JP6894750B2 - Compounds and compositions containing compounds - Google Patents

Description

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

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

As such a film, Patent Document 1 describes (CH ₃ ) ₃ SiO− (Si (CH ₃ ) ₂ O) ₄₆ −Si (CH ₃ ) ₂₋ (CH ₂ ) ₂ −Si (NCO) ₃ , as a surface treatment agent. A surface treatment layer formed by using (CH ₃ ) ₃ SiO− (Si (CH ₃ ) ₂ O) ₁₀ −Si (CH ₃ ) ₂₋ (CH ₂ ) ₂₋ Si (NCO) _{3 etc. has been proposed.} There is.

JP-A-2002-166506

Conventionally known films may not have sufficient substrate adhesion. The present invention has been made in view of such circumstances, and an object of the present invention is to provide a compound capable of forming a film capable of achieving both water repellency, droplet slipperiness and substrate adhesion.

［式（Ｉ）中、Ｒ^s1は、炭素数１〜４の炭化水素基又は（Ｒ^s3）₃ＳｉＯ−を表し、Ｒ^s2及びＲ^s3は、それぞれ独立に、炭素数１〜４のアルキル基を表す。該Ｒ^s1の炭化水素基及びＲ^s3のアルキル基に含まれる水素原子は、フッ素原子に置換されていてもよい。ただし、Ｒ^s1が全て炭化水素基である場合、Ｒ^s1はアルキル基である。
Ｘ^s1は、イソシアナト基以外の加水分解性基、炭化水素基又はシリルオキシ基含有基を表し、該Ｘ^s1の炭化水素基に含まれる−ＣＨ₂−は−Ｏ−に置き換わっていてもよい。ただしＳｉ原子に隣接する−ＣＨ₂−は−Ｏ−に置き換わることはなく、連続する２つの−ＣＨ₂−が同時に−Ｏ−に置き換わることはない。
ｎ１は、１以上の整数を表す。
ｐ１及びｐ２は、それぞれ独立に、１〜３であり、その合計は４以下である。］
［３］Ｒ^s1が（Ｒ^s3）₃ＳｉＯ−を表す［２］に記載のシランイソシアネート化合物。
［４］［１］〜［３］のいずれかに記載のシランイソシアネート化合物及び溶剤を含むコーティング組成物。
［５］さらに、少なくとも１つの加水分解性基が中心金属原子に結合している金属化合物を含む［４］に記載のコーティング組成物。
［６］式（Ｉ−Ｘ１）で表される化合物と式（Ｉ−Ｘ２）で表される化合物とを反応させることを特徴とする［１］〜［３］のいずれかに記載の化合物の製造方法。

［式（Ｉ−Ｘ１）中、
Ｒ^s1は、炭素数１〜４の炭化水素基又は（Ｒ^s3）₃ＳｉＯ−を表し、Ｒ^s2及びＲ^s3は、それぞれ独立に、炭素数１〜４のアルキル基を表す。該Ｒ^s1の炭化水素基及びＲ^s3のアルキル基に含まれる水素原子は、フッ素原子に置換されていてもよい。ただし、Ｒ^s1が全て炭化水素基である場合、Ｒ^s1はアルキル基である。
ｎ１は、１以上の整数を表す。
式（Ｉ−Ｘ２）中、
Ｘ^s1は、イソシアナト基以外の加水分解性基、炭化水素基、又はシリルオキシ基含有基を表し、該Ｘ^s1の炭化水素基に含まれる−ＣＨ₂−は−Ｏ−に置き換わっていてもよい。ただしＳｉ原子に隣接する−ＣＨ₂−は−Ｏ−に置き換わることはなく、連続する２つの−ＣＨ₂−が同時に−Ｏ−に置き換わることはない。
ｐ３は、２〜４の整数を表す。］ In earnest studies to solve the above problems, the present inventors have achieved both water repellency, droplet slipperiness and substrate adhesion by using a compound in which an isocyanato group and a specific group are bonded to a central silicon atom. We have found that it is possible to form a film that can be formed.
The present invention includes the following inventions.
[1] A silane isocyanate compound in which a trialkylsilyloxy group having 1 to 4 carbon atoms in an alkyl group and an isocyanato group-bonded silicon atom are linked by a polysilyloxy group.
[2] The silane isocyanate compound according to [1] represented by the formula (I).

[In the formula (I), R ^s1 represents a hydrocarbon group having 1 to 4 carbon atoms or (R ^s3 ) ₃ SiO−, and R ^s2 and R ^s3 are independently alkyl groups having 1 to 4 carbon atoms. Represents. The hydrogen atom contained in the hydrocarbon group of ^{R s1 and the alkyl group of R s3} may be substituted with a fluorine atom. However, if R ^s1 is all hydrocarbon groups, then R ^s1 is an alkyl group.
X ^s1 is a hydrolyzable group other than isocyanate group, a hydrocarbon group or a silyloxy group-containing group, -CH ₂ contained in the hydrocarbon group of the X ^s1 - may be replaced to -O-. _{However, -CH 2-} adjacent to the Si atom is not replaced by -O-, and two consecutive -CH _2- are not replaced by -O- at the same time.
n1 represents an integer of 1 or more.
p1 and p2 are independently 1 to 3, and the total is 4 or less. ]
[3] The silane isocyanate compound according to [2], wherein ^{R s1} represents (R ^s3 ) _{3 SiO−.}
[4] A coating composition containing the silane isocyanate compound according to any one of [1] to [3] and a solvent.
[5] The coating composition according to [4], further comprising a metal compound in which at least one hydrolyzable group is bonded to a central metal atom.
[6] The compound according to any one of [1] to [3], which comprises reacting a compound represented by the formula (IX1) with a compound represented by the formula (IX2). Production method.

