KR20190131111A - Composition - Google Patents

Abstract

In the conventionally known composition, there is a case that the droplet slipperiness may not be sufficiently satisfied. 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), and content of the said roughness regulator (C) is It 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). [R ¹ represents a hydrocarbon group having 6 or more carbon atoms, and -CH ₂ -included 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 represents an integer of 0 or 1.]

Description

Composition

The present invention relates to a composition.

In various display devices, optical elements, building materials, automobile parts, factory facilities, etc., liquid droplets adhere to the surface of the substrate to contaminate or corrode the substrate, and the contamination or corrosion cannot exhibit desired performance. Problems may arise. Therefore, in these fields, it is desired that the water repellency of the substrate surface is good.

For example, Patent Document 1 describes a mixed solution containing tetraethoxysilane, fluoroalkylsilane, and ITO ultrafine particles. Patent Document 2 describes the preparation of a coating composition containing tetraalkoxysilane, methyltrimethoxysilane, and metal alkoxide. In patent document 3, the composition containing octyl triethoxysilane or decyl triethoxysilane, and tetraethoxysilane is described.

Japanese Unexamined Patent Application Publication No. 7-330378 Japanese Patent Laid-Open No. 8-304605 International Publication No. 2016/068103

In the said composition known conventionally, there existed a case where droplet slipperiness | lubricacy cannot fully be satisfied.

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 regulator (C) are included, and the content of the roughness regulator (C) is the silane The composition which is 1 mass part or more and 20 mass parts or less with respect to a total of 100 mass parts of a compound (A) and the said silane compound (B).

[Formula 1]

In formula (1),

R ¹ represents a hydrocarbon group having 6 or more carbon atoms, and -CH ₂ -included in the hydrocarbon group may be substituted with -O-.

X ¹ represents a hydrolyzable group.]

[Formula 2]

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 adjusting agent (C) is a metal oxide particle having a median diameter of 10 nm or more and 500 nm or less.

[3] The composition according to [1] or [2], wherein the molar ratio (B / A) of the silane compound (A) and the silane compound (B) is 2 or more and 100 or less.

[4] The composition according to any of [1] to [3], wherein a content rate of the total 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.

[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 mean height Sa on 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 of 7.5 × 10 ¹³ Ω / sq or less and having an arithmetic mean height Sa of the surface calculated according to ISO25178 to 0.04 μm or more.

[8] An article having a 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), and content of the said roughness regulator (C) is It 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).

[Formula 3]

In the equation (1) of, R ¹ represents a hydrocarbon group having a carbon number of at least 6, -CH ₂ groups contained art hydrocarbon-is, or may be substituted with -O-.

X ¹ represents a hydrolyzable group.]

[Formula 4]

[In formula (2), R <^2> represents a C1-C5 hydrocarbon group. 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 becomes good, and by including the roughness adjusting agent (C) in a predetermined ratio, a suitable degree of roughness can be imparted to the surface of the film. Droplet slipperiness can be improved while maintaining. As for content of a roughness adjuster (C), with respect to a total of 100 mass parts of a silane compound (A) and a silane compound (B), Preferably it is 1 mass part or more, More preferably, it is 2 mass parts or more, More preferably, 3 It is more than a mass part, Preferably it is 30 mass parts or less, More preferably, it is 20 mass parts or less, More preferably, it is 15 mass parts or less, Especially preferably, it is 10 mass parts or less.

In addition, each component and functional group illustrated below can be used individually or in combination, respectively.

When the ratio of the silane compound (A) to the silane compound (B) is within a certain range, it is preferable 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, even more preferably 4 parts by mass or more, based on 100 parts by mass of the silane compound (B). 70 mass parts or less, More preferably, it is 40 mass parts or less, More preferably, it is 10 mass parts or less.

In Formula (1) which shows the said silane compound (A), it is preferable that R <^1> is a saturated hydrocarbon group, It is more preferable that it is a linear or branched alkyl group, It is more preferable that it is a linear alkyl group. Examples of the hydrocarbon group represented by R ¹ include a hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group.

