KR20190003631A - Composition - Google Patents

Abstract

It is an object of the present invention to provide a hand-coatable composition having water repellency, oil repellency and abrasion resistance.
The present invention relates to a process for producing an organosilicon compound (A1) in which at least one hydrolyzable group is bonded to a silicon atom and an alkyl group having 6 to 20 carbon atoms in which a part of the methylene group may be substituted with an oxygen atom, ),
Further, at least one hydrolyzable group is bonded to the metal atom, and a hydrocarbon chain-containing group in which the maximum chain length of the hydrocarbon chain portion is shorter than the maximum chain length of the organic silicon compound (A1) or (A2) A metal compound (B)
A high boiling point solvent (C) satisfying predetermined requirements, and a low boiling point solvent (D)
The concentration of the high boiling point solvent (C) is not less than 0.088 parts by mass and less than 1.74 parts by mass based on 100 parts by mass of the composition.

Description

Composition

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

Problems such as deterioration of visibility due to contamination of the surface of the window glass and defective appearance may occur in various vehicles and outdoor facilities. Therefore, it is desired that the surface of the substrate such as glass has good water repellency and oil repellency. It is desired not only to prevent adhesion of droplets to the substrate surface, but also to facilitate removal of adhered droplets.

For example, in Patent Document 1, a coating solution for obtaining a sol-gel film has a silicon oxide oligomer having a solid content and a solvent, and a solid component obtained by hydrolysis and polycondensation of an alkoxysilane in an acidic aqueous solution, and the solvent is ethylene glycol monoalkyl Ether and the above-mentioned acidic aqueous solution. As the alkoxysilane, methyltriethoxysilane and? -Glycidoxypropyltrimethoxysilane are specifically disclosed.

Patent Document 2 discloses an example in which a solution containing an organic solvent, water and a catalyst having a vapor pressure higher than that of water is spin-coated on a glass substrate by mixing the organosilane and the metal alkoxide at a predetermined ratio.

Patent Document 3 discloses that a water repellent agent for glass containing aminosilane is applied by hand spray to a water repellent agent comprising an amino-modified polysiloxane, an acid, and an activator. Patent Document 4 discloses a method of spraying an automotive light-emitting composition containing amino-modified dimethylpolysiloxane, alcohols and water.

Japanese Patent Application Laid-Open No. 2010-31188 Japanese Unexamined Patent Application Publication No. 2013-213181 Japanese Patent Application Laid-Open No. 2009-173491 Japanese Patent Application Laid-Open No. 2009-40936

The coating liquid described in Patent Document 1 does not have water repellency and oil repellency. As a coating method of the water-repellent / oil-repellent coating, a spin coating method is used in Patent Document 2, and a spray coating method is also used in Patent Documents 3 and 4. However, without using any special equipment or mechanism used in this method, It is very advantageous in terms of cost and simplicity that the coating can be applied. In addition, Patent Document 1 discloses a method of forming a film of a hand coating, but it is necessary to wipe the excess component with a finish, which is not a simple method. In addition, when the coating film is subjected to friction or the like, it tends to be broken and the liquid droplets may adhere or become difficult to be removed. As a result, the substrate may be contaminated or corroded, Durability is also required.

Therefore, it is an object of the present invention to provide a hand-coatable composition having water repellency, oil repellency and abrasion resistance.

According to the present invention,

An alkyl group having 6 to 20 carbon atoms in which a part of the methylene group may be substituted with an oxygen atom and an organosilicon compound (A1) in which at least one hydrolyzable group is bonded to a silicon atom, or at least one trialkylsilyl group- , An organosilicon compound (A2) in which at least one hydrolyzable group is bonded to a silicon atom,

Further, at least one hydrolyzable group is bonded to the metal atom, and a hydrocarbon chain-containing group in which the maximum chain length of the hydrocarbon chain portion is shorter than the maximum chain length of the organic silicon compound (A1) or (A2) A metal compound (B)

(C) having a solubility parameter of 8.0 (cal / cm < ³ >) ^1/2 or more and at least one of those having a vapor pressure at 20 DEG C of 1000 Pa or less and a boiling point of 120 DEG C or more,

(D) having a vapor pressure at 20 DEG C of more than 1000 Pa and a boiling point of less than 120 DEG C,

The concentration of the high boiling point solvent (C) is not less than 0.088 parts by mass and less than 1.74 parts by mass based on 100 parts by mass of the composition.

The molar ratio of the metal compound (B) to the organosilicon compound (A1) or (A2) is preferably 2 or more and 48 or less.

The organosilicon compound (A1) is preferably represented by the following formula (AI).

[Chemical Formula 1]

[In the formula (AI), R ^a1 represents an alkyl group having 6 to 20 carbon atoms in which a part of the methylene group may be substituted with an oxygen atom,

A plurality of A ^a1 each independently represent a hydrolyzable group.

Z ^a1 represents a hydrocarbon chain-containing group or a hydrolysable group, and when Z ^a1 is a hydrocarbon chain-containing group, R ^a1 and Z ^a1 may be the same or different, and when Z ^a1 is a hydrolysable group, Z ^a1 and A ^a1 are the same The chart may be different. R ^a1 and Z ^a1 may be the same or different in the plurality of formulas (AI).]

The organosilicon compound (A2) is preferably represented by the following formula (AII).

(2)

[In the formula (AII), R ^a2 represents a trialkylsilyl group-containing molecular chain, and a plurality of A ^a2 each independently represent a hydrolyzable group. Z ^a2 represents a trialkylsilyl group-containing molecular chain, a hydrocarbon chain-containing group, a siloxane skeleton-containing group or a hydrolyzable group.

The metal compound (B) is preferably represented by the following formula (BI).

(3)

[In the formula (BI)

R ^b1 represents a hydrocarbon chain-containing group or a hydrolyzable group in which the maximum chain length of the hydrocarbon chain portion is shorter than the maximum chain length of the alkyl group having 6 to 20 carbon atoms.

A ^b1 each independently represents a hydrolyzable group.

M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr or Ta.

and m represents an integer of 1 to 4, depending on the valence of M.]

In the formula (BI), R ^b1 and A ^b1 are preferably the same group.

In the formula (BI), M is preferably Si.

According to the composition of the present invention, an alkyl group having 6 to 20 carbon atoms, in which a part of the methylene group may be substituted with an oxygen atom, and an organosilicon compound (A1) in which the hydrolyzable group is bonded to a silicon atom or at least one trialkylsilyl group (B) having a hydrolyzable group bonded to a metal atom, a high boiling point solvent (C), a low boiling point solvent (C), and a low boiling point solvent Since the solvent (D) is contained, the coating film having water repellency, oil repellency and abrasion resistance can be applied to the substrate without unevenness by hand coating.

The composition of the present invention comprises an alkyl group having 6 to 20 carbon atoms in which a part of the methylene group may be substituted with an oxygen atom and an organosilicon compound (A1) in which at least one hydrolyzable group is bonded to a silicon atom or at least one trialkyl (A2) in which at least one hydrolyzable group is bonded to a silicon atom, at least one hydrolyzable group is bonded to a metal atom, and the maximum chain length of the hydrocarbon chain portion is at least one of the organosilicon compound And a metal compound (B) in which a hydrocarbon chain-containing group shorter than the maximum chain length of the compound (A1) or (A2) may be bonded to the metal atom. From such a composition, a silicon atom or a hydrolyzable group bonded to a metal atom is hydrolyzed and polycondensed to form a film. Further, according to the composition of the present invention, it is not necessary to wipe the excess portion in the finish at the time of film formation.

When the organosilicon compound (A1) is used, the coating film is formed by adding an alkyl group having 6 to 20 carbon atoms, which may be partially substituted with an oxygen atom, to some silicon atoms of the silicon atoms forming the coating Or an alkyl group having 6 to 20 carbon atoms). The alkyl group having 6 to 20 carbon atoms imparts a water-repellent / oil-repellent function to the coating film. Further, in the case of using the (A2) as the organosilicon compound, a film having a trialkylsilyl group-containing molecular chain bonds to a part of the silicon atoms forming the film. By this trialkylsilyl group, a water-repellent / oil-repellent function is imparted to the coating film.

An element (for example, the metal atom) to which the alkyl group having 6 to 20 carbon atoms and the trialkylsilyl group are not bonded can function substantially as a spacer in the film, and the wear resistance can be improved. In the preferred embodiment of the composition of the present invention, since the molar ratio of the organosilicon compound (A1) or (A2) to the metal compound (B) is adjusted to a specific range, Or the trialkylsilyl group and the spacer are present in a specific ratio, so that the water-repellent / oil-repellent function can be enhanced, and a coating film with higher abrasion resistance can be provided.

In addition, the composition of the present invention comprises a high boiling point solvent (C) which meets certain requirements. By including the high-boiling point solvent, it becomes possible to apply the composition without unevenness by the high-boiling point solvent (C) remaining on the substrate without volatilization when the composition is applied to the substrate by hand coating.

Each of the organosilicon compounds (A1) and (A2) will be described below.

(1-1) Organosilicon compound (A1)

Regarding water repellency and oil repellency, in the present invention, a hydrocarbon chain-containing group (hereinafter referred to as a first hydrocarbon chain-containing group) is bonded to the central silicon atom of the organosilicon compound (A1) Is that an alkyl group having 6 to 20 carbon atoms is bonded to a silicon atom. This alkyl group having 6 to 20 carbon atoms imparts water repellency and oil repellency to the obtained coating interface (surface). Particularly, the coefficient of friction between the droplet (water droplet, oil droplet, etc.) and the coating film becomes small, and the droplet becomes easy to move. The alkyl group having 6 to 20 carbon atoms preferably has a carbon number of 7 or more and 17 or less, more preferably 8 or more and 15 or less.