[In the formula (IX1),
R ^s1 represents a hydrocarbon group having 1 to 4 carbon atoms or (R ^s3 ) ₃ SiO−, and R ^s2 and R ^s3 independently represent an alkyl group having 1 to 4 carbon atoms. The hydrogen atom contained in the hydrocarbon group of ^{R s1 and the alkyl group of R s3} may be substituted with a fluorine atom. However, if R ^s1 is all hydrocarbon groups, then R ^s1 is an alkyl group.
n1 represents an integer of 1 or more.
In formula (IX2),
X ^s1 is a hydrolyzable group other than isocyanate group, a hydrocarbon group, or a silyloxy group-containing group, -CH ₂ contained in the hydrocarbon group of the X ^s1 - may be replaced to -O-. _{However, -CH 2-} adjacent to the Si atom is not replaced by -O-, and two consecutive -CH _2- are not replaced by -O- at the same time.
p3 represents an integer of 2-4. ]

In the silane isocyanate compound (a) of the present invention, a trialkylsilyloxy group and an isocyanato group-bonded silicon atom are linked by a polysilyloxy group, so that the water-repellent film formed from the silane isocyanate compound (a) is , Water repellency, slipperiness of droplets and substrate adhesion are good.

FIG. 1 shows an emission spectrum of “SP-9 250DB” manufactured by Ushio, Inc.

In the silane isocyanate compound (a) of the present invention, a trialkylsilyl group and an isocyanato group-bonded silicon atom (silaneisocyanate) are linked by a polysilyloxy group. Therefore, the silane isocyanate compound (a) can form a film capable of achieving both water repellency, droplet slipperiness, and substrate adhesion. In particular, in the silane isocyanate compound (a) of the present invention, the molecular chain that bonds the trialkylsilyloxy group and the isocyanato group-bonded silicon atom is composed of a polysilyloxy group and does not contain a carbon-carbon bond. , A film having good light resistance can be formed.

The trialkylsilyloxy group may be bonded to the polysilyloxy group alone, and a group formed by bonding a plurality of the trialkylsilyloxy group to one silyloxy group (hereinafter, may be referred to as a composite group) is the poly. It may be bonded to a silyloxy group. These single trialkylsilyl groups and complex groups are preferably groups represented by the formula (s1).

[In the formula (s1), R ^s1 represents a hydrocarbon group or (R ^s3 ) ₃ SiO−, and R ^s3 represents an alkyl group having 1 to 4 carbon atoms. The hydrogen atom contained in the hydrocarbon group of ^{R s1 and the alkyl group of R s3} may be substituted with a fluorine atom. However, if R ^s1 is all hydrocarbon groups, then R ^s1 is an alkyl group. * Represents a bond with a polysilyloxy group. ]

The hydrocarbon group of R ^s1 preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and further preferably 1 to 2 carbon atoms. When ^{all R s1s} are hydrocarbon groups, ^{the total number of carbon atoms of the three Rs1s} is preferably 9 or less, more preferably 6 or less, still more preferably 4 or less.
As ^{the hydrocarbon group of 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, a butyl group and the like. The plurality of R ^s1s may be the same or different, and are preferably the same.

The alkyl group of R ^s3 preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and further preferably 1 to 2 carbon atoms. ^Examples of the alkyl group of R s3 include a methyl group, an ethyl group, a propyl group, a butyl group and the like, and a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.

Further, the hydrogen atom contained in the hydrocarbon group of ^{R s1 and the alkyl group of R s3} may be substituted with a fluorine atom. When the number of carbon atoms is A, the number of substitutions of fluorine atoms is preferably 1 or more, more preferably 3 or more, and preferably 2 × A + 1 or less. If hydrogen atoms contained in the alkyl group of the hydrocarbon group or R ^s3 of R ^s1 is substituted by fluorine atom, the number of alkyl groups of the hydrocarbon group or R ^s3 of R ^s1 to be replaced, R ^s1 or R ^s3 It can be appropriately selected in the range of 1 to 3 per silicon atom to which is bonded.

^{Most preferably, as (R s1} ) ₃ SiO− or (R ^s3 ) ₃ SiO− (all of which are trialkylsilyloxy groups) in which R ^s1 is a hydrocarbon group (alkyl group), the following formula is used. Examples include the groups represented. In the formula, * represents a bond.

Further, the total number of carbon atoms of ^{R s1} or R ^{s3 contained in (R s1} ) ₃ SiO− or (R ^s3 ) ₃ SiO− in which ^{R s1} is an all hydrocarbon group (alkyl group) shall be 9 or less. Is preferable, more preferably 6 or less, still more preferably 4 or less. Further, ^{at least one of R s1} or R ^s3 contained in ^{(R s1} ) ₃ SiO− or (R ^s3 ) ₃ ^{SiO− in which all R s1} is a hydrocarbon group (alkyl group) is a methyl group. It is preferable that two or more R ^s1 or R ^s3 are methyl groups, and it is particularly preferable that all ^{three R s1} or R ^{s3 are methyl groups.}

Examples of the group in which at least one of R ^{s1 is (R s3} ) ₃ SiO− (trialkylsilyloxy group) includes a group represented by the following formula.

The polysilyloxy group may be a linear divalent group, a branched chain trivalent or higher group, and is preferably a polydialkylsiloxy group. The polysilyloxy group is preferably a group represented by the formula (s2).

[In the formula (s2), R ^s2 represents an alkyl group having 1 to 4 carbon atoms. n1 represents an integer of 1 or more. The * on the left side represents the bond with the group represented by the formula (s1), and the * on the right side represents the bond with the isocyanato group-bonded silicon atom. ]

The alkyl group of R ^s2 preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and further preferably 1 to 2 carbon atoms. ^Examples of the alkyl group of R s2 include a methyl group, an ethyl group, a propyl group, a butyl group and the like, 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 isocyanato group-bonded silicon atom may have one or more isocyanato groups, and a silicon atom to which one isocyanato group is bonded (monoisocyanato silicon atom) and two isocyanato groups are bonded to each other. It may be any of a silicon atom (diisocyanato silicon atom) and a silicon atom (triisocyanato silicon atom) to which three isocyanato groups are bonded. In the case of a mono or diisocyanato silicon atom, a hydrolyzable group, a hydrocarbon group, or a silyloxy group-containing group other than the isocyanato group may be bonded to the silicon atom, and -CH contained in the hydrocarbon group. ₂ − may be replaced with −O −. _{However, -CH 2-} adjacent to the Si atom is not replaced by -O-, and two consecutive -CH _2- are not replaced by -O- at the same time.
Examples of such an isocyanato group-bonded silicon atom include a group represented by the formula (s3).

