WO2017188331A1

WO2017188331A1 - Composition

Info

Publication number: WO2017188331A1
Application number: PCT/JP2017/016588
Authority: WO
Inventors: 彩香櫻井; 花岡　秀典
Original assignee: 住友化学株式会社
Priority date: 2016-04-28
Filing date: 2017-04-26
Publication date: 2017-11-02
Also published as: JP6914714B2; KR20190004732A; JP2017201009A; CN109071819B; CN109071819A; TWI721160B; KR102370256B1; TW201809100A

Abstract

The purpose of the present invention is to provide a composition that achieves both water and oil repellency for a coating and can also improve film formation properties. This coating composition includes: an organic silicon compound (a) having bonded, to a silicon atom, at least one trialkylsilyl group-containing molecular chain and at least one hydrolysable group; a metal alkoxide (b); and a flourine-containing organic silicon compound (f) having bonded, to a silicon atom, a fluorine-containing group and a hydrolysable group. The compound (a) can be a compound indicated by formula (I).

Description

Composition

The present invention relates to a composition for forming a film capable of imparting water repellency and oil repellency to various substrates.

In various display devices, optical elements, semiconductor elements, building materials, automobile parts, nanoimprint technology, etc., droplets adhere to the surface of the substrate, resulting in contamination and corrosion of the substrate, and further from this contamination and corrosion. Problems such as performance degradation may occur. Therefore, in these fields, it is required that the water repellency and oil repellency of the substrate surface are good.

In Patent Document 1, as a treating agent that can be applied to a glass substrate having a bent shape to produce a water-slidable glass article, it contains linear polydimethylsiloxane and fluoroalkylsilane, and further includes a solvent and a catalyst. A composition comprising

JP 2006-259511 A

The inventors of the present invention have found that the film described in Patent Document 1 may not have sufficient oil repellency, adhesion and film-forming properties. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition capable of improving the film forming property while achieving both the water repellency and the oil repellency of the film.

As a result of intensive studies in view of the above circumstances, the present inventors have achieved both the water repellency and oil repellency of the resulting film when using a composition containing a predetermined organosilicon compound, metal alkoxide, and fluorine-containing organosilicon compound. In addition, the present invention has been completed by finding that the film-forming property can be improved. The present invention includes the following inventions.
[1] Hydrolysis of organosilicon compound (a), metal alkoxide (b) and fluorine-containing group in which at least one trialkylsilyl group-containing molecular chain and at least one hydrolyzable group are bonded to a silicon atom A coating composition comprising a fluorine-containing organosilicon compound (f) having a functional group bonded to a silicon atom.
[2] The coating composition according to [1], wherein the compound (a) is a compound represented by the formula (I).

[In formula (I), R ^a represents a trialkylsilyl group-containing molecular chain, and A ^a1 independently represents a hydrolyzable group. Z ^a1 represents a trialkylsilyl group-containing molecular chain, a hydrocarbon chain-containing group, a siloxane skeleton-containing group, or a hydrolyzable group. ]
[3] The coating composition according to [1] or [2], wherein the metal alkoxide (b) is a compound represented by the formula (II).

[In formula (II), M represents a trivalent or tetravalent metal atom capable of forming a metal alkoxide. A ^b1 independently represents an alkoxy group having 1 to 4 carbon atoms. k represents an integer of 3 or 4 depending on M.
]
[4] The coating composition according to any one of [1] to [3], wherein the compound (f) is a compound represented by any one of formulas (III-1) and (III-2).

[In the formula (III-1), R ^f1 represents a fluorocarbon-containing group having 1 to 8 carbon atoms. A ^f1 independently represents a hydrolyzable group. Z ^f1 represents a siloxane skeleton-containing group, a hydrocarbon chain-containing group, or a hydrolyzable group. ]

[In the above formula (III-2), R ^f2 represents a hydrolyzable silane oligomer residue. A ^f2 independently represents a hydrolyzable group, a fluorine-containing alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. ]
[5] The content ratio of the fluorine-containing organosilicon compound (f) and the organosilicon compound (a) (fluorine-containing organosilicon compound (f) / organosilicon compound (a)) is 7 / The coating composition according to any one of [1] to [4], which is 1 or more and 20/1 or less.
[6] The content ratio of the metal alkoxide (b) to the fluorine-containing organosilicon compound (f) (metal alkoxide (b) / fluorine-containing organosilicon compound (f)) is 0.01 or more in molar ratio. The coating composition according to any one of [1] to [5], which is 50 or less.
[7] A film formed from the coating composition according to [1] to [6].

Since the composition of the present invention contains a predetermined organosilicon compound, metal alkoxide, and fluorine-containing organosilicon compound, it is possible to achieve both the water repellency, oil repellency and adhesion of the resulting film, and also film forming properties. It becomes good.

The composition of the present invention (hereinafter sometimes simply referred to as “composition”) is an organic compound in which at least one trialkylsilyl group-containing molecular chain and at least one hydrolyzable group are bonded to a silicon atom. A silicon compound (a); a metal alkoxide (b); and a fluorine-containing organosilicon compound (f) in which a fluorine-containing group and a hydrolyzable group are bonded to a silicon atom. Although the metal alkoxide (b) itself contributes less to water repellency and oil repellency than the organosilicon compound or the fluorine-containing organosilicon compound (f), the metal alkoxide (b) It is considered that the water- and oil-repellent properties of the trialkylsilyl group-containing molecular chain and the fluorine-containing group are emphasized, and the homogeneity of the resulting film is also improved.

The organosilicon compound (a) includes, in one molecule, at least one trialkylsilyl group-containing molecular chain bonded to the central silicon atom, and at least one hydrolyzable group bonded to the central silicon atom. Have As the organosilicon compound (a), a compound in which one trialkylsilyl group-containing molecular chain and three hydrolyzable groups are bonded to the central silicon atom; one trialkylsilyl group-containing molecular chain, and 1 Compound in which one siloxane skeleton-containing group and two hydrolyzable groups are bonded to the central silicon atom; one trialkylsilyl group-containing molecular chain, one hydrocarbon chain-containing group, and two hydrolyzable groups A compound in which the group is bonded to the central silicon atom;

Specifically, the organosilicon compound (a) is preferably a compound represented by the following formula (I).

[In formula (I), R ^a represents a trialkylsilyl group-containing molecular chain, and A ^a1 independently represents a hydrolyzable group. Z ^a1 represents a trialkylsilyl group-containing molecular chain, a hydrocarbon chain-containing group, a siloxane skeleton-containing group, or a hydrolyzable group. ]

The trialkylsilyl group-containing molecular chain is a monovalent group having a structure in which the trialkylsilyl-containing group is bonded to the end of the molecular chain, and the trialkylsilyl-containing group is bonded to the molecular chain. The water repellency and oil repellency of the film formed from the composition of the invention are improved. Further, the presence of the trialkylsilyl group-containing molecular chain reduces the friction between the droplet (water droplet, oil droplet, etc.) and the coating, and facilitates the movement of the droplet. Furthermore, by having a trialkylsilyl group, chemical durability and / or physical durability are improved, and heat resistance and light resistance are improved. Even in the case where the alkyl group of the trialkylsilyl-containing group is replaced with a fluoroalkyl group, the water repellency and oil repellency at the film interface (surface) can be similarly improved.

The trialkylsilyl-containing group is a group containing at least one trialkylsilyl group, preferably two or more, more preferably three trialkylsilyl groups. The trialkylsilyl-containing group is preferably a group represented by the formula (s1).

[In formula (s1), R ^s1 represents a hydrocarbon group or a trialkylsilyloxy group, and the hydrogen atom contained in the hydrocarbon group or the trialkylsilyloxy group may be substituted with a fluorine atom. However, when all R ^s1 is a hydrocarbon group, R ^s1 is an alkyl group. * Represents a bond. ]

The hydrocarbon group represented by R ^s1 preferably has 1 to 4 carbon atoms, more preferably 1 to 3, and still more preferably 1 to 2. When all R ^s1 are hydrocarbon groups, the total carbon number of the three R ^s1 is preferably 9 or less, more preferably 6 or less, and even more preferably 4 or less.
The hydrocarbon group represented by R ^s1 is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. A plurality of R ^s1 may be the same or different and are preferably the same. Is preferably at least one of methyl group of the three R ^s1, more preferably at least two of a methyl group, and particularly preferably all three R ^s1 is a methyl group.

Moreover, the hydrogen atom contained in the trialkylsilyl group and trialkylsilyloxy group represented by R ^s1 may be substituted with a fluorine atom. The number of fluorine atoms substituted is preferably 1 or more, more preferably 3 or more, and preferably 2 × A + 1 or less, where A is the number of carbon atoms. When the hydrogen atom contained in the alkyl group is substituted with a fluorine atom, the number of substituted alkyl groups can be appropriately selected within a range of 1 to 3 per silicon atom.