The silicon atom of the organosilicon compound (A1) may be bonded to the first hydrocarbon chain-containing group in addition to one alkyl group having 6 to 20 carbon atoms. Although the first hydrocarbon chain-containing group (including an alkyl group having 6 to 20 carbon atoms) is usually composed only of a hydrocarbon group (hydrocarbon chain), if necessary, the methylene group (-CH ₂ -) of a part of the hydrocarbon chain is And may be substituted with an oxygen atom. Since the hydrocarbon chain is present in the remainder of the portion in which a part of the oxygen atom is substituted, it is classified as a hydrocarbon chain-containing group. Further, the methylene group (-CH ₂ -) adjacent to the Si atom is not substituted by an oxygen atom, and two consecutive methylene groups (-CH ₂ -) are not simultaneously substituted by an oxygen atom. In the following, a, for group-containing alkyl group and a hydrocarbon chain of an oxygen Beach cyclic (i. E. Monovalent hydrocarbon group) Examples described groups containing the first hydrocarbon chain, but unless otherwise noted, any explanation, the methylene group (-CH ₂ - Can be replaced with an oxygen atom.

The first hydrocarbon chain-containing group, which may be further bonded to the alkyl group having 6 to 20 carbon atoms in the first hydrocarbon chain-containing group bonded to the silicon atom of the organosilicon compound (A1), has a carbon number of 6 Or more and 20 or less, more preferably 7 or more and 17 or less carbon atoms, and still more preferably 8 or more and 15 or less carbon atoms.

When the methylene group of a part of the first hydrocarbon chain-containing group is substituted with an oxygen atom, the carbon number of such a group means the carbon number before substitution with an oxygen atom.

The first hydrocarbon chain-containing group (in the case of a hydrocarbon group) containing an alkyl group having 6 to 20 carbon atoms may be branched or straight-chain. The first hydrocarbon chain-containing group (in the case of a hydrocarbon group) which may be further bonded in addition to the alkyl group having 6 to 20 carbon atoms is preferably a saturated or unsaturated aliphatic hydrocarbon chain-containing group and is preferably a saturated aliphatic hydrocarbon chain- desirable. The saturated aliphatic hydrocarbon chain-containing group (in the case of a hydrocarbon group) is more preferably a saturated aliphatic hydrocarbon group.

Examples of the alkyl group having 6 to 20 carbon atoms and the saturated aliphatic hydrocarbon group include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, , Hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, and the like.

When a methylene group (-CH ₂ -) of a hydrocarbon group of the first hydrocarbon chain-containing group is substituted with an oxygen atom, the hydrocarbon group is preferably a saturated aliphatic hydrocarbon group. Specific examples of the group in which the methylene group (-CH ₂ -) of the hydrocarbon group is substituted with an oxygen atom in the first hydrocarbon chain-containing group include a group having a (poly) ethylene glycol unit and a group having a (poly) propylene glycol unit And the like.

In the organosilicon compound (A1), the number of the first hydrocarbon chain-containing groups bonded to the central silicon atom is usually 1 or more, preferably 2 or less, including the number of alkyl groups having 6 to 20 carbon atoms, (That is, only the alkyl group having 6 to 20 carbon atoms as the first hydrocarbon chain-containing group) is particularly preferable.

The hydrolyzable group of the organosilicon compound (A1) may be any group that imparts a hydroxyl group (silanol group) by hydrolysis. Examples of the hydrolyzable group include a methoxy group, an ethoxy group, a propoxy group, An alkoxy group of 4; A hydroxy group; An acetoxy group; Chlorine atom; Isocyanato group; And the like. Among them, 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 (A1), the number of hydrolyzable groups bonded to the central silicon atom is usually 1 or more, preferably 2 or more, and usually 3 or less.

The silicon atom of the organosilicon compound (A1) may contain, in addition to the alkyl group having 6 to 20 carbon atoms and the hydrolyzable group, a hydrocarbon chain-containing group having a smaller number of carbon atoms in the hydrocarbon chain moiety than the alkyl group having 6 to 20 carbon atoms Chain-containing group) may be bonded.

The length of the alkyl group having 6 to 20 carbon atoms and the second hydrocarbon chain-containing group can be evaluated as the length (longest chain length) of the longest straight chain (hereinafter also referred to as " main chain ") containing an element bonding to a metal atom such as Si have. In order to make the length of the main chain shorter than that of the alkyl group having 6 to 20 carbon atoms in the second hydrocarbon chain-containing group, for example, it is preferable that the number of carbon atoms in the hydrocarbon chain portion is smaller than the number of carbon atoms in the alkyl group having 6 to 20 carbon atoms. Usually, the second hydrocarbon chain-containing group is composed of only a hydrocarbon group (hydrocarbon chain) like the above-mentioned alkyl group having 6 to 20 carbon atoms, but if necessary, a part of the methylene group (-CH ₂ -) of the hydrocarbon chain is substituted with an oxygen atom . In addition, the methylene group (-CH ₂ -) adjacent to the Si atom is not substituted by an oxygen atom, and two consecutive methylene groups (-CH ₂ -) are not simultaneously substituted by an oxygen atom.

The carbon number of the hydrocarbon chain portion means the number of carbon atoms constituting the hydrocarbon group (hydrocarbon chain) in the oxygen-containing cyclic hydrocarbon chain-containing group. In the oxygen-substituted hydrocarbon chain-containing group, (-CH ₂ -), respectively.

In the following, a, group-containing hydrocarbon chain of an oxygen-containing Beach annular described groups containing the second hydrocarbon chain (i. E. Monovalent hydrocarbon group) as an example, but unless otherwise noted, any explanation, the methylene group (-CH ₂ -) of It is possible to replace a part with an oxygen atom.

When the hydrocarbon-containing group is a hydrocarbon group, the number of carbon atoms in the second hydrocarbon-chain-containing group is preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less. The second hydrocarbon chain-containing group (in the case of a hydrocarbon group) may be branched or straight-chain.

The second hydrocarbon chain-containing group (in the case of a hydrocarbon group) is preferably a saturated or unsaturated aliphatic hydrocarbon chain-containing group, more preferably a saturated aliphatic hydrocarbon chain-containing group. As the saturated aliphatic hydrocarbon chain-containing group (in the case of a hydrocarbon group), a saturated aliphatic hydrocarbon group is more preferable. Examples of the saturated aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group.

When a methylene group (-CH ₂ -) of a part of the hydrocarbon group is substituted with an oxygen atom, the hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, and the group in which a part of the hydrocarbon group is substituted with an oxygen atom is the methylene group (-CH ₂ - , Specifically, groups having (poly) ethylene glycol units, and the like.

In the organosilicon compound (A1), the number of the second hydrocarbon chain-containing groups bonded to the central silicon atom is preferably 2 or less, more preferably 1 or less, and particularly preferably 0.

Specifically, the organosilicon compound (A1) is preferably a compound represented by the following formula (AI).

[Chemical Formula 4]

[In the formula (AI), R ^a1 represents an alkyl group having 6 to 20 carbon atoms in which a part of the methylene group may be substituted with an oxygen atom, and a plurality of A ^a1 each independently represent a hydrolyzable group. Z ^a1 represents a hydrocarbon chain-containing group or a hydrolyzable group, and when Z ^a1 is a hydrocarbon chain-containing group, R ^a1 and Z ^a1 may be the same or different, and when Z ^a1 is a hydrolysable group, Z ^a1 and A ^a1 May be the same or different. R ^a1 and Z ^a1 may be the same or different in the plurality of formulas (AI).]

Equation (AⅠ) wherein (the carbon number of 6 to 20 include an alkyl group) group-containing hydrocarbon chain of Z ^{a1, a1} A, hydrolyzable group of Z ^a1, each containing a first hydrocarbon chain group, and the second hydrocarbon chain-containing group , And the hydrolyzable group can be appropriately selected from the ranges described above.

In the formula (AI), Z ^a1 is preferably a second hydrocarbon chain-containing group or a hydrolyzable group, more preferably a hydrolyzable group.

As the organic silicon compound (A1), a compound having one alkyl group having 6 to 20 carbon atoms and three hydrolyzable groups; A compound having one alkyl group having 6 to 20 carbon atoms, one hydrocarbon group having a second hydrocarbon group, and one hydrolyzable group; And the like.

In the compound having one alkyl group having 6 to 20 carbon atoms and three hydrolyzable groups, three hydrolyzable groups are bonded to a silicon atom. Examples of the group in which the three hydrolyzable groups are bonded to the silicon atom include trialkoxysilyl groups such as trimethoxysilyl group, triethoxysilyl group, tripropoxysilyl group and tributoxysilyl group; A trihydroxysilyl group; Triacetoxysilyl group; Trichlorosilyl group; Triisocyanatosilyl groups; And the like.

In the compound having one alkyl group having 6 to 20 carbon atoms, one hydrocarbon group having two hydrocarbon chains, and two hydrolyzable groups, one second hydrocarbon chain-containing group and two hydrolyzable groups are bonded to a silicon atom . Examples of the group in which one second hydrocarbon chain-containing group and two hydrolysable groups are bonded to a silicon atom include methyldimethoxysilyl group, ethyldimethoxysilyl group, methyldiethoxysilyl group, ethyldiethoxysilyl group, methyldipropoxy An alkyldialkoxysilyl group such as a silyl group; And the like.

Specific examples of the compound having one alkyl group having 6 to 20 carbon atoms and three hydrolyzable groups include alkyltrimethoxysilane having an alkyl group having 6 to 20 carbon atoms and alkyltriethoxy having an alkyl group having 6 to 20 carbon atoms Alkyltrialkoxysilane having an alkyl group having 6 to 20 carbon atoms such as silane; Alkyl trihydroxysilanes having an alkyl group having 6 to 20 carbon atoms; Alkyltriacetoxysilane having an alkyl group having 6 to 20 carbon atoms; Alkyl trichlorosilane having an alkyl group having 6 to 20 carbon atoms; Alkyl triisocyanatosilanes having an alkyl group having 6 to 20 carbon atoms; And the like.