[In the formula (s3), X ^s1 represents a hydrolyzable group, a hydrocarbon group, or a silyloxy group-containing group other than the isocyanato group, and _{−CH 2} − contained in the hydrocarbon group of ^{X s1} is −O−. May be replaced with. _{However, -CH 2-} adjacent to the Si atom is not replaced by -O-, and two consecutive -CH _2- are not replaced by -O- at the same time. p1 and p2 are independently 1 to 3, and the total is 4 or less. * Represents a bond with a polysilyloxy group. ]

p1 is preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1. p2 is preferably 1 to 3, more preferably 2 to 3, and particularly preferably 3. 4-p1-p2 is preferably 0 to 1, more preferably 0.
Examples of the hydrolyzable group other than the isocyanato group include an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group; an acetoxy group; a chlorine atom; and the like, and have 1 to 4 carbon atoms. Alkoxy group is preferable, and an alkoxy group having 1 to 2 carbon atoms is more preferable.

As the silane isocyanate compound (a), the compound represented by the formula (I) is preferable.

[In the formula (I), R ^s1 represents a hydrocarbon group having 1 to 4 carbon atoms or (R ^s3 ) ₃ SiO−, and R ^s2 and R ^s3 are independently alkyl groups having 1 to 4 carbon atoms. Represents. The hydrogen atom contained in the hydrocarbon group of ^{R s1 and the alkyl group of R s3} may be substituted with a fluorine atom. However, if R ^s1 is all hydrocarbon groups, then R ^s1 is an alkyl group. X ^s1 is a hydrolyzable group other than isocyanate group, a hydrocarbon group, or a silyloxy group-containing group, -CH ₂ contained in the hydrocarbon group of the X ^s1 - may be replaced to -O-. _{However, -CH 2-} adjacent to the Si atom is not replaced by -O-, and two consecutive -CH _2- are not replaced by -O- at the same time. n1 represents an integer of 1 or more. p1 and p2 are independently 1 to 3, and the total is 4 or less. ]

The compound represented by the formula (I) has a group represented by the formula (s1) as a trialkylsilyloxy group and a group represented by the formula (s2) as a polysilyloxy group. It has a group represented by the above formula (s3) as an isocyanato group-bonded silicon atom, and preferred embodiments of the (s1) applicable portion, (s2) applicable portion, and (s3) applicable portion in the formula (I) are , (S1), (s2), and (s3) described above.

The silyloxy group-containing group is a monovalent group containing a silyloxy group (-Si-O-), and has a structure enclosed in p1 of the formula (I) (hereinafter, "trialkylsilyloxy group-containing group"). It is preferable that it is composed of a smaller number of atoms.
The silyloxy group-containing group is preferably a group represented by the following formula (s4).

[In equation (s4), R ^s2 is synonymous with the above. R ^s5 represents a hydrocarbon group or a hydroxy group having 1 to 4 carbon atoms, and −CH ₂ − contained in the hydrocarbon group may be replaced with −O−, and a 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₋ contained in the divalent hydrocarbon group may be replaced with −O−. _{However, -CH 2-} adjacent to the Si atom is not replaced by -O-, and two consecutive -CH _2- are not replaced by -O- at the same time. Y ^s2 represents a single bond or −L ^s2 −Si (R ^s2 ) ₂₋ . L ^s2 represents a divalent hydrocarbon group, -CH ₂ contained in the divalent hydrocarbon group wherein - may be replaced to -O-. _{However, -CH 2-} adjacent to the Si atom is not replaced by -O-, and two consecutive -CH _2- are not replaced by -O- at the same time. n2 represents an integer from 0 to 5. * Represents a bond with a silicon atom. ]

Examples of the hydrocarbon group of R ^s5 include a group similar to the hydrocarbon group of ^{R s1.} Examples of the divalent hydrocarbon group of Z ^s2 or L ^s2 include an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a propylene group and a butylene group, and more preferably an alkylene group having 1 to 3 carbon atoms. It is a group, more preferably a methylene group having 1 carbon atom. When it is a methylene group, a film having better light resistance can be obtained. The silyloxy group-containing group preferably includes a group represented by the following formula.

As ^{the hydrocarbon group of X s1} , an alkyl group such as a methyl group, an ethyl group or a propyl group is preferable. Examples of the group in which −CH ₂ − contained in the hydrocarbon group is replaced with −O− include a group having a (poly) ethylene glycol unit.

Among them, the silane isocyanate compound (a) is preferably a compound represented by the following formula (I-1), and may be a compound represented by the formula (I-2).

[In formulas (I-1) and (I-2), R ^s2 , R ^s3 , and n1 have the same meanings as described above. ]

As the silane isocyanate compound (a), a compound represented by the following formula is particularly preferable. In the formula, n10 represents an integer of 1 to 30.

The silane isocyanate compound (a) can be produced by reacting a compound in which a trialkylsilyloxy group and a hydroxy group are linked by a polysilyloxy group with a silicon isocyanatated compound, for example, according to the above formula (I). The compound represented can be produced by reacting the compound represented by the formula (IX1) with the compound represented by the formula (IX2).

[In the formula (IX1) ^{, R s1} represents a hydrocarbon group or (R ^s3 _{) 3} SiO−, and R ^s2 and R ^s3 independently represent an alkyl group having 1 to 4 carbon atoms. The hydrogen atom contained in the hydrocarbon group of ^{R s1 and the alkyl group of R s3} may be substituted with a fluorine atom. However, if R ^s1 is all hydrocarbon groups, then R ^s1 is an alkyl group. n1 represents an integer of 1 or more.
In the formula (I-X2), X ^s1 represents a hydrolyzable group, a hydrocarbon group, or a silyloxy group-containing group other than the isocyanato group, and _{−CH 2} − contained in the hydrocarbon group of ^{X s1} is −O. It may be replaced with-. _{However, -CH 2-} adjacent to the Si atom is not replaced by -O-, and two consecutive -CH _2- are not replaced by -O- at the same time. p3 represents an integer of 2 or more. ]

Compound (I-X2), relative to compound (I-X1) 1 mol, is preferably 1 mol or more, more preferably 1.5 mol or more on, further preferably 2 mol or more, 5 mol It is preferably less than or equal to, more preferably 3 mol or less.

