.15% or less, more preferably 0.12% or less. The lower limit of the haze value is, for example, 0.01%.

By using the composition of the present invention, it is possible to provide a film excellent in droplet slidability and appearance. The film is useful for building materials, auto parts, factory equipment, and the like.

[Example]

Hereinafter, examples will be given to describe the present invention more specifically. The present invention is not limited to the following examples, and of course can be implemented with appropriate changes within the scope of the above-mentioned and later-described gist, and these are included in the technical scope of the present invention.

Example 1

Dissolve 1.5×10 ^-3 mol of n-decyltrimethoxysilane as the silane compound (A) and 3.0×10 ^-3 mol of tetraethylorthosilicate (tetraethoxysilane) as the silane compound (B) in isopropanol (2-propanol) in 2.72ml, and stirred at room temperature for 20 minutes. 1.17 ml of 0.01 M hydrochloric acid aqueous solution was dripped at the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 1 was produced. The sample solution 1 was diluted with isopropanol to a volume ratio of 300 times to prepare a coating solution 1 . A 5 cm x 5 cm glass substrate (EAGLE XG, manufactured by Corning) was set at an elevation angle of 80°, sprayed with 1.5 ml of coating solution 1 using a spray, and left at room temperature for 24 hours. This was dried to form a film on the glass substrate.

Example 2

Dissolve 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) in 2.63 ml of isopropanol, and stirred at room temperature for 20 minutes. 1.27 ml of 0.01 M hydrochloric acid aqueous solution was dripped at the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 2 was produced. The sample solution 2 was diluted with isopropanol to a volume ratio of 300 times to prepare a coating solution 2 . Except having used the coating solution 2, it carried out similarly to Example 1, and formed the film on the glass substrate.

Example 3

Dissolve 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) in 2.56 ml of isopropanol, and stirred at room temperature for 20 minutes. 1.33 ml of 0.01 M hydrochloric acid aqueous solution was dripped at the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 3 was produced. The sample solution 3 was diluted with isopropanol to a volume ratio of 300 times to prepare a coating solution 3 . Except having used the coating solution 3, it carried out similarly to Example 1, and formed the film on the glass substrate.

Example 4

Dissolve 1.8×10 ^-4 mol of n-decyltrimethoxysilane as the silane compound (A) and 4.8×10 ^-3 mol of tetraethyl orthosilicate as the silane compound (B) in 2.50 ml of isopropanol, and stirred at room temperature for 20 minutes. 1.39 ml of 0.01 M hydrochloric acid aqueous solution was dripped at the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 4 was produced. The sample solution 4 was diluted with isopropanol to a volume ratio of 300 times to prepare a coating solution 4 . Except having used the coating solution 4, it carried out similarly to Example 1, and formed the film on the glass substrate.

Example 5

Dissolve 1.5×10 ^-3 mol of n-decyltrimethoxysilane as the silane compound (A) and 3.0×10 ^-3 mol of tetraethyl orthosilicate as the silane compound (B) in 2.72 ml of isopropanol, and stirred at room temperature for 20 minutes. 1.17 ml of 0.01 M hydrochloric acid aqueous solution was dripped at the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 5 was produced. The sample solution 5 was diluted to 500 times the volume ratio with isopropanol to prepare a coating solution 5 . Except having used the coating solution 5, it carried out similarly to Example 1, and formed the film on the glass substrate.

Example 6

Dissolve 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) in 2.63 ml of isopropanol, and stirred at room temperature for 20 minutes. 1.27 ml of 0.01 M hydrochloric acid aqueous solution was dripped at the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 6 was produced. The sample solution 6 was diluted to 500 times the volume ratio with isopropanol to prepare a coating solution 6 . A film was formed on a glass substrate in the same manner as in Example 1 except that coating solution 6 was used.

Example 7

Dissolve 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) in 2.56 ml of isopropanol, and stirred at room temperature for 20 minutes. 1.33 ml of 0.01M hydrochloric acid aqueous solution was dripped at the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 7 was produced. The sample solution 7 was diluted to 500 times the volume ratio with isopropanol to prepare a coating solution 7 . Except having used the coating solution 7, it carried out similarly to Example 1, and formed the film on the glass substrate.