Specific examples of the group (trialkylsilyl group) in which R ^s1 is a hydrocarbon group (alkyl group) include groups represented by the following formulas. In the formula, * represents a bond.

At least one of R ^s1 may be a trialkylsilyloxy group. Examples of the trialkylsilyloxy group include a group in which an oxygen atom is bonded to a silicon atom of a group (trialkylsilyl group) in which R ^s1 is a hydrocarbon group (alkyl group).

^Examples of the group in which at least one of R ^s1 is a trialkylsilyloxy group include groups represented by the following formulae.

In a trialkylsilyl group-containing molecular chain, the trialkylsilyl group may be bonded to the end (free end side) of the molecular chain, particularly to the end (free end side) of the main chain (longest straight chain) of the molecular chain. preferable.

The molecular chain to which the trialkylsilyl group is bonded is preferably linear or branched, and is preferably linear. The molecular chain preferably includes a dialkylsiloxane chain, and preferably includes a linear dialkylsiloxane chain. The molecular chain may contain a divalent hydrocarbon group. Even if a part of the molecular chain is a divalent hydrocarbon group, since the remainder is a dialkylsiloxane chain, the chemical durability and / or physical durability of the resulting film is good.
The molecular chain is preferably a group represented by the formula (s2).

[In the formula (s2), R ^s2 represents an alkyl group having 1 to 4 carbon atoms. Z ^s1 represents —O— or a divalent hydrocarbon group, and —CH ₂ — contained in the divalent hydrocarbon group may be replaced by —O—. Y ^s1 represents a single bond or —Si (R ^s2 ) ₂ —L ^s1 —. L ^s1 represents a divalent hydrocarbon group, and —CH ₂ — contained in the divalent hydrocarbon group may be replaced by —O—. * On the left side represents a bond with a central silicon atom, and * on the right side represents a bond with a trialkylsilyl-containing group. ]

The number of carbon atoms of the alkyl group represented by R ^s2 is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2. ^Examples of the alkyl group represented by R ^s2 include a methyl group, an ethyl group, a propyl group, and a butyl group. A methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.

N1 is preferably 1 to 100, more preferably 1 to 80, still more preferably 1 to 50, and particularly preferably 1 to 30.

The number of carbon atoms of the divalent hydrocarbon group represented by Z ^s1 or L ^s1 is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4. The divalent hydrocarbon group is preferably chain-like, and when it is chain-like, it may be either linear or branched.
The divalent hydrocarbon group is preferably a divalent aliphatic hydrocarbon group, and preferably an alkanediyl group. Examples of the divalent hydrocarbon group include a methylene group, an ethylene group, a propylene group, and a butylene group.

Furthermore, a part of —CH ₂ — contained in the divalent hydrocarbon group may be replaced by —O—. In this case, two consecutive —CH ₂ — are not simultaneously replaced with —O—, and —CH ₂ — adjacent to the Si atom is not replaced with —O—. When two or more —CH ₂ — are replaced by —O—, the number of carbon atoms between —O— and —O— is preferably 2 to 4, and more preferably 2 to 3 preferable. Specific examples of the group in which a part of the divalent hydrocarbon group is replaced by —O— include a group having a (poly) ethylene glycol unit, a group having a (poly) propylene glycol unit, and the like. it can.

In the formula (s2), it is preferable that Z ^s1 is —O— and Y ^s1 is a single bond, that is, the molecular chain is composed only of repeating dialkylsilyloxy groups. When the dialkylsiloxane chain consists only of repeating dialkylsilyloxy groups, the resulting film has good chemical durability and / or physical durability.

Examples of the molecular chain contained in the trialkylsilyl group-containing molecular chain include a molecular chain represented by the following formula. In the formula, p1 represents an integer of 1 to 30, and * represents a bond bonded to a silicon atom or a trialkylsilyl group forming a polysiloxane skeleton.

The total number of atoms constituting the trialkylsilyl group-containing molecular chain is preferably 24 or more, more preferably 40 or more, still more preferably 50 or more, and preferably 1200 or less. Is 700 or less, more preferably 250 or less.

The trialkylsilyl group-containing molecular chain is preferably a group represented by the following formula (s1).

[In the formula (s1), R ^s1 , R ^s2 , Z ^s1 , Y ^s1 , and n1 are as defined above. * Represents a bond with a silicon atom. ]

The trialkylsilyl group-containing molecular chain is more preferably a group represented by the following formula (s1-1), and even more preferably a group represented by the following formula (s1-1-1).

[In the formulas (s1-1) and (s1-1-1), R ^s2 , Y ^s1 , Z ^s1 , and n1 are as defined above. R ^s3 represents an alkyl group having 1 to 4 carbon atoms. * Represents a bond with a silicon atom. ]

In addition, the trialkylsilyl group-containing molecular chain is preferably a group represented by the following formula (s1-2), more preferably a group represented by the following formula (s1-2-1).

[In the formulas (s1-2) and (s1-2-1), R ^s2 , R ^s3 , Y ^s1 , Z ^s1 , and n1 are as defined above. * Represents a bond with a silicon atom. ]

Examples of the alkyl group represented by R ^s3 include the same groups as the alkyl groups exemplified as the hydrocarbon group represented by R ^s1 , and the alkyl group preferably has 1 to 3 carbon atoms. Preferably it is 1-2. Further, the total carbon number of R ^s3 contained in * ^-Si (R ^s3 ) ₃ is preferably 9 or less, more preferably 6 or less, and still more preferably 4 or less.
Further, among R ^s3 contained in * ^-Si (R ^s3 ) ₃ , at least one is preferably a methyl group, two or more R ^s3 are preferably methyl groups, and all three R ^s3 are all A methyl group is particularly preferred.

Examples of the trialkylsilyl group-containing molecular chain include a group represented by the formula (s1-I). The following formulas (s1-I-1) to (s1-I-50) are specific examples of the group represented by the formula (s1-I), but are not limited thereto. In the group represented by the formula (s1-I), a plurality of R ^s20 and a plurality of R ^s10 contained therein may be the same or different.

In the organosilicon compound (a), the number of trialkylsilyl group-containing molecular chains bonded to the central silicon atom is preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1.

When the hydrolyzable group is bonded to a silicon atom, the hydrolyzable group may be a group that gives a hydroxy group (silanol group) by hydrolysis. For example, the number of carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group Preferred examples include 1-4 alkoxy groups; acetoxy groups; chlorine atoms; isocyanate groups; Among these, an alkoxy group having 1 to 4 carbon atoms is preferable, and an alkoxy group having 1 to 2 carbon atoms is more preferable.
In the organosilicon compound (a), the number of hydrolyzable groups bonded to the central silicon atom is 1 to 3, and preferably 2 to 3.
Hereinafter, a group in which a hydrolyzable group is bonded to a silicon atom may be referred to as a hydrolyzable silicon group.

The siloxane skeleton-containing group is a monovalent group containing a siloxane unit (Si—O—), and may be composed of a smaller number of atoms than the number of atoms constituting the trialkylsilyl group-containing molecular chain. That's fine. As a result, the siloxane skeleton-containing group is a group having a shorter length than the trialkylsilyl group-containing molecular chain or a small steric spread (bulk height). The siloxane skeleton-containing group may contain a divalent hydrocarbon group.

The siloxane skeleton-containing group is preferably a group represented by the following formula (s2).

[In formula (s2), R ^s2 has the same ^meaning as described above. R ^s5 represents a hydrocarbon group or a hydroxy group, —CH ₂ — contained in the hydrocarbon group may be replaced by —O—, and the hydrogen atom contained in the hydrocarbon group is a fluorine atom. May be substituted. Z ^s2 represents —O— or a divalent hydrocarbon group, and —CH ₂ — contained in the divalent hydrocarbon group may be replaced with —O—. Y ^s2 represents a single bond or —Si (R ^s2 ) ₂ —L ^s2 —. L ^s2 represents a divalent hydrocarbon group, and —CH ₂ — contained in the divalent hydrocarbon group may be replaced by —O—. n2 represents an integer of 0 to 5. * Represents a bond with a silicon atom. ]

Examples of the hydrocarbon group represented by R ^s5 include the same groups as the hydrocarbon group represented by R ^s1 , an aliphatic hydrocarbon group is preferable, and an alkyl group is more preferable. The number of carbon atoms is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2.
Examples of the divalent hydrocarbon group represented by Z ^s2 or L ^s2 include the same groups as the divalent hydrocarbon group represented by Z ^s1 , and the number of carbon atoms is preferably 1 to 10. More preferably, it is 1-6, and more preferably 1-4. The divalent hydrocarbon group represented by Z ^s2 or L ^s2 is preferably a divalent aliphatic hydrocarbon group, and more preferably a linear or branched alkanediyl group. .

N2 is preferably 1 to 5, and more preferably 1 to 3.