The above reaction is preferably carried out in a solvent. Examples of the solvent include ether solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran and dioxyanisole. The reaction temperature is preferably −10 to 50 ° C., more preferably −5 to 40 ° C.

The compound (IX1) includes a compound in which halogen atoms are bonded to both ends of a dialkylsiloxane chain (hereinafter, “dihalogenated dialkylsiloxane”) or a cyclic dialkylsiloxane, a tris (trialkylsilyloxy) silyl group, and M. It can be produced by reacting with a compound (hereinafter, "alkali metal silyl oxide") to which ¹ O-group (M ^{1 represents an alkali metal) is bonded.}
Examples of the halogen atom contained in the dihalogenated dialkylsiloxane include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a chlorine atom is preferable. Further, as the alkali metal, lithium is preferable.
The number of silicon atoms contained in the cyclic dialkylsiloxane is preferably 2 or more and 10 or less, more preferably 2 or more and 5 or less, and further preferably 2 or more and 4 or less.
The alkali metal silyl oxide can be produced by reacting an alkyl alkali metal with a compound represented by ^{(R s1} ) _{3 Si-OH.} Examples of the alkyl alkali metal include alkyl lithium such as n-butyllithium, sec-butyllithium and tert-butyllithium, and n-butyllithium is particularly preferable.

The composition containing the silane isocyanate compound (a) and the solvent (c) is also included in the scope of the present invention. Since the silane isocyanate compound (a) has an isocyanato group bonded to the central silicon atom, it has good adhesion to various substrates, and forms a film capable of achieving both water repellency, droplet slipperiness and light resistance. It is possible.

The content of the silane isocyanate compound (a) is preferably 0.001% by mass or more, more preferably 0.1% by mass or more, still more preferably 1% by mass or more in 100% by mass of the composition. It is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less.
In particular, when the composition does not contain the metal compound (b) described later, the content of the silane isocyanate compound (a) is preferably 0.01% by mass or more, more preferably 0.01% by mass or more, based on 100% by mass of the composition. Is 0.05% by mass or more.
When the composition contains the metal compound (b) described later, the content of the silane isocyanate compound (a) is preferably 10% by mass or less, more preferably 5% by mass, based on 100% by mass of the composition. % Or less.

The composition may further contain a metal compound (b) in which at least one hydrolyzable group is bonded to a metal atom, and the silyloxy group-containing group or the hydrocarbon chain-containing group is the said. It may be bonded to a metal atom. The number of atoms of the silyloxy group-containing group and the number of carbon atoms of the hydrocarbon chain portion of the hydrocarbon chain-containing group are atoms constituting the trialkylsilyl group-containing molecular chain bonded to the central silicon atom of the silane isocyanate compound (a), respectively. Since the number is less than the number, a portion having a spacer function can be formed in the film formed from the composition of the present invention. As a result, the water repellency improving effect of the trialkylsilyl group-containing molecular chain can be enhanced. As the group bonded to the metal atom, a silyloxy group-containing group is preferable.

The metal compound (b) is preferably a compound represented by the formula (II-1), (II-2) or (II-3). Each of these compounds may be used alone, or a plurality of these compounds may be used in combination. Further, the compound represented by the formula (II-1), (II-2) or (II-3) may be a hydrolyzed condensate thereof. Here, the hydrolyzed condensate means a compound in which all or part of the hydrolyzable groups contained in each compound (II) are condensed by hydrolysis.

[In formula (II-1), M represents a trivalent or tetravalent metal atom capable of forming a metal alkoxide. R ^b1 represents a silyloxy group-containing group, a hydrocarbon group or a hydrolyzable group, and _{−CH 2} − contained in the hydrocarbon group of ^{R b1} may be replaced with −O−. _{However, -CH 2-} adjacent to the silicon atom is not replaced by -O-, and two consecutive -CH _2- are not replaced by -O- at the same time. A ^b1 represents a hydrolyzable group. k is a number 2 less than the valence of M.
In formula (II-2), R ^f1 represents a fluorocarbon-containing group. A ^f1 represents a hydrolyzable group. Z ^f1 represents a silyloxy group-containing group, a hydrocarbon group or a hydrolyzable group, and _{−CH 2} − contained in the hydrocarbon group of ^{Z f1} may be replaced with −O−. _{However, -CH 2-} adjacent to the silicon atom is not replaced by -O-, and two consecutive -CH _2- are not replaced by -O- at the same time.
In formula (II-3), R ^f2 represents a hydrolyzable silane oligomer residue. A ^f2 independently represents a hydrolyzable group, a fluoroalkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. ]

M is a metal atom that can be bonded to an alkoxy group to form a metal alkoxide, and the metal atom also includes a metalloid such as Si and Ge. Examples of M include trivalent metals such as Al, Fe and In; tetravalent metals such as Hf, Si, Ti, Sn and Zr; and the like, preferably Si.
Examples of the hydrolyzable group of R ^b1 , A ^b1 , A ^f1 , Z ^f1 or A ^f2 include a group similar to the hydrolyzable group in the silane isocyanate compound (a) and an isocyanato group, which have 1 to 4 carbon atoms. An alkoxy group is preferable, and an alkoxy group having 1 to 2 carbon atoms is more preferable.
The silyloxy group-containing group or hydrocarbon group of R ^b1 or Z ^f1 can be appropriately selected from the ranges described as the silyloxy group-containing group or hydrocarbon group of ^{X s1, and the number thereof is preferably 1 or less.} It is particularly preferably 0.

