JP6909613B2 - Composition - Google Patents

Description

The present invention relates to compositions.

In various display devices, optical elements, building materials, automobile parts, factory equipment, etc., the base material becomes dirty or corroded due to the adhesion of droplets on the surface of the base material, and this dirt or corrosion causes desired Various problems may occur, such as inability to demonstrate performance. Therefore, in these fields, it is required that the surface of the base material has good water repellency and oil repellency.

^{For example, Patent Document 1 describes the general formula I: R 1} −Y _u − (CH ₂ ) ₂ Si (CH ₃ ) _q (R ² ) for the purpose of obtaining an oil-repellent, water-repellent, and stain-repellent coating. _{Represented by 3-q} , R ¹ is a predetermined alkyl fluoride group or aryl fluoride group, R ² is an alkoxy group having a chlorine atom or 1 to 4 carbon atoms, and q is 0 or 1. Fluoroalkylsilane and / or general formula II: represented by R ³ Si (CH ₃ ) _p (R ⁴ ) _3-p , where R ³ is the given alkyl group and R ⁴ is the chlorine atom or 1 to 4 A two-component system containing an alkylsilane which is an alkoxy group having a carbon atom and p is 0 or 1 is disclosed. Further, Patent Document 2 describes an organic silicon compound (A) in which at least one first hydrocarbon chain-containing group and at least one hydrolyzable group are bonded to a silicon atom, and at least one hydrolysis. A water- and oil-repellent coating composition containing a metal compound (B) in which a sex group is bonded to a metal atom is disclosed.

Japanese Patent Application Laid-Open No. 2007-501304 International Publication No. 2016/068103

In addition to water repellency, it is important that water droplets easily slip off when the base material is tilted in order to suppress the adhesion of water droplets on the surface of the base material, and the water repellency and slipperiness performance are maintained for a long period of time. In order to maintain it, the abrasion resistance of the film provided on the surface of the base material is also required.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a composition capable of realizing a water-repellent film having excellent sliding property and abrasion resistance.

The present invention
Formula (1): An _{alkylsilane compound (A) represented by C m} H _{2m + 1-} SiX ₃ (m is an integer of 4 to 30, X is a hydrolyzable group), and
Formula (2): Alkoxysilane compound (B) represented by ^{Si (OR 1} ) ₄ (R ^{1 is an alkyl group) and}
Formula (3): ^{A fluoroalkylsilane compound represented by R 2-} SiY ₃ (R ² is a group in which one or more hydrogen atoms of an alkyl group are substituted with a fluorine atom, and Y is a hydrolyzable group). C) is a composition containing and
A composition in which the molar ratio (C / A) of the fluoroalkylsilane compound (C) to the alkylsilane compound (A) is 0.1 to 50.

The composition of the present invention preferably further satisfies at least one of the following requirements (i) to (v).
(I) The molar ratio (B / A) of the alkoxysilane compound (B) to the alkylsilane compound (A) is 0.1 to 30 (ii) the formula (1) representing the alkylsilane compound (A). X is an alkoxy group having 1 to 6 carbon atoms (iii) R ¹ in the formula (2) representing the alkoxysilane compound (B) is an alkyl group having 1 to 6 carbon atoms (iv) The fluoroalkylsilane Y in the formula (3) representing the compound (C) is an alkoxy group or a cyano group (v) The total ratio of the alkylsilane compound (A), the alkoxysilane compound (B) and the fluoroalkylsilane compound (C) is The solid content concentration is 3 to 60% by mass.

The present invention also includes a surface-treated porous base material having a film composed of any of the above-mentioned compositions of the present invention on the surface of the porous base material.

The present invention also includes a method for producing a surface-treated porous substrate, which is obtained by applying any of the compositions of the present invention described above to the surface of the porous substrate and curing the surface at room temperature.

Since the present invention is a composition containing three components, an alkylsilane compound (A), an alkoxysilane compound (B) and a fluoroalkylsilane compound (C), which are represented by predetermined formulas, respectively, it has slip resistance and abrasion resistance. An excellent water-repellent film can be realized.

The alkylsilane compound (A), the alkoxysilane compound (B) and the fluoroalkylsilane compound (C) contained in the composition of the present invention will be described below.

(1) Alkylsilane compound (A)
The alkylsilane compound (A) (hereinafter, may be simply referred to as “compound (A)”) is represented by the formula (1): C _m H _{2m + 1} −SiX ₃ , where m is an integer of 4 to 30. X represents a hydrolyzable group. By setting m to 4 to 30, the water repellency, sliding property and abrasion resistance of the obtained film can be improved, and the appearance of the film can be improved. In particular, when m exceeds 30, the appearance of the film deteriorates. C _m H _{2m + 1} in formula (1) - alkyl group represented by imparts water repellency to the film obtained. C _m H _{2m + 1} - alkyl group represented by may be linear, may be branched but is preferably linear. The value of m, that is, the lower limit of the number of carbon atoms of the alkyl group bonded to the silicon atom is preferably 6 or more, more preferably 7 or more, still more preferably 8 or more, and the upper limit of the number of carbon atoms is preferably 20 or less. It is preferably 15 or less, and more preferably 13 or less.