Carbon number of the hydrocarbon group represented by R <^1> is 6 or more, Preferably it is 7 or more, More preferably, it is 8 or more, Preferably it is 30 or less, More preferably, it is 20 or less, More preferably, it is 15 or less.

Examples of the group in which the -CH ₂ -contained in the hydrocarbon group is substituted with -O- include a group containing 1 or 2 or more alkyleneoxy units. Examples of the alkyleneoxy units include ethyleneoxy units and propyleneoxy units, with ethyleneoxy units being preferred. As the group in which -CH ₂ -contained in the hydrocarbon group is substituted with -O-, -R ^3- (R ⁴ -O) _n1 -R ⁵ is preferable. 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, R ⁵ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and n1 is The integer of 1-10 is shown. However, the sum total of the number of carbon and oxygen contained in the said group is six or more.

As a bivalent hydrocarbon group represented by R <^3> , bivalent saturated hydrocarbon groups, such as a methylene group, an ethylene group, a propylene group, butylene group, are mentioned. As R <^3> , it is preferable that it is a bivalent hydrocarbon group.

As a bivalent hydrocarbon group represented by R <^4> , bivalent saturated hydrocarbon groups, such as an ethylene group and a propylene group, are mentioned.

As a monovalent hydrocarbon group represented by R <^5> , monovalent saturated hydrocarbon groups, such as a methyl group, an ethyl group, a propyl group, and a butyl group, are mentioned. As R ^{5, a} monovalent hydrocarbon group is preferable.

In Formula (1), as a hydrolysable group represented by X <^1> , the group which gives a hydroxyl group (silanol group) by hydrolysis is mentioned, Preferably it is a C1-C6 alkoxy group, a cyano group, a hydroxyl group, Acetoxy group, a chlorine atom, an isocyanato group, etc. are mentioned. As X <^1> , a C1-C6 (more preferably 1-4) alkoxy group or cyano group is preferable, C1-C6 (more preferably 1-4) alkoxy group is more preferable, All X <^1> It is more preferable that it is this C1-C6 (more preferably 1-4) alkoxy group. Three X <^1> may be same or different, and the same thing is preferable.

As a silane compound (A), it is preferable that R <^1> is a C7-C13 linear alkyl group and all X <^1> is the same group and it is a C1-C6 (more preferably 1-4) alkoxy group.

As a silane compound (A), specifically, hexyl trimethoxysilane, hexyl triethoxysilane, heptyl trimethoxysilane, heptyl triethoxysilane, octyl trimethoxysilane, octyl triethoxysilane, nonyltrimeth Methoxysilane, nonyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, undecyltrimethoxysilane, undecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tri Decyltrimethoxysilane, tridecyltriethoxysilane, butadidecyltrimethoxysilane, butadidecyltriethoxysilane, pentadecyltrimethoxysilane, pentadecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyl Triethoxysilane, heptadecyl trimethoxysilane, heptadecyl triethoxysilane, an octadecyl trimethoxysilane, an octadecyl triethoxysilane, etc. are mentioned, octyl trimethoxysilane, octyl triethoxysilane, Decyltrimethoxysilane, Siltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, butadidecyltrimethoxysilane, butadidecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyl Trimethoxysilane and octadecyl triethoxysilane are preferable.

Content of a silane compound (A) is in 100 mass parts of compositions, Preferably it is 0.01 mass part or more, More preferably, it is 0.1 mass part or more, More preferably, it is 0.2 mass part or more, Preferably 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 Formula (2) which shows the said silane compound (B), it is preferable that R <^2> is a saturated hydrocarbon group, It is more preferable that it is a linear or branched alkyl group, It is more preferable that it is a linear alkyl group. As a hydrocarbon group represented by R <^2> , a methyl group, an ethyl group, a propyl group, etc. are mentioned.

