JP2018172646A - Composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problem in which: conventionally known compositions may sometimes have insufficient droplet slipperiness.SOLUTION: A composition has a silane compound (A) represented by formula (1), a silane compound (B) represented by formula (2) and a roughness modifier (C). The content of the roughness modifier (C) is 1 pts.mass or more and 20 pts.mass or less relative to the total 100 pts.mass of the silane compound (A) and the silane compound (B). [Ris a hydrocarbon group having 6 or more carbon atoms, where -CH- in the hydrocarbon group is optionally substituted with -O-. Xis a hydrolyzable group, Ris a C1-5 hydrocarbon group, Xis a hydrolyzable group, and n is an integer of 0 or 1].SELECTED DRAWING: None

Description

  The present invention relates to a composition.

  In various display devices, optical elements, building materials, automobile parts, factory equipment, etc., the base material becomes dirty or corroded due to liquid droplets adhering to the surface of the base material. Various problems may occur, such as inability to demonstrate performance. Therefore, in these fields, the substrate surface is required to have good water repellency.

  For example, Patent Document 1 describes a mixed solution containing tetraethoxysilane, fluoroalkylsilane, and ITO ultrafine particles. Patent Document 2 describes that a coating composition containing tetraalkoxysilane, methyltrimethoxysilane, and metal alkoxide was prepared. Patent Document 3 describes a composition containing octyltriethoxysilane or decyltriethoxysilane and tetraethoxysilane.

JP 7-330378 A JP-A-8-304605 International Publication No. 2016/068103

  In the above-described compositions known hitherto, there are cases where the droplet slipperiness is not sufficiently satisfactory.

［式（１）中、
Ｒ¹は、炭素数６以上の炭化水素基を表し、該炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−に置き換わっていてもよい。
Ｘ¹は、加水分解性基を表す。］

［式（２）中、
Ｒ²は、炭素数１〜５の炭化水素基を表す。
Ｘ²は、加水分解性基を表す。
ｎは、０又は１の整数を表す。］
［２］前記粗さ調整剤（Ｃ）が、メジアン径が１０ｎｍ以上５００ｎｍ以下の金属酸化物粒子である［１］に記載の組成物。
［３］前記シラン化合物（Ａ）と前記シラン化合物（Ｂ）とのモル比（Ｂ／Ａ）が、２以上１００以下である［１］又は［２］に記載の組成物。
［４］前記シラン化合物（Ａ）と前記シラン化合物（Ｂ）の合計の含有率が、組成物１００質量％中、１質量％以上５０質量％以下である［１］〜［３］のいずれかに記載の組成物。
［５］［１］〜［４］のいずれかに記載の組成物を硬化した膜。
［６］ＩＳＯ２５１７８に準拠して算出した表面の算術平均高さＳａが、０．０４μｍ以上０．９０μｍ以下である［５］に記載の膜。
［７］表面抵抗値が７．５×１０¹³Ω／ｓｑ以下であり、ＩＳＯ２５１７８に準拠して算出した表面の算術平均高さＳａが、０．０４μｍ以上となる撥水膜。
［８］［５］〜［７］のいずれかに記載の膜を有する物品。 The present invention includes the following inventions.
[1] A silane compound (A) represented by formula (1), a silane compound (B) represented by formula (2), and a roughness modifier (C), wherein the roughness modifier (C) The composition whose content is 1 mass part or more and 20 mass parts or less with respect to a total of 100 mass parts of the said silane compound (A) and the said silane compound (B).

[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. ]

[In Formula (2),
R ² represents a hydrocarbon group having 1 to 5 carbon atoms.
X ² represents a hydrolyzable group.
n represents an integer of 0 or 1. ]
[2] The composition according to [1], wherein the roughness modifier (C) is metal oxide particles having a median diameter of 10 nm to 500 nm.
[3] The composition according to [1] or [2], wherein a molar ratio (B / A) between the silane compound (A) and the silane compound (B) is 2 or more and 100 or less.
[4] Any of [1] to [3], wherein a total content of the silane compound (A) and the silane compound (B) is 1% by mass or more and 50% by mass or less in 100% by mass of the composition. A composition according to 1.
[5] A film obtained by curing the composition according to any one of [1] to [4].
[6] The film according to [5], wherein the arithmetic average height Sa of the surface calculated in accordance with ISO25178 is 0.04 μm or more and 0.90 μm or less.
[7] A water repellent film having a surface resistance value of 7.5 × 10 ¹³ Ω / sq or less and an arithmetic average height Sa of a surface calculated in accordance with ISO25178 of 0.04 μm or more.
[8] An article having the film according to any one of [5] to [7].