Further, X in the formula (1) is a hydrolyzable group and may be a group that imparts a hydroxy group (silanol group) by hydrolysis, for example, an alkoxy group having 1 to 6 carbon atoms, a cyano group, a hydroxy group, or an acetoxy group. , Chlorine atom, isocyanate group and the like. As X, an alkoxy group having 1 to 6 carbon atoms (more preferably 1 to 4) and a cyano group are preferable, and an alkoxy group having 1 to 6 carbon atoms (more preferably 1 to 4) is more preferable. The three Xs may be the same or different, and it is preferable that the three Xs are the same. It is preferable that all Xs are alkoxy groups having 1 to 6 carbon atoms (more preferably 1 to 4 carbon atoms). As the compound (A), in particular, C _m H _{2m + 1} − is a linear alkyl group, the value of m is 7 or more and 13 or less, and all X have 1 to 6 carbon atoms (more preferable). Is an alkoxy group of 1 to 4), and it is preferable that the three Xs are the same.

Only one type of compound (A) may be used, or two or more types may be used in combination.

(2) Alkoxysilane compound (B)
The alkoxysilane compound (B) (hereinafter, may be simply referred to as “compound (B)”) is represented by the ^{formula (2): Si (OR 1} ) ₄ ^{, where R 1} is an alkyl group and four Rs. ¹ may be the same or different, but is preferably the same. R ¹ is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and it is further preferable that ^{four R 1s are the same at these times.}

Only one type of compound (B) may be used, or two or more types may be used in combination.

(3) Fluoroalkylsilane compound (C)
The fluoroalkylsilane compound (C) (hereinafter, may be simply referred to as “compound (C)”) is represented by the ^{formula (3): R 2-} SiY ₃ ^{, where R 2} is one or more hydrogen atoms of an alkyl group. The atom is a group substituted with a fluorine atom, and Y is a hydrolyzable group. R ² may be linear, may be branched, and is preferably linear. The carbon number of R ² is preferably 1 to 15, more preferably 3 to 13, and even more preferably 5 to 10. The number of fluorine atoms in R ² is preferably 3 or more, it is preferable that the perfluoroalkyl group at the end of R ² having the number of carbon atoms of more than half of the total number of carbon atoms in R ² is present.

Examples of Y as the hydrolyzable group include hydrolyzable groups similar to those of X above, where Y is an alkoxy group (preferably having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms) or A cyano group is preferred. The three Ys may be the same or different, and it is preferable that the three Ys are the same. It is preferable that all Ys are alkoxy groups having 1 to 6 carbon atoms (more preferably 1 to 4), and it is further preferable that the three Ys are the same at this time.

The compound (C) is preferably represented by the formula (3-1): CpF _{2p + 1} −C _q H _2q −SiY ₃ , where p is an integer of 3 to 10 and q is an integer of 0 to 5. .. Y in the formula (3-1) means the same as Y in the above formula (3). In particular, it is preferable that p is 6 to 10, q is 1 to 5, and CpF _{2p + 1} −C _q H _2q − is linear, in which case Y has 1 to 6 carbon atoms (particularly carbon). It is more preferably the alkoxy group of Nos. 1 to 4) and the three Ys being the same.

Only one type of compound (C) may be used, or two or more types may be used in combination.

^{Since R 1} in compound (B) is an alkyl group, OR ¹ forms an alkoxy group, but when X in compound (A) is an alkoxy group and Y in compound (C) is an alkoxy group. , The alkoxy group of the compound (A), the compound (B) and the compound (C) is preferably an alkoxy group having 1 to 6 carbon atoms (more preferably 1 to 4 carbon atoms), and at this time, the compound (A). ), (B) and (C) may have different alkoxy groups.

It is also one of the preferable embodiments that the compounds (A), (B) and (C) satisfy the following conditions at the same time.
Compound (A) is represented by the formula (1): C _m H _{2m + 1} −SiX _{3 , C m} H _{2m + 1} − is a linear alkyl group, and the value of m is 7 or more and 13 or less. At the same time, all Xs are alkoxy groups having 1 to 6 carbon atoms (more preferably 1 to 4), and the condition that all three Xs are the same is satisfied.
Compound (B) is represented by the formula (2): Si (OR ¹ ) ₄ ^{, R 1} is an alkyl group having 1 to 6 carbon atoms (more preferably 1 to 4 carbon atoms), and four R ^1s are the same. Satisfy the condition that
Compound (C) is represented by the formula (3-1): CpF _{2p + 1} −C _q H _2q −SiY ₃ , p is 6 to 10, q is 1 to 5, and CpF _{2p + 1} −C. _{The condition that q} H _2q − is linear, Y is an alkoxy group having 1 to 6 carbon atoms (more preferably 1 to 4 carbon atoms), and three Ys are the same is satisfied.