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, cyano group, acetoxy group, A chlorine atom, an isocyanato group, etc. are mentioned, It is more preferable that the alkyl group in an alkoxy group is a linear or branched alkyl group. As X ² , an alkoxy group or isocyanato group having 1 to 6 carbon atoms (more preferably 1 to 4) is preferable, an alkoxy group having 1 to 6 carbon atoms (more preferably 1 to 4) is more preferable, and all It is further more preferable that X <^2> is a C1-C6 (more preferably 1-4) alkoxy group. Three X <^2> may be same or different, and the same thing is preferable.

In Formula (2), it is preferable that n is zero.

As the silane compound (B), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, etc. And tetramethoxysilane and tetraethoxysilane are preferable.

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, Usually 100 It is mol or less, Preferably it is 60 mol or less, More preferably, it is 40 mol or less, More preferably, it is 30 mol or less.

The content rate of the sum total of a silane compound (A) and a silane compound (B) is in 100 mass% of compositions, Preferably it is 1 mass% or more, More preferably, it is 3 mass% or more, More preferably, it is 5 mass% or more, Preferably Preferably it is 50 mass% or less, More preferably, it is 40 mass% or less, More preferably, it is 25 mass% or less.

Only 1 type may be used for a silane compound (A), or it may use plurality together. Only 1 type may be used for a silane compound (B), and it may use plurality together.

The roughness regulator (C) may have a function of adjusting the surface roughness of the film formed from the composition of the present invention as a cured product.

Examples of the roughness regulator (C) include polymer particles and inorganic particles such as metal particles and metal oxide particles. From the viewpoint of uniformly dispersing the roughness regulator (C), the inorganic particles are preferably inorganic particles. More preferably, they are metal oxide particle. Specific examples of the metal oxide particles include silicon dioxide, titanium oxide, manganese oxide, yttrium oxide (III), zirconium oxide, aluminum oxide, zinc oxide, indium oxide (III), tin oxide (II), and tin oxide (IV). Single metal oxides such as antimony trioxide; Complex metal oxides such as indium tin oxide and tin-antimony oxide (especially antimony-doped tin oxide); And particles of silicon dioxide, tin oxide (IV) and tin-antimony-based oxides (particularly antimony-doped tin oxide) are preferable. From the viewpoint of the film appearance, particles of tin oxide (IV) or tin-antimony oxide (particularly antimony-doped tin oxide) are more preferable.

It is preferable that the said roughness regulator (C) is particle | grains. 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, for example, 10 nm or more, or even 15 nm or more. The smaller the particle diameter of the roughness adjusting agent (C), the more the transparency of the resulting film can be maintained, and when the particle diameter is large or larger, the stability of the composition tends to be improved.

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

The density of the roughness adjusting agent (C) is preferably 3 g / cm 3 or more, more preferably 4 g / cm 3 or more, more preferably 5 g / cm 3 or more, preferably 8 g / cm 3 or less Preferably it 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 or more, further 10 ³ Ω / sq or more.

Only 1 type may be used for a roughness regulator (C), and it may use multiple together.

It is preferable that the composition of this invention contains a solvent (D) further. 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 or may use 2 or more types together.

Examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, and the like. Dietherethane, tetrahydrofuran, dioxane, and the like are mentioned as the ether solvent. Examples of the ketone solvents include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the ester solvents include ethyl acetate and butyl acetate. Examples of the amide solvents include dimethylformamide and the like. . Especially, it is preferable to use an alcohol solvent and a ketone solvent.

The solvent can be adjusted to the material of the substrate to be described later. For example, it is preferable to use a ketone solvent when the organic material is used for the substrate, and to use an alcohol solvent when the inorganic material is used for the substrate. Do.

The composition of this invention may or may not contain the catalyst (E) for hydrolysis and polycondensation of a silane compound (A) and a silane compound (B). As said catalyst (E), acidic compounds, such as hydrochloric acid, nitric acid, and acetic acid, basic compounds, such as ammonia and an amine, organometallic compounds, such as an aluminum ethyl acetoacetate compound, etc. can be used.