Example 8

Dissolve 1.5×10 ^-3 mol of n-decyltrimethoxysilane as the silane compound (A) and 3.0×10 ^-3 mol of tetraethyl orthosilicate as the silane compound (B) in 2.72 ml of isopropanol, and stirred at room temperature for 20 minutes. 1.17 ml of 0.01 M hydrochloric acid aqueous solution was dripped at the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 8 was produced. The sample solution 8 was diluted with isopropanol to a volume ratio of 1500 times to prepare a coating solution 8 . Except having used the coating solution 8, it carried out similarly to Example 1, and formed the film on the glass substrate.

Example 9

Dissolve 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) in 2.63 ml of isopropanol, and stirred at room temperature for 20 minutes. 1.27 ml of 0.01 M hydrochloric acid aqueous solution was dripped at the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 9 was produced. The sample solution 9 was diluted to 200 times the volume ratio with isopropanol to prepare a coating solution 9 . Except having used the coating solution 9, it carried out similarly to Example 1, and formed the film on the glass substrate.

Example 10

Dissolve 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) in 2.63 ml of isopropanol, and stirred at room temperature for 20 minutes. 1.27 ml of 0.01 M hydrochloric acid aqueous solution was dripped at the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 10 was produced. The sample solution 10 was diluted with isopropanol to a volume ratio of 500 times to prepare a coating solution 10 . A 5 cm x 5 cm glass substrate (EAGLE XG, manufactured by Corning) was set at an elevation angle of 80°, and 1.5 ml of coating solution 10 was poured over the entire surface of the glass substrate using a dropper. It was left to stand at normal temperature for 24 hours and dried to form a film on the glass substrate.

Example 11

Dissolve 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) in 2.63 ml of isopropanol, and stirred at room temperature for 20 minutes. 1.27 ml of 0.01 M hydrochloric acid aqueous solution was added dropwise to the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 11 was produced. The sample solution 11 was diluted to 500 times the volume ratio with isopropanol to prepare the coating solution 11 . A 5 cm x 5 cm glass substrate (EAGLE XG, manufactured by Corning) was dipped in a container filled with the coating solution 11 for more than 1 second, then pulled upward, and left at room temperature for 24 hours. This dried to form a film on the glass substrate.

Example 12

Dissolve 2.8×10 ^-3 mol of n-decyltrimethoxysilane as the silane compound (A) and 1.4×10 ^-3 mol of tetraethyl orthosilicate as the silane compound (B) in 2.92 ml of isopropanol, and stirred at room temperature for 20 minutes. 0.97 ml of 0.01 M hydrochloric acid aqueous solution was dripped at the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 12 was produced. The sample solution 12 was diluted with acetone to 50 times the volume ratio to prepare the coating solution 12 . 1.5 ml of the coating solution 12 was infiltrated into Bencot (Bemcot) (registered trademark, manufactured by Asahi Kasei Co., Ltd.), and placed on a 5 cm×5 cm glass substrate (EAGLE XG, manufactured by Corning) On the glass substrate, the coating was repeated three times continuously at the same position without time interval by manual coating, and left at room temperature for 24 hours to dry, thereby forming a film on the glass substrate.

Example 13

Dissolve 2.2×10 ^{-3 mol of n-decyltrimethoxysilane as the silane compound (A) and 2.2×10 -3 mol} of tetraethyl orthosilicate as the silane compound (B) in 2.82 ml of isopropanol, and stirred at room temperature for 20 minutes. 1.07 ml of 0.01 M hydrochloric acid aqueous solution was added dropwise to the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 13 was produced. The sample solution 13 was diluted with acetone to 50 times the volume ratio to prepare the coating solution 13 . A film was formed on a glass substrate in the same manner as in Example 12 except that coating solution 13 was used.

Example 14

Dissolve 1.5×10 ^-3 mol of n-decyltrimethoxysilane as the silane compound (A) and 3.0×10 ^-3 mol of tetraethyl orthosilicate as the silane compound (B) in 2.72 ml of isopropanol, and stirred at room temperature for 20 minutes. 1.17 ml of 0.01 M hydrochloric acid aqueous solution was added dropwise to the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 14 was produced. The sample solution 14 was diluted to 50 times the volume ratio with acetone to prepare the coating solution 14 . A film was formed on a glass substrate in the same manner as in Example 12 except that coating solution 14 was used.