In the composition of the present invention capable of realizing a water-repellent film having good sliding property and abrasion resistance, it is also preferable to adjust the mutual content ratio of the compound (A), the compound (B) and the compound (C). As a result, the sliding property and wear resistance can be further improved, and the appearance of the film can be improved.

The molar ratio (B / A) of compound (B) to compound (A) is preferably 0.1 to 30. The lower limit of the molar ratio of B / A is more preferably 1 or more, and further preferably 2 or more. The upper limit of the molar ratio of B / A is more preferably 20 or less, still more preferably 15 or less.

The molar ratio (C / A) of compound (C) to compound (A) is 0.1 to 50. The lower limit of the molar ratio of C / A is preferably 0.2 or more, more preferably 0.5 or more, and further preferably 1 or more. The upper limit of the molar ratio of C / A is preferably 30 or less, more preferably 25 or less, and even more preferably 10 or less.

The molar ratio (B / (A + C)) of the compound (B) to the total of the compounds (A) and (C) is preferably 0.01 to 15. The lower limit of the molar ratio of B / (A + C) is more preferably 0.1 or more, still more preferably 1 or more. The upper limit of the molar ratio of B / (A + C) is more preferably 10 or less, still more preferably 8 or less.

The molar ratio (C / (A + B)) of the compound (C) to the total of the compounds (A) and (B) is preferably 0.01 to 15. The lower limit of the molar ratio of C / (A + B) is more preferably 0.1 or more, still more preferably 0.3 or more. The upper limit of the molar ratio of C / (A + B) is more preferably 10 or less, still more preferably 5 or less.

The total ratio of the compounds (A), (B) and (C) in the composition of the present invention is preferably 3 to 60% by mass in terms of solid content concentration. The total solid content concentration of the compounds (A), (B) and (C) is more preferably 5% by mass or more, further preferably 10% by mass or more, and further preferably 50% by mass or less, further preferably. It is 45% by mass or less.

The total ratio of the compounds (A) and (C) in the composition of the present invention is preferably 2 to 60% by mass in terms of solid content concentration. The total solid content concentration of the compounds (A) and (C) is more preferably 4% by mass or more, further preferably 6% by mass or more, still more preferably 40% by mass or less, still more preferably 30% by mass or less. Is.

The composition of the present invention preferably contains a solvent in addition to containing the compounds (A), (B) and (C). Examples of the solvent include hydrophilic organic solvents such as alcohol-based solvents, ether-based solvents, ketone-based solvents, ester-based solvents, and amide-based solvents. Only one of these solvents may be used, or two or more of these solvents may be used in combination.

Examples of the alcohol solvent include methanol, ethanol, 1-propanol, isopropanol, butanol, ethylene glycol, propylene glycol, diethylene glycol and the like, and examples of the ether solvent include dimethoxyethane, tetrahydrofuran, dioxane and the like, and the ketone solvent. Examples thereof include acetone and methyl ethyl ketone, examples of the ester solvent include ethyl acetate and butyl acetate, and examples of the amide solvent include dimethylformamide. Above all, it is preferable to use an alcohol solvent.

The composition of the present invention is an antioxidant, a rust preventive, an ultraviolet absorber, a light stabilizer, a fungicide, an antibacterial agent, a biological adhesion inhibitor, a deodorant, and a pigment as long as the effects of the present invention are not impaired. , Flame retardant, antistatic agent and the like may be contained.

The composition of the present invention containing the above-mentioned three components (A) to (C) is brought into contact with a base material, and the hydrolyzable groups contained in the compounds (A) to (C) are hydrolyzed and polycondensed. As a result, a water-repellent film can be formed on the surface of the base material. In the case of hydrolysis, the reaction is usually carried out in the presence of a catalyst, but in the composition of the present invention, the hydrolysis reaction proceeds satisfactorily even if the hydrolysis catalyst is not included, and a film can be formed. However, it may contain a catalyst, and the catalyst includes acidic compounds such as hydrochloric acid, nitric acid and acetic acid generally used in the Zolgel method, basic compounds such as ammonia and amines, and organic metals such as aluminum ethylacetate acetate compounds. Compounds and the like can be used. When a catalyst is contained, the catalyst content with respect to the total of the compound (A), the compound (B), the compound (C) and the catalyst is preferably 11 mol% or less in terms of molar ratio, and 60% by mass or less in terms of mass ratio. preferable.