In the case of containing the catalyst (E), the content of the catalyst (E) is preferably 0.001 parts by mass or more, and more preferably 0.005 mass based on 100 parts by mass in total of the silane compound (A) and the silane compound (B). Or more, more preferably 0.01 mass part or more, preferably 3 mass parts or less, more preferably 1 mass part or less, and still more preferably 0.1 mass part or less.

The composition of the present invention is an antioxidant, a rust preventive agent, an ultraviolet absorber, a light stabilizer, an antifungal agent, an antibacterial agent, a biofouling agent, a deodorant, a pigment, a flame retardant, and an antistatic agent within a range that does not impair the effects of the present invention. Other components, such as various additives, may be contained.

The composition of this invention can be manufactured by mixing a silane compound (A), a silane compound (B), and a roughness regulator (C), and the solvent (D), catalyst (E), and other components used as needed. Although the mixing order is not specifically limited, For example, after mixing a silane compound (A), a silane compound (B), and the solvent (D) used as needed, and then mixing with the catalyst (E) used as needed You may mix roughness modifier (C). By mixing in such an order, gelation of the composition can be prevented.

The roughness regulator (C) may be previously dispersed in a part of the solvent (D) to form a roughness regulator (C) -containing liquid, and then mixed with the silane compound (A), the silane compound (B), or the like. When dispersing a roughness adjuster (C) beforehand, a dispersion solvent and the solvent used at the time of composition preparation may be same or different. In the case where the roughness regulator (C) is previously dispersed in a part of the solvent (D), the content rate of the roughness regulator (C) is preferably 100% by mass or more, more preferably 15% by mass in 100% by mass of the dispersion. It is above, Preferably it is 40 mass% or less, More preferably, it is 30 mass% or less.

The film which is a hardened | cured material of the composition of this invention is also included in the technical scope of this invention.

Arithmetic mean height Sa of the said film surface becomes like this. Preferably it is 0.90 micrometer or less, More preferably, it is 0.8 micrometer or less, More preferably, it is 0.1 micrometer or less, Preferably it is 0.04 micrometer or more, More preferably, it is 0.05 micrometer or more.

The surface roughness of the film can be calculated based on ISO25178. The image used as the basis of the calculation of the surface roughness of the film can be obtained by, for example, an optical microscope (especially, a confocal laser microscope).

The contact angle of water with respect to the said membrane becomes like this. Preferably it is 90 degrees or more, More preferably, it is 95 degrees or more, More preferably, it is 100 degrees or more, 120 degrees or less, 115 degrees or less may be sufficient.

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, still more preferably 170 × 10 ¹³ Ω / sq or less, particularly 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 at least 10 nm, more preferably at least 20 nm, even more preferably at least 50 nm, preferably at most 500 nm, more preferably at most 300 nm, even more preferably at 200 nm. It is as follows.

Another form of the cured film of this invention is a water-repellent film whose surface resistance value is 7.5x10 <^{13> (} ohm) / sq or less, and whose arithmetic mean height Sa of a film surface becomes 0.04 micrometer 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, 10 ¹² Ω / sq or more, or 10 ¹³ Ω / sq or more. do.

The arithmetic mean height Sa of the said water repellent membrane becomes like this. Preferably it is 0.9 micrometer or less, More preferably, it is 0.8 micrometer or less, More preferably, it is 0.1 micrometer or less, Preferably it is 0.04 micrometer or more, More preferably, it is 0.05 micrometer or more.

The contact angle of water with respect to the said water repellent film becomes like this. Preferably it is 90 degrees or more, More preferably, it is 95 degrees or more, More preferably, it is 100 degrees or more, 120 degrees or less, 115 degrees or less may be sufficient.

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

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

As a method of bringing the composition of the present invention into contact with the substrate, a method of coating the composition on the substrate may be mentioned. As the coating method, a spin coating method, a dip coating method, a spray coating method, a roll coating method, a bar coating method, a hand coating (a method of coating a substrate by infiltrating a liquid to a cloth, etc.), or spraying (using a dropper, etc.) And the method of coating onto the substrate as it is, spraying (the method of applying to the substrate by spraying), or a combination thereof. From the viewpoint of workability, spin coating, spray coating, hand coating, spraying, spraying, or a combination thereof is preferred.