  The film formed from the composition of the present invention has good droplet slipperiness.

  The composition of this invention contains the silane compound (A) represented by Formula (1), the silane compound (B) represented by Formula (2), and a roughness regulator (C), The said roughness regulator Content of (C) is 1 to 20 mass parts with respect to a total of 100 mass parts of the silane compound (A) and the silane compound (B).

［式（１）中、Ｒ¹は、炭素数６以上の炭化水素基を表し、該炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−に置き換わっていてもよい。
Ｘ¹は、加水分解性基を表す。］

[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. ]

［式（２）中、Ｒ²は、炭素数１〜５の炭化水素基を表す。Ｘ²は、加水分解性基を表す。ｎは、０又は１の整数を表す。］

[In formula (2), R ² represents a hydrocarbon group having 1 to 5 carbon atoms. X ² represents a hydrolyzable group. n represents an integer of 0 or 1. ]

By including the silane compound (A) and the silane compound (B), the water repellency of the film is improved, and by including the roughness adjusting agent (C) in a predetermined ratio, an appropriate roughness is imparted to the surface of the film. Therefore, the slipperiness of the droplets can be improved while maintaining water repellency. The content of the roughness adjusting agent (C) is preferably 1 part by mass or more, more preferably 2 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). It is 3 parts by mass or more, preferably 30 parts by mass or less, more preferably 20 parts by mass or less, further preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.
In addition, each component and functional group illustrated below can be used individually or in combination, respectively.

  It is preferable for the ratio of the silane compound (A) to the silane compound (B) to be within a certain range because the droplet slipperiness can be improved while maintaining a good appearance. The content of the silane compound (A) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 4 parts by mass or more, preferably 70 parts by mass with respect to 100 parts by mass of the silane compound (B). It is not more than part by mass, more preferably not more than 40 parts by mass, still more preferably not more than 10 parts by mass.

In the formula (1) representing the silane compound (A), R ¹ is preferably a saturated hydrocarbon group, more preferably a linear or branched alkyl group, and a linear alkyl group. More preferably. Examples of the hydrocarbon group represented by R ¹ include a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.
The hydrocarbon group represented by R ¹ has 6 or more, preferably 7 or more, more preferably 8 or more, preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.

Examples of the group in which —CH ₂ — contained in the hydrocarbon group is replaced by —O— include groups containing one or more alkyleneoxy units. Examples of the alkyleneoxy unit include ethyleneoxy units and propyleneoxy units, with ethyleneoxy units being preferred. The group in which —CH ₂ — contained in the hydrocarbon group is replaced by —O— is preferably —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 to 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 total number of carbon and oxygen contained in the group is 6 or more.
Examples of the divalent hydrocarbon group represented by R ³ include divalent saturated hydrocarbon groups such as a methylene group, an ethylene group, a propylene group, and a butylene group. R ³ is preferably a divalent hydrocarbon group.
Examples of the divalent hydrocarbon group represented by R ⁴ include divalent saturated hydrocarbon groups such as an ethylene group and a propylene group.
Examples of the monovalent hydrocarbon group represented by R ⁵ include monovalent saturated hydrocarbon groups such as a methyl group, an ethyl group, a propyl group, and a butyl group. R ⁵ is preferably a monovalent hydrocarbon group.

In the formula (1), examples of the hydrolyzable group represented by X ¹ include groups that give a hydroxy group (silanol group) by hydrolysis, and preferably an alkoxy group having 1 to 6 carbon atoms, a cyano group, and a hydroxy group. Group, acetoxy group, chlorine atom and isocyanate group. X ¹ is preferably an alkoxy group having 1 to 6 carbon atoms (more preferably 1 to 4) or a cyano group, more preferably an alkoxy group having 1 to 6 carbon atoms (more preferably 1 to 4), and all X ¹ is more preferably an alkoxy group having 1 to 6 carbon atoms (more preferably 1 to 4). The three X ^{1 s} may be the same or different and are preferably the same.
Silane compound as the (A), R ¹ is a linear alkyl group having 7 to 13 carbon atoms, all of X ¹ are the same group, having 1 to 6 carbon atoms (more preferably 1 to 4) Those having an alkoxy group are preferred.