Further, examples of the method of bringing the composition of the present invention into contact with the base material include a method of coating the composition on the base material, such as a spin coating method, a dip coating method, a spray coating method, a roll coating method, and a bar coating method. , Hand-painting (a method of soaking a cloth with liquid and applying it to the base material), pouring (a method of applying the liquid as it is to the base material using a dropper, etc.), spraying (a method of applying the liquid to the base material using a sprayer) Method of application) and the like. In particular, from the viewpoint of workability, the hand coating, flushing, spraying, and spray coating methods are preferable. By allowing the composition of the present invention to stand in the air at room temperature (for example, 10 hours to 48 hours) in contact with the base material, the moisture in the air is taken in and the hydrolyzable group is hydrolyzed. Polycondensation is promoted and a film can be formed on the substrate. It is also preferable to further dry the obtained film. The film thickness can be, for example, about 0.1 to 1000 nm.

The base material with which the composition of the present invention is brought into contact is not particularly limited, and the shape of the base material 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. Further, the material of the base material is not limited, and may be composed of either an organic material or an inorganic material. 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, and non-plastic material. Thermocurable resins such as saturated polyester, silicone resin, and urethane resin; and the like; examples of the inorganic material include ceramics; glass; metals such as iron, silicon, copper, zinc, and aluminum; alloys containing the metals; etc. Can be mentioned.

Further, the surface texture of the base material is not particularly limited. Normally, when a porous base material (for example, a hardened cement product such as concrete or mortar) is used, the composition permeates in the depth direction of the base material, and the performance such as water repellency is sufficiently exhibited. However, the composition of the present invention can form a water-repellent film having excellent sliding property and abrasion resistance on the substrate even on a porous substrate. Therefore, the present invention also includes a surface-treated porous substrate having a film made of the composition of the present invention on the surface of the porous substrate. Such a surface-treated porous substrate can be produced by applying the composition of the present invention to the surface of the porous substrate and allowing the composition to stand at room temperature to cure the composition.

The base material may be subjected to an easy-adhesion treatment in advance. Examples of the easy-adhesion treatment include hydrophilization treatments such as corona treatment, plasma treatment, and ultraviolet treatment. Further, a primer treatment with a resin, a silane coupling agent, a tetraalkoxysilane, or the like may be used. Further, a primer treatment with a resin, a silane coupling agent, a tetraalkoxysilane or the like may be performed, or a glass film such as polysilazane may be applied to the base material in advance.

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited by the following examples, and it is of course possible to carry out the invention with appropriate modifications within the range that can be adapted to the above-mentioned purpose, and all of them are technical of the present invention. Included in the range.

Example 1
(Preparation of coating liquid)
^{N-decyltrimethoxysilane 2.2 × 10 -3} mol as alkylsilane compound (A), tetraethyl orthosilicate (tetraethoxysilane) 4.4 × 10 ^-3 mol as alkoxysilane compound (B), fluoroalkylsilane compound ^{As (C), after dissolving 4.4 × 10 -4} mol of triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane in 4.6 ml of isopropyl alcohol, 2.4 ml of 0.01 M hydrochloric acid aqueous solution Was dropped. Stirring was performed for 24 hours from the start of liquid preparation to obtain a coating liquid 1.

(Preparation of film)
3 ml of coating liquid 1 was soaked in BEMCOT (registered trademark) manufactured by Asahi Kasei Corporation, and the coating liquid 1 was manually applied to a concrete base material 5 x 5 cm whose surface was wiped clean, and left at room temperature for 24 hours. It was dried to obtain a film. When the appearance of the film was visually evaluated, some fading was observed on the base material (evaluation ○).

Example 2
^{N-decyltrimethoxysilane 2.2 × 10 -3} mol as alkylsilane compound (A), tetraethyl orthosilicate 4.4 × 10 ^-3 mol as alkoxysilane compound (B), triethoxy as fluoroalkylsilane compound (C) ^{After dissolving 2.2 × 10 -3} mol of -1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane in 4.6 ml of isopropyl alcohol, 2.9 ml of a 0.01 M hydrochloric acid aqueous solution was added dropwise. The mixture was stirred for 24 hours from the start of liquid preparation to obtain a coating liquid 2, and a film was obtained in the same manner as in Example 1 with respect to the preparation of a film. When the appearance of the film was visually evaluated, some fading was observed on the base material (evaluation ○).

Example 3
^{N-decyltrimethoxysilane 1.4 × 10 -3} mol as the alkylsilane compound (A), tetraethyl orthosilicate 2.8 × 10 ^-3 mol as the alkoxysilane compound (B), and triethoxy as the fluoroalkylsilane compound (C). ^{After dissolving 7.0 × 10 -3} mol of -1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane in 2.9 ml of isopropyl alcohol, 3.4 ml of a 0.01 M hydrochloric acid aqueous solution was added dropwise. The mixture was stirred for 24 hours from the start of liquid preparation to obtain a coating liquid 3, and a film was obtained in the same manner as in Example 1 with respect to the preparation of a film. When the appearance of the film was visually evaluated, some fading was observed on the base material (evaluation ○).