Specific examples of the compound having one alkyl group having 6 to 20 carbon atoms, one second hydrocarbon group-containing group, and two hydrolyzable groups include alkylmethyldimethoxysilane having an alkyl group having 6 to 20 carbon atoms, Alkylmethyldialkoxysilanes such as alkylmethyldiethoxysilane having 6 to 20 alkyl groups; Alkylmethyl dihydroxysilane having an alkyl group having 6 to 20 carbon atoms; Alkylmethyldiacetoxysilane having an alkyl group having 6 to 20 carbon atoms; Alkylmethyldichlorosilane having an alkyl group having 6 to 20 carbon atoms; Alkylmethyldiisocyanatosilane having an alkyl group having 6 to 20 carbon atoms; And the like.

Among them, a compound having one alkyl group having 6 to 20 carbon atoms and three hydrolyzable groups is preferable, and an alkyltrialkoxysilane having an alkyl group having 6 to 20 carbon atoms is more preferable.

(1-2) Organosilicon compound (A2)

The organosilicon compound (A2) has, 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. As the organosilicon compound (A2), a compound having one trialkylsilyl group-containing molecular chain and three hydrolyzable groups bonded to a central silicon atom; A compound having one trialkylsilyl group-containing molecular chain, one siloxane skeleton-containing group, and two hydrolyzable groups bonded to a central silicon atom; A compound having one trialkylsilyl group-containing molecular chain, one hydrocarbon chain-containing group, and two hydrolyzable groups bonded to a central silicon atom; And the like.

Specifically, the organosilicon compound (A2) is preferably a compound represented by the following formula (AII).

[Chemical Formula 5]

[In the formula (AII), R ^a2 represents a trialkylsilyl group-containing molecular chain, and a plurality of A ^a2 each independently represent a hydrolyzable group. Z ^a2 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 a trialkylsilyl-containing group is bonded to the end of the molecular chain, and a trialkylsilyl-containing group is bonded to the molecular chain. Thus, The water repellency and oil repellency of the water-repellent layer are improved. Further, the existence of the trialkylsilyl group-containing molecular chain reduces the friction between the droplet (water droplet, oil droplet, etc.) and the coating film, and the droplet is easily moved. Further, by having a trialkylsilyl group, the chemical and physical durability is enhanced, and the heat resistance and the light resistance are improved. In the case where the alkyl group of the trialkylsilyl-containing group is substituted with a fluoroalkyl group, likewise, the water repellency and oil repellency of the coating interface (surface) can be improved.

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

[Chemical Formula 6]

[In the 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. Provided that when R ^s1 is a hydrocarbon group, R ^s1 is an alkyl group. * Indicates a combined hand.]

The number of carbon atoms of the hydrocarbon group represented by R ^s1 is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2. When all of R ^s1 are hydrocarbon groups, the total number of carbon atoms of three R ^s1 is preferably 9 or less, more preferably 6 or less, still more preferably 4 or less.

As the hydrocarbon group represented by R ^s1 , an aliphatic hydrocarbon group is preferable, and an alkyl group is more preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. The plurality of R ^{s1 s} may be the same or different and are preferably the same. At least one of the three R ^s1 is preferably a methyl group, more preferably at least two methyl groups, and most preferably all three R ^s1's are methyl groups.

The hydrogen atom contained in the trialkylsilyl group and the trialkylsilyloxy group represented by R ^s1 may be substituted with a fluorine atom. The substitution number of the fluorine atom is preferably 1 or more, more preferably 3 or more, and preferably 2 x A + 1 or less when the number of carbon atoms is A, When the hydrogen atoms contained in the alkyl group are substituted with fluorine atoms, the number of alkyl groups to be substituted may be appropriately selected from the range of from 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, * denotes a binding hand.

(7)

At least one of R ^s1 may be a trialkylsilyloxy group. Even in such a case, the trialkylsilyl group-containing molecular chain has a trialkylsilyl group. Examples of the trialkylsilyloxy group include groups in which an oxygen atom is bonded to a silicon atom of a group (trialkylsilyl group) in which all of R ^s1 is a hydrocarbon group (alkyl group).

As the group in which at least one of R ^s1 is a trialkylsilyloxy group, a group represented by the following formula can be mentioned.

[Chemical Formula 8]

In the trialkylsilyl group-containing molecular chain, it is preferable that the trialkylsilyl group is bonded to the terminal (free end side) of the molecular chain, particularly to the terminal (free end side) of the main chain (longest straight chain) of the molecular chain.

The molecular chain to which the trialkylsilyl group is bonded is preferably a straight chain or branched chain, and is preferably a straight chain. The molecular chain preferably includes a dialkylsiloxane chain, and preferably includes a straight chain dialkylsiloxane chain. The molecular chain may contain a divalent hydrocarbon group. Since the remaining part of the molecular chain has a divalent hydrocarbon group and the remaining part is a dialkylsiloxane chain, the resulting film has good chemical and physical durability. The molecular chain is preferably a group represented by formula (s2).

[Chemical Formula 9]

[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 - included in the divalent hydrocarbon group may be substituted with -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 substituted with -O-. The * on the left represents the bond with the central silicon atom, and the * on the right represents the bond with the 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. As the alkyl group represented by R ^s2 , a methyl group, an ethyl group, a propyl group, a butyl group and the like are exemplified, and 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 still more preferably 1 to 4. The bivalent hydrocarbon group is preferably a chain type, and when it is a chain type, it may be either a straight chain type or a branched chain type. The bivalent hydrocarbon group is preferably a divalent aliphatic hydrocarbon group, and is preferably an alkanediyl group. Examples of the divalent hydrocarbon group include a methylene group, an ethylene group, a propylene group and a butylene group.

In addition, some of -CH ₂ - included in the above-mentioned divalent hydrocarbon group may be substituted with -O-. In this case, two consecutive -CH ₂ - are not simultaneously substituted with -O-, and -CH ₂ - adjacent to the Si atom is not replaced with -O-. When two or more -CH ₂ - are substituted with -O-, the number of carbon atoms between -O- and -O- is preferably 2 to 4, more preferably 2 to 3. Specific examples of the group in which a part of the divalent hydrocarbon group is substituted with -O- include a group having a (poly) ethylene glycol unit and a group having a (poly) propylene glycol unit.

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

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

[Chemical formula 10]

(11)

[Chemical Formula 12]

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, preferably 1,200 or less, more preferably 700 or less , More preferably 250 or less.

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

[Chemical Formula 13]

[In formula (s1), R ^s1 , R ^s2 , Z ^s1 , Y ^s1 and n1 have the same meaning as above. * Represents the bonding bond with the silicon atom.]

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

[Chemical Formula 14]

Equation (s1-1) and (s1-1-1) of, R ^{s2, s1} Z, Y ^s1, n1 is the agreement with. R ^s3 represents an alkyl group having 1 to 4 carbon atoms. * Represents the bonding bond with the silicon atom.]

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

[Chemical Formula 15]

Equation (s1-2) and formula (s1-2-1) ^{of, R s2, R s3, Z} s1, Y s1, n1 is the agreement with. * Represents the bonding bond with the silicon atom.]

The alkyl group represented by R ^s3 includes the same groups as the alkyl group exemplified as the hydrocarbon group represented by R ^s1 , and the number of carbon atoms of the alkyl group is preferably 1 to 3, more preferably 1 to 2. The total number of carbon atoms of R ^s3 included in * -Si (R ^s3 ) ₃ is preferably 9 or less, more preferably 6 or less, further preferably 4 or less. At least one of R ^s3 included in * -Si (R ^s3 ) ₃ is preferably a methyl group, more preferably two or more R ^s3 is a methyl group, and particularly preferably all three R ^s3's are methyl groups .

Examples of the trialkylsilyl group-containing molecular chain include groups represented by the formula (s1-I).

[Chemical Formula 16]

[Table 1]

[Table 2]

In the organosilicon compound (A2), 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 imparts a hydroxy group (silanol group) by hydrolysis. For example, the hydrolyzable group may have 1 to 20 carbon atoms, such as methoxy group, ethoxy group, propoxy group, An alkoxy group of 4; A hydroxy group; An acetoxy group; Chlorine atom; Isocyanato group; And the like. Among them, 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 (A2), the number of hydrolyzable groups bonded to the central silicon atom is 1 to 3, preferably 2 to 3.

Hereinafter, the group in which the hydrolyzable group is bonded to the silicon atom is sometimes referred to as a hydrolyzable silicon group.

The siloxane skeleton-containing group may be a monovalent group containing a siloxane unit (Si-O-) and composed of a smaller number of elements than the number of atoms constituting the trialkylsilyl group-containing molecular chain. As a result, the siloxane skeleton-containing group is shorter in length than the trialkylsilyl group-containing molecular chain or has a three-dimensional spread (volume size). 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).

[Chemical Formula 17]

[In the formula (s2), R ^s2 is the same as the above. R ^s5 represents a hydrocarbon group or a hydroxy group, and -CH ₂ - included in the hydrocarbon group may be substituted with -O-, and the hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom. Z ^s2 represents -O- or a divalent hydrocarbon group, and -CH ₂ - included in the divalent hydrocarbon group may be substituted 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 - included in the divalent hydrocarbon group may be substituted with -O-. n2 represents an integer of 0 to 5; * Represents the bonding bond with the silicon atom.]

As the hydrocarbon group represented by R ^s5 , a group similar to the hydrocarbon group represented by R ^s1 is exemplified, and 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.

The divalent hydrocarbon group represented by Z ^s2 or L ^s2 includes the same group as the divalent hydrocarbon group represented by Z ^s1 , and the number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, still more preferably Is 1 to 4. The divalent hydrocarbon group represented by Z ^s2 or L ^s2 is preferably a divalent aliphatic hydrocarbon group, more preferably a straight chain or branched chain alkanediyl group.

n2 is preferably 1 to 5, more preferably 1 to 3.

The total number of atoms of the siloxane skeleton-containing group is preferably 100 or less, more preferably 50 or less, still more preferably 30 or less, and preferably 10 or more. The difference in the number of atoms of the trialkylsilyl group-containing molecular chain and the siloxane skeleton-containing group is preferably 10 or more, more preferably 20 or more, and preferably 1,000 or less, more preferably 500 or less, Is 200 or less.