In the state in which the composition of the present invention is in contact with the substrate, by standing in the air at room temperature (for example, 10 hours to 48 hours), moisture in the air is collected to promote hydrolysis and polycondensation of the hydrolyzable group. A film can be formed on a base material. It is also preferable to further dry the obtained film.

When the composition of the present invention is brought into contact with a substrate, it may be diluted with a solvent (dilution solvent) as necessary from the viewpoint of workability. As said dilution solvent, the solvent similar to the solvent which may be contained in the said composition is mentioned, An alcoholic solvent and a ketone solvent are preferable. It is preferable to use a ketone solvent when the base material is an organic material, and to use an alcohol solvent when the base material is an inorganic material. Dilution magnification becomes like this. Preferably it is 2-50 times, More preferably, it is 3-20 times.

The shape of the base material which contacts the composition of this invention may be a planar or curved surface, and the three-dimensional structure which many surfaces were combined may be sufficient. Moreover, organic materials and inorganic materials are mentioned as a material of a base material. Examples of the organic materials include thermoplastic resins such as acrylic resins, polycarbonate resins, polyester resins, styrene resins, acrylic-styrene copolymer resins, cellulose resins, and polyolefin resins; Thermosetting resins such as phenol resins, urea resins, melamine resins, epoxy resins, unsaturated polyesters, silicone resins and urethane resins; And the like, and examples of the inorganic material include ceramics; Glass; Metals such as iron, silicon, copper, zinc and aluminum; An alloy comprising the metal; Etc. can be mentioned.

The substrate may be subjected to easy adhesion treatment in advance. Examples of the easy adhesion treatment include hydrophilization treatments such as corona treatment, plasma treatment, and ultraviolet treatment. Moreover, you may use the primer process by resin, a silane coupling agent, tetraalkoxysilane, etc. Moreover, you may perform the primer process by resin, a silane coupling agent, tetraalkoxysilane, etc., and may apply | coat a glass film, such as polysilazane, to a base material beforehand.

By using the composition of this invention, the film | membrane excellent in droplet slipperiness | lubricacy can be provided. The film is useful for a display device, an optical element, a building material, an automobile part, a factory facility, and the like.

Example

Although an Example is given to the following and this invention is demonstrated to it further more concretely, this invention is not restrict | limited by the following example originally, It is also possible to carry out by changing suitably in the range which may be suitable for the meaning of the previous and the later. Of course, they are possible and they are all included in the technical scope of the present invention. In the following, unless otherwise indicated, "part" means "mass part" and "%" means "mass%."

The measuring method in this invention is as follows.

[Appearance visual evaluation]

In the environment of roughness 1000 lux, the film was visually observed, and the presence or absence of coloring or foreign matter (hereinafter collectively referred to as "contamination") was evaluated by sensory evaluation as follows.

◎: contamination cannot be confirmed

○: If you look carefully you can see contamination

X: contamination can be easily confirmed

[Contact angle evaluation]

The contact angle of the water of the surface of the film was measured by the droplet method (interpretation method: (theta) / 2 method, the amount of water: 3.0 microliters) using the contact angle measuring device (DM700, Kyogawa Interface Co., Ltd.).

(Slide speed)

50 microliters of water drops were dripped on the board | substrate inclined at 20 degree | times, and the time to slide 1.5 cm from the initial dropping position was measured, and the slide speed was computed. In addition, when water droplets do not slide more than 1.5 cm within 2 minutes, it was said that it does not slide.

(Surface resistance measurement)

The measurement sample was placed in a large diameter electrode for flat plate (SME-8310 manufactured by Dong-A DKK Co., Ltd.), a voltage of 10 V was applied, and a resistance after 4 minutes with a digital insulator (DSM-8103 manufactured by Dong-A DKK Co., Ltd.). The value was measured and the surface resistance value was computed based on the value.