Example 15

Dissolve 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) in 2.63 ml of isopropanol, and stirred at room temperature for 20 minutes. 1.27 ml of 0.01 M hydrochloric acid aqueous solution was added dropwise to the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 15 was produced. The sample solution 15 was diluted with acetone to 50 times the volume ratio to prepare a coating solution 15 . A film was formed on a glass substrate in the same manner as in Example 12 except that coating solution 15 was used.

Example 16

Dissolve 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) in 2.56 ml of isopropanol, and stirred at room temperature for 20 minutes. 1.33 ml of 0.01 M hydrochloric acid aqueous solution was added dropwise to the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 16 was produced. The sample solution 16 was diluted with acetone to 50 times the volume ratio to prepare the coating solution 16 . A film was formed on a glass substrate in the same manner as in Example 12 except that coating solution 16 was used.

Example 17

Dissolve 3.8×10 ^-4 mol of n-decyltrimethoxysilane as the silane compound (A) and 4.5×10 ^-3 mol of tetraethyl orthosilicate as the silane compound (B) in 2.54 ml of isopropanol, and stirred at room temperature for 20 minutes. 1.35 ml of 0.01 M hydrochloric acid aqueous solution was dripped at the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 17 was produced. The sample solution 17 was diluted to 50 times the volume ratio with acetone to prepare the coating solution 17 . A film was formed on a glass substrate in the same manner as in Example 12 except that coating solution 17 was used.

Example 18

Dissolve 3.5×10 ^-3 mol of n-decyltrimethoxysilane as the silane compound (A) and 3.5×10 ^-4 mol of tetraethyl orthosilicate as the silane compound (B) in 3.05 ml of isopropanol, and stirred at room temperature for 20 minutes. 0.85 ml of 0.01M hydrochloric acid aqueous solution was added dropwise to the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 18 was produced. The coating solution 18 was prepared by diluting the sample solution 18 with acetone to a volume ratio of 150 times. A film was formed on a glass substrate in the same manner as in Example 12 except that coating solution 18 was used.

Example 19

Dissolve 2.8×10 ^-3 mol of n-decyltrimethoxysilane as the silane compound (A) and 1.4×10 ^-3 mol of tetraethyl orthosilicate as the silane compound (B) in 2.92 ml of isopropanol, and stirred at room temperature for 20 minutes. 0.97 ml of 0.01 M hydrochloric acid aqueous solution was added dropwise to the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 19 was produced. The coating solution 19 was prepared by diluting the sample solution 19 with acetone to a volume ratio of 150 times. A film was formed on a glass substrate in the same manner as in Example 12 except that coating solution 19 was used.

Example 20

Dissolve 2.2×10 ^{-3 mol of n-decyltrimethoxysilane as the silane compound (A) and 2.2×10 -3 mol} of tetraethyl orthosilicate as the silane compound (B) in 2.82 ml of isopropanol, and stirred at room temperature for 20 minutes. 1.07 ml of 0.01 M hydrochloric acid aqueous solution was dripped at the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 20 was produced. The coating solution 20 was prepared by diluting the sample solution 20 with acetone to a volume ratio of 150 times. Except having used the coating solution 20, it carried out similarly to Example 12, and formed the film on the glass substrate.

Example 21

Dissolve 1.5×10 ^-3 mol of n-decyltrimethoxysilane as the silane compound (A) and 3.0×10 ^-3 mol of tetraethyl orthosilicate as the silane compound (B) in 2.72 ml of isopropanol, and stirred at room temperature for 20 minutes. 1.17 ml of 0.01 M hydrochloric acid aqueous solution was added dropwise to the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 21 was produced. The sample solution 21 was diluted with acetone to 150 times the volume ratio to prepare the coating solution 21 . A film was formed on a glass substrate in the same manner as in Example 12 except that the coating solution 21 was used.