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

[Chemical Formula 18]

The hydrocarbon chain-containing group may be a monovalent group containing a hydrocarbon chain, and may have a smaller number of carbon atoms in the hydrocarbon chain moiety than the number of atoms constituting the molecular chain of the trialkylsilyl group-containing molecular chain. It is also preferable that the number of carbon atoms in 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), -CH ₂ - contained in the hydrocarbon chain may be substituted with -O-, and is preferably composed of only a hydrocarbon group (hydrocarbon chain). However, -CH ₂ - adjacent to a silicon atom is not substituted with -O-, and two consecutive -CH ₂ - are not simultaneously replaced with -O-.

The carbon number of the hydrocarbon chain portion means the number of carbon atoms constituting the hydrocarbon group (hydrocarbon chain) in the oxygen-containing cyclic hydrocarbon chain-containing group, and -O- in the oxygen substitution type hydrocarbon chain- Quot; means the number of carbon atoms calculated by substituting -CH ₂ -. Hereinafter, one, for the group containing a hydrocarbon chain of an oxygen Beach cyclic (i. E. Monovalent hydrocarbon group) Examples described groups containing the hydrocarbon chain, however, in any explanation unless otherwise noted, the -CH ₂ - in some of the -O- It is possible to substitute.

The number of carbon atoms of the hydrocarbon chain-containing group is preferably 1 to 3, and more preferably 1. The hydrocarbon chain-containing group (in the case of a hydrocarbon group) may be branched or straight-chain. The hydrocarbon chain-containing group (in the case of a hydrocarbon group) is preferably a saturated or unsaturated aliphatic hydrocarbon chain-containing group, 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.

And a group having a (poly) ethylene glycol unit when -CH ₂ - contained in the hydrocarbon chain is substituted with -O-.

Among them, the organosilicon compound (A2) is preferably a compound represented by the following formula (I-1), more preferably a compound represented by the formula (I-1-1)

[Chemical Formula 19]

In the formulas (I-1) and (I-1-1), A ^a2 , Z ^a2 , Z ^s1 , Y ^s1 , R ^s2 , R ^s3 and n1 are as defined above.

The organosilicon compound (A2) may be a compound represented by the formula (I-2), preferably a compound represented by the formula (I-2-1).

[Chemical Formula 20]

In the formulas (I-2) and (I-2-1), A ^a2 , Z ^a2 , Z ^s1 , Y ^s1 , R ^s2 , R ^s3 and n1 are as defined above.

Specific examples of the organosilicon compound (A2) include groups represented by the formula (I-I).

[Chemical Formula 21]

[Table 3-1]

[Table 3-2]

[Table 4-1]

[Table 4-2]

Examples of the method for synthesizing the organosilicon compound (A2) include the following methods. As a first method, there can be prepared a compound obtained by reacting a compound in which a trialkylsilyl group-containing molecular chain is bonded with a halogen atom (preferably a chlorine atom) and a compound in which a hydrolyzable group is bonded to a silicon atom in three or more have.

As the second synthesis method, a dialkyl siloxane compound halogen atom bonded to both ends of the chain (referred to as "di-halogenated dialkyl siloxane"), a tris (trialkyl silyloxy) silyl group, M ¹ O- group (M ¹ is (Hereinafter referred to as " alkali metal silyloxide ") and a compound in which four hydrolyzable groups are bonded to a silicon atom. Although the order of the reaction of these compounds is not limited, it is preferable to first react a dihalogenated dialkylsiloxane and an alkali metal silyloxide, and then to react a compound having four silicon-bonded hydrolyzable groups.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable. As the alkali metal, lithium is preferable.

The alkali metal silyloxide can be produced, for example, by reacting a compound having a tris (trialkylsilyloxy) silyl group and a hydroxy group with an alkyl alkali metal. Examples of the organic alkali metal compound include alkyllithiums such as n-butyllithium, sec-butyllithium and tert-butyllithium, and particularly preferred is n-butyllithium.

As the third synthesis method, the organosilicon compound (A2) is reacted with, for example, an alkali metal silyloxide and a cyclic dimethylsiloxane, followed by reacting a silicon atom with three hydrolyzable groups and a halogen atom, Chlorine atoms) are combined with each other. The number of silicon atoms contained in the cyclic dimethylsiloxane is, for example, preferably 2 or more and 10 or less, more preferably 2 or more and 5 or less, still more preferably 2 or more and 4 or less.

Further, as the fourth synthesis method, the organosilicon compound (A2) can be produced by, for example, reacting alkali metal silyloxide and cyclic dimethylsiloxane, and reacting the resulting hydroxyl-terminated dimethyl siloxane compound with tetraalkoxysilane.

The metal compound (B) contained in the composition together with the organosilicon compound (A1) or (A2) is such that at least one hydrolyzable group is bonded to the central metal atom, and the second hydrocarbon chain- Or may be combined. The longest chain length of the second hydrocarbon chain-containing group is shorter than the longest chain length of the alkyl group having 6 to 20 carbon atoms and bonded to the central silicon atom of the organosilicon compound (A1) The length of the longest chain of the metal compound (B) is shorter than the length of the longest chain of the organosilicon compound, because it is shorter than the trialkylsilyl group-containing molecular chain bonded to the atom. Therefore, the structure derived from the metal compound (B) is not bulky than the structure derived from the organosilicon compound (A1) or (A2), and the metal compound (B) It is possible to form a portion having a function.

The central metal atom of the metal compound (B) may be a metal atom capable of forming a metal alkoxide by bonding with an alkoxy group, and the metal in this case also includes a semi-metal such as Si and Ge. Specific examples of the central metal atom of the metal compound (B) include trivalent metals such as Al, Fe and In; Ge, Hf, Si, Ti, Sn, and Zr; A pentavalent metal such as Ta; , And preferably a trivalent metal such as Al; Si, Ti, Zr, and Sn; more preferably Al, Si, Ti, Zr, and more preferably Si.

Examples of the hydrolyzable group of the metal compound (B) include the same hydrolyzable groups as the hydrolyzable groups of the organosilicon compound (A1) or (A2), preferably an alkoxy group having 1 to 4 carbon atoms and an alkoxy group having 1 to 2 carbon atoms desirable. The hydrolyzable groups of the organosilicon compound (A1) and the metal compound (B) may be the same or different. The hydrolyzable group of the organosilicon compound (A1) and the metal compound (B) is preferably an alkoxy group having 1 to 4 carbon atoms. In the metal compound (B), the number of hydrolyzable groups is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and 4 or less.

The second hydrocarbon chain-containing group of the metal compound (B) can be appropriately selected from the ranges described above, and the number thereof is preferably 1 or less, and particularly preferably 0.

Specifically, the metal compound (B) is preferably a compound represented by the following formula (BI).

[Chemical Formula 22]

[In the formula (BI), R ^b1 represents a second hydrocarbon chain-containing group or a hydrolyzable group. A ^b1 each independently represents a hydrolyzable group. M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr or Ta. and m represents an integer of 1 to 4, depending on the metal atom.

Equation (BⅠ) wherein the hydrolyzable group of R ^b1 second hydrocarbon chain-containing group, R ^{b1, b1} A of each claim may be properly selected from the range described above as a two-chain hydrocarbon-containing groups, hydrolyzable groups.

In the formula (BI), R ^b1 is preferably a hydrolyzable group. When R ^b1 is a hydrolyzable group, R ^b1 and A ^b1 may be the same or different and are preferably the same. The hydrolyzable groups of the organosilicon compound (A1) and the metal compound (B) may be the same or different.

In the formula (BI), M is preferably Al, Si, Ti, Zr or Sn, more preferably Al, Si, Ti or Zr, and more preferably Si. Alkoxides of these metal atoms are easily liquefied and it is easy to increase the uniformity of distribution of the structure (b) in the coating film that can function as a spacer. In the formula (BI), m represents 2 when M is a trivalent metal such as Al, Fe or In, and M represents a tetravalent metal such as Ge, Hf, Si, Ti, 3, and when M is a pentavalent metal such as Ta, it indicates 4.

As the metal compound (B), a compound having only a hydrolyzable group; A compound having one second hydrocarbon chain-containing group and two hydrolysable groups; And the like.

Examples of the compound having only a hydrolyzable group include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane; Trialkoxy aluminum such as triethoxy aluminum, tripropoxy aluminum and tributoxy aluminum; Trialkoxy iron such as triethoxy iron; Trialkoxy indiums such as trimethoxy indium, triethoxy indium, tripropoxy indium and tributoxy indium; Tetraalkoxy germanium such as tetramethoxy germanium, tetraethoxy germanium, tetrapropoxy germanium and tetrabutoxy germanium; Tetraalkoxy hafnium such as tetramethoxy hafnium, tetraethoxy hafnium, tetrapropoxy hafnium and tetrabutoxy hafnium; Tetraalkoxytitaniums such as tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium and tetrabutoxytitanium; Tetraalkoxy tin such as tetramethoxy tin, tetraethoxy tin, tetrapropoxy tin and tetrabutoxy tin; Tetraalkoxyzirconium such as tetramethoxyzirconium, tetraethoxyzirconium, tetrapropoxyzirconium and tetrabutoxyzirconium; Pentaalkoxy tantalum such as pentamethoxy tantalum, pentaethoxy tantalum, pentapropoxytantal, and pentabutoxytantal; And the like.

Examples of the compound having a second hydrocarbon chain-containing group and a hydrolyzable group include alkyltrialkoxysilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane and methyltripropoxysilane; Alkenyltrialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; And the like.

In a preferred embodiment of the composition of the present invention, since the organosilicon compound (A1) or (A2) and the metal compound (B) are contained in a specific ratio, it is possible to improve the water- And the like. Specifically, in the composition of the present invention, the molar ratio (metal compound (B) / organic silicon compound (A1) or (A2)) of the metal compound (B) and the organosilicon compound (A1) More preferably 2 or more (more preferably 15 or more), preferably 48 or less, more preferably 44 or less, still more preferably 40 or less, particularly preferably 36 or less.