Example 4
^{N-decyltrimethoxysilane 9.4 × 10 -4} mol as alkylsilane compound (A), tetraethyl orthosilicate 1.9 × 10 ^-3 mol as alkoxysilane compound (B), triethoxy as fluoroalkylsilane compound (C) ^{After dissolving 9.4 × 10 -3} mol of -1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane in 2.0 ml of isopropyl alcohol, 3.7 ml of 0.01 M hydrochloric acid aqueous solution was added dropwise. The mixture was stirred for 24 hours from the start of liquid preparation to obtain a coating liquid 4, and a film was obtained in the same manner as in Example 1 with respect to the preparation of a film. When the appearance of the film was visually evaluated, black fading was observed on the substrate (evaluation Δ).

Example 5
^{N-decyltrimethoxysilane 4.4 × 10 -4} mol as alkylsilane compound (A), tetraethyl orthosilicate 8.8 × 10 ^-4 mol as alkoxysilane compound (B), triethoxy as fluoroalkylsilane compound (C) ^{After dissolving 1.3 × 10 −2} mol of -1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane in 0.9 ml of isopropyl alcohol, 4.0 ml of a 0.01 M hydrochloric acid aqueous solution was added dropwise. The mixture was stirred for 24 hours from the start of liquid preparation to obtain a coating liquid 5, and a film was obtained in the same manner as in Example 1 with respect to the preparation of a film. When the appearance of the film was visually evaluated, black fading was observed on the substrate (evaluation Δ).

Example 6
^{N-decyltrimethoxysilane 2.9 × 10 -3} mol as alkylsilane compound (A), tetraethyl orthosilicate 3.0 × 10 ^-4 mol as alkoxysilane compound (B), triethoxy as fluoroalkylsilane compound (C) ^{After dissolving 2.9 × 10 -3} mol of -1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane in 6.2 ml of isopropyl alcohol, 1.8 ml of a 0.01 M hydrochloric acid aqueous solution was added dropwise. The mixture was stirred for 24 hours from the start of liquid preparation to obtain a coating liquid 6, and a film was obtained in the same manner as in Example 1 with respect to the preparation of a film. When the appearance of the film was visually evaluated, some fading was observed on the base material (evaluation ○).

Example 7
^{N-decyltrimethoxysilane 1.6 × 10 -3} mol as the alkylsilane compound (A), tetraethyl orthosilicate 8.0 × 10 ^-3 mol as the alkoxysilane compound (B), and triethoxy as the fluoroalkylsilane compound (C). ^{After dissolving 1.6 × 10 -3} mol of -1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane in 3.3 ml of isopropyl alcohol, 3.9 ml of a 0.01 M hydrochloric acid aqueous solution was added dropwise. The mixture was stirred for 24 hours from the start of liquid preparation to obtain a coating liquid 7, and a film was obtained in the same manner as in Example 1 with respect to the preparation of a film. When the appearance of the film was visually evaluated, the original state of the base material was maintained (evaluation ◎).

Example 8
Alkyl silane compound (A) as n- decyl trimethoxysilane 1.1 × 10 ^-3 mol, the alkoxysilane compound (B) as tetraethyl orthosilicate 1.1 × 10 ^-2 mol, triethoxy as fluoroalkyl silane compound (C) ^{After dissolving 1.1 × 10 -3} mol of -1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane in 3.3 ml of isopropyl alcohol, 3.9 ml of a 0.01 M hydrochloric acid aqueous solution was added dropwise. The mixture was stirred for 24 hours from the start of liquid preparation to obtain a coating liquid 8, and a film was obtained in the same manner as in Example 1 with respect to the preparation of a film. When the appearance of the film was visually evaluated, the original state of the base material was maintained (evaluation ◎).

Example 9
Alkyl silane compound (A) as n- decyl trimethoxysilane 4.7 × 10 ^-4 mol, the alkoxysilane compound (B) as tetraethyl orthosilicate 1.4 × 10 ^-2 mol, triethoxy as fluoroalkyl silane compound (C) ^{After dissolving 4.7 × 10 -4} mol of -1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane in 3.3 ml of isopropyl alcohol, 3.9 ml of a 0.01 M hydrochloric acid aqueous solution was added dropwise. The mixture was stirred for 24 hours from the start of liquid preparation to obtain a coating liquid 9, and a film was obtained in the same manner as in Example 1 with respect to the preparation of the film. When the appearance of the film was visually evaluated, the original state of the base material was maintained (evaluation ◎).