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

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

The fluoroalkyl group of R ^f3 or R ^f4 has 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms. Further, the ^{number of substitutions of fluorine atoms in the fluoroalkyl group of R f3} or R ^f4 is 1 or more and 2A + 1 or less, that is, 2A + 1 when the number of carbon atoms contained in the fluoroalkyl group is A. The fluoroalkyl group is preferably a perfluoroalkyl group. Examples of the alkyl group of R ^b4 include the same groups as the alkyl group exemplified as the hydrocarbon group of ^{R s1.} As L ^f1 , -O-, -COO-, or -OCO- is preferable.
h1 is preferably 1 to 30, more preferably 1 to 25, further preferably 1 to 10, particularly preferably 1 to 5, and most preferably 1 to 2. h2 is preferably 0 to 15, more preferably 0 to 10. h3 is preferably 0 to 5, more preferably 0 to 2. h4 is preferably 0 to 4, more preferably 0 to 2. h5 is preferably 0 to 4, more preferably 0 to 2. The total value of h1 to h5 is preferably 3 or more, more preferably 5 or more, more preferably 80 or less, more preferably 50 or less, still more preferably 20 or less.

In particular, R ^f3 is a perfluoroalkyl group ^{having 1 to 5 carbon atoms, R f4} is a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, R ^b4 is a hydrogen atom, and h3, h4 and h5 are any of them. Is also 0, h1 is preferably 1 to 5, and h2 is preferably 0 to 5.

Examples of the fluorocarbon-containing group include a group represented by the following formula. In the formula, R ^f3 and R ^b4 are synonymous with the above, R ^f3 is preferably a perfluoroalkyl group having 1 to 12 carbon atoms, and R ^b4 is preferably a hydrogen atom. Further, r2 is 5 to 20 (preferably 8 to 15), r3 is 1 to 7 (preferably 2 to 6), r4 is 1 to 10 (preferably 3 to 7), and r5 is 1. ~ 6 (preferably 2-4).

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

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

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

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

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

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

In formula (II-3), ^{the hydrolyzable silane oligomer residue of R f2} may be a compound containing a silicon atom and a hydrolyzable group bonded to the silicon atom (hereinafter, referred to as "hydrolyzable silane monomer"). It means a monovalent group derived from the hydrolyzed condensate of). The number of silicon atoms contained in the hydrolyzable silane oligomer residue is preferably 3 or more, more preferably 5 or more, and further preferably 7 or more. The number of silicon atoms contained in the hydrolyzable silane oligomer residue is preferably 15 or less, more preferably 13 or less, still more preferably 10 or less.
When the hydrolyzable silane oligomer residue has an alkoxy group, examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like, preferably a methoxy group, an ethoxy group and the like. The hydrolyzable silane oligomer residue can have one or more of these alkoxy groups, preferably one.

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

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

Examples of the hydrolyzable group of A ^{f3 include a group similar to the hydrolyzable group of R b1} , preferably an alkoxy group, and having 1 to 4 carbon atoms (preferably 1 to 2) such as an ethoxy group and a methoxy group. Alkoxy group; isocyanato group is preferable.
h6 is preferably 0 or more and 10 or less, and more preferably 0 or more and 7 or less. As A ^f3 , a hydrolyzable group or a fluoroalkyl group having 1 to 4 carbon atoms is preferable, and ^{at least one of A f3} is preferably a fluoroalkyl group having 1 to 4 carbon atoms. Further, ^{at least one of A f3} is preferably a hydrolyzable group (particularly a methoxy group or an ethoxy group).

As the hydrolyzable silane oligomer residue, a group represented by the following formula is preferable.

R ^b1 is preferably a silyloxy group-containing group or a hydrolyzable group, and more preferably a hydrolyzable group. When a ^{plurality of R b1s} are contained, it is preferable that all of them are hydrolyzable groups. In this case, ^{it is preferable that R b1} and A ^b1 are the same hydrolyzable group. Z ^f1 is preferably a silyloxy group-containing group or a hydrolyzable group, and more preferably a hydrolyzable group. A ^f2 is preferably a fluoroalkyl group or a hydrolyzable group.

Examples of the compound (II-1) include a compound having only a hydrolyzable group; a compound having a silyloxy group-containing group and a hydrolyzable group; a compound having two silyloxy group-containing groups and a hydrolyzable group; a hydrocarbon group. And a compound having a hydrolyzable group; a compound having two hydrocarbon groups and a hydrolyzable group; and the like.
Examples of the compound having only a hydrolyzable group include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane; trialkoxyaluminum such as triethoxyaluminum, tripropoxyaluminum, and tributoxyaluminum; triethoxy. Trialkoxy iron such as iron; trialkoxy indium such as trimethoxyindium, triethoxyindium, tripropoxyindium, tributoxydium; tetraalkoxyhafnium such as tetramethoxyhafnium, tetraethoxyhafnium, tetrapropoxyhafnium, tetrabutoxyhafnium; tetra Tetraalkoxytitaniums such as methoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium; tetraalkoxytins such as tetramethoxytin, tetraethoxytin, tetrapropoxytin, tetrabutoxystin; tetramethoxyzinczyl, tetraethoxyzaldehyde, tetra Tetraalkoxyzylonzyl such as propoxyzyroxide and tetrabutoxyzaldehyde; and the like can be mentioned.

Examples of the compound having a silyloxy group-containing group and a hydrolyzable group include trimethylsilyloxytrialkoxysilanes such as trimethylsilyloxytrimethoxysilane, trimethylsilyloxytriethoxysilane, and trimethylsilyloxytripropoxysilane;
Examples of the compound having two silyloxy group-containing groups and a hydrolyzable group include di (trimethylsilyloxy) such as di (trimethylsilyloxy) dimethoxysilane, di (trimethylsilyloxy) diethoxysilane, and di (trimethylsilyloxy) dipropoxysilane. Dialkoxysilane; and the like.