The composition of the present invention further contains a high boiling point solvent (C) in addition to the above-mentioned organosilicon compound (A1) or (A2) and the metal compound (B). (A) or (A2) and the metal compound (B) are spread evenly on the substrate without unevenness, because the high boiling point solvent (C) remains on the substrate without volatilizing when the composition is applied by hand coating It is possible to realize a coating film having good water and oil repellency, wear resistance, and good surface properties.

In the present invention, the high boiling point solvent (C) means that the vapor pressure at 20 캜 is at most 1000 Pa and the boiling point is at least 120 캜. In the present invention, since a low boiling point solvent (D) is used in combination with the high boiling point solvent (C), a high boiling point solvent (C) having a solubility parameter in a predetermined range is selected in consideration of compatibility with the low boiling point solvent (D) . In this specification, the solubility parameter (SP value) is a value calculated by the method described in RFFedors, Polym. Eng. Sci., 14 [2], 147-154 (1974). In the present invention, an SP value [(cal / cm ³ ) ^1/2 ] of at least 8.0 is used as the high boiling point solvent (C). The SP value [(cal / cm ³ ) ^1/2 ] of the high boiling point solvent (C) is preferably 13.0 or less. As a solvent satisfying such requirements, 1-butanol or ethylene glycol monohexyl ether may be mentioned.

The vapor pressure of the high boiling point solvent (C) at 20 캜 is preferably 800 Pa or lower, more preferably 600 Pa or lower, and the lower limit is not particularly limited, but is, for example, 5 Pa. The boiling point of the high boiling point solvent (C) is preferably 150 占 폚 or higher, more preferably 170 占 폚 or higher, and the upper limit is not particularly limited, but is, for example, 300 占 폚.

The composition of the present invention further comprises a low boiling point solvent (D) in addition to the organosilicon compound (A), the metal compound (B) and the high boiling point solvent (C). The low-boiling point means that the vapor pressure at 20 占 폚 is more than 1000 Pa and the boiling point is less than 120 占 폚.

Examples of such a low-boiling solvent (D) include alcohol solvents, ketone solvents, ether solvents and alicyclic hydrocarbon solvents. Alcohol solvents, ketone solvents and ether solvents are particularly preferred. Examples of the alcoholic solvent include methanol, ethanol, 1-propanol, isopropyl alcohol, 2,2,2-trifluoroethanol, 2-butanol, isobutyl alcohol and the like. Examples of the ketone solvent include acetone, ethyl methyl ketone, and the like. Examples of the ether solvent include diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether and the like. The alicyclic hydrocarbon-based solvent includes hexane.

The vapor pressure of the low boiling point solvent (D) at 20 캜 is preferably not less than 2000 Pa, more preferably not less than 3000 Pa, and the upper limit is not particularly limited, but is, for example, 13000 Pa. The boiling point of the high boiling point solvent (D) is preferably 100 占 폚 or lower, more preferably 85 占 폚 or lower.

Each of the high boiling point solvent (C) and the low boiling point solvent (D) may be used singly or two or more kinds of solvents may be used in combination. In order to prepare the composition of the present invention, the organosilicon compound (A) and the metal compound (B) are added to a mixed solution obtained by previously mixing a part of the low boiling point solvent (D) with the high boiling point solvent (C) (For example, stirring at room temperature for about 10 to 30 minutes), preferably by further adding a catalyst (E), stirring the solution for 10 to 30 hours or the like, and then adding the solution to the remaining low boiling point solvent D). The dilution magnification in the low boiling point solvent (D) is preferably about 5 to 40 times. Of course, the composition of the present invention may or may not contain a solvent other than the high boiling solvent (C) and the low boiling solvent (D) (hereinafter, may be referred to as other solvent).

The organosilicon compound (A) (hereinafter sometimes referred to as the organosilicon compound (A) in combination with the organosilicon compounds (A1) and (A2)) is used in an amount of 0.01 to 0.15 mass% , And more preferably 0.03 to 0.13 mass%. The metal compound (B) is preferably 0.1 to 1.2% by mass, more preferably 0.15 to 1.0% by mass with respect to the low boiling point solvent (D). The high boiling point solvent (C) is preferably used in an amount of 0.05 to 1.8% by mass, more preferably 0.1 to 1.8% by mass, and 1.5% by mass or less and 1.2% by mass or less based on the low boiling point solvent (D) .

The organosilicon compound (A) is preferably contained in an amount of 0.03 to 0.15 mass% relative to 100 mass% of the total of the high boiling point solvent (C), the low boiling point solvent (D) 0.035 to 0.12 mass%. The amount of the metal compound (B) is preferably from 0.1 to 1.5% by mass, more preferably from 0.1 to 1.5% by mass based on the total 100% by mass of the high boiling point solvent (C), the low boiling point solvent (D) Is from 0.15 to 1.2% by mass. The total ratio of the organosilicon compound (A) and the metal compound (B) to the total 100 mass% of the high boiling point solvent (C), the low boiling point solvent (D) ) / (C + D + E)), preferably 0.13 to 1.65 mass%, more preferably 0.185 to 1.32 mass%, further preferably 0.2 to 1.1 mass%.

Further, the composition of the present invention may optionally contain the catalyst (E). The catalyst (E) may be an acid catalyst such as hydrochloric acid, formic acid or acetic acid, which is generally used in the sol-gel process; Base catalyst; Organic metal catalysts and the like.

The acid catalyst (especially preferably hydrochloric acid) is preferably at least 1 time, more preferably at least 1.3 times, and at most 8 times the mass ratio of the organosilicon compound (A) and the metal compound (B) More preferably not more than 7 times, and more preferably not more than 6.5 times.

When the organosilicon compound (A) and the metal compound (B) are brought into contact with the base material, any of the other solvents (either the high boiling solvent (C) or the low boiling solvent (D) Various additives such as antioxidants, rust inhibitors, ultraviolet absorbers, light stabilizers, antifungal agents, antimicrobial agents, antifouling agents, deodorants, pigments, flame retardants and antistatic agents may be coexistent .

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

Examples of the phenolic antioxidant include n-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 2,6- (3-t-butyl-4-hydroxyphenyl) propionate], tri-ethylene glycol-bis- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} - Tetraoxaspiro [5.5] undecane, tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionic acid} 2- [1- (2-hydroxy-3-hydroxy-5-methylbenzyl) Di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 1,3,5-trimethyl-2,4,6-tris (3,5- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-t- -2,6- Dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -thione, 2,2'-methylenebis (6-t- 4,4'-butylidenebis (6-t-butyl-3-methylphenol), and 4,4'-thiobis (6-t-butyl-3-methylphenol).

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

Examples of the phosphorus antioxidant include bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4- Butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-di-cumylphenyl) pentaerythritol diphosphite, tetrakis (2,4- 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 占 폚), poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine- (2,2,6,6-tetramethyl-4-piperidyl) imino} -1,6-hexamethylene {(2,2,6,6-tetramethyl- ] And the like.

Examples of the rust inhibitor include alkanolamines such as triethanolamine; Quaternary ammonium salts; Alkanethiol; Imazoles such as imidazoline, imidazole, alkylimidazoline derivatives, benzimidazole, 2-mercaptobenzimidazole and benzotriazole; Sodium metavanadate; Bismuth citrate; Phenol derivatives; Amine compounds such as aliphatic amines such as alkylamines and polyalkenylamines, aromatic amines, aliphatic diamines such as ethoxylated amines, cyanoalkylamines, cyclohexylamine benzoate, alkylenediamines, and aromatic diamines; An amide of the amine compound and a carboxylic acid; Alkyl esters; Pyrimidine; Naphthenic acid; Sulfonic acid complex; Nitrites such as calcium nitrite, sodium nitrite, and dicyclohexylamine nitrite; Polyol compounds such as polyalcohol and polyphenol; Heteropolyacid salts such as sodium molybdate, sodium tungstate, sodium phosphonate, sodium chromate and sodium silicate; gelatin; Polymers of carboxylic acid; Nitro compounds; Formaldehyde; Acetylene alcohol; Thiol compounds such as aliphatic thiols, aromatic thiols, and acetylenethiols; Sulfide compounds such as aliphatic sulfide, aromatic sulfide, and acetylene sulfide; Sulfoxide compounds such as sulfoxide and dibenzyl sulfoxide; Thiourea; Amine or a combination of a quaternary ammonium salt and a halogen ion; A combination of alkylamine and potassium iodide; A combination of tannin and sodium phosphate; A combination of triethanolamine and lauryl sarcosine; A combination of triethanolamine and lauryl sarcosine and benzotriazole; Combinations of alkylamines, benzotriazoles, sodium nitrite, and sodium phosphate; And the like.

Examples of the ultraviolet absorber / light stabilizer include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy- Phenyl-2H-benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) (Molecular weight of about 300) and methyl 3- [3-t-butyl-5- (2H-benzotriazole- Hydroxyphenyl benzotriazole derivatives, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5 [(hexyl) oxy] -phenol, 2- -2'-ethyl-oxalic acid bisanilide.

Examples of the antibacterial / antifungal agent include 2- (4-thiazolyl) benzimidazole, sorbic acid, 1,2-benzisothiazolin-3on, sodium (2-pyridylthio- Methyl-5-chloro-4-isothiazolone complex, 2,4,5,6-tetrachlorophthalonitrile, methyl 2-benzimidazolecarbamate, 1- (butylcarbamoyl) -2- Methylbenzimidazolecarbamate, mono- or dibromo-cyanoacetamides, 1,2-dibromo-2,4-dicyanobutane, 1,1-dibromo-1-nitropropanol and 1,1- -Dibromo-1-nitro-2-acetoxypropane, and the like.

Examples of the bioadhesive agent include tetramethylthiuram disulfide, zinc bis (N, N-dimethyldithiocarbamate), 3- (3,4-dichlorophenyl) -1,1-dimethylurea, dichloro- ((Dimethylamino) sulfonyl) fluoro-N- (P-tolyl) methane sulfenamide, pyridine-triphenylborane and N, N-dimethyl- Mead, cuprous thiocyanate (1), cuprous oxide, tetrabutyl thiuram disulfide, 2,4,5,6-tetrachloroisophthalonitrile, zinc ethylene bisdithiocarbamate, 2,3,5 , Bis (2-pyridinethiol-1-oxide) zinc salt, bis (2-pyridine) Thio-1-oxide) copper salt, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 4,5- 3-one, furan compounds, alkylpyridine compounds, gramein compounds, isonite There may be mentioned compounds.