Example 10
^{N-decyltrimethoxysilane 2.2 × 10 -3} mol as alkylsilane compound (A), tetraethyl orthosilicate 4.4 × 10 ^-3 mol as alkoxysilane compound (B), triethoxy as fluoroalkylsilane compound (C) ^{After dissolving 2.2 × 10 -3} mol of -1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane in 4.6 ml of isopropyl alcohol, 2.9 ml of a 0.01 M hydrochloric acid aqueous solution was added dropwise. The mixture was stirred for 24 hours from the start of the liquid preparation, and the obtained liquid was diluted 3-fold with isopropyl alcohol to obtain a coating liquid 10, and a film was obtained in the same manner as in Example 1 with respect to the preparation of the film. When the appearance of the film was visually evaluated, some fading was observed on the base material (evaluation ○).

Example 11
^{N-decyltrimethoxysilane 2.2 × 10 -3} mol as alkylsilane compound (A), tetraethyl orthosilicate 4.4 × 10 ^-3 mol as alkoxysilane compound (B), triethoxy as fluoroalkylsilane compound (C) ^{After dissolving 2.2 × 10 -3} mol of -1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane in 4.6 ml of isopropyl alcohol, 2.9 ml of a 0.01 M hydrochloric acid aqueous solution was added dropwise. The mixture was stirred for 24 hours from the start of the liquid preparation, and the obtained liquid was diluted 5-fold with isopropyl alcohol to obtain a coating liquid 11, and a film was obtained in the same manner as in Example 1 with respect to the preparation of the film. When the appearance of the film was visually evaluated, the original state of the base material was maintained (evaluation ◎).

Example 12
^{N-decyltrimethoxysilane 2.2 × 10 -3} mol as alkylsilane compound (A), tetraethyl orthosilicate 4.4 × 10 ^-3 mol as alkoxysilane compound (B), triethoxy as fluoroalkylsilane compound (C) ^{After dissolving 2.2 × 10 -3} mol of -1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane in 4.6 ml of isopropyl alcohol, 2.9 ml of a 0.01 M hydrochloric acid aqueous solution was added dropwise. The mixture was stirred for 24 hours from the start of the liquid preparation, and the obtained liquid was diluted 7-fold with isopropyl alcohol to obtain a coating liquid 12, and a film was obtained in the same manner as in Example 1 with respect to the preparation of the film. When the appearance of the film was visually evaluated, the original state of the base material was maintained (evaluation ◎).

Example 13
^{N-decyltrimethoxysilane 2.2 × 10 -3} mol as alkylsilane compound (A), tetraethyl orthosilicate 4.4 × 10 ^-3 mol as alkoxysilane compound (B), triethoxy as fluoroalkylsilane compound (C) ^{After dissolving 2.2 × 10 -3} mol of -1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane in 4.6 ml of isopropyl alcohol, 2.9 ml of a 0.01 M hydrochloric acid aqueous solution was added dropwise. The mixture was stirred for 24 hours from the start of the liquid preparation, and the obtained liquid was diluted 10-fold with isopropyl alcohol to obtain a coating liquid 13, and a film was obtained in the same manner as in Example 1 with respect to the preparation of the film. When the appearance of the film was visually evaluated, the original state of the base material was maintained (evaluation ◎).

Example 14
^{N-octyltrimethoxysilane 1.1 × 10 -3} mol as alkylsilane compound (A), tetraethyl orthosilicate 2.2 × 10 ^-3 mol as alkoxysilane compound (B), triethoxy as fluoroalkylsilane compound (C) ^{After dissolving 1.1 × 10 -3} mol of -1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane in 2.3 ml of isopropyl alcohol, 1.5 ml of a 0.01 M hydrochloric acid aqueous solution was added dropwise. The mixture was stirred for 24 hours from the start of liquid preparation to obtain a coating liquid 14, and a film was obtained in the same manner as in Example 1 with respect to the preparation of the film. When the appearance of the film was visually evaluated, black fading was observed on the substrate (evaluation Δ).

Example 15
^{N-decyltrimethoxysilane 2.5 × 10 -3} mol as alkylsilane compound (A), tetraethyl orthosilicate 5.0 × 10 ^-3 mol as alkoxysilane compound (B), triethoxy as fluoroalkylsilane compound (C) -1H, 1H, 2H, 2H-tridecafluoro-n- ^{octylsilane 2.5 × 10 -3} mol was dissolved in 5.3 ml of isopropyl alcohol. The mixture was stirred for 24 hours from the start of liquid preparation to obtain a coating liquid 15, and a film was obtained in the same manner as in Example 1 with respect to the preparation of a film. When the appearance of the film was visually evaluated, the original state of the base material was maintained (evaluation ◎).

Example 16
^{N-octadecyltrimethoxysilane 1.8 × 10 -3} mol as alkylsilane compound (A), tetraethyl orthosilicate 3.6 × 10 ^-3 mol as alkoxysilane compound (B), triethoxy as fluoroalkylsilane compound (C) ^{After dissolving 1.8 × 10 -3} mol of -1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane in 5.4 ml of isopropyl alcohol, 2.4 ml of a 0.01 M hydrochloric acid aqueous solution was added dropwise. The mixture was stirred for 24 hours from the start of liquid preparation to obtain a coating liquid 16, and a film was obtained in the same manner as in Example 1 with respect to the preparation of the film. When the appearance of the film was visually evaluated, black fading was observed on the substrate (evaluation Δ).