Specific examples of the siloxane skeleton-containing group include groups represented by the following formulas.

The hydrocarbon chain-containing group is a monovalent group including a hydrocarbon chain and has a hydrocarbon chain portion having a smaller number of carbon atoms than the number of atoms constituting the molecular chain of the trialkylsilyl group-containing molecular chain. Good. Moreover, it is preferable that the number of carbon atoms of the longest straight chain of the hydrocarbon chain is smaller than the number of atoms constituting the longest straight chain of the trialkylsilyl group-containing molecular chain.
The hydrocarbon chain-containing group may be composed only of a hydrocarbon group (hydrocarbon chain), and —CH ₂ — contained in the hydrocarbon chain may be replaced by —O—, and the hydrocarbon group ( It is preferably composed of only hydrocarbon chains. However, —CH ₂ — adjacent to the Si atom is not replaced with —O—, and two consecutive —CH ₂ — are not replaced with —O— at the same time.
In addition, the carbon number of the hydrocarbon chain portion means the number of carbon atoms constituting the hydrocarbon group (hydrocarbon chain) in the oxygen non-substituted hydrocarbon chain-containing group, and includes the oxygen-substituted hydrocarbon chain. In the group, it means the number of carbon atoms counted by replacing —O— with —CH ₂ —. Hereinafter, unless otherwise specified, a hydrocarbon chain-containing group will be described by taking an oxygen-nonsubstituted hydrocarbon chain-containing group (that is, a monovalent hydrocarbon group) as an example. In any description, —CH ₂ — It is possible to replace some of them with —O—.

The number of carbon atoms of the hydrocarbon chain-containing group is preferably 1 to 3, more preferably 1. The hydrocarbon chain-containing group (in the case of a hydrocarbon group) may be branched or linear. The hydrocarbon chain-containing group (in the case of a hydrocarbon group) is preferably a saturated or unsaturated aliphatic hydrocarbon chain-containing group, and more preferably a saturated aliphatic hydrocarbon chain-containing group. The saturated aliphatic hydrocarbon chain-containing group is preferably an alkyl group such as a methyl group, an ethyl group, or a propyl group.

When —CH ₂ — contained in the hydrocarbon chain is replaced by —O—, a group having a (poly) ethylene glycol unit can be exemplified.

Among these, the organosilicon compound (a) is preferably a compound represented by the following formula (I-1), and more preferably a compound represented by the formula (I-1-1).

[In the formulas (I-1) and (I-1-1), A ^a1 , Z ^a1 , Z ^s1 , Y ^s1 , R ^s2 , R ^s3 , n1 are as defined above. ]

The organosilicon compound (a) may be a compound represented by the formula (I-2), preferably a compound represented by the formula (I-2-1).

[In the formulas (I-2) and (I-2-1), A ^a1 , Z ^a1 , Z ^s1 , Y ^s1 , R ^s2 , R ^s3 , and n2 are as defined above. ]

Specific examples of the organosilicon compound (a) include groups represented by the formula (II). The following formulas (II-1) to (II-100) are specific examples of the group represented by the formula (II), but are not limited thereto. In the group represented by the formula (s1-I), a plurality of A ^a10 , a plurality of R ^s20, and a plurality of R ^s10 contained therein may be the same or different.

Examples of the method for synthesizing the organosilicon compound (a) include the following methods. As a first method, a compound in which a trialkylsilyl group-containing molecular chain and a halogen atom (preferably a chlorine atom) are bonded, and a compound in which three or more (especially four) hydrolyzable groups are bonded to a silicon atom, It can manufacture by making this react.
As a second synthesis method, a compound in which halogen atoms are bonded to both ends of a dialkylsiloxane chain (hereinafter, “dihalogenated dialkylsiloxane”), a tris (trialkylsilyloxy) silyl group, an M ¹ O— group ( M ¹ represents an alkali metal) and can be produced by reacting a compound (hereinafter referred to as “alkali metal silyl oxide”) and a compound having four hydrolyzable groups bonded to a silicon atom. Although the reaction order of these compounds is not limited, it is preferable to first react a dihalogenated dialkylsiloxane and an alkali metal silyl oxide, and then react a compound having four hydrolyzable groups bonded to a silicon atom.
As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A chlorine atom is preferable. The alkali metal is preferably lithium.
The alkali metal silyl oxide can be produced, for example, by reacting an alkyl alkali metal with a compound in which a tris (trialkylsilyloxy) silyl group and a hydroxy group are bonded. Examples of the organic alkali metal compound include alkyllithiums such as n-butyllithium, sec-butyllithium and tert-butyllithium, with n-butyllithium being particularly preferred.

As a third synthesis method, for example, the organosilicon compound (a) is prepared by reacting, for example, alkali metal silyloxide and cyclic dimethylsiloxane, and then the silicon atom has three hydrolyzable groups and a halogen atom (particularly a chlorine atom). It can also be produced by reacting a compound in which one) is bonded.

As a fourth synthesis method, for example, the organosilicon compound (a) is reacted with alkali metal silyl oxide and cyclic dimethylsiloxane to obtain dimethylsiloxane having a hydroxyl group at the terminal, and then reacted with tetraalkoxysilane. It can also be manufactured.

The content of the organosilicon compound (a) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more in 100% by mass of the composition. Yes, it is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less.

The metal alkoxide (b) is a compound in which an alkoxy group is bonded to a metal atom, and a site having a spacer function can be formed in a film formed from the composition of the present invention. As a result, the water repellency and oil repellency improving action by the trialkylsilyl group-containing molecular chain and fluorine-containing group can be enhanced, and the film-forming property is also improved.

Specifically, the metal alkoxide (b) is preferably a compound represented by the formula (II). The compound represented by the formula (II) may be a hydrolysis condensate thereof. Here, the hydrolysis-condensation product means a compound in which all or a part of alkoxy groups contained in each compound (II) are condensed by hydrolysis.

[In formula (II), M represents a trivalent or tetravalent metal atom capable of forming a metal alkoxide. A ^b1 independently represents an alkoxy group having 1 to 4 carbon atoms. k represents an integer of 3 or 4 depending on the valence of M. ]

M is a metal atom that can be bonded to an alkoxy group to form a metal alkoxide, and the metal atom includes a semimetal such as Si or Ge. Examples of M include trivalent metals such as Al, Fe and In; tetravalent metals such as Hf, Si, Ti, Sn and Zr; and preferably trivalent metals such as Al; Si, Ti, Sn, Tetravalent metals such as Zr; more preferably Al, Si, Ti, Zr, and particularly preferably Si. These metal alkoxides can be easily liquefied. Further, when M is a trivalent metal, k represents 3, and when M is a tetravalent metal, k represents 4.

The alkoxy group represented by A ^b1 is more preferably an alkoxy group having 1 to 2 carbon atoms.
Further, the hydrolyzable group of the organosilicon compound (a) and the alkoxy group of the metal alkoxide (b) may be the same or different, but are preferably the same, both of which are alkoxy groups having 1 to 4 carbon atoms. It is preferable that

Examples of the metal alkoxide (b) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane; trialkoxyaluminums such as triethoxyaluminum, tripropoxyaluminum, and tributoxyaluminum; Trialkoxy iron; trialkoxy indium such as trimethoxy indium, triethoxy indium, tripropoxy indium, tributoxy indium; tetraalkoxy hafnium such as tetramethoxy hafnium, tetraethoxy hafnium, tetrapropoxy hafnium, tetrabutoxy hafnium; tetramethoxy titanium, Tetraalkoxy such as tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, etc. Tan; tetramethoxy tin, tetraethoxy tin, tetra propoxy tin, tetraalkoxy tin, such as tetrabutoxy tin; tetramethoxy zirconium, tetraethoxy zirconium, tetra propoxy zirconium, tetra-alkoxy zirconium, such as tetrabutoxyzirconium; and the like.

The content of the metal alkoxide (b) is preferably 0.01% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more in 100% by mass of the composition. The content is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less.
In the composition of the present invention, the ratio of metal alkoxide (b) to organosilicon compound (a) (metal alkoxide (b) / organosilicon compound (a)) is preferably 1/10 or more on a molar basis, More preferably 1/1 or more, still more preferably 2/1 or more, and preferably 100/1 or less, more preferably 50/1 or less, still more preferably 30/1 or less, and even more preferably 25 / 1 or less.

The fluorine-containing organosilicon compound (f) has at least one fluorine-containing group bonded to the central silicon atom and at least one hydrolyzable group bonded to the central silicon atom in one molecule. . By including the fluorine-containing organosilicon compound in the composition, the water repellency and oil repellency of the resulting film are easily improved.
The fluorine-containing group is a group including a structure in which a carbon atom and a fluorine atom are bonded, and may be a fluorinated hydrocarbon group which may have a substituent. It may be a group in which bonded silicon atoms and —O— are alternately arranged (sometimes referred to as a hydrolyzable silane oligomer residue).