Examples of the deodorant 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, Organic acids such as dicarboxylic acid, cycloalkene-1,2-dicarboxylic acid and naphthalenesulfonic acid; Fatty acid metal such as zinc undecylenearate, zinc 2-ethylhexanoate and zinc ricinoleate; Metal (iron, copper, cobalt, etc.) phthalocyanine, metal (iron, copper, cobalt, etc.) phthalocyanine, metal (iron, copper, cobalt, etc.), zinc oxide, Metal compounds such as tetrasulfonic acid phthalocyanine, titanium dioxide, and visible light-responsive titanium dioxide (nitrogen doped type); cyclodextrins such as? -,? -, or? -cyclodextrin, methyl derivatives thereof, hydroxypropyl derivatives, glucosyl derivatives, and maltosyl derivatives; Aromatic polymer such as polyacrylic acid polymer such as polyacrylic acid polymer, porous methacrylic acid polymer and porous acrylic acid polymer, porous divinylbenzene polymer, porous styrene-divinylbenzene-vinylpyridine polymer and porous divinylbenzene-vinylpyridine polymer, Chitin, chitosan, activated carbon, silica gel, activated alumina, zeolite, ceramics and the like.

Examples of the pigments include carbon black, titanium oxide, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, perylene or perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, Disazo condensate pigments, benzimidazolone pigments, and the like.

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

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, tertiary amine salts, Cationic surfactants such as quaternary amine salts and pyridine derivatives, sulfated oils, soaps, sulfated ester oils, sulfated amide oils, sulfated ester salts of olefins, fatty alcohol sulfuric acid ester salts, alkyl sulfuric acid ester salts, fatty acid ethylsulfonic acid Anionic surfactants such as salts of alkylnaphthalenesulfonic acid salts, alkylbenzenesulfonic acid salts, succinic acid ester sulfonic acid salts and phosphoric acid ester salts, partial fatty acid esters of polyhydric alcohols, ethylene oxide adducts of fatty alcohols, ethylene oxide adducts of fatty acids, fatty Ethylene oxide adducts of amino or fatty acid amides, ethylene oxide adducts of alkylphenols, Ethylene oxide adducts of defense ester, and the like ampholytic surfactants, such as water or polyethylene glycol, and the like of nonionic surfactant, carboxylic acid derivatives and imidazoline derivatives.

Further, lubricants, fillers, plasticizers, nucleating agents, anti-blocking agents, foaming agents, emulsifiers, brighteners, binders and the like may be coexisted as additives.

When such an additive is included, the content of the additive in the composition containing the organosilicon compound (A) and the metal compound (B) is usually from 0.1 to 70 mass%, preferably from 0.1 to 50 mass% By mass to 0.5% by mass, and more preferably 2% by mass to 15% by mass.

The total content of the organosilicon compound (A) and the metal compound (B) is preferably 0.1 to 1.5% by mass relative to 100% by mass of the total of the high boiling point solvent (C), the low boiling point solvent (D) , More preferably 0.15 to 1.2 mass%.

In addition, the composition of the present invention comprises an organosilicon compound (A1) having one alkyl group having 7 or more carbon atoms and 9 or less (particularly 8) and three hydrolyzable groups bonded to silicon atoms, and four hydrolyzable groups (B) a metal compound (B) bonded to an atom (in particular, a silicon atom) and the high boiling point solvent (C) and a low boiling point solvent (D) It is particularly preferable that the metal compound (B) / the organosilicon compound (A)) is 5 or more (more preferably 15 or more) and 36 or less. By adjusting the structure or the molar ratio of the organosilicon compound (A) and the metal compound (B) in this way, the hardness of the obtained coating film is more highly compatible with the water repellency and oil repellency.

The composition of the present invention can be brought into contact with the substrate by a hand coating without stain, and the hydrolyzable group of the organosilicon compound (A) and the metal compound (B) is hydrolyzed and polycondensed to form a film on the surface of the substrate. In carrying out the evaluation of the hand coating in the present invention, the following method is employed to reproduce a state close to actual use. First, two pseudo-fingers (Mono One Dust Catch manufactured by TOMBO Co., Ltd.) were placed on a 벰 coat, mounted on a steel wool tester (manufactured by Dai-ichi Kogyo), and 1 mL of the coating solution 1 was impregnated on the 벰 coat. Subsequently, only a forward route was applied to the substrate under the conditions of a stroke of 50 mm and a speed of 60 r / min while applying a load of 1 kg, and the glass substrate was shifted without any time, and only the core was coated again so as to form an overlapping portion. By performing the application in this manner, the hand coating was quantitatively reproduced.

Further, when the composition and the substrate are kept in contact with each other in air (for example, about 10 to 48 hours), moisture in the air is absorbed and the hydrolysis and polycondensation of the hydrolyzable group is promoted desirable. Further, the obtained coating film may be dried. The temperature for warm-drying is usually 40 to 250 占 폚, preferably 60 to 200 占 폚, and more preferably 60 to 150 占 폚.

Coatings obtained when the organosilicon compound (A1) is used and when the organosilicon compound (A2) is used are described below, respectively.

(2-1) Coating in the case of using the organosilicon compound (A1)

The film thus obtained has a mesh-like skeleton in which a silicon atom or the above metal atom (preferably silicon atom only) is bonded via an oxygen atom and is derived from the organosilicon compound (A1) And a structure in which a first hydrocarbon chain-containing group is bonded to a silicon atom of a part of silicon atoms to be formed.

The structure in which the alkyl group having 6 to 20 carbon atoms is bonded to a silicon atom is preferably a structure (a1) represented by the following formula (1).

(23)

R ^a3 represents an alkyl group having 6 to 20 carbon atoms, Z ^a3 represents a hydrocarbon chain-containing group or -O- group, and when Z ^a3 is a hydrocarbon chain-containing group, R ^a3 and Z ^a3 are And R ^a3 and Z ^a3 may be the same or different in the plurality of formulas (1).]

In the formula (1), the hydrocarbon chain-containing group of Z ^a3 can be appropriately selected from the range of the above-mentioned first hydrocarbon chain-containing group (including an alkyl group having 6 to 20 carbon atoms) and the first hydrocarbon chain-containing group .

Among them, Z ^a3 is preferably a second hydrocarbon chain-containing group or -O- group, and particularly preferably -O- group.

As the structure (a1), for example, a structure represented by the following formulas (1-1) to (1-32) can be preferably exemplified.

≪ EMI ID =

(25)

(26)

In the coating film obtained by using the composition of the present invention, it is preferable that the coating film derived from the metal compound (B) has a silicon atom (second silicon atom) different from the silicon atom to which the alkyl group having 6 to 20 carbon atoms is bonded, Containing group, a hydroxy group, an alkoxy group, or a group condensed with a hydroxy group may be bonded. The second silicon atom may be substituted with another metal atom (for example, Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr or Ta). Such a second silicon atom or other metal atom also functions as a spacer because the second hydrocarbon chain-containing group, the hydroxyl group, the alkoxy group or the hydroxyl group having a shorter chain length is bonded to the alkyl group having the carbon number of 6 to 20, It is possible to enhance the water-repellent / oil-repellent property improving action by the alkyl group having 6 to 20 carbon atoms.

The alkoxy group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms. For example, a butoxy group, a propoxy group, an ethoxy group and a methoxy group.

Further, the hydroxy group condenses with other hydroxy group, alkoxy group or the like to form -O-, but a group condensed with such a hydroxy group may be bonded to the metal atom.

As the structure in which the second hydrocarbon chain-containing group or the hydroxy group is bonded to the second silicon atom or another metal atom, the structure (b) represented by the following formula (2) is preferable.

(27)

[In the formula (2), R ^b2 represents a second hydrocarbon chain-containing group or a hydroxy group, and A ^b2 represents a hydroxy group or -O-. M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr or Ta. and n represents an integer of 0 to 3 according to M.]

In the formula (2), the second hydrocarbon chain-containing group of R ^b2 can be appropriately selected from the ranges described above. R ^b2 is preferably a hydroxy group.

In the formula (2), M is a trivalent metal such as Al; A tetravalent metal such as Si, Ti, Sn, or Zr is preferable, and Al, Si, Ti, and Zr are more preferable, and Si is particularly preferable. In the formula (2), n represents 1 when M is a trivalent metal such as Al, Fe or In, and M represents a tetravalent metal such as Ge, Hf, Si, Ti, 2, and when M is a pentavalent metal such as Ta, it indicates 3.

As the structure (b), when M is Si, for example, a structure represented by the following formulas (2-1) to (2-11) can be preferably exemplified.

(28)

[Chemical Formula 29]

In the obtained film, the abundance ratio (structure (a) / structure (b)) of structure (a) and structure (b) is preferably 0.01 or more, more preferably 0.02 or more, and still more preferably 0.03 , More preferably not more than 0.2, even more preferably not more than 0.1, still more preferably not more than 0.09.

(2-2) Coating in the case of using the organosilicon compound (A2)

The structure (a2) derived from the organosilicon compound (A2) is represented by the formula (3).

(30)

[In the formula (3), R ^a4 represents a trialkylsilyl group-containing molecular chain and Z ^a4 represents a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, a hydrocarbon chain-

In the formula (3), the trialkylsilyl group-containing molecular chain of R ^a4 , Z ^a4 , the siloxane skeleton-containing group of Z ^a4 , and the hydrocarbon chain-containing group may be each a trialkylsilyl group-containing molecular chain, a siloxane skeleton- Containing group can be appropriately selected from the range described above.

Among them, in the formula (3), Z ^a4 is preferably a siloxane skeleton-containing group or -O-, more preferably -O-.

The structure (a2) includes a structure represented by the formula (3-1).

(31)

[Table 5]

[Table 6]

The structure (b) derived from the metal compound (B) is the same as that in the case of using the organosilicon compound (A1).