  Specific examples of the silane compound (A) include hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, nonyltrimethoxysilane, nonyltri. Ethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, undecyltrimethoxysilane, undecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tridecyltrimethoxysilane, tridecyltriethoxysilane, butadecyltri Methoxysilane, butadecyltriethoxysilane, pentadecyltrimethoxysilane, pentadecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxy Silane, heptadecyltrimethoxysilane, heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, etc. Methoxysilane, dodecyltriethoxysilane, butadecyltrimethoxysilane, butadecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, and octadecyltriethoxysilane are preferred.

  The content of the silane compound (A) is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, further preferably 0.2 parts by mass or more, preferably 100 parts by mass of the composition. It is 10 mass parts or less, More preferably, it is 5 mass parts or less, More preferably, it is 3 mass parts or less.

In the formula (2) representing the silane compound (B), R ² is preferably a saturated hydrocarbon group, more preferably a linear or branched alkyl group, and a linear alkyl group. More preferably. Examples of the hydrocarbon group represented by R ² include a methyl group, an ethyl group, and a propyl group.

In the 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 and a cyano group. , An acetoxy group, a chlorine atom, an isocyanate group, and the like, and the alkyl group in the alkoxy group is more preferably a linear or branched alkyl group. X ² is preferably an alkoxy group having 1 to 6 carbon atoms (more preferably 1 to 4) or an isocyanate group, more preferably an alkoxy group having 1 to 6 carbon atoms (more preferably 1 to 4), and all X More preferably, ² is an alkoxy group having 1 to 6 (more preferably 1 to 4) carbon atoms. The three X ^{2 s} may be the same or different and are preferably the same.
In the formula (2), n is preferably 0.

  Examples of the silane compound (B) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, and methyltributoxysilane. Silane and tetraethoxysilane are preferred.

  Content of a silane compound (B) is 1 mol or more normally with respect to 1 mol of silane compounds (A), Preferably it is 2 mol or more, More preferably, it is 5 mol or more, More preferably, it is 10 mol or more, and is 100 normally. Or less, preferably 60 mol or less, more preferably 40 mol or less, and even more preferably 30 mol or less.

  The total content of the silane compound (A) and the silane compound (B) is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, preferably in 100% by mass of the composition. Is 50% by mass or less, more preferably 40% by mass or less, and still more preferably 25% by mass or less.

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

The said roughness regulator (C) should just have an effect | action which adjusts the surface roughness of the film | membrane formed as a hardened | cured material from the composition of this invention.
Examples of the roughness adjusting agent (C) include polymer particles and inorganic particles such as metal particles and metal oxide particles, and are preferable from the viewpoint of uniformly dispersing the roughness adjusting agent (C). Are inorganic particles, more preferably metal oxide particles. Specific examples of the metal oxide particles include silicon dioxide, titanium oxide, manganese oxide, yttrium (III) oxide, zirconium oxide, aluminum oxide, zinc oxide, indium (III) oxide, tin oxide (II), and tin oxide. (IV), single metal oxides such as antimony trioxide; composite metal oxides such as indium tin oxide and tin-antimony oxides (especially antimony-doped tin oxide); Particles of (IV) and tin-antimony oxide (particularly antimony-doped tin oxide) are preferred. From the viewpoint of film appearance, tin (IV) oxide or tin-antimony oxide (particularly antimony-doped tin oxide) particles are more preferable.

  The roughness adjuster (C) is preferably a particle. The median diameter of the roughness adjusting agent (C) is preferably 500 nm or less, more preferably 100 nm or less, still more preferably 50 nm or less, and may be, for example, 10 nm or more, further 15 nm or more. As the particle size of the roughness adjusting agent (C) is smaller, the transparency of the resulting film can be maintained. When the particle size is larger than a certain value, the stability of the composition tends to be improved.

  The solubility of the roughness modifier (C) in water at 25 ° C. is preferably 0 to 100 mg / 100 mL, more preferably 0 to 10 mg / 100 mL, and still more preferably 0 to 5 mg / 100 mL.

The density of the roughness adjusting agent (C) is preferably 3 g / cm ³ or more, more preferably 4 g / cm ³ or more, further preferably 5 g / cm ³ or more, preferably 8 g / cm ³ or less, more preferably Is 7.5 g / cm ³ or less.

The surface resistance value of the roughness adjusting agent (C) is preferably 10 ¹⁴ Ω / sq or less, more preferably 10 ¹² Ω / sq or less, still more preferably 10 ¹⁰ Ω / sq or less, for example 10 ² Ω / sq. It may be sq or more, and further 10 ³ Ω / sq or more.