Example 22

Dissolve 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) in 2.63 ml of isopropanol, and stirred at room temperature for 20 minutes. 1.27 ml of 0.01M hydrochloric acid aqueous solution was added dropwise to the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 22 was produced. The sample solution 22 was diluted to 50 times the volume ratio with a mixed solution of acetone and isopropanol, and the volume ratio of acetone and isopropanol was about 50/50, thereby preparing the coating solution 22 . A film was formed on a glass substrate in the same manner as in Example 12 except that the coating solution 22 was used.

Example 23

Dissolve 1.0×10 ^-3 mol of hexyltrimethoxysilane as silane compound (A) and 4.0×10 ^-3 mol of tetraethylorthosilicate as silane compound (B) in 2.54ml of isopropanol, and place in Stir at room temperature for 20 minutes. 1.34 ml of 0.01 M hydrochloric acid aqueous solution was added dropwise to the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 23 was produced. The sample solution 23 was diluted to 500 times the volume ratio with isopropanol to prepare the coating solution 23 . Except having used the coating solution 23, it carried out similarly to Example 1, and formed the film on the glass substrate.

Example 24

Dissolve 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) in 2.58 ml of isopropanol, and stirred at room temperature for 20 minutes. After dripping 1.30 ml of 0.01 M hydrochloric acid aqueous solution as a catalyst (E) in the obtained solution, it stirred for 24 hours, and produced the sample solution 24. The sample solution 24 was diluted to 500 times the volume ratio with isopropanol to prepare the coating solution 24 . Except having used the coating solution 24, it carried out similarly to Example 1, and formed the film on the glass substrate.

Example 25

Dissolve 9.1×10 ^-4 mol of dodecyltrimethoxysilane as the silane compound (A) and 3.6×10 ^-3 mol of tetraethylorthosilicate as the silane compound (B) in 2.66 ml of isopropanol , and stirred at room temperature for 20 minutes. After adding 1.22 ml of 0.01 M hydrochloric acid aqueous solution as a catalyst (E) dropwise to the obtained solution, it stirred for 24 hours, and produced the sample solution 25. The sample solution 25 was diluted to 500 times the volume ratio with isopropanol to prepare a coating solution 25 . Except having used the coating solution 25, it carried out similarly to Example 1, and formed the film on the glass substrate.

Example 26

Dissolve 8.9×10 ^-4 mol of dodecyltriethoxysilane as the silane compound (A) and 3.5×10 ^-3 mol of tetraethylorthosilicate as the silane compound (B) in 2.71ml of isopropanol and stirred at room temperature for 20 minutes. After dropping 1.18 ml of 0.01 M hydrochloric acid aqueous solution as a catalyst (E) to the obtained solution, it stirred for 24 hours, and produced the sample solution 26. The sample solution 26 was diluted to 500 times the volume ratio with isopropanol to prepare the coating solution 26 . A film was formed on a glass substrate in the same manner as in Example 1 except that the coating solution 26 was used.

Comparative example 1

Dissolve 1.5×10 ^-3 mol of n-decyltrimethoxysilane as the silane compound (A) and 3.0×10 ^-3 mol of tetraethyl orthosilicate as the silane compound (B) in 2.72 ml of isopropanol, and stirred at room temperature for 20 minutes. 1.17 ml of 0.01 M hydrochloric acid aqueous solution was added dropwise to the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 27 was produced. The sample solution 27 was diluted with isopropanol to a volume ratio of 2000 times to prepare a coating solution 27 . Except having used the coating solution 27, it carried out similarly to Example 1, and formed the film on the glass substrate.

Comparative example 2

Dissolve 1.8×10 ^-4 mol of n-decyltrimethoxysilane as the silane compound (A) and 4.8×10 ^-3 mol of tetraethyl orthosilicate as the silane compound (B) in 2.50 ml of isopropanol, and stirred at room temperature for 20 minutes. 1.39 ml of 0.01 M hydrochloric acid aqueous solution was added dropwise to the obtained solution as a catalyst (E), and it stirred at room temperature for 24 hours, and the sample solution 28 was produced. The sample solution 28 was diluted to 30 times the volume ratio with isopropanol to prepare the coating solution 28 . A film was formed on a glass substrate in the same manner as in Example 12 except that the coating solution 28 was used.

About the film on the glass substrate obtained in Example 1-Example 26, Comparative Example 1, and Comparative Example 2, it evaluated by the method of following (1)-(3).