Specifically, the fluorine-containing organosilicon compound (f) is preferably a compound represented by either the following formula (III-1) or (III-2). In addition, each of the compounds represented by the formula (III-1) or (III-2) may be a hydrolysis condensate (a group in which a hydrolyzable group contained in the compound is condensed by hydrolysis). Good.

[In the above formula (III-2), R ^f2 represents a hydrolyzable silane oligomer residue. A ^f2 independently represents a hydrolyzable group, a fluorine-containing alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. ]

Examples of the hydrolyzable group represented by A ^f1 , A ^f2 and Z ^f1 include the same groups as the hydrolyzable groups of the organosilicon compound (a), preferably an alkoxy group or an isocyanate group, An alkoxy group having 4 carbon atoms is more preferable, and an alkoxy group having 1 to 2 carbon atoms is more preferable.
Further, the hydrolyzable groups of the fluorine-containing organosilicon compound (f) and the organosilicon compound (a) may be the same or different and are preferably the same, both of which are alkoxy groups having 1 to 4 carbon atoms. Preferably there is.

The number of atoms of the siloxane skeleton-containing group represented by Z ^f1 , the hydrocarbon chain-containing group, and the fluorocarbon-containing group represented by R ^f1 is the molecular chain (preferably trialkylsilyl group and hydrolysate in the organic compound (a)). The number of atoms is preferably smaller than the number of atoms of the chain or cyclic hydrocarbon and / or the chain or cyclic dialkylsiloxane connecting the decomposable silicon group. In addition, the longest straight chain carbon number contained in the siloxane skeleton-containing group, hydrocarbon chain-containing group or R ^f1 represented by R ^f1 in Z ^f1 is greater than the number of atoms in the trialkylsilyl group-containing molecular chain. It is preferable that the amount is small. Thereby, in the film formed from the composition of the present invention, the structure derived from the metal alkoxide (b) can act as a spacer.
Siloxane skeleton-containing group represented by Z ^f1, the hydrocarbon chain-containing group, a siloxane skeleton-containing group represented by Z ^a2, include hydrocarbon chains containing groups and each similar group.

The fluorocarbon-containing group represented by R ^f1 is a monovalent group including a structure in which a fluorine atom is bonded to a carbon atom, and is preferably a group having a fluoroalkyl group at the end, and a fluoroalkyl group (preferably trifluoro). A group having a methyl group) at the terminal is preferable. As the fluorocarbon-containing group, a group represented by the formula (f1) is preferable.

[In the above formula (f1),
R ^f3 represents a fluorine-containing alkyl group having 1 to 20 carbon atoms. R ^f4 represents a fluorine atom or a fluoroalkyl group having 1 to 20 carbon atoms. R ^b4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. L represents any of —O—, —COO—, —OCO—, —NR ^f5 —, —NR ^f5 CO—, and —CONR ^f5 —. R ^f5 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluorine-containing alkyl group having 1 to 4 carbon atoms. h1 to h5 are integers of 0 to 100, and the total value of h1 to h5 is 100 or less. Further, the order of each repeating unit attached with h1 to h5 and enclosed in parentheses is arbitrary in the formula. * Represents a bond. ]

The fluorine-containing alkyl group represented by R ^f3 or R ^f4 has 1 to 20, preferably 1 to 12, more preferably 1 to 10, and more preferably 1 to 5. Further preferred. The number of fluorine atoms substituted in the fluorine-containing alkyl group represented by R ^f3 or R ^f4 is 1 or more and 2A + 1 or less, where A is the number of carbon atoms contained in the fluorine-containing alkyl group, and 2A + 1 That is, the fluorine-containing alkyl group is preferably a perfluoroalkyl group.
Examples of the alkyl group represented by R ^b4 include the same groups as the alkyl groups exemplified as the hydrocarbon group represented by R ^s1 .
L ^f1 is preferably any one of —O—, —COO—, and —OCO—.
h1 is preferably 1 to 30, more preferably 1 to 25, still more preferably 1 to 10, particularly preferably 1 to 5, and most preferably 1 to 2. h2 is preferably from 0 to 15, and more preferably from 0 to 10. h3 is preferably 0 to 5, and more preferably 0 to 2. h4 is preferably from 0 to 4, more preferably from 0 to 2. h5 is preferably from 0 to 4, more preferably from 0 to 2. The total value of h1 to h5 is preferably 3 or more, more preferably 5 or more, and preferably 80 or less, more preferably 50 or less, and still more preferably 20 or less.

In particular, R ^f3 is a perfluoroalkyl having 1 to 5 carbon atoms, R ^f4 is a fluorine atom or a perfluoroalkyl having 1 to 5 carbon atoms, R ^b4 is a hydrogen atom, and h3, h4, and h5 are all 0. It is preferable that h1 is 1 to 5 and h2 is 0 to 5.

Examples of the fluorocarbon-containing group include groups represented by the following formulas. In the formula, R ^f3 and R ^b4 are as defined above, R ^f3 is preferably a C ^1-12 perfluoroalkyl group, and R ^b4 is preferably a hydrogen atom. R2 is 5 to 20, preferably 8 to 15. r3 is 1 to 7, preferably 2 to 6. r4 is 1 to 10, preferably 3 to 7. r5 is 1 to 6, preferably 2 to 4.

Examples of the group represented by the formula (f1-1) include a group represented by the following formula.

Examples of the group represented by the formula (f1-2) include a group represented by the following formula. L ^f2 represents an alkanediyl group having 5 to 20 carbon atoms.

Examples of the group represented by the formula (f1-3) include a group represented by the following formula. L ^f2 represents an alkanediyl group having 5 to 20 carbon atoms.

Examples of the group represented by the formula (f1-4) include a group represented by the following formula. L ^f2 represents an alkanediyl group having 5 to 20 carbon atoms.

Examples of the group represented by the formula (f1-5) include a group represented by the following formula. L ^f3 represents an alkanediyl group having 1 to 6 carbon atoms.

The fluorocarbon-containing group may be a fluoroalkylaryl group, a fluoroalkylalkenyl group, a fluoroalkylalkynyl group, or the like. Examples of the fluoroalkylaryl group include (fluoro C _1-8 alkyl) phenyl group and (fluoro C _1-8 alkyl) naphthyl group. _{Examples of the} fluoroalkylalkenyl group include (fluoro C _1-17 alkyl) vinyl group. Examples of the fluoroalkylalkynyl group include a ( _{fluoroC 1-17} alkyl) ethynyl group.

Z ^f1 is preferably a siloxane skeleton-containing group or a hydrolyzable group, and more preferably a hydrolyzable group.

In formula (III-2), the hydrolyzable silane oligomer residue represented by R ^f2 is a compound containing a silicon atom and a hydrolyzable group bonded to the silicon atom (hereinafter referred to as “hydrolyzable silane monomer”). A monovalent group derived from the hydrolytic condensate. The number of silicon atoms contained in the hydrolyzable silane oligomer residue is, for example, 3 or more, preferably 5 or more, more preferably 7 or more. The number of silicon atoms contained in the hydrolyzable silane oligomer residue is preferably 15 or less, more preferably 13 or less, and even more preferably 10 or less.
When the hydrolyzable silane oligomer residue has an alkoxy group, examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a methoxy group and an ethoxy group are preferable. The hydrolyzable silane oligomer residue may have one or more of these alkoxy groups, and preferably has one.

The hydrolyzable silane oligomer residue is preferably a group represented by the formula (f2).

[In Formula (f2), A ^f3 independently represents a hydrolyzable group, an alkyl group having 1 to 4 carbon atoms, or a fluorine-containing alkyl group having 1 to 4 carbon atoms. h6 is an integer of 0 or more and 100 or less. * Represents a bond with Si. ]

Examples of the hydrolyzable group represented by A ^f3 include an alkoxy group having 1 to 4 carbon atoms (preferably 1 to 2) such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; a hydrogen atom; a cyano group; an allyl group An alkoxy group is preferable, and an ethoxy group, a methoxy group, and an isocyanate group are more preferable. h6 is preferably 0 or more and 10 or less, and more preferably 0 or more and 7 or less.
A ^f3 is preferably a hydrolyzable group or a fluorinated alkyl group having 1 to 4 carbon atoms, and at least one of A ^f3 is preferably a fluorinated alkyl group having 1 to 4 carbon atoms. Further, at least one of A ^f3 is preferably a hydrolyzable group (particularly a methoxy group or an ethoxy group).

Examples of the hydrolyzable silane oligomer residue include groups represented by the following formulas.

Examples of the compound represented by the formula (III-1) include a compound represented by the following formula. In the formula, r1 is 1 to 15, preferably 1 to 12, and more preferably 1 to 6.