  As the roughness adjusting agent (C), only one kind may be used, or a plurality thereof may be used in combination.

  The composition of the present invention preferably further contains a solvent (D). Examples of the solvent include hydrophilic organic solvents such as alcohol solvents, ether solvents, ketone solvents, ester solvents and amide solvents. These solvent may use only 1 type and may use 2 or more types together.

Examples of alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol, butanol, ethylene glycol, propylene glycol, and diethylene glycol. Ether solvents include dimethoxyethane, tetrahydrofuran, and dioxane, and ketones. Examples of the solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the ester solvent include ethyl acetate and butyl acetate. Examples of the amide solvent include dimethylformamide. Of these, alcohol solvents and ketone solvents are preferably used.
The solvent can be adjusted according to the material of the base material to be described later. For example, when an organic material is used for the base material, a ketone solvent is preferably used, and when an inorganic material is used for the base material, an alcohol system is used. It is preferable to use a solvent.

The composition of the present invention may or may not contain a silane compound (A) and a catalyst (E) for hydrolysis / polycondensation of the silane compound (B). As said catalyst (E), acidic compounds, such as hydrochloric acid, nitric acid, and an acetic acid, basic compounds, such as ammonia and an amine, organometallic compounds, such as an aluminum ethyl acetoacetate compound, etc. can be used.
When the catalyst (E) is contained, the content of the catalyst (E) is preferably 0.001 part by mass or more, more preferably 0 with respect to 100 parts by mass in total of the silane compound (A) and the silane compound (B). 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, preferably 3 parts by mass or less, more preferably 1 part by mass or less, and further preferably 0.1 parts by mass or less.

  The composition of the present invention is an antioxidant, a rust inhibitor, an ultraviolet absorber, a light stabilizer, a fungicide, an antibacterial agent, an anti-bioadhesive agent, a deodorant, and a pigment as long as the effects of the present invention are not impaired. In addition, other components such as various additives such as a flame retardant and an antistatic agent may be contained.

The composition of the present invention is obtained by mixing the silane compound (A), the silane compound (B), the roughness adjusting agent (C), and the solvent (D), catalyst (E) and other components used as necessary. Can be manufactured. Although the mixing order is not particularly limited, for example, the silane compound (A), the silane compound (B) and the solvent (D) used as necessary are mixed, and then mixed with the catalyst (E) used as necessary. Thereafter, the roughness adjusting agent (C) may be mixed. By mixing in such an order, gelation of the composition can be prevented.
The roughness adjuster (C) is preliminarily dispersed in a part of the solvent (D) to obtain a roughness adjuster (C) -containing liquid, and then mixed with the silane compound (A), the silane compound (B) and the like. Also good. When the roughness adjusting agent (C) is dispersed in advance, the dispersion solvent and the solvent used in preparing the composition may be the same or different. When the roughness adjusting agent (C) is previously dispersed in a part of the solvent (D), the content of the roughness adjusting agent (C) is preferably 10% by mass or more in 100% by mass of the dispersion. Preferably it is 15 mass% or more, Preferably it is 40 mass% or less, More preferably, it is 30 mass% or less.

A film which is a cured product of the composition of the present invention is also included in the technical scope of the present invention.
The arithmetic average height Sa of the film surface is preferably 0.90 μm or less, more preferably 0.8 μm or less, still more preferably 0.1 μm or less, preferably 0.04 μm or more, more preferably 0.05 μm or more. It is.
The surface roughness of the film can be calculated in accordance with ISO25178. An image serving as a basis for calculating the surface roughness of the film can be obtained by, for example, an optical microscope (particularly, a confocal laser microscope).

  The contact angle of water with respect to the film is preferably 90 ° or more, more preferably 95 ° or more, still more preferably 100 ° or more, 120 ° or less, or 115 ° or less.

The surface resistance value of the film is preferably 250 × 10 ¹³ Ω / sq or less, more preferably 200 × 10 ¹³ Ω / sq or less, further preferably 170 × 10 ¹³ Ω / sq or less, and even more preferably 7.5 ×. 10 ¹³ Ω / sq or less, 10 ¹² Ω / sq or more, or 10 ¹³ Ω / sq or more.