Examples of the compound having a hydrocarbon group and a hydrolyzable group include alkyltrialkoxysilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, and methyltripropoxysilane; vinyltrimethoxysilane, Alkenyltrialkoxysilanes such as vinyltriethoxysilane; and the like.
Examples of the compound having two hydrocarbon groups and a hydrolyzable group include dialkyldialkoxysilanes such as dimethyldimethoxysilane, diethyldimethoxysilane, dimethyldiethoxysilane and diethyldiethoxysilane;

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

Examples of the compound (II-3) include compounds represented by the following formulas.

When the composition contains the metal compound (b), the content thereof is preferably 0.02% by mass or more, more preferably 0.05% by mass or more, and further preferably 0 in 100% by mass of the composition. .1% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 7% by mass or less.

When the composition of the present invention contains the metal compound (b), the ratio of the metal compound (b) to the silane isocyanate compound (a) (metal compound (b) / silane isocyanate compound (a)) is 1 on a molar basis. It is preferably 1/10 or more, more preferably 1/1 or more, still more preferably 2/1 or more, preferably 100/1 or less, more preferably 50/1 or less, still more preferably 40/10. It is 1 or less, more preferably 30/1 or less.

The composition of the present invention preferably contains the solvent (c). The solvent (c) includes water; a hydrophilic organic solvent such as an alcohol solvent, an ether solvent, a ketone solvent, an ester solvent, and an amide solvent; and a hydrophobic solvent such as an aromatic hydrocarbon solvent and a saturated hydrocarbon solvent. These include sex organic solvents, which may be used alone or in combination of two or more.
Examples of the alcohol solvent include methanol, ethanol, propanol, isopropyl alcohol, butanol, ethylene glycol, propylene glycol, diethylene glycol and the like, and examples of the ether solvent include dimethoxyethane, tetrahydrofuran, dioxane and the like, and ketone type. Examples of the solvent include acetone, methyl ethyl ketone and the like, examples of the ester solvent include ethyl acetate and butyl acetate, examples of the amide solvent include dimethylformamide, and examples of the aromatic hydrocarbon solvent include dimethylformamide. Examples thereof include benzene, toluene and xylene, and examples of the saturated hydrocarbon solvent include hexane and cyclohexane.
Of these, ether solvents and saturated hydrocarbon solvents are preferable.

The solvent (c) is 0.1 part by mass or more with respect to 1 part by mass in total of the silane isocyanate compound (a) (when the metal compound (b) is contained, the silane isocyanate compound (a) and the metal compound (b)). It is more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, particularly preferably 12 parts by mass or more, preferably 100 parts by mass or less, and more preferably 80 parts by mass or less. More preferably, it is 50 parts by mass or less. When the amount of the solvent (c) is in this range, it is easy to control the thickness of the film.

The composition of the present invention does not have to contain the catalyst (d), but may contain the catalyst (d) if necessary. The catalyst (d) may act as a hydrolysis catalyst for the isocyanato group and other hydrolyzable groups bonded to the silicon atom, and examples thereof include acidic compounds; basic compounds; organometallic compounds; and the like. Examples of the acidic compound include inorganic acids such as hydrochloric acid and nitric acid; organic acids such as acetic acid; and the like. Examples of the basic compound include ammonia; amine; and the like. Examples of the organometallic compound include an organometallic compound having a metal element such as Al, Fe, Zn, and Sn as a central metal, and an organometallic compound such as an aluminum acetylacetone complex and an aluminum ethylacetacetate complex; Organic iron compounds; organic zinc compounds such as zinc acetylacetonate monohydrate, zinc naphthenate, zinc octylate; organic tin compounds such as dibutyltin diacetate complex; and the like.

When the catalyst (d) is contained, the content thereof is based on 100 parts by mass of the total of the silane isocyanate compound (a) (when the metal compound (b) is contained, the silane isocyanate compound (a) and the metal compound (b)). , 0.0001 parts by mass or more, more preferably 0.0002 parts by mass or more, further preferably 0.001 parts by mass or more, preferably 20 parts by mass or less, and more preferably 10 parts by mass. Parts or less, more preferably 5 parts by mass or less.

Further, the composition of the present invention is an antioxidant, a rust preventive, an ultraviolet absorber, a light stabilizer, a fungicide, an antibacterial agent, a biological adhesion inhibitor, a deodorant, as long as the effect of the present invention is not impaired. It may contain various additives such as pigments, flame retardants, and antistatic agents.

Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, a hydride-based antioxidant, and the like.
Examples of the phenolic antioxidant include n-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, 2,6-di-t-butyl-4-methylphenol, 2, 2-thio-diethylene-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], tri-ethylene glycol-bis- [3- (3-t-butyl-5-methyl) -4-Hydroxyphenyl) propionate], 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2, 4,8,10-Tetraoxaspiro [5.5] undecane, tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionic acid} pentaerythrityl ester, 2-t-butyl -6- (3-t-Butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl]- 4,6-di-t-pentylphenyl acrylate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (3,5) -Di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2 , 4,6- (1H, 3H, 5H) -trione, 2,2'-methylenebis (6-t-butyl-4-methylphenol), 4,4'-butylidenebis (6-t-butyl-3-methyl) Phenol), 4,4'-thiobis (6-t-butyl-3-methylphenol) and the like.

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

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

Examples of the hindered amine-based antioxidant include bis sebacate (2,2,6,6-tetramethyl-4-piperidyl) ester (melting point 81-86 ° C.) and 2,2,6,6-tetramethyl-4-. Piperidine methacrylate (melting point 58 ° C.), poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6) 6-Tetramethyl-4-piperidyl) imino} -1,6-hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] and the like can be mentioned.