Examples of the compound represented by the formula (III-1) also include a compound represented by the following formula.
In the formula, r2 is 5 to 20, preferably 8 to 15. r3 is 1 to 7, preferably 2 to 6. r4 is 1 to 10, preferably 2 to 8, and more preferably 2 to 5. r5 is 1 to 5, preferably 2 to 4. r6 is 2 to 10, preferably 2 to 8. r7 is 2 to 10, preferably 3 to 7.

Examples of the compound represented by the formula (III-2) include compounds represented by the following formula.

The content of the fluorine-containing organosilicon compound (f) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 1% by mass or more in 100% by mass of the composition. It is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 7% by mass or less.
In the composition of the present invention, the ratio of the fluorine-containing organosilicon compound (f) to the organosilicon compound (a) (fluorine-containing organosilicon compound (f) / organosilicon compound (a)) is 1 in molar ratio. / 1 or more, more preferably 7/1 or more, still more preferably 10/1 or more, and preferably 100/1 or less, more preferably 50/1 or less, and even more preferably 25 / 1 or less, more preferably 20/1 or less, particularly preferably 15/1 or less.
In the composition of the present invention, the content ratio of the metal alkoxide (b) and the fluorine-containing organosilicon compound (f) (metal alkoxide (b) / fluorine-containing organosilicon compound (f)) is 0.01 by molar ratio. Preferably, it is 0.1 or more, more preferably 0.2 or more, and preferably 50 or less, more preferably 10 or less, and even more preferably 5 or less.

The composition of the present invention preferably further contains a solvent (c). Solvent (c) includes water; hydrophilic organic solvents such as alcohol solvents, ether solvents, ketone solvents, ester solvents and amide solvents; hydrophobic solvents such as aromatic hydrocarbon solvents and saturated hydrocarbon solvents These may be used alone or in combination of two or more.
Examples of the alcohol solvent include methanol, ethanol, propanol, isopropyl alcohol, butanol, ethylene glycol, propylene glycol, and diethylene glycol. Examples of the ether solvent include dimethoxyethane, tetrahydrofuran, and dioxane. Examples of the solvent include acetone and methyl ethyl ketone, examples of the ester solvent include ethyl acetate and butyl acetate, examples of the amide solvent include dimethylformamide, and examples of the aromatic hydrocarbon solvent include Examples of the saturated hydrocarbon solvent include benzene, toluene, and xylene. Examples of the saturated hydrocarbon solvent include hexane and cyclohexane.
Among these, alcohol solvents and ketone solvents are preferable and may contain water.
When water is contained, the content of water in the solvent (c) is preferably 0.1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and preferably 90% by mass or less. More preferably, it is 70 mass% or less, More preferably, it is 50 mass% or less.

The solvent (c) is preferably 0.1 parts by mass or more, more preferably with respect to 1 part by mass in total of the organosilicon compound (a), the metal alkoxide (b) and the fluorinated organosilicon compound (f). Is 5 parts by mass or more, more preferably 10 parts by mass or more, particularly preferably 12 parts by mass or more, preferably 100 parts by mass or less, more preferably 80 parts by mass or less, still more preferably 50 parts by mass or less. is there. When the amount of the solvent (c) is within this range, the thickness of the film can be easily controlled.

The composition of the present invention may further contain a catalyst (d). The catalyst (d) is not particularly limited as long as it can act as a hydrolysis catalyst for a hydrolyzable group bonded to a silicon atom, and examples thereof include acidic compounds; basic compounds; organometallic compounds; Examples of the acidic compound include inorganic acids such as hydrochloric acid and nitric acid; organic acids such as acetic acid; Examples of the basic compound include ammonia, amines, and the like. Examples of the organometallic compound include organometallic compounds having a metal element such as Al, Fe, Zn, and Sn as a central metal, and organoaluminum compounds such as aluminum acetylacetone complex and aluminum ethylacetoacetate complex; Organic iron compounds; organic zinc compounds such as zinc acetylacetonate monohydrate, zinc naphthenate, and zinc octylate; organic tin compounds such as dibutyltin diacetate complex;
Especially, as a catalyst (d), an organometallic compound and an acidic compound are preferable, and an organoaluminum compound and hydrochloric acid are more preferable.

The catalyst (d) is preferably 0.0001 parts by mass or more, more preferably 100 parts by mass or more with respect to 100 parts by mass in total of the organosilicon compound (a), the metal alkoxide (b) and the fluorine-containing organosilicon compound (f). Is 0.0002 parts by mass or more, more preferably 0.001 parts by mass or more, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less.
Further, when an acidic compound is used as the catalyst, the catalyst (d) is 0.001 mass relative to 100 mass parts in total of the organosilicon compound (a), the metal alkoxide (b) and the fluorinated organosilicon compound (f). Preferably, it is 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.5 parts by mass or less. is there.
Further, when an organometallic compound is used as the catalyst, the catalyst (d) is 0.0001 with respect to 100 parts by mass in total of the organosilicon compound (a), the metal alkoxide (b) and the fluorinated organosilicon compound (f). It is preferably at least part by mass, more preferably at least 0.0002 part by mass, even more preferably at least 0.001 part by mass, preferably at most 0.1 part by mass, more preferably at least 0.05 part by mass. Or less.

Furthermore, the composition of the present invention is an antioxidant, a rust inhibitor, a UV absorber, a light stabilizer, a fungicide, an antibacterial agent, an anti-bioadhesive agent, a deodorant, as long as the effects of the present invention are not impaired. Various additives such as pigments, flame retardants and antistatic agents may be included.

Examples of the antioxidant include phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, hindered amine-based antioxidants, and the like.

Examples of the phenolic antioxidant include n-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 2,6-di-t-butyl-4-methylphenol, 2, 2-thio-diethylene-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], tri-ethylene glycol-bis- [3- (3-t-butyl-5-methyl -4-hydroxyphenyl) propionate], 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2, 4,8,10-tetraoxaspiro [5.5] undecane, tetrakis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid} pentaeryth Cyl ester, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t -Pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) Benzene, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1, 3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 2,2′-methylenebis (6-tert-butyl-4-methylphenol), 4,4′-butylidenebis (6- t-bu -3-methylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol) and the like.

Examples of the sulfur-based antioxidant include 3,3′-thiodipropionic acid di-n-dodecyl ester, 3,3′-thiodipropionic acid di-n-tetradecyl ester, and 3,3′-thiodipropion ester. Examples include acid di-n-octadecyl ester, tetrakis (3-dodecylthiopropionic acid) pentaerythritol ester, and the like.

Examples of the phosphorus antioxidant include tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6- Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-di-cumylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4 Examples include '-biphenylene diphosphonite, bis- [2,4-di-t-butyl, (6-methyl) phenyl] ethyl phosphite, and the like.

Examples of the hindered amine antioxidant include sebacic acid bis (2,2,6,6-tetramethyl-4-piperidyl) ester (melting point: 81 to 86 ° C.), 2,2,6,6-tetramethyl-4- Piperidyl methacrylate (melting point: 58 ° C.), poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6, 6-tetramethyl-4-piperidyl) imino} -1,6-hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] and the like.

Examples of the rust inhibitor include alkanolamines such as triethanolamine; quaternary ammonium salts; alkanethiols; imidazoles such as imidazoline, imidazole, alkylimidazoline derivatives, benzimidazole, 2-mercaptobenzimidazole, and benzotriazole; metavanadic acid Sodium; bismuth citrate; phenol derivatives; aliphatic amines such as alkylamines and polyalkenylamines, aromatic amines, ethoxylated amines, cyanoalkylamines, cyclohexylamine benzoate, aliphatic diamines such as alkylenediamine, aromatic diamines, etc. Amides of the above amine compounds and carboxylic acids; alkyl esters; pyrimidines; naphthenic acids; sulfonic acid complexes; calcium nitrite, sodium nitrite, disulphite nitrite Nitrites such as rohexylamine; polyol compounds such as polyalcohols and polyphenols; heteropolyacid salts such as sodium molybdate, sodium tungstate, sodium phosphonate, sodium chromate, sodium silicate; gelatin; polymer of carboxylic acid; nitro Compound: formaldehyde; acetylene alcohol; thiol compound such as aliphatic thiol, aromatic thiol, acetylene thiol; sulfide compound such as aliphatic sulfide, aromatic sulfide, acetylene sulfide; sulfoxide compound such as sulfoxide, dibenzyl sulfoxide; thiourea; Combination of amine or quaternary ammonium salt and halogen ion; Combination of alkylamine and potassium iodide; Combination of tannin and sodium phosphate; Triethanolamine Triethanolamine lauryl sarcosinate and combinations benzotriazole; alkylamine benzotriazole and combinations of sodium nitrite and sodium phosphate; and the like lauryl sarcosine combination with.

Examples of the ultraviolet absorber / light stabilizer include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl]. -2H-benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, Condensates with methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol (molecular weight about 300), hydroxyphenylbenzotriazole derivatives, 2 -(4,6-diphenyl-1,3,5-triazin-2-yl) -5 [(hexyl) oxy]- Phenol, 2-ethoxy-2'-ethyl-oxalic acid bisanilide and the like.