  The thickness of the film is preferably 10 nm or more, more preferably 20 nm or more, still more preferably 50 nm or more, preferably 500 nm or less, more preferably 300 nm or less, and even more preferably 200 nm or less.

Another form of the cured film of the present invention is a water-repellent film having a surface resistance value of 7.5 × 10 ¹³ Ω / sq or less and an arithmetic average height Sa of the film surface of 0.04 μm or more. .

The surface resistance value of the water repellent film is preferably 5.0 × 10 ¹³ Ω / sq or less, more preferably 4.0 × 10 ¹³ Ω / sq or less, and even 10 ¹² Ω / sq or more. It may be 10 ¹³ Ω / sq or more.

  The arithmetic average height Sa of the water repellent film is preferably 0.9 μm or less, more preferably 0.8 μm or less, still more preferably 0.1 μm or less, preferably 0.04 μm or more, more preferably 0.05 μm. That's it.

  The contact angle of water with respect to the water repellent film is preferably 90 ° or more, more preferably 95 ° or more, further preferably 100 ° or more, 120 ° or less, or 115 ° or less. .

  The thickness of the water repellent film is preferably 10 nm or more, more preferably 20 nm or more, further preferably 50 nm or more, preferably 500 nm or less, more preferably 300 nm or less, and further preferably 200 nm or less.

  The said film | membrane can be formed by making the composition and base material of this invention contact, and hydrolyzing and polycondensing the hydrolysable group contained in a silane compound (A) and a silane compound (B).

Examples of the method of bringing the composition of the present invention into contact with a substrate include a method of coating the composition on a substrate. Examples of the coating method include spin coating method, dip coating method, spray coating method, roll coating method, bar coating method, hand coating (a method in which a liquid is soaked in a cloth, etc., and applied to a substrate), and a pouring (liquid is applied). For example, a method of directly applying to a base material using a dropper or the like, spraying (a method of applying to a base material using a spray), or a combination of these. From the viewpoint of workability, a spin coating method, a spray coating method, hand coating, pouring, spraying, or a combination of these is preferable.
By leaving the composition of the present invention in contact with the base material in the air at room temperature (for example, 10 hours to 48 hours), moisture in the air is taken in and hydrolysis of the hydrolyzable group is performed. Polycondensation is promoted and a film can be formed on the substrate. It is also preferable to further dry the obtained film.

  When contacting the composition of this invention with a base material, you may dilute with a solvent (dilution solvent) as needed from a viewpoint of workability | operativity. As said dilution solvent, the solvent similar to the solvent which may be contained in the said composition can be mentioned, An alcohol solvent and a ketone solvent are preferable. When the substrate is an organic material, a ketone solvent is preferably used. When the substrate is an inorganic material, an alcohol solvent is preferably used. The dilution factor is preferably 2 to 50 times, more preferably 3 to 20 times.

  The shape of the substrate with which the composition of the present invention is brought into contact may be either a flat surface or a curved surface, or may be a three-dimensional structure in which a large number of surfaces are combined. Examples of the material for the substrate include organic materials and inorganic materials. Examples of the organic material include thermoplastic resins such as acrylic resin, polycarbonate resin, polyester resin, styrene resin, acrylic-styrene copolymer resin, cellulose resin, and polyolefin resin; phenol resin, urea resin, melamine resin, epoxy resin, Examples of inorganic materials include ceramics; glass; metals such as iron, silicon, copper, zinc, and aluminum; alloys containing the above metals; etc. Is mentioned.

  The substrate may be subjected to an easy adhesion treatment in advance. Examples of the easy adhesion treatment include hydrophilic treatment such as corona treatment, plasma treatment, and ultraviolet treatment. Further, primer treatment with a resin, a silane coupling agent, tetraalkoxysilane, or the like may be used. In addition, 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.

  By using the composition of the present invention, it is possible to provide a film having excellent droplet slipperiness. The film is useful for display devices, optical elements, building materials, automobile parts, factory equipment, and the like.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention. In the following, “part” means “part by mass” and “%” means “% by mass” unless otherwise specified.
The measuring method in the present invention is as follows.

(Visual appearance evaluation)
In an environment with an illuminance of 1000 lux, the film was visually observed, and the presence or absence of coloring or foreign matter (hereinafter collectively referred to as “dirt”) was evaluated by sensory evaluation as follows.
◎: Dirt cannot be confirmed ○: Dirt can be confirmed by careful observation ×: Dirt can be easily confirmed

[Contact angle evaluation]
Using a contact angle measuring device (DM700, manufactured by Kyowa Interface Science Co., Ltd.), the water contact angle on the surface of the film was measured by the droplet method (analysis method: θ / 2 method, water droplet amount: 3.0 μL). .