Examples of the rust preventive include alkanolamines such as triethanolamine; quaternary ammonium salts; alcanthiol; imidazolines, imidazoles, alkylimidazoline derivatives, benzimidazoles, 2-mercaptobenzimidazoles, benzotriazoles and other azoles; metavanazic acid. Sodium; bismuth citrate; phenol derivatives; aliphatic amines such as alkylamines and polyalkenylamines, aromatic amines, ethoxylated amines, cyanoalkylamines, cyclohexylamine benzoate, aliphatic diamines such as alkylenediamine, aromatic diamines, etc. Amine compounds; amides of the amine compounds and carboxylic acids; alkyl esters; pyrimidines; naphthenic acids; sulfonic acid complexes; nitrites such as calcium nitrite, sodium nitrite, dicyclohexylamine nitrite; polyalcohols, polyphenols, etc. Polyol compounds; heteropolyates such as sodium molybdate, sodium tungstate, sodium phosphonate, sodium chromate, sodium silicate; gelatin; carboxylic acid polymers; nitro compounds; formaldehyde; acetylene alcohols; aliphatic thiols, aromatic thiols , Thiol compounds such as acetylene thiol; sulfide compounds such as aliphatic sulfides, aromatic sulfides and acetylene sulfides; sulfoxide compounds such as sulfoxides and dibenzyl sulfoxides; thioureas; combinations of amines or quaternary ammonium salts and halogen ions; alkyl Amine and potassium iodide combination; Tannin and sodium phosphate combination; Triethanolamine and lauryl sarcosin combination; Triethanolamine, lauryl sarcosin and benzotriazole combination; Alkylamine, benzotriazole, sodium nitrite and sodium phosphate Combination of; etc.

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

As the fungicide / antimicrobial agent, 2- (4-thiazolyl) Ben's imidazole, sorbic acid, 1,2-benzisothiazolin-3 - one, (2-pyridylthio-1-oxide) sodium dehydroacetate, 2 -Methyl-5-chloro-4-isothiazolone complex, 2,4,5,6-tetrachlorophthalonitrile, methyl 2-benzimidazole carbamate, methyl 1- (butylcarbamoyl) -2-benzimidazole carbamate, mono or Examples thereof include dibromocyanoacetamides, 1,2-dibromo-2,4-dicyanobutane, 1,1-dibromo-1-nitropropanol and 1,1-dibromo-1-nitro-2-acetoxypropane.

Examples of the bioadhesion inhibitor include tetramethylthiuram disulfide, bis (N, N-dimethyldithiocarbamic acid) zinc, 3- (3,4-dichlorophenyl) -1,1-dimethylurea, and dichloro-N-((dimethylamino). ) Sulfonyl) Fluoro-N- (P-tolyl) methanesulfenamide, pyridine-triphenylborane, N, N-dimethyl-N'-phenyl-N'-(fluorodichloromethylthio) sulfamide, ferrous thiosocyanate ( 1), cuprous oxide, tetrabutylthiuram disulfide, 2,4,5,6-tetrachloroisophthalonitrile, zincethylenebisdithiocarbamate, 2,3,5,6-tetrachloro-4- (methyl) Sulfonyl) Pyridine, N- (2,4,6-trichlorophenyl) maleimide, bis (2-pyridinethiol-1-oxide) zinc salt, bis (2-pyridinthiol-1-oxide) copper salt, 2-methylthio- 4-t-Butylamino-6-cyclopropylamino-s-triazine, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, furanones, alkylpyridine compounds, grammine compounds, isonitrile compounds And so on.

Examples of the deodorant include lactic acid, succinic acid, malic acid, citric acid, maleic acid, malonic acid, ethylenediaminepolyacetic acid, alkane-1,2-dicarboxylic acid, alken-1,2-dicarboxylic acid, and cycloalcan-1. , 2-Dicarboxylic acid, cycloalkene-1,2-dicarboxylic acid, organic acids such as naphthalene sulfonic acid; fatty acid metals such as zinc undecylate, zinc 2-ethylhexanoate, zinc ricinolate; iron oxide, iron sulfate, Zinc oxide, zinc sulfate, zinc chloride, silver oxide, copper oxide, metal (iron, copper, etc.) sodium chlorophyllin, metal (iron, copper, cobalt, etc.) phthalocyanine, metal (iron, copper, cobalt, etc.) phthalocyanate tetrasulfonate, Metal compounds such as titanium dioxide and visible light responsive titanium dioxide (nitrogen-doped type, etc.); cyclodextrins such as α-, β- or γ-cyclodextrin, methyl derivatives thereof, hydroxypropyl derivatives, glucosyl derivatives, maltosyl derivatives, etc.; Acrylic polymers such as porous methacrylic acid polymer and porous acrylic acid polymer, aromatic polymers such as porous divinylbenzene polymer, porous styrene-divinylbenzene-vinylpyridine polymer, and porous divinylbenzene-vinylpyridine polymer, and copolymers thereof. In addition, polymers such as chitin, chitosan, activated charcoal, silica gel, active alumina, zeolite, and ceramic can be mentioned.

Examples of the pigments include carbon black, titanium oxide, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, perylene or perinine pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, disazo condensation pigments and the like. Benz imidazolone pigments and the like can be mentioned.

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

Examples of the antistatic agent include a quaternary ammonium salt type cationic surfactant, a betaine type amphoteric surfactant, an alkyl phosphate type anionic surfactant, a primary amine salt, a secondary amine salt, and a third. Cationic surfactants such as tertiary amine salts, quaternary amine salts and pyridine derivatives, sulfated oils, soaps, sulfated ester oils, sulfated amide oils, olefin sulfated ester salts, fatty alcohol sulfate ester salts, alkyl sulfates Anionic surfactants such as ester salts, fatty acid ethyl sulfonates, alkylnaphthalene sulfonates, alkylbenzene sulfonates, amber acid ester sulfonates and phosphoric acid ester salts, partial fatty acid esters of polyhydric alcohols, ethylene of fatty alcohols. Nonionic surfactants such as oxide adducts, ethylene oxide adducts of fatty acids, ethylene oxide adducts of fatty aminos or fatty acid amides, ethylene oxide adducts of alkylphenols, ethylene oxide adducts of partial fatty acid esters of polyhydric alcohols, and polyethylene glycol. Examples thereof include amphoteric surfactants such as agents, carboxylic acid derivatives and imidazoline derivatives.

Further, as an additive, a lubricant, a filler, a plasticizer, a nucleating agent, an anti-blocking agent, a foaming agent, an emulsifier, a brightener, a binder and the like may coexist.