Examples of the fungicide / antibacterial agent include 2- (4-thiazolyl) benzimidazole, sorbic acid, 1,2-benzisothiazolin-3-one, (2-pyridylthio-1-oxide) sodium, dehydroacetic acid, 2-methyl -5-chloro-4-isothiazolone complex, 2,4,5,6-tetrachlorophthalonitrile, methyl 2-benzimidazole carbamate, methyl 1- (butylcarbamoyl) -2-benzimidazole carbamate, mono or dibromocyano Examples include acetamides, 1,2-dibromo-2,4-dicyanobutane, 1,1-dibromo-1-nitropropanol and 1,1-dibromo-1-nitro-2-acetoxypropane.

Examples of the biological adhesion inhibitor include tetramethylthiuram disulfide, bis (N, N-dimethyldithiocarbamate) zinc, 3- (3,4-dichlorophenyl) -1,1-dimethylurea, dichloro-N-((dimethylamino ) Sulfonyl) fluoro-N- (P-tolyl) methanesulfenamide, pyridine-triphenylborane, N, N-dimethyl-N′-phenyl-N ′-(fluorodichloromethylthio) sulfamide, cuprous thiocyanate ( 1), cuprous oxide, tetrabutylthiuram disulfide, 2,4,5,6-tetrachloroisophthalonitrile, zinc ethylenebisdithiocarbamate, 2,3,5,6-tetrachloro-4- (methyl) Sulfonyl) pyridine, N- (2,4,6-trichlorophenyl) maleimide, bis ( -Pyridinethiol-1-oxide) zinc salt, bis (2-pyridinethiol-1-oxide) copper salt, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 4,5- Examples include dichloro-2-n-octyl-4-isothiazolin-3-one, furanones, alkylpyridine compounds, gramine compounds, isonitrile compounds, and the like.

Examples of the deodorizer include lactic acid, succinic acid, malic acid, citric acid, maleic acid, malonic acid, ethylenediaminepolyacetic acid, alkane-1,2-dicarboxylic acid, alkene-1,2-dicarboxylic acid, cycloalkane-1 , 2-dicarboxylic acid, cycloalkene-1,2-dicarboxylic acid, organic acids such as naphthalenesulfonic acid; fatty acid metals such as zinc undecylenate, zinc 2-ethylhexanoate, zinc ricinoleate; iron oxide, iron sulfate, Zinc oxide, zinc sulfate, zinc chloride, silver oxide, copper oxide, metal (iron, copper, etc.) chlorophyllin sodium, metal (iron, copper, cobalt etc.) phthalocyanine, metal (iron, copper, cobalt etc.) tetrasulfonic acid phthalocyanine, Metal compounds such as titanium dioxide, visible light responsive titanium dioxide (nitrogen doped type, etc.); α-, β- or γ-cyclodex Cyclodextrins such as phosphorus, its methyl derivatives, hydroxypropyl derivatives, glucosyl derivatives, maltosyl derivatives; acrylic polymers such as porous methacrylic acid polymers and porous acrylic acid polymers, porous divinylbenzene polymers, porous styrene-divinylbenzene-vinylpyridine Examples thereof include polymers, aromatic polymers such as porous divinylbenzene-vinylpyridine polymer, copolymers thereof, and porous materials such as chitin, chitosan, activated carbon, silica gel, activated alumina, zeolite, and ceramic.

Examples of the pigment include carbon black, titanium oxide, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, perylene or perine pigment, quinophthalone pigment, diketopyrrolo-pyrrole pigment, dioxazine pigment, disazo condensation pigment, Examples include benzimidazolone pigments.

Examples of the flame retardant include decabromobiphenyl, antimony trioxide, phosphorus flame retardant, aluminum hydroxide and the like.

Examples of the antistatic agent include quaternary ammonium salt type cationic surfactants, betaine type amphoteric surfactants, alkyl phosphate type anionic surfactants, primary amine salts, secondary amine salts, thirds. Cationic surfactants such as quaternary amine salts, quaternary amine salts and pyridine derivatives, sulfated oils, soaps, sulfated ester oils, sulfated amide oils, sulfated ester salts of olefins, fatty alcohol sulfate esters, alkyl sulfates Anionic surfactants such as ester salts, fatty acid ethyl sulfonates, alkyl naphthalene sulfonates, alkyl benzene sulfonates, oxalate sulfonates and phosphate ester salts, partial fatty acid esters of polyhydric alcohols, fatty alcohol ethylenes Oxide adduct, fatty acid ethylene oxide adduct, fatty amino acid or fatty acid amino acid Ethylene oxide adducts of alkylphenols, ethylene oxide adducts of alkylphenols, ethylene oxide adducts of partial fatty acid esters of polyhydric alcohols, nonionic surfactants such as polyethylene glycol, amphoteric surfactants such as carboxylic acid derivatives and imidazoline derivatives, etc. Can be mentioned.

Further, as additives, lubricants, fillers, plasticizers, nucleating agents, antiblocking agents, foaming agents, emulsifiers, brighteners, binders, and the like may coexist.

When these additives are included, the content of the additive is usually 0.1 to 70% by mass, preferably 0.1 to 50% by mass, more preferably 0.5 to 30% in the composition. % By mass, more preferably 2 to 15% by mass.

Further, the sum of the organosilicon compound (a), the metal alkoxide (b) and the fluorinated organosilicon compound (f) (when the solvent (c) is included, the organosilicon compound (a), the metal alkoxide (b) and the fluorinated organic The content of the silicon compound (f) and the solvent (c)) is usually 60% by mass or more, preferably 75% by mass or more, more preferably 85% by mass or more, and still more preferably 95% in the composition. % Or more.

Examples of the method of bringing the organosilicon compound (a), the metal alkoxide (b), and the fluorine-containing organosilicon compound (f) into contact with the substrate include, for example, a spin coating method, a dip coating method, a spray coating method, a roll coating method, Examples thereof include a bar coating method and a die coating method, and a spin coating method and a spray coating method are preferable. According to the spin coating method and the spray coating method, the thickness of the film can be easily adjusted.

At this time, the composition may be further diluted as necessary. The dilution factor is, for example, 2 to 100 times, preferably 5 to 50 times that of the composition before dilution. As a dilution solvent, the solvent illustrated as a solvent (c) can be used suitably.

By leaving the composition of the present invention and the substrate in contact with each other in the air, moisture in the air is taken in and hydrolyzable groups are hydrolyzed to form a siloxane skeleton, thereby forming a film. Is done. When allowed to stand, it may be kept at 40 to 250 ° C.

A film formed from the above composition is also included in the scope of the present invention. The coating includes a structure derived from the organosilicon compound (a), the metal alkoxide (b), and the fluorine-containing organosilicon compound (f).

The initial contact angle of water θ ₀₁ for the film of the present invention is preferably 80 ° or more, more preferably 90 ° or more, still more preferably 100 ° or more, and may be 140 ° or less. It may be 130 ° or less.
The contact angle means a value measured by the θ / 2 method using 3.0 μL of water.

The initial contact angle θ ₀₂ of the oil with respect to the film of the present invention is preferably 55 ° or more, more preferably 60 ° or more, still more preferably 65 ° or more, and may be 120 ° or less. It may be 110 ° or less.
The contact angle means a value measured by the θ / 2 method using hexadecane having a liquid volume of 3.0 μL.

The film of the present invention has a contact angle change rate d _w2 represented by the following formula of −25% or more when the contact angle after immersion in ion exchange water at 70 ° C. for 12 hours is θ _w2. Preferably, it is -15% or more, more preferably -12% or more, and preferably 0%, but it is also acceptable that it is -1% or less, and further -5% or less.
Contact angle change rate d _w2 (%) = (θ _w2 −θ ₀₁ ) / θ ₀₁ × 100

The structure (A) derived from the organosilicon compound (a) is represented by the formula (IA).

[In the formula (IA), R ^a represents a trialkylsilyl group-containing molecular chain, and Z ^a1 represents a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, a hydrocarbon chain-containing group, or an —O— group. ]

In the formula (IA), ^a trialkylsilyl group-containing molecular chain of R ^a , Z ^a1 , a siloxane skeleton-containing group of Z ^a1 , and a hydrocarbon chain-containing group are respectively a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, The hydrocarbon chain-containing group can be appropriately selected from the range described above.
In particular, in the formula (IA), Z ^a1 is preferably a siloxane skeleton-containing group or an —O— group, and more preferably an —O— group.

As the structure (A), a structure represented by the formula (IA-I) can be given. The following formulas (IA-I-1) to (IA-I-50) are specific examples of the structure represented by the formula (IA-I), but are not limited thereto. In the structure represented by the formula (IA-I), the plurality of R ^s20 and the plurality of R ^s10 included therein may be the same or different.