[Measurement of Surface Roughness]

The surface of the film | membrane obtained was observed at the magnification 20x using the laser microscope (OLS4000, Olympus make). Arithmetic mean height Sa was evaluated based on ISO25178. Arithmetic mean height Sa was made into the average value of N = 2.

Example 1

0.29 g of decyltrimethoxysilane as the silane compound (A) and 5.99 g of orthosilicate tetraethyl (tetraethoxysilane) as the silane compound (B) were used as 12.07 g of 2-butanone (manufactured by Kanto Chemical Co., Ltd.) as a main solvent. It was dissolved and stirred at room temperature for 20 minutes. To the obtained solution, 8.32 g of hydrochloric acid (0.01 mol / L aqueous solution) as a catalyst was mixed and stirred at room temperature for 24 hours to prepare a sample solution. 0.315 g of S-2000 (20 mass% methyl isobutyl ketone dispersion liquid containing the particle | grains which consist of tin oxide with a median diameter of 15-20 nm, the Mitsubishi Material Electronics Chemical Co., Ltd. make) in the said sample solution as a roughness adjuster (C) containing liquid ( As for the roughness regulator (C), 1.0 mass part) is added with respect to a total of 100 mass parts of a silane compound (A) and a silane compound (B), and a roughening agent (C) is disperse | distributed in a sample solution by ultrasonic treatment for 30 minutes. To obtain a coating composition. The obtained coating composition was diluted with 2-butanone by 3 times of dilution ratio, and the coating solution was obtained. After spraying about 700 microliters of coating solutions by spraying on an acryl plate (made by Sumitomo Chemical Co., Ltd.) as a base material, it formed into a film by the spin coater (made by MIKASA) on conditions of rotation speed 300 rpm and 60 sec, and then dried at room temperature. To obtain a coating film.

Example 2

The addition amount of S-2000 as the roughness regulator (C) -containing liquid was changed to 1.57 g (the roughness regulator (C) was 5 parts by mass based on 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 for the above.

Example 3

3.14 g (roughness adjuster (C) is 10 mass parts with respect to a total of 100 mass parts of a silane compound (A) and a silane compound (B)) by changing the addition amount of S-2000 as a roughness adjuster (C) containing liquid. A coating film was produced in the same manner as in Example 1 except for the above.

Example 4

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

Example 5

0.29 g of decyltrimethoxysilane as a silane compound (A) and 5.99 g of ortho silicate tetraethyl (tetraethoxysilane) as a silane compound (B) are dissolved in 11.7 g of 2-propanol (manufactured by Kanto Chemical Co., Ltd.) as a main solvent. And stirred at room temperature for 20 minutes. To the obtained solution, 8.32 g of hydrochloric acid (0.01 mol / L aqueous solution) as a catalyst was mixed and stirred at room temperature for 24 hours to prepare a sample solution. 0.314 g of S-2000 (20 mass% methyl isobutyl ketone dispersion containing Mitsubishi Material Electron Co., Ltd. containing the particle | grains which consist of tin oxide of median diameter 15-20 nm, manufactured by Mitsubishi Material Electronics Chemical Co., Ltd.) as a roughness adjuster (C) containing liquid in the said sample solution As for the roughness regulator (C), 1.0 mass part) is added with respect to a total of 100 mass parts of a silane compound (A) and a silane compound (B), and a roughening agent (C) is disperse | distributed in a sample solution by ultrasonic treatment for 30 minutes. The mixture was diluted with 3-propanol to 3 times the dilution ratio to obtain a coating solution. As a base material, the glass substrate ("EAGLE XG" made by Corning Corporation) which activated the surface of a base material by the atmospheric pressure plasma apparatus (made by Fuji Machine Co., Ltd.) on condition of an irradiation speed of 800 mm / sec, a gap of 10 mm, and the number of irradiation times is used. It was. Other than that was carried out similarly to Example 1, and produced the coating film.

Example 6

3.14 g (roughness adjuster (C) is 10 mass parts with respect to a total of 100 mass parts of a silane compound (A) and a silane compound (B)) by changing the addition amount of S-2000 as a roughness adjuster (C) containing liquid. A coating film was produced in the same manner as in Example 5 except for the above.