When these additives are contained, the content of the additives in the composition is preferably 0.1 to 70% by mass, more preferably 0.1 to 50% by mass, and even more preferably 0.5. It is ~ 30% by mass, more preferably 2 to 15% by mass.

The total content of the silane isocyanate compound (a), the metal compound (b) and / or the solvent (c) is 60% by mass or more, more preferably 75% by mass or more in the composition. , More preferably 85% by mass or more, still more preferably 95% by mass or more.

A film formed from the above composition is also included in the scope of the present invention. The film contains a structure derived from the silane isocyanate compound (a).

The film of the present invention has a contact angle change rate d expressed by the following formula, where the initial contact angle of water with respect to the film is θ ₀₁ and the contact angle after immersion in ion-exchanged water at 70 ° C. for 12 hours is θ _{w2. w2} is preferably -10% or more, more preferably -5% or more, further preferably -1% or more, preferably 0%, but 2% or less, further 5% or less. It is also acceptable to be.
Contact angle change rate d _w2 (%) = (θ _w2 −θ ₀₁ ) / θ ₀₁ × 100

_{The initial contact angle θ 01} of water with respect to the film of the present invention is preferably 80 ° or more, more preferably 90 ° or more, still more preferably 100 ° or more, and may be 140 ° or less, and further. It may be 130 ° or less.
The contact angle means a value measured by the θ / 2 method using water having a liquid volume of 3.0 μL.

_{The falling angle α w} of water in the film of the present invention is preferably 40 ° or less, more preferably 35 ° or less, still more preferably 30 ° or less, particularly preferably 25 ° or less, and 5 ° or more. It may be 10 ° or more.
_{Further, the contact angle hysteresis Δθ w} of water in the film of the present invention is preferably 20 ° or less, more preferably 15 ° or less, still more preferably 10 ° or less, and may be 1 ° or more.

The contact angle hysteresis Δθ _w and the falling angle α _w of the water can be measured by the sliding method using water having a liquid volume of 6.0 μL.

The sliding speed of the film of the present invention is preferably 1 mm / sec or more, more preferably 5 mm / sec or more, still more preferably 10 mm / sec or more, and particularly preferably 20 mm / sec or more.
The sliding speed is a value obtained by tilting the base material having the film of the present invention by 20 ° and dividing the moving distance when 50 μL of droplets (water) are dropped by the time required for moving. Specifically, it can be measured by using the dynamic sliding method of a contact angle meter manufactured by Kyowa Interface Science Co., Ltd.

The film of the present invention has an initial contact angle of water with respect to the film of A ₁ , a mercury lamp having a bright line in a region of 300 nm or less, an intensity of 200 ± 10 mW / cm ² on the irradiation surface, a temperature of 20 to 40 ° C., and humidity. 30 to 75% in the atmosphere, the contact angle after irradiation for 6 hours when the B _Z, the rate of change of the contact angle before and after the irradiation is calculated based on the following formula, preferably 10% or more, It is more preferably −4.5% or more, further preferably -4% or more, and for example, 0% or less, further -1% or less is also allowed.
Contact angle change rate (%) = {(B _Z −A ₁ ) / A ₁ } × 100 (%)

The structure (A) derived from the silane isocyanate compound (a) has a structure in which a trialkylsilyloxy group having 1 to 4 carbon atoms and a polysilyloxy group are bonded (trialkylsilyloxy group). It is preferable that the structure contains (containing group) and is represented by the formula (IA).

[In formula (IA), R ^s1 , R ^s2 and n1 are synonymous with the above. Z ^a1 represents (R ^s1 ) ₃ Si-O- (Si (R ^s2 ) _2- O-) _n1- , silyloxy group-containing group, hydrocarbon group or -O-, and the hydrocarbon group of ^{Z a1} The included −CH ₂₋ may be replaced by −O−. _{However, -CH 2-} adjacent to the Si atom is not replaced by -O-, and two consecutive -CH _2- are not replaced by -O- at the same time. ]

In compounds represented by formula (IA), a silyloxy group-containing group Z ^a1, hydrocarbon groups, respectively, a silyloxy group-containing group can be appropriately selected from the range above described hydrocarbon group. Z ^a1 is preferably a silyloxy group-containing group or —O—, and more preferably —O−.

As the structure (A), a structure represented by the formula (IA-1) is preferable.

[In formula (IA-1), R ^s1 , R ^s2 and n1 are synonymous with the above. ]

As the structure (A), a structure represented by the following formula is particularly preferable. In the formula, n10 represents an integer of 1 to 30.

It is also preferable that the film formed from the composition of the present invention contains a structure derived from the metal compound (b). In the structure (B) derived from the metal compound (b), a group bonded to a metal atom (however, when the metal atom is a silicon atom, it is different from the silicon atom to which the trialkylsilyl group-containing molecular chain is bonded) ( Since the number of constituent elements of the hydrocarbon group, silyloxy group-containing group, hydroxy group, etc.) is smaller than that of the trialkylsilyl group-containing molecular chain, the structure (B) acts as a spacer, resulting in the trialkylsilyl group-containing molecular chain. The water repellency improving effect is easily enhanced.

The structure (B) derived from the metal compound (b) is preferably a structure represented by the formula (IIB1), (IIB2) or (IIB3).

[In formula (IIB1), M represents a trivalent or tetravalent metal atom capable of forming a metal alkoxide. R ^b2 represents a silyloxy group-containing group, a hydrocarbon group, a hydroxy group or an −O− group, and _{−CH 2−} contained in the hydrocarbon group of ^{R b2} may be replaced with −O−. _{However, -CH 2-} adjacent to the silicon atom is not replaced by -O-, and two consecutive -CH _2- are not replaced by -O- at the same time. k represents an integer of 1 or 2 depending on the valence of M.
In formula (IIB2), R ^f1 represents a fluorocarbon-containing group. Z ^f2 represents a silyloxy group-containing group, a hydrocarbon group, a hydroxy group or −O−, and _{−CH 2−} contained in the hydrocarbon group of ^{Z f2} may be replaced with −O−. _{However, -CH 2-} adjacent to the