(1) Determination of sliding speed

Using a contact angle measuring device (DM700, manufactured by Kyowa Interface Science Co., Ltd.), 50 μL of water droplets are dropped on the film of a glass substrate inclined at 20°, and the time until the water drop slides 1.5 cm from the initial drop position is measured to calculate the film The sliding speed of water droplets on the surface.

(2) Determination of haze value

The haze (turbidity) of the surface was measured using a haze meter (HZ-2, manufactured by Sugatest Co., Ltd.) with a D65 light source (average sunlight).

(3) Visual evaluation of appearance

In an environment with an illuminance of 1000 lux, the film was covered on a light source, and the presence or absence of coloring or foreign matter (hereinafter collectively referred to as "stains") was visually evaluated according to the following criteria.

○: No stain at all

×: Slight staining can be confirmed

(4) Determination of film thickness

For embodiment 6, embodiment 8, embodiment 15, embodiment 23, embodiment 26 For Comparative Example 1 and Comparative Example 2, the film thickness of the obtained film was measured in the following manner.

An X-ray reflectance measuring device (SmartLab) manufactured by Rigaku Corporation was used for the measurement. As the X-ray source, a 45kW X-ray generator, a CuKα ray wavelength λ=0.15418nm or a CuKα1 ray wavelength λ=0.15406nm of a Cu target was used, and a monochromator was not used. As setting conditions, the sampling width is set to 0.01°, and the scanning range is set to 0.0° to 2.5°. Then, measurement is carried out under the above-described setting conditions to obtain a reflectance measurement value. The obtained measured values were analyzed using Rigaku's analysis software ((global fitting) GlobalFit).

About film thickness, embodiment 6 is 2.9nm, embodiment 8 is 2.5nm, embodiment 15 is 2.6nm, embodiment 23 is 2.6nm, embodiment 26 is 3.5nm, comparative example 1 is 0.3nm, comparative example 2 is 16.3nm.

The measurement results of (1) to (3) are shown in Tables 1 to 4.

According to the composition of the present invention containing the silane compound (A) and the silane compound (B) in a total of 0.015% by mass or more and 0.70% by mass or less, slipping properties and Films with excellent haze and appearance (Example 1 to Example 26). On the other hand, in Comparative Example 1 in which the total content of the silane compound (A) and the silane compound (B) was small, the sliding properties of water droplets decreased. In addition, in Comparative Example 2 in which the total content of the silane compound (A) and the silane compound (B) was large, the haze value increased, the transparency of the film deteriorated, and the appearance was also poor.

Claims (7)

A composition characterized in that it comprises a silane compound (A) represented by the following formula (1), a silane compound (B) represented by the following formula (2), a solvent (C) and a catalyst (E), the The total content of the silane compound (A) and the silane compound (B) in 100% by mass of the composition is not less than 0.015% by mass and not more than 0.70% by mass, relative to the silane compound (A) and the silane The total amount of compound (B) is 100 parts by mass, the content of the catalyst (E) is 0.1 parts by mass or less, and the catalyst (E) is hydrogen chloride, nitric acid or acetic acid; R ¹ -Si(X ¹ ) ₃ (1 )[In formula (1), R ¹ represents a hydrocarbon group with 6 or more carbon atoms, and the -CH ₂ - contained in the hydrocarbon group may be substituted with -O-; X ¹ represents a hydrolyzable group] Si(R ² ) _n (X ² ) _4-n (2) [In the formula (2), R ² represents a hydrocarbon group with 1 to 5 carbons; X ² represents a hydrolyzable group; n is 0 or 1]. The composition as described in claim 1, wherein the molar ratio of the silane compound (B) to the silane compound (A) is not less than 0.1 and not more than 48. The composition described in claim 2, wherein the molar ratio of the silane compound (B) to the silane compound (A) is 0.1 to 12. The composition as described in any one of the first to third claims of the patent application, wherein the solvent (C) is an alcoholic solvent. The composition as described in claim 4, further comprising a solvent (D) having a higher vapor pressure at 20° C. than the solvent (C). The composition according to claim 5, wherein the solvent (D) has a vapor pressure of 8.0 kPa or more at 20°C. A film, which is formed by hardening the composition described in any one of the first to sixth claims of the patent application.