Example 7

The addition amount of S-2000 as a roughness adjuster (C) containing liquid was changed into 4.71 g (roughness adjuster (C) is 15 mass parts with respect to a total of 100 mass parts of a silane compound (A) and a silane compound (B)). A coating film was produced in the same manner as in Example 5 except for the above.

Example 8

6.28 g (roughness adjuster (C) is 20 mass parts with respect to a total of 100 mass parts of a silane compound (A) and a silane compound (B)) by changing the addition amount of S-2000 as a roughness adjuster (C) containing liquid. A coating film was produced in the same manner as in Example 5 except for the above.

Example 9

Instead of using 0.314 g of S-2000 as the roughness adjusting agent (C) -containing liquid, 20 mass% 3-methoxy-3-methyl containing particles composed of T-1 (tin-antimony-based oxide having a median diameter of 100 nm) 1.57 g of the 1-butanol dispersion liquid and the Mitsubishi Material Electrochemical Co., Ltd. product (roughness regulator (C) were used 5 mass parts with respect to a total of 100 mass parts of a silane compound (A) and a silane compound (B)) except that In the same manner as in Example 5, a coating film was produced.

Example 10

Instead of using 0.314 g of S-2000 as the roughness adjusting agent (C) -containing liquid, 0.31 g of SiO ₂ powder (Sadomapine SO-E1, median diameter 250 nm, manufactured by Adomattex Co., Ltd.) as the roughness adjusting agent (C) A roughness adjusting agent (C) was produced in the same manner as in Example 5 except that 5 parts by mass was used based on 100 parts by mass of the total of the silane compound (A) and the silane compound (B).

Example 11

Instead of using 0.314 g of S-2000 as the roughness adjusting agent (C) -containing liquid, 0.31 g of SiO ₂ powder (amorphine SO-E2, median diameter 500 nm, manufactured by Adomattex Co., Ltd.) as the roughness adjusting agent (C) A roughness adjusting agent (C) was produced in the same manner as in Example 5 except that 5 parts by mass was used based on 100 parts by mass of the total of the silane compound (A) and the silane compound (B).

Example 12

The addition amount of S-2000 as the roughness regulator (C) -containing liquid was changed to 1.57 g (the roughness regulator (C) was 5 parts by mass based on 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 for the above.

Example 13

Change the addition amount of S-2000 as the roughness regulator (C) -containing liquid to 1.57 g (the roughness regulator (C) is 5 parts by mass based on 100 parts by mass in total of the silane compound (A) and the silane compound (B)) And a coating film were produced in the same manner as in Example 5 except that the dilution ratio with 2-propanol was increased to 7 times.

Example 14

Change the addition amount of S-2000 as the roughness regulator (C) -containing liquid to 1.57 g (the roughness regulator (C) is 5 parts by mass based on 100 parts by mass in total of the silane compound (A) and the silane compound (B)) , Except that the dilution ratio by 2-propanol was increased to 10 times, a coating film was prepared in the same manner as in Example 5.

Example 15

Change the addition amount of S-2000 as the roughness regulator (C) -containing liquid to 1.57 g (the roughness regulator (C) is 5 parts by mass based on 100 parts by mass in total of the silane compound (A) and the silane compound (B)) , Except that the dilution ratio by 2-propanol was increased to 20 times, a coating film was prepared in the same manner as in Example 5.

Example 16

0.79 g is used instead of 0.29 g of decyltrimethoxysilane as the silane compound (A), and 1.25 g is used instead of 5.99 g of orthosilicate tetraethyl (tetraethoxysilane) as the silane compound (B). Instead of using 11.7 g of 2-propanol (manufactured by Kanto Chemical Co., Ltd.) as a solvent, 4.25 g was used, and 2.34 g of hydrochloric acid (0.01 mol / L aqueous solution) was used instead of 8.32 g, and the roughness adjusting agent (C) -containing liquid was used. Example 5 except that 0.51 g (roughness adjusting agent (C) was used 5 parts by mass based on 100 parts by mass in total of the silane compound (A) and the silane compound (B)) instead of using 0.314 g of S-2000 as In the same manner as above, a coating film was produced.