The coating film obtained by using the composition of the present invention usually has a thickness of about 3 to 50 nm.

The coating film obtained by using the composition of the present invention has a silicon atom or a network skeleton in which the metal atom (preferably silicon atom only) is bonded through an oxygen atom, and the silicon atom Since the silicon atom has a structure in which an alkyl group having 6 to 20 carbon atoms is bonded to a part of silicon atoms, the sliding property of the droplet, and further, the water repellency and oil repellency are excellent. The water repellency can be evaluated by, for example, a water contact angle of 3 mu L with a liquid amount obtained by the &thetas; / 2 method. The contact angle is, for example, 97 DEG or more, more preferably 100 DEG or more, And the upper limit is not particularly limited, but is, for example, 110 °. The sliding property of the droplet can be evaluated, for example, by a sliding angle (sliding angle) of the droplet adhered on the substrate or contact angle hysteresis. Concretely, the numerical value of the numerical aperture of 6 μL is preferably 23 ° or less, more preferably 21 ° or less, further preferably 20 ° or less, and the lower limit is, for example, 5 °. The contact angle hysteresis is preferably 8.0 DEG or less, more preferably 7 DEG or less, still more preferably 6 DEG or less, and the lower limit is 1.0 DEG, for example.

A coating film can be formed by coating the composition of the present invention on a substrate, and the shape of the substrate may be either flat or curved. The substrate may be composed of an organic material or an inorganic material. Examples of the organic material include an acrylic resin, a polycarbonate resin, a polyester resin, a styrene resin, an acryl-styrene copolymer resin, a cellulose resin and a polyolefin resin Thermoplastic resin; Thermosetting resins such as phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester, silicone resin and urethane resin; And examples of the inorganic material include ceramics; Glass; Metals such as iron, silicon, copper, zinc and aluminum; An alloy comprising the metal; And the like.

The base material may be previously subjected to adhesion (easy adhesion) treatment. Examples of the adhesion treatment include a hydrophilic treatment such as a corona treatment, a plasma treatment, and an ultraviolet ray treatment. In addition, a primer treatment with a resin, a silane coupling agent, tetraalkoxysilane or the like may be used.

According to the composition of the present invention, it is possible to provide a coating film that combines water repellency and oil repellency with abrasion resistance by hand coating, and can be suitably used for windowpanes of various vehicles and buildings.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples. However, it is needless to say that the present invention is not limited by the following examples, but the present invention is not limited to the following examples. Of course, all of which are within the technical scope of the present invention.

The measurement method used in the embodiment of the present invention is as follows.

(1) Measurement of static contact angle

Using a contact angle measuring apparatus (DM700 manufactured by Kyoei Interface Science Co., Ltd.), the contact angle of water on the surface of the coating film was measured by the? / 2 method at a liquid amount of 3 占 L.

(2) Measurement of dynamic contact angle (sliding angle and contact angle hysteresis)

Using the DM700 manufactured by Kyowa Interface Science Co., Ltd., the sliding method (analysis method: tangential method, water amount: 6.0 μL, inclination method: continuous inclination, slip detection: after slip, moving determination: forward angle, , Dynamic water repellency (contact angle hysteresis, sliding angle) of the coating surface was measured.

(3) Evaluation of sliding performance

A numerical value of 3 mu L was applied to the surface of the film, and the sliding state of the number when tilted from the horizontal direction by 90 degrees was evaluated as a sensory evaluation of the sliding speed as follows.

◎: The water droplet swelled very quickly.

○: Numbers were smooth

△: Numbers slowly slowed down

X: Numbers did not move

(4) Visual evaluation of the coating surface

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

◎: No pollution at all

○: If you look closely, you can check the contamination

?: Partial contamination of the membrane can be confirmed

X: Whole contamination of the membrane can be confirmed

(5) Haze evaluation

The haze (haze) of the surface was measured using a haze meter HZ-2 (Suga tester) in a D65 light source (average daylight) to evaluate the hand coating property.

(6) Evaluation of abrasion resistance

(5), the haze was 0.50 or less, and the wear resistance was evaluated. A steel wool tester (manufactured by Dai-ichi Kikai) equipped with an eraser-attached HB pencil (Mitsubishi Pencil Co., Ltd.) was used. The abrasion test was carried out under a load of 500 g while the eraser was in contact with the surface of the film, and the test was repeated until the naked eye peeled off or the scratch was confirmed or the contact angle of water decreased by 15 degrees or more from the contact angle before the test.

Example 1-1

2.2 × 10 ^-4 mol of triethoxy-n-octylsilane (octyltriethoxysilane) as the organosilicon compound (A1) and 3.5 × 10 ^-3 mol of tetraethyl orthosilicate (tetraethoxysilane) as the metal compound (B) mol was dissolved in a mixed solution of 0.95 ml of isopropyl alcohol and 0.95 ml of 1-butanol, and the mixture was stirred at room temperature for 20 minutes. 1.0 ml of hydrochloric acid (0.01 mol / L aqueous solution) as a catalyst was added dropwise to the obtained solution, and the mixture was stirred for 24 hours to prepare a sample solution. The sample solution was diluted 30 times with isopropyl alcohol to prepare a coating solution 1-1.

The coating solution 1 was coated on a glass substrate (5 cm x 5 cm, EAGLE XG, manufactured by Corning) coated with alkaline cleaned by impregnating the coating solution 1 on a 벰 coat (Wiper, registered trademark, manufactured by Asahi Chemical Industry Co., Ltd.) and left standing at room temperature for 1 day. The coating was carried out by the following method. Two pseudo-fingers (Mono One Dust Catch manufactured by TOMBO Co., Ltd.) were placed on the top of the coat, mounted on a steel wool tester (manufactured by Dai-Hei Kasei KK), and 1 mL of the coating solution 1 was impregnated on the coat. Subsequently, while applying a load of 1 kg, only the core was coated on the substrate under the conditions of a stroke of 50 mm and a speed of 60 r / min, and the core was shifted without any time, thereby applying the core only to the core. By performing the application in this manner, the hand coating can be quantitatively reproduced. This coating method is sometimes referred to as a hand coating.

Initial static and dynamic contact angles, abrasion resistance, and haze were evaluated for the resulting coatings. As the sensory evaluation, numerical sliding property and visual observation of the film surface were carried out.

Examples 1-2

The coating solution 1-2 was prepared in the same manner as in Example 1-1 except that the ratio of 1-butanol in the coating solution was changed to the value described in Table 7-1, and a film was formed in the same manner as in Example 1-1 And evaluated.

Example 1-3

Coating solution 1-3 was prepared in the same manner as in Example 1-1 except that the ratio of 1-butanol in the coating solution was changed to the value described in Table 7-1, and a film was formed in the same manner as in Example 1-1 And evaluated.

Example 2-1

2.2 × 10 ^-4 mol of triethoxy-n-octylsilane (octyltriethoxysilane) as the organosilicon compound (A1) and 3.5 × 10 ^-3 mol of tetraethyl orthosilicate (tetraethoxysilane) as the metal compound (B) mol were dissolved in a mixed solution of 1.8 ml of isopropyl alcohol and 0.095 ml of ethylene glycol monohexyl ether, and the mixture was stirred at room temperature for 20 minutes. 1.0 ml of hydrochloric acid (0.01 mol / L aqueous solution) as the catalyst (E) was added dropwise to the obtained solution, followed by stirring for 24 hours to prepare a sample solution. The sample solution was diluted 30-fold with isopropyl alcohol to prepare a coating solution 2-1. A coating film was formed and evaluated in the same manner as in Example 1-1 except for the above.

Example 2-2

A coating solution 2-2 was prepared in the same manner as in Example 2-1 except that the ratio of ethylene glycol monohexyl ether in the coating solution was changed to the value described in Table 7-1, And evaluated.

Example 3-1

1.8 × 10 ^-4 mol of triethoxy-n-decylsilane (decyltriethoxysilane) as the organosilicon compound (A1) and 3.7 × 10 ^-3 mol of tetraethyl orthosilicate (tetraethoxysilane) as the metal compound (B) mol were dissolved in a mixed solution of 1.0 ml of isopropyl alcohol and 1.0 ml of 1-butanol, and the mixture was stirred at room temperature for 20 minutes. 1.1 ml of hydrochloric acid (0.01 mol / L aqueous solution) as a catalyst was added dropwise to the obtained solution, which was then stirred for 24 hours to prepare a sample solution. The sample solution was diluted 30-fold with isopropyl alcohol to prepare a coating solution 3-1. A coating film was formed and evaluated in the same manner as in Example 1-1 except for the above.

Example 3-2

Except that triethoxy-n-dodecylsilane (dodecyltriethoxysilane) was used instead of triethoxy-n-decylsilane (decyltriethoxysilane) as the organosilicon compound (A1) A coating solution 3-2 was prepared in the same manner as above, and a film was formed and evaluated in the same manner as in Example 1-1.

Example 3-3

The procedure of Example 3-2 was repeated except that the sample solution was diluted 50 times with isopropyl alcohol to prepare a coating solution 3-3.

Example 4

1.2 × 10 ^-3 mol of triethoxy-n-octylsilane (octyltriethoxysilane) as the organosilicon compound (A1), 6.0 × 10 ^-3 mol of the silicate 40 as the metal compound (B), 1.5 mol of isopropyl alcohol ml and 5.1 ml of 1-butanol, and the mixture was stirred at room temperature for 20 minutes. To the obtained solution, 5.4 ml of hydrochloric acid (0.01 mol / L aqueous solution) as a catalyst was added dropwise, and the mixture was stirred for 24 hours to prepare a sample solution. The sample solution was diluted 30-fold with isopropyl alcohol to prepare a coating solution 4. Thereafter, a film was formed and evaluated in the same manner as in Example 1-1.

Example 5

2.2 × 10 ^-4 mol of triethoxy-n-octylsilane (octyltriethoxysilane) as the organosilicon compound (A1) and 3.5 × 10 ^-3 mol of tetraethyl orthosilicate as the metal compound (B) were dissolved in isopropyl alcohol And 0.95 ml of 1-butanol, and the mixture was stirred at room temperature for 20 minutes. A film was formed and evaluated in the same manner as in Example 1-1, except that 2.1 mL of formic acid (1 mol / L aqueous solution) was used instead of 1.0 mL of hydrochloric acid as the catalyst (E).