Further, in the structure (B) derived from the metal alkoxide (b), it is bonded to a metal atom (however, when the metal atom is a silicon atom, it is different from the silicon atom to which the trialkylsilyl group-containing molecular chain is bonded). Since the group (hydrocarbon chain-containing group, siloxane skeleton-containing group, hydroxy group, etc.) has fewer constituent atoms than the trialkylsilyl group-containing molecular chain, the structure (B) acts as a spacer. The effect of improving water repellency by the group-containing molecular chain is likely to be enhanced. In addition, by including the metal alkoxide (b), it is possible to obtain a film having high warm water resistance and excellent practical durability.

The structure (B) derived from the metal alkoxide (b) is represented by the formula (IIB).

[In formula (IIB), M and k are as defined above. R ^b2 represents a hydroxy group or a —O— group. ]

Structure (B) includes a structure represented by the following formula when M is Si.

The structure (F) derived from the fluorine-containing organosilicon compound (f) is represented by the formula (IIIF-1) or (IIIF-2).

[In Formula (IIIF-1) and Formula (IIIF-2), R ^f1 and R ^f2 are as defined above. Z ^f2 represents a siloxane skeleton-containing group, a hydrocarbon chain-containing group, a hydroxy group, or an —O— group. A ^f3 represents a fluorine-containing alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a hydroxy group, or an —O— group. ]

The siloxane skeleton-containing group or a hydrocarbon chain-containing group represented by Z ^f2, a siloxane skeleton-containing group represented by Z ^a2, include hydrocarbon chains containing groups and each similar group.

Structure (F) includes a structure represented by the following formula. In the formula, r8 is an integer of 1 to 20, preferably an integer of 1 to 10. r9 is an integer of 1 to 10, preferably an integer of 1 to 5. r10 is an integer of 1 to 10, preferably an integer of 1 to 5.

The film formed from the composition of the present invention has a trialkylsilyl group-containing molecular chain and a fluorine-containing group, and has a part that can function as a spacer derived from the metal alkoxide (b). Therefore, both water repellency and oil repellency can be achieved, and the smoothness of the coating surface is also good.

A film-treated substrate in which the film of the present invention is formed on the substrate is also included in the scope of the present invention. The shape of the substrate 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. The substrate may be composed of any organic material or inorganic material. Examples of the organic material include acrylic resin, polycarbonate resin, polyester resin, styrene resin, acrylic-styrene copolymer resin, cellulose Thermoplastic resins such as resins, polyolefin resins, polyvinyl alcohol, etc .; thermosetting resins such as phenol resins, urea resins, melamine resins, epoxy resins, unsaturated polyesters, silicone resins, urethane resins; Are ceramics; glass; metals such as iron, silicon, copper, zinc, and aluminum; alloys containing the metals;
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.

The primer layer is preferably a layer formed from a primer layer forming composition containing a component (P) capable of forming a siloxane skeleton (hereinafter sometimes referred to as component (P)). The composition for forming a primer layer comprises a compound represented by the following formula (Pa) as the component (P) (hereinafter sometimes referred to as a compound (Pa)) and / or a partial hydrolysis condensate thereof (P1). It is preferable to include a component.
Si (X ^P2 ) ₄ (Pa)
[In the formula (Pa), X ^P2 represents a halogen atom, an alkoxy group or an isocyanate group. ]

In the above formula (Pa), X ^P2 is preferably a chlorine atom, an alkoxy group having 1 to 4 carbon atoms or an isocyanate group, and preferably four X ^P2 are the same.

As the compound (Pa), can be used alone or in _{combination, Si (NCO) 4, Si} (OCH 3) 4, Si (OC 2 H 5) 4 and the like are preferable.

(P1) component contained in the primer layer forming composition may be a partial hydrolysis-condensation product of the compound (Pa). The partial hydrolysis-condensation product of compound (Pa) can be produced by a general hydrolysis-condensation method using an acid catalyst or a base catalyst. The degree of condensation (degree of multimerization) of the partially hydrolyzed condensate is preferably such that the product is dissolved in the solvent. The component (Pa) may be a compound (Pa) or a partial hydrolysis condensate of the compound (Pa), and a mixture of the compound (Pa) and its partial hydrolysis condensate, for example, It may be a partially hydrolyzed condensate of the compound (Pa) containing the reaction compound (Pa). A commercial item can also be used as a compound (Pa) and its partial hydrolysis-condensation product.

The primer layer forming composition further comprises, as component (P), a compound represented by formula (Pb) (hereinafter sometimes referred to as compound (Pb)) and / or a partially hydrolyzed condensate thereof ( P2) component may be included.
(X ^P3 ) ₃ Si— (CH ₂ ) _p —Si (X ^P3 ) ₃ (Pb)
[In the formula (Pb), X ^P3 independently represents a hydrolyzable group or a hydroxyl group, and p is an integer of 1 to 8. ]

In the formula (Pb), examples of the hydrolyzable group represented by X ^P3 include the same groups or atoms as those of X ^P2 . In view of the balance between the stability of the compound (Pb) and the ease of hydrolysis, X ^P3 is preferably an alkoxy group or an isocyanate group, and particularly preferably an alkoxy group.
As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable. A plurality of X ^P3 present in the compound (Pb) may be the same group or different groups, and the same group is preferable from the viewpoint of availability.

As the compound (Pb), one or more kinds can be used, and (CH ₃ O) ₃ SiCH ₂ CH ₂ Si (OCH ₃ ) ₃ , (OCN) ₃ SiCH ₂ CH ₂ Si (NCO) ₃ , _{_{_{_{Cl 3 SiCH 2 CH 2 SiCl 3}}}} , (C 2 H 5 O) 3 SiCH 2 CH 2 Si (OC 2 H 5) 3, (CH 3 O) 3 SiCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 Si ( OCH ₃ ) _{3 and the} like.

Component (P2) may be a partially hydrolyzed condensate of compound (Pb). The partially hydrolyzed condensate of compound (Pb) can be obtained by the same method as described in the production of the partially hydrolyzed condensate of compound (Pa). The degree of condensation (degree of multimerization) of the partially hydrolyzed condensate is preferably such that the product is dissolved in the solvent. Component (P2) may be compound (Pb) or a partial hydrolysis condensate of compound (Pb), and a mixture of compound (Pb) and its partial hydrolysis condensate, for example, It may be a partial hydrolysis-condensation product of the compound (Pb) containing the reaction compound (Pb). Commercially available products can also be used as the compound (Pb) and its partial hydrolysis condensate.
The primer layer forming composition may contain a cohydrolysis condensate by cohydrolysis of the compound (Pb) and the compound (Pa) as the component (P), and various polysilazanes are contained. Also good.

The composition for forming a primer layer usually contains an organic solvent in consideration of economic efficiency, workability, ease of control of the thickness of the resulting primer layer, etc., in addition to the solid content as a layer constituent component. The organic solvent is preferably one that dissolves the solid content contained in the primer layer forming composition, and examples thereof include the same solvents as the solvent (c) used in the composition. The organic solvent is not limited to one kind, and two or more kinds of solvents having different polarities and evaporation rates may be mixed and used.
When the composition for primer layer formation contains a partial hydrolysis-condensation product and a partial hydrolysis-condensation product, it may contain the solvent used in order to manufacture these.

Furthermore, in the composition for forming a primer layer, even if it does not contain a partial hydrolysis condensate or partial hydrolysis cocondensate, in order to promote the hydrolysis cocondensation reaction, It is also preferable to blend a catalyst such as an acid catalyst that is generally used. Even when a partially hydrolyzed condensate or a partially hydrolyzed cocondensate is included, when the catalyst used for the production thereof does not remain in the composition, it is preferable to add a catalyst. The composition for forming a primer layer may contain water for the above-described components to undergo a hydrolysis condensation reaction or a hydrolysis cocondensation reaction.

As a method for forming the underlayer using the primer layer forming composition, a known method for an organosilane compound-based surface treatment agent can be used. For example, the base layer forming composition is applied to the surface of the substrate by brush coating, flow coating, spin coating, dip coating, squeegee coating, spray coating, hand coating, or the like, and is necessary in the air or in a nitrogen atmosphere. The base layer can be formed by curing after drying according to the above. Curing conditions are appropriately controlled depending on the type and concentration of the composition used. In addition, you may perform hardening of the composition for primer layer formation simultaneously with hardening of a composition.

The thickness of the primer layer is not particularly limited as long as it can provide moisture resistance, adhesion, and barrier properties such as alkali from the substrate to the film formed thereon.