Example 17

0.15 g is used instead of 0.29 g of decyltrimethoxysilane as the silane compound (A), and 1.92 g is used instead of 5.99 g of orthosilicate tetraethyl (tetraethoxysilane) as the silane compound (B). Instead of using 11.7 g of 2-propanol (manufactured by Kanto Chemical Co., Ltd.) as a solvent, 2.94 g of hydrochloric acid (0.01 mol / L aqueous solution) is used instead of 8.32 g, and the roughness adjusting agent (C) -containing liquid is used. Example 5 except that 0.52 g (roughness adjusting agent (C) was used 5 parts by mass based on 100 parts by mass in total of the silane compound (A) and the silane compound (B)) instead of using 0.314 g of S-2000 as In the same manner as above, a coating film was produced.

Example 18

0.06 g is used instead of 0.29 g of decyltrimethoxysilane as the silane compound (A), and 2.02 g is used instead of 5.99 g of orthosilicate tetraethyl (tetraethoxysilane) as the silane compound (B). Instead of using 11.7 g of 2-propanol (manufactured by Kanto Chemical Co., Ltd.) as a solvent, 3.89 g is used, and 2.80 g of hydrochloric acid (0.01 mol / L aqueous solution) is used instead of 8.32 g, and the roughness adjusting agent (C) -containing liquid Example 5 except that 0.52 g (roughness adjusting agent (C) was used 5 parts by mass based on 100 parts by mass in total of the silane compound (A) and the silane compound (B)) instead of using 0.314 g of S-2000 as In the same manner as above, a coating film was produced.

Comparative Example 1

Except not adding a roughness modifier (C), it carried out similarly to Example 1, and produced the coating film.

Comparative Example 2

Except not adding a roughness modifier (C), it carried out similarly to Example 5, and produced the coating film.

Table 1 shows the evaluation results of the visual appearance, contact angle, surface resistance value, slide speed, and surface roughness of 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 slide speed is based on the numerical value of Comparative Example 1 when the acrylic substrate is used as the substrate and the numerical value of Comparative Example 2 when the glass substrate is the reference value, respectively. The value obtained by dividing the corresponding reference value by the surface resistance value in the examples, or the value obtained by dividing the value of the slide speed in each example by the corresponding reference value.

TABLE 1

Industrial availability

By using the composition of this invention, the film | membrane excellent in droplet slipperiness | lubricacy can be provided. The film is useful for a display device, an optical element, a building material, an automobile part, a factory facility and the like.

Claims (8)

The silane compound (A) represented by Formula (1), the silane compound (B) represented by Formula (2), and a roughness modifier (C) are included,
The content of the said roughness regulator (C) 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).
[Formula 1]

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

In formula (2),
R <^2> represents a C1-C5 hydrocarbon group.
X ² represents a hydrolyzable group.
n represents an integer of 0 or 1.] The method of claim 1,
The roughness adjusting agent (C) is a metal oxide particle having a median diameter of 10 nm or more and 500 nm or less. The method according to claim 1 or 2,
The composition in which the molar ratio (B / A) of the said silane compound (A) and the said silane compound (B) is 2 or more and 100 or less. The method according to any one of claims 1 to 3,
The composition of the sum total of the said silane compound (A) and the said silane compound (B) is 1 mass% or more and 50 mass% or less in 100 mass% of compositions. The film | membrane which hardened the composition of any one of Claims 1-4. The method of claim 5,
The film whose arithmetic mean height Sa of the surface computed based on ISO25178 is 0.04 micrometer or more and 0.90 micrometer or less. The water-repellent film whose surface resistance value is 7.5x10 <^{13> (} ohm) / sq or less and whose arithmetic mean height Sa of the surface calculated based on ISO25178 becomes 0.04 micrometer or more. An article having the membrane according to any one of claims 5 to 7.