[Sliding speed]
A 50 μL water droplet was dropped on the substrate tilted at 20 degrees, and the sliding time of 1.5 cm from the initial dropping position was measured to calculate the sliding speed. In addition, when a water droplet did not slide down 1.5 cm or more within 2 minutes, it was set as x: not sliding down.

(Surface resistance measurement)
A measurement sample was placed on a large-diameter electrode for a flat plate sample (SME-8310 manufactured by Toa DKK Corporation), a voltage of 10 V was applied, and after 4 minutes with a digital insulation meter (DSM-8103 manufactured by Toa DKK Corporation) The resistance value was measured, and the surface resistance value was calculated based on the measured value.

[Measurement of surface roughness]
The surface of the obtained film was observed at a magnification of 20 times using a laser microscope (OLS4000, manufactured by Olympus). The arithmetic average height Sa was evaluated according to ISO25178. The arithmetic average height Sa was an average value of N = 2.

Example 1
0.29 g of decyltrimethoxysilane as the silane compound (A), 5.99 g of tetraethyl orthosilicate (tetraethoxysilane) as the silane compound (B), and 12.07 g of 2-butanone (manufactured by Kanto Chemical Co., Inc.) as the main solvent And stirred at room temperature for 20 minutes. 8.32 g of hydrochloric acid (0.01 mol / L aqueous solution) as a catalyst was mixed with the obtained solution and stirred at room temperature for 24 hours to prepare a sample solution. S-2000 (20 mass% methyl isobutyl ketone dispersion containing particles of tin oxide having a median diameter of 15 to 20 nm, manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.) as a liquid containing a roughness adjusting agent (C) in the sample solution. 315 g (the roughness modifier (C) is 1.0 part by mass with respect to a total of 100 parts by mass of the silane compound (A) and the silane compound (B)), and is subjected to roughness by ultrasonic treatment for 30 minutes. The modifier (C) was dispersed in the sample solution to obtain a coating composition. The obtained coating composition was diluted with 2-butanone at a dilution ratio of 3 to obtain a coating solution. About 700 μL of the coating solution was sprayed on an acrylic plate (manufactured by Sumitomo Chemical Co., Ltd.) as a substrate by spraying, and the film was formed on a spin coater (manufactured by MIKASA) under conditions of a rotation speed of 300 rpm and 60 sec, and then dried at room temperature A coating film was obtained.

Example 2
The addition amount of S-2000 as a liquid containing a roughness modifier (C) is 1.57 g (the roughness modifier (C) is 100 parts by mass in total of the silane compound (A) and the silane compound (B)). A coating film was produced in the same manner as in Example 1 except that the content was changed to 5 parts by mass.

Example 3
3.14 g of the addition amount of S-2000 as the liquid containing the roughness adjusting agent (C) (the roughness adjusting agent (C) is based on 100 parts by mass of the silane compound (A) and the silane compound (B)). A coating film was produced in the same manner as in Example 1 except that the amount was changed to 10 parts by mass.

Example 4
A coating film was prepared in the same manner as in Example 3 except that the coating composition was used without being diluted.

Example 5
0.29 g of decyltrimethoxysilane as the silane compound (A), 5.99 g of tetraethyl orthosilicate (tetraethoxysilane) as the silane compound (B), 11.7 g of 2-propanol (manufactured by Kanto Chemical Co., Inc.) as the main solvent And stirred at room temperature for 20 minutes. 8.32 g of hydrochloric acid (0.01 mol / L aqueous solution) as a catalyst was mixed with the obtained solution and stirred at room temperature for 24 hours to prepare a sample solution. S-2000 (20 mass% methyl isobutyl ketone dispersion containing particles of tin oxide having a median diameter of 15 to 20 nm, manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.) as a liquid containing a roughness adjusting agent (C) in the sample solution. 314 g (the roughness adjusting agent (C) is 1.0 part by mass with respect to 100 parts by mass in total of the silane compound (A) and the silane compound (B)), and is roughened by ultrasonic treatment for 30 minutes. The adjusting agent (C) was dispersed in the sample solution and diluted with 2-propanol at a dilution ratio of 3 to obtain a coating solution. As a base material, a glass substrate (“EAGLE XG” manufactured by Corning) with the surface of the base material activated by an atmospheric pressure plasma apparatus (manufactured by Fuji Machinery Co., Ltd.) under the conditions of an irradiation speed of 800 mm / sec, a gap of 10 mm, and a single irradiation. )It was used. Other than that was carried out similarly to Example 1, and produced the coating film.