Example 17
^{N-decyltrimethoxysilane 2.5 × 10 -3} mol as alkylsilane compound (A), tetraethyl orthosilicate 5.0 × 10 ^-3 mol as alkoxysilane compound (B), triethoxy as fluoroalkylsilane compound (C) ^{After dissolving 2.5 × 10 -4} mol of -1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane in 5.3 ml of isopropyl alcohol, 2.3 ml of a 0.01 M hydrochloric acid aqueous solution was added dropwise. The mixture was stirred for 24 hours from the start of liquid preparation to obtain a coating liquid 17, and a film was obtained in the same manner as in Example 1 with respect to the preparation of the film. When the appearance of the film was visually evaluated, some fading was observed on the base material (evaluation ○).

Comparative Example 1
Refrepaset A (manufactured by Sumitomo Osaka Cement Co., Ltd.) was prepared as a coating liquid, and a film was obtained in the same manner as in Example 1 for preparing a film. When the appearance of the film was visually evaluated, some fading was observed on the base material (evaluation ○).

Comparative Example 2
Refrepaset A1000 (manufactured by Sumitomo Osaka Cement Co., Ltd.) was prepared as a coating liquid, and a film was obtained in the same manner as in Example 1 for preparing a film. When the appearance of the film was visually evaluated, some fading was observed on the base material (evaluation ○).

Comparative Example 3
Dissolve n-decyltrimethoxysilane as the alkylsilane compound (A) in 2.2 × 10 ^-3 mol, tetraethyl orthosilicate as the alkoxysilane compound (B) in 4.4 × 10 ^-3 mol, and 4.6 ml of isopropyl alcohol. After that, 2.3 ml of a 0.01 M aqueous hydrochloric acid solution was added dropwise. The mixture was stirred for 24 hours from the start of liquid preparation to obtain a coating liquid 18, and a film was obtained in the same manner as in Example 1 with respect to the preparation of the film. When the appearance of the film was visually evaluated, black fading was observed on the substrate (evaluation Δ).

Comparative Example 4
Dissolve n-decyltrimethoxysilane as the alkylsilane compound (A) in 5.0 × 10 ^-4 mol, tetraethyl orthosilicate as the alkoxysilane compound (B) in 1.5 × ^10-2 mol, and 1.0 ml of isopropyl alcohol. After that, 5.7 ml of a 0.01 M aqueous hydrochloric acid solution was added dropwise. The mixture was stirred for 24 hours from the start of liquid preparation to obtain a coating liquid 19, and a film was obtained in the same manner as in Example 1 with respect to the preparation of the film. When the appearance of the film was visually evaluated, the original state of the base material was maintained (evaluation ◎).

Comparative Example 5
^{2.2 × 10 -3} mol of n-decyltrimethoxysilane as the alkylsilane compound (A) and triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane as the fluoroalkylsilane compound (C). After dissolving in 2.2 × 10 ^-3 mol and 4.6 ml of isopropyl alcohol, 1.3 ml of a 0.01 M aqueous hydrochloric acid solution was added dropwise. The mixture was stirred for 24 hours from the start of liquid preparation to obtain a coating liquid 20, and a film was obtained in the same manner as in Example 1 with respect to the preparation of the film. When the appearance of the film was visually evaluated, black fading was observed on the substrate (evaluation Δ).

Comparative Example 6
^{1.4 × 10 -4} mol of n-decyltrimethoxysilane as the alkylsilane compound (A) and triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane as the fluoroalkylsilane compound (C). After dissolving in 1.4 × ^10-2 mol and 0.3 ml of isopropyl alcohol, 4.2 ml of a 0.01 M aqueous hydrochloric acid solution was added dropwise. The mixture was stirred for 24 hours from the start of liquid preparation to obtain a coating liquid 21, and a film was obtained in the same manner as in Example 1 with respect to the preparation of the film. When the appearance of the film was visually evaluated, the original state of the base material was maintained (evaluation ◎).

Comparative Example 7
^{N-decyltrimethoxysilane 2.2 × 10 -3} mol as alkylsilane compound (A), tetraethyl orthosilicate 4.4 × 10 ^-3 mol as alkoxysilane compound (B), triethoxy as fluoroalkylsilane compound (C) ^{After dissolving 1.1 × 10 -4} mol of -1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane in 4.6 ml of isopropyl alcohol, 2.3 ml of a 0.01 M hydrochloric acid aqueous solution was added dropwise. The mixture was stirred for 24 hours from the start of liquid preparation to obtain a coating liquid 22, and a film was obtained in the same manner as in Example 1 with respect to the preparation of the film. When the appearance of the film was visually evaluated, black fading was observed on the substrate (evaluation Δ).