Example 6

<Synthesis Example of Alkoxysilane Compound>

Into a three-necked flask, 4.69 g of tris (trimethylsiloxy) silanol and 21.0 g of THF were placed and stirred. The solution was cooled to -40 DEG C, and 9.38 mL of n-BuLi hexane solution (1.6 mol / L) was added dropwise. 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 캜, THF (tetrahydrofuran), ion-exchanged water and hexane were added in order to the reaction solution, and the organic layer was separated. Washed with ion-exchanged water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain colorless transparent intermediate (1).

9.47 g of the intermediate (1), 8.97 g of tetramethyl orthosilicate, and 151.2 μL of t-butylamine were placed and reacted at 30 ° C for 5 hours with stirring. The mixture was concentrated under reduced pressure at 12 hPa and 140 deg. C to obtain the following alkoxysilane compound.

(32)

In the alkoxysilane compound, the average number of repetitions n calculated from the NMR spectrum is 9.

1.4 x 10 ^-4 mol of the alkoxysilane compound represented by the above formula and 1.4 x 10 ^-3 mol of tetraethyl orthosilicate serving as the metal compound (B) were added as the organosilicon compound (A2), 6.7 ml of isopropyl alcohol and 1 ml of 1- Butanol (2.0 ml), and the mixture was stirred at room temperature for 20 minutes. A coating film was prepared and evaluated in the same manner as in Example 1-1 except that 2.8 mL of hydrochloric acid (0.01 mol / L aqueous solution) as the catalyst (E) was added dropwise to the obtained solution, followed by stirring for 24 hours.

Comparative Example 1

3.59 g of methyltriethoxysilane instead of the organosilicon compound (A) and 10.92 g of tetraethylorthosilicate (tetraethoxysilane) as the metal compound (B) were dissolved in 5.03 g of ethylene glycol monobutyl ether, Min. To the obtained solution, 10.46 g of acetic acid (0.5 mol / L aqueous solution) as a catalyst was added dropwise, and the mixture was stirred for 24 hours to prepare a coating solution a. Using this coating solution a, a glass substrate was coated with a hand coating in the same manner as in Example 1-1, and the coating was allowed to stand at room temperature for one day, and a film was formed and evaluated.

Comparative Example 2

2.8 g of triethoxy-n-octylsilane (octyltriethoxysilane) as the organosilicon compound (A) and 4.6 g of tetramethyl orthosilicate (tetramethoxysilane) as the metal compound (B) were dissolved in 1.7 g of ethanol And the mixture was stirred at room temperature for 20 minutes. To the obtained solution, 0.28 g of hydrochloric acid (0.01 mol / L aqueous solution) as a catalyst was added dropwise and stirred for 24 hours to prepare a coating solution b. Using this coating solution b, a glass substrate was coated with a hand coating in the same manner as in Example 1-1, and the coating was allowed to stand at room temperature for 1 day, and a film was formed and evaluated.

Comparative Example 3-1

2.2 × 10 ^-4 mol of triethoxy-n-octylsilane (octyltriethoxysilane) as the organosilicon compound (A) and 3.5 × 10 ^-3 mol of tetraethyl orthosilicate (tetraethoxysilane) as the metal compound (B) mol was dissolved in a mixed solution of 1.9 ml of 1-butanol, and the mixture was stirred at room temperature for 20 minutes. To the obtained solution, 1.0 ml of hydrochloric acid (0.01 mol / L aqueous solution) as a catalyst was added dropwise, followed by stirring for 24 hours. A coating film was formed and evaluated in the same manner as in Example 1-1 except for the above.

Comparative Example 3-2

2.2 × 10 ^-4 mol of triethoxy-n-octylsilane (octyltriethoxysilane) as the organosilicon compound (A) and 3.5 × 10 ^-3 mol of tetraethyl orthosilicate (tetraethoxysilane) as the metal compound (B) mol was dissolved in a mixed solution of 1.8 mL of isopropyl alcohol and 0.095 mL of 1-butanol, and the mixture was stirred at room temperature for 20 minutes, and a coating film was formed and evaluated in the same manner as in Example 1-1.

Comparative Example 4-1

2.2 × 10 ^-4 mol of triethoxy-n-octylsilane (octyltriethoxysilane) as the organosilicon compound (A) and 3.5 × 10 ^-3 mol of tetraethyl orthosilicate (tetraethoxysilane) as the metal compound (B) mol were dissolved in a mixed solution of 1.8 ml of isopropyl alcohol and 0.095 ml of methyl ethyl ketone, and the mixture was stirred at room temperature for 20 minutes. 1.0 ml of hydrochloric acid (0.01 mol / L aqueous solution) as a catalyst was added dropwise to the obtained solution, and the mixture was stirred for 24 hours to prepare a sample solution. The sample solution was diluted 7-fold with isopropyl alcohol to prepare a coating solution d-1. Using this coating solution d-1, a glass substrate was coated with a hand coating in the same manner as in Example 1-1, and the coating was allowed to stand at room temperature for one day to prepare a coating film.

Comparative Example 4-2

A coating solution d-2 was prepared in the same manner as in Comparative Example 4-1 except that 0.095 ml of dimethyl sulfoxide was used instead of methyl ethyl ketone. Using this coating solution d-2, a glass substrate was coated with a hand coating in the same manner as in Example 1-1, and the coating was allowed to stand at room temperature for one day, and a film was formed and evaluated.

Comparative Example 5

A coating solution e was prepared in the same manner as in Comparative Example 4-2 except that 0.095 ml of n-octane was used instead of dimethyl sulfoxide. Using the coating solution e, a glass substrate was coated with a hand coating in the same manner as in Example 1-1, and the coating was allowed to stand at room temperature for one day to prepare a coating film.

Comparative Example 6

A coating solution f was prepared in the same manner as in Comparative Example 5 except that dodecane was used instead of octane. Using this coating solution f, a glass substrate was coated with a hand coating in the same manner as in Example 1-1, and the coating was allowed to stand at room temperature for one day, and a film was formed and evaluated.

Comparative Example 7

A coating solution g was prepared in the same manner as in Comparative Example 6 except that 1,2-dimethoxyethane was used instead of dodecane. Using this coating solution g, a glass substrate was coated with a hand coating in the same manner as in Example 1-1, and the coating was allowed to stand at room temperature for one day, and a film was formed and evaluated.

The results are shown in Tables 7-1, 7-2, 8 and 9. Table 10 shows the vapor pressures and boiling points of various solvents at 20 占 폚.

[Table 7-1]

[Table 7-2]

[Table 8]

[Table 9]

[Table 10]

From the above results, it can be seen that, according to the composition of the present invention, it is possible to neatly coat the coating film which is compatible with water-repellent and oil repellency with hand coating.

Claims (7)

An alkyl group having 6 to 20 carbon atoms in which a part of the methylene group may be substituted with an oxygen atom and an organosilicon compound (A1) in which at least one hydrolyzable group is bonded to a silicon atom, or at least one trialkylsilyl group- , An organosilicon compound (A2) in which at least one hydrolyzable group is bonded to a silicon atom,
Further, at least one hydrolyzable group is bonded to the metal atom, and a hydrocarbon chain-containing group in which the maximum chain length of the hydrocarbon chain portion is shorter than the maximum chain length of the organic silicon compound (A1) or (A2) A metal compound (B)
And at least meet one, and also the solubility parameter is 8.0 (cal / cm ^{3) 1/2} or more high boiling point solvents (C) of what a vapor pressure of at least 20 ℃ not more than 1000Pa, and a boiling point of 120 ℃,
(D) having a vapor pressure at 20 DEG C of more than 1000 Pa and a boiling point of less than 120 DEG C,
Wherein the concentration of the high boiling point solvent (C) is not less than 0.088 parts by mass and less than 1.74 parts by mass based on 100 parts by mass of the composition. The method according to claim 1,
Wherein the molar ratio of the metal compound (B) to the organosilicon compound (A1) or (A2) is 2 or more and 48 or less. 3. The method according to claim 1 or 2,
Wherein the organosilicon compound (A1) is represented by the following formula (AI).
(33)

[In the formula (AI), R ^a1 represents an alkyl group having 6 to 20 carbon atoms in which a part of the methylene group may be substituted with an oxygen atom,
A plurality of A ^a1 each independently represent a hydrolyzable group.
Z ^a1 represents a hydrocarbon chain-containing group or a hydrolysable group, and when Z ^a1 is a hydrocarbon chain-containing group, R ^a1 and Z ^a1 may be the same or different, and when Z ^a1 is a hydrolysable group, Z ^a1 and A ^a1 are the same The chart may be different. R ^a1 and Z ^a1 may be the same or different in the plurality of formulas (AI).] 4. The method according to any one of claims 1 to 3,
Wherein the organosilicon compound (A2) is represented by the following formula (AII).
(34)

[In the formula (AII), R ^a2 represents a trialkylsilyl group-containing molecular chain, and a plurality of A ^a2 each independently represent a hydrolyzable group. Z ^a2 represents a trialkylsilyl group-containing molecular chain, a hydrocarbon chain-containing group, a siloxane skeleton-containing group or a hydrolyzable group. 5. The method according to any one of claims 1 to 4,
Wherein the metal compound (B) is represented by the following formula (BI).
(35)

[In the formula (BI)
R ^b1 represents a hydrocarbon chain-containing group or a hydrolyzable group in which the maximum chain length of the hydrocarbon chain portion is shorter than the maximum chain length of the alkyl group having 6 to 20 carbon atoms.
A ^b1 each independently represents a hydrolyzable group.
M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr or Ta.
and m represents an integer of 1 to 4, depending on the valence of M.] 6. The method of claim 5,
Wherein, in the formula (BI), R ^b1 and A ^b1 are the same group. The method according to claim 5 or 6,
In the formula (BI), M is Si.