The film formed from the composition of the present invention can achieve both water repellency and oil repellency, adhesion and film-forming properties, display devices such as touch panel displays, optical elements, semiconductor elements, building materials, automobile parts, nanoimprint technology, etc. It is useful as a base material. The film formed from the composition of the present invention is suitably used as an article such as a body, window glass (front glass, side glass, rear glass), mirror, bumper and the like in transportation equipment such as trains, automobiles, ships, and airplanes. Moreover, it can also be used for outdoor uses, such as a building outer wall, a tent, a solar power generation module, a sound insulation board, and concrete. It can also be used for fishing nets, insect nets, water tanks, and the like. Furthermore, it can be used for various indoor facilities such as kitchens, bathrooms, washstands, mirrors, toilet articles, ceramics such as chandeliers and tiles, artificial marble, and air conditioners. It can also be used as an antifouling treatment for jigs, inner walls, pipes and the like in factories. It is also suitable for goggles, glasses, helmets, slingshots, textiles, umbrellas, play equipment, soccer balls and the like. Furthermore, it can also be used as an anti-adhesive agent for various packaging materials such as food packaging materials, cosmetic packaging materials, and the inside of pots.

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 be adapted to the above and the following. 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 “mass%” unless otherwise specified.

Contact angle evaluation Using DM700 manufactured by Kyowa Interface Science Co., Ltd., the contact angle of water and hexadecane on the film surface was measured by the droplet method (analysis method: θ / 2 method). The amount of water droplets is 3.0 μL, and the amount of oil droplets is 3.0 μL.

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, and the film forming property was evaluated as follows.
◎: No dirt at all ○: Dirt can be confirmed by looking closely △: Partial dirt on the film can be confirmed ×: Overall dirt on the film can be confirmed

Hot water test The film was immersed in ion exchange water at 70 ° C. for 12 hours, and the contact angle of water before and after immersion was measured.
Comprehensive evaluation of the hot water test resistance was performed from the contact angle and change rate after the test.
◎: Contact angle is 99 ° or more and the change rate of contact angle is −10% or more ○: Contact angle is less than 99 ° to 90 ° or more, and the contact angle change rate is −10% or more ×: Contact angle is less than 90 ° Or contact angle change rate is less than -10%

Example 1-1
A three-necked flask was charged with 4.69 g of tris (trimethylsiloxy) silanol and 21.0 g of tetrahydrofuran (THF) and stirred. After cooling to −40 ° C., 9.38 mL of n-BuLi hexane solution (1.6 mol / L) was added dropwise. The temperature was raised to 0 ° C., 10.01 g of hexamethylcyclotrisiloxane dissolved in 21 g of THF was added dropwise, and the mixture was stirred for 17 hours. After cooling to −40 ° C., THF, ion-exchanged water, and hexane were sequentially added to the reaction solution, followed by liquid separation to separate the organic layer. The extract was washed with ion-exchanged water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain colorless and transparent intermediate 1.
9.47 g of Intermediate 1, 8.97 g of tetramethoxysilane (TMOS) and 151.2 μL of t-butylamine were charged and reacted at 30 ° C. for 5 hours with stirring. Concentration under reduced pressure at 12 hPa and 140 ° C. gave Compound 1 represented by the following formula. In the formula, the average number of repeating units in parentheses was calculated from the NMR spectrum and found to be 8.

Example 1-2
A four-necked flask was charged with 0.72 g of trimethylsilanol and 6.72 mL of THF and stirred. After cooling to −40 ° C., 5.00 mL of n-BuLi hexane solution (1.6 mol / L) was added dropwise. The temperature was raised to 0 ° C., 14.24 g of hexamethylcyclotrisiloxane dissolved in 16.43 mL of THF was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 17 hours. The mixture was cooled to −40 ° C., and 1.59 g of chlorotriethoxysilane was added dropwise. Hexane was added and filtered. The filtrate was concentrated at 13 hPa and 25 ° C. to obtain compound 2. In the formula, the average number of repeating units in parentheses was calculated from the NMR spectrum and found to be 8.

Example 2-1
Compound 1 as organosilicon compound (a), tetraethoxysilane (TEOS) as metal alkoxide (b), triethoxy (1H, 1H, 2H, 2H-nonafluorohexyl) silane as fluorine-containing organosilicon compound (f) (C ₄ F ₉ —C ₂ H ₄ —Si— (OC ₂ H ₅ ) ₃ ), 0.01 M hydrochloric acid as the catalyst (d), and methyl ethyl ketone (MEK) as the solvent (c) are shown in Table 7. The mixture was mixed at a ratio and stirred for 24 hours to obtain a coating solution. A coating solution obtained using a spin coater (manufactured by MIKASA) obtained on an alkali-cleaned glass substrate (EAGLE XG, Corning) was coated at 3000 rpm for 20 s and allowed to stand at room temperature for 1 day. The film was cured at a temperature of

Examples 2-2 to 2-8, Comparative Examples 1 to 4
After mixing at a composition ratio shown in Table 9 to obtain a coating solution, a film was obtained in the same manner as in Example 2-1. About the produced membrane | film | coat, the contact angle (water or hexadecane) and the contact angle after a warm water test were evaluated.

In the table, Comparative Compound 1 represents a compound represented by the following formula. In the formula, the average number of repeating units in parentheses was 24 calculated from the NMR spectrum.

The compositions obtained in the examples were excellent in film forming properties during film formation, and the resulting films were excellent in water and oil repellency, adhesion and film forming properties. On the other hand, all of the compositions obtained in the comparative examples were inferior in film forming properties during film formation. Furthermore, the film obtained from the composition of Comparative Example 4 is inferior in water repellency and oil repellency, and the film obtained from the compositions of Comparative Example 2 and Comparative Example 4 has adhesiveness as a result of the hot water test. I found it inferior.

The film formed from the composition of the present invention can achieve both water repellency and oil repellency and film forming properties, and is a base material for display devices such as touch panel displays, optical elements, semiconductor elements, building materials, automobile parts, nanoimprint technology, etc. Useful as. The film formed from the composition of the present invention is suitably used as an article such as a body, window glass (front glass, side glass, rear glass), mirror, bumper and the like in transportation equipment such as trains, automobiles, ships, and airplanes. Moreover, it can also be used for outdoor uses, such as a building outer wall, a tent, a solar power generation module, a sound insulation board, and concrete. It can also be used for fishing nets, insect nets, water tanks, and the like. Furthermore, it can be used for various indoor facilities such as kitchens, bathrooms, washstands, mirrors, toilet articles, ceramics such as chandeliers and tiles, artificial marble, and air conditioners. It can also be used as an antifouling treatment for jigs, inner walls, pipes and the like in factories. It is also suitable for goggles, glasses, helmets, slingshots, textiles, umbrellas, play equipment, soccer balls and the like. Furthermore, it can also be used as an anti-adhesive agent for various packaging materials such as food packaging materials, cosmetic packaging materials, and the inside of pots.

Claims

Organosilicon compound (a), metal alkoxide (b), fluorine-containing group and hydrolyzable group in which at least one trialkylsilyl group-containing molecular chain and at least one hydrolyzable group are bonded to a silicon atom A composition comprising a fluorine-containing organosilicon compound (f) in which is bonded to a silicon atom.
The composition according to claim 1, wherein the organosilicon compound (a) is a compound represented by the formula (I).

[In formula (I), R a represents a trialkylsilyl group-containing molecular chain, and A a1 independently represents a hydrolyzable group. Z a1 represents a trialkylsilyl group-containing molecular chain, a hydrocarbon chain-containing group, a siloxane skeleton-containing group, or a hydrolyzable group. ]
The composition according to claim 1 or 2, wherein the metal alkoxide (b) is a compound represented by the formula (II).

[In formula (II), M represents a trivalent or tetravalent metal atom capable of forming a metal alkoxide. A b1 independently represents an alkoxy group having 1 to 4 carbon atoms. k represents an integer of 3 or 4 depending on the valence of M. ]
The composition according to any one of claims 1 to 3, wherein the fluorine-containing organosilicon compound (f) is a compound represented by any one of formulas (III-1) and (III-2).

[In the formula (III-1), R f1 represents a fluorocarbon-containing group having 1 to 8 carbon atoms. A f1 independently represents a hydrolyzable group. Z f1 represents a siloxane skeleton-containing group, a hydrocarbon chain-containing group, or a hydrolyzable group. ]

[In the above formula (III-2), R f2 represents a hydrolyzable silane oligomer residue. A f2 independently represents a hydrolyzable group, a fluorine-containing alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. ]
The ratio of the content of the fluorine-containing organosilicon compound (f) and the organosilicon compound (a) (fluorine-containing organosilicon compound (f) / organosilicon compound (a)) is 7/1 or more in molar ratio, The composition according to any one of claims 1 to 4, which is 20/1 or less.
The ratio of the content of the metal alkoxide (b) and the fluorine-containing organosilicon compound (f) (metal alkoxide (b) / fluorine-containing organosilicon compound (f)) is 0.01 or more in terms of molar ratio. The composition according to any one of claims 1 to 5, which is 50 or less.
A film formed from the composition according to claims 1 to 6.