The following measurements were carried out on the films obtained in the above Examples and Comparative Examples.

(1) Evaluation of water repellency One drop (about 0.025 g) of water was dropped on the film with a dropper, and the contact angle of water was visually determined. Those with a visual contact angle of 100 ° or more are ◎, those with a visual contact angle of about 80 ° or more and less than 100 ° are ○, those with a contact angle of less than about 80 ° are △, and water has soaked into the base material without water repellency. Things were evaluated as x.

(2) Measurement of abrasion resistance Sabina (registered trademark) MX (wiping cloth manufactured by KB Seiren Co., Ltd.) is pressed against the film, and one drop (about 0.025 g) of water is dropped with a dropper every 50 round trips on the film surface. Then, the contact angle was visually determined in the same manner as in the evaluation of water repellency. The number of reciprocations at the time when the above-mentioned determination of Δ (visual contact angle is less than about 80 °) was defined as the number of wear resistance.

(3) Measurement of sliding angle The base material on which the film was formed was tilted at about 45 °, and one drop (about 0.025 g) of water was dropped with a dropper to evaluate the sliding property of the water droplet. Water droplets that slipped about 5 cm within 0.5 seconds ◎, water droplets that slipped about 5 cm within 1 second over 0.5 seconds ○, water droplets that slipped off but remained on the film △, water droplets did not slip The thing was evaluated as ×.

The compositions of the compositions of Examples and Comparative Examples are shown in Tables 1-1 and 1-2, and the evaluation results of the films obtained from the compositions of Examples and Comparative Examples are shown in Table 2.

According to Table 1-1, Table 1-2, and Table 2, Examples 1 to 17 using the compositions satisfying the requirements of the present invention show good water repellency and abrasion resistance of 200 times or more. The slipperiness evaluated by ○ or ◎ was realized, and a water-repellent film that could achieve both wear resistance and slipperiness at the same time was realized. On the other hand, in Comparative Examples 1 and 2 using the existing refrepa set A or refrepa set A1000, both wear resistance and slip resistance are inferior. Further, in Comparative Examples 3 and 4 which do not contain the compound (C) in the present invention, and Comparative Example 7 which does not contain the compound (C) in the present invention in a predetermined molar ratio, although the water repellency is good, the abrasion resistance or The result was that the sliding property was inferior. Further, Comparative Examples 5 and 6 containing no compound (B) had good water repellency but poor wear resistance.

By using the composition of the present invention, it is possible to provide a water-repellent film having excellent wear resistance and sliding property, and it can be usefully used for display devices, optical elements, building materials, automobile parts, factory equipment and the like. can.

Claims (6)

Formula (1): An _{alkylsilane compound (A) represented by C m} H _{2m + 1-} SiX ₃ (m is an integer of 4 to 30, X is a hydrolyzable group), and
Formula (2): Alkoxysilane compound (B) represented by ^{Si (OR 1} ) ₄ (R ^{1 is an alkyl group) and}
Formula (3): ^{A fluoroalkylsilane compound represented by R 2-} SiY ₃ (R ² is a group in which one or more hydrogen atoms of an alkyl group are substituted with a fluorine atom, and Y is a hydrolyzable group). C) is a composition containing and
The molar ratio (C / A) of the fluoroalkylsilane compound (C) to the alkylsilane compound (A) is 0.1 to 50.
The molar ratio (B / A) of the alkoxysilane compound (B) to the alkylsilane compound (A) is 0.1 to 30.
The total ratio of the alkylsilane compound (A), the alkoxysilane compound (B) and the fluoroalkylsilane compound (C) is 3 to 60% by mass in terms of solid content concentration.
A composition that does not contain a catalyst or contains a catalyst and has a catalyst content of 11 mol% or less based on the total of the alkylsilane compound (A), the alkoxysilane compound (B), the fluoroalkylsilane compound (C), and the catalyst. thing. The composition according to claim 1, wherein X in the formula (1) representing the alkylsilane compound (A) is an alkoxy group having 1 to 6 carbon atoms. The composition according to claim 1 or 2, wherein ^{R 1} in the formula (2) representing the alkoxysilane compound (B) is an alkyl group having 1 to 6 carbon atoms. The composition according to any one of claims 1 to 3, wherein Y in the formula (3) representing the fluoroalkylsilane compound (C) is an alkoxy group or a cyano group. Claims 1 to 4 in which the contact angle measured by dropping 0.025 g of water droplets on a film obtained by allowing the composition to stand in air at room temperature for 10 hours or more and 48 hours or less is 80 ° or more. The composition according to any one of. A method for producing a surface-treated porous substrate, wherein the composition according to any one of claims 1 to 5 is applied to the surface of the porous substrate and cured at room temperature.