Example 6
3.14 g of the addition amount of S-2000 as the liquid containing the roughness adjusting agent (C) (the roughness adjusting agent (C) is based on 100 parts by mass of the silane compound (A) and the silane compound (B)). The coating film was prepared in the same manner as in Example 5 except that the amount was changed to 10 parts by mass.

Example 7
The amount of S-2000 added as the liquid containing the roughness adjusting agent (C) is 4.71 g (the roughness adjusting agent (C) is 100 parts by mass in total of the silane compound (A) and the silane compound (B). A coating film was produced in the same manner as in Example 5 except that the amount was changed to 15 parts by mass).

Example 8
The amount of S-2000 added as the liquid containing the roughness adjusting agent (C) is 6.28 g (the roughness adjusting agent (C) is 100 parts by mass in total of the silane compound (A) and the silane compound (B)). A coating film was produced in the same manner as in Example 5 except that the amount was changed to 20 parts by mass.

Example 9
Instead of using 0.314 g of S-2000 as the roughness adjusting agent (C) -containing liquid, T-1 (20 mass% 3-methoxy-3-containing particles composed of tin-antimony oxide having a median diameter of 100 nm) 1.57 g of methyl-1-butanol dispersion (manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.) (roughness adjuster (C) is 100 parts by mass of silane compound (A) and silane compound (B)). 5 parts by mass) A coating film was prepared in the same manner as in Example 5 except that it was used.

Example 10
Instead of using 0.314 g of S-2000 as the roughness adjusting agent (C) -containing liquid, SiO ₂ powder (Admafine SO-E1, median diameter 250 nm, manufactured by Admatechs Co., Ltd.) is used as the roughness adjusting agent (C). Except that 0.31 g (the roughness modifier (C) was 5 parts by mass with respect to 100 parts by mass in total of the silane compound (A) and the silane compound (B)) was used in the same manner as in Example 5. Thus, a coating film was prepared.

Example 11
Instead of using 0.314 g of S-2000 as the roughness adjusting agent (C) -containing liquid, SiO ₂ powder (Admafine SO-E2, median diameter 500 nm, manufactured by Admatechs Co., Ltd.) is used as the roughness adjusting agent (C). Except that 0.31 g (the roughness modifier (C) was 5 parts by mass with respect to 100 parts by mass in total of the silane compound (A) and the silane compound (B)) was used in the same manner as in Example 5. Thus, a coating film was prepared.

Example 12
The added amount of S-2000 as the liquid containing the roughness adjusting agent (C) is 1.57 g (the roughness adjusting agent (C) is 100 parts by mass in total of the silane compound (A) and the silane compound (B)). A coating film was produced in the same manner as in Example 5 except that the content was changed to 5 parts by mass).

Example 13
The added amount of S-2000 as the liquid containing the roughness adjusting agent (C) is 1.57 g (the roughness adjusting agent (C) is 100 parts by mass in total of the silane compound (A) and the silane compound (B)). The coating film was prepared in the same manner as in Example 5 except that the dilution ratio with 2-propanol was changed to 7 times.

Example 14
The added amount of S-2000 as the liquid containing the roughness adjusting agent (C) is 1.57 g (the roughness adjusting agent (C) is 100 parts by mass in total of the silane compound (A) and the silane compound (B)). The coating film was prepared in the same manner as in Example 5 except that the dilution ratio with 2-propanol was changed to 10 times.

Example 15
The added amount of S-2000 as the liquid containing the roughness adjusting agent (C) is 1.57 g (the roughness adjusting agent (C) is 100 parts by mass in total of the silane compound (A) and the silane compound (B)). The coating film was prepared in the same manner as in Example 5 except that the dilution ratio with 2-propanol was changed to 20 times.

Example 16
Instead of using 0.29 g of decyltrimethoxysilane as the silane compound (A), 0.79 g is used as the silane compound (B), and using 1.25 g of tetraethyl orthosilicate (tetraethoxysilane) as the silane compound (B) as the main solvent. Rather than using 11.7 g of 2-propanol (manufactured by Kanto Chemical Co., Inc.), 4.25 g was used, and instead of using 8.32 g of hydrochloric acid (0.01 mol / L aqueous solution) as a catalyst, 2.34 g was used to adjust the roughness. Instead of using 0.314 g of S-2000 as the agent (C) -containing liquid, 0.51 g (the roughness adjusting agent (C) is based on 100 parts by mass of the silane compound (A) and the silane compound (B)) 5 parts by mass) was used in the same manner as in Example 5 except that a coating film was prepared.

Example 17
Instead of using 0.29 g of decyltrimethoxysilane as the silane compound (A), 0.15 g is used, and instead of using 5.99 g of tetraethyl orthosilicate (tetraethoxysilane) as the silane compound (B), 1.92 g is used as the main solvent. Rather than using 11.7 g of 2-propanol (manufactured by Kanto Chemical Co., Inc.), using 3.94 g, and using 2.74 g of hydrochloric acid (0.01 mol / L aqueous solution) as a catalyst instead of using 8.32 g, the roughness was adjusted. Instead of using 0.314 g of S-2000 as the agent (C) -containing liquid, 0.52 g (roughness adjusting agent (C) is based on 100 parts by mass of the silane compound (A) and the silane compound (B). 5 parts by mass) was used in the same manner as in Example 5 except that a coating film was prepared.

Example 18
Instead of using 0.29 g of decyltrimethoxysilane as the silane compound (A), 0.06 g is used, and instead of using 5.99 g of tetraethyl orthosilicate (tetraethoxysilane) as the silane compound (B), the main solvent is used. Roughness adjustment was performed using 3.89 g instead of 11.7 g of 2-propanol (manufactured by Kanto Chemical Co., Inc.) and 2.80 g of hydrochloric acid (0.01 mol / L aqueous solution) as a catalyst instead of using 8.32 g. Instead of using 0.314 g of S-2000 as the agent (C) -containing liquid, 0.52 g (roughness adjusting agent (C) is based on 100 parts by mass of the silane compound (A) and the silane compound (B). 5 parts by mass) was used in the same manner as in Example 5 except that a coating film was prepared.

Comparative Example 1
A coating film was produced in the same manner as in Example 1 except that the roughness adjusting agent (C) was not added.

Comparative Example 2
A coating film was produced in the same manner as in Example 5 except that the roughness adjusting agent (C) was not added.

  Table 1 shows the evaluation results of visual appearance, contact angle, surface resistance value, sliding speed, and surface roughness for the coating films of Examples 1 to 18 and Comparative Examples 1 and 2. However, the improvement ratio of the surface resistance value and the sliding speed is based on the numerical value of Comparative Example 1 when an acrylic substrate is used as the substrate, and the numerical value of Comparative Example 2 when the glass substrate is used as the substrate. The value obtained by dividing the corresponding reference value by the surface resistance value in each example, or the value obtained by dividing the sliding speed value in each example by the corresponding reference value.

  By using the composition of the present invention, it is possible to provide a film having excellent droplet sliding properties. The film is useful for display devices, optical elements, building materials, automobile parts, factory equipment, and the like.

Claims (8)

Including a silane compound (A) represented by the formula (1), a silane compound (B) represented by the formula (2) and a roughness adjusting agent (C),
The composition whose content of the said roughness regulator (C) is 1 to 20 mass parts with respect to a total of 100 mass parts of the said silane compound (A) and the said silane compound (B).

[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. ]

[In Formula (2),
R ² represents a hydrocarbon group having 1 to 5 carbon atoms.
X ² represents a hydrolyzable group.
n represents an integer of 0 or 1. ]   The composition according to claim 1, wherein the roughness adjusting agent (C) is a metal oxide particle having a median diameter of 10 nm to 500 nm.   The composition according to claim 1 or 2, wherein a molar ratio (B / A) between the silane compound (A) and the silane compound (B) is 2 or more and 100 or less.   The total content of the silane compound (A) and the silane compound (B) is 1% by mass or more and 50% by mass or less in 100% by mass of the composition. .   The film | membrane which hardened | cured the composition in any one of Claims 1-4.   The film according to claim 5, wherein the arithmetic average height Sa of the surface calculated in accordance with ISO25178 is 0.04 µm or more and 0.90 µm or less. A water repellent film having a surface resistance value of 7.5 × 10 ¹³ Ω / sq or less and an arithmetic average height Sa of the surface calculated in accordance with ISO25178 of 0.04 μm or more.   An article having the film according to any one of claims 5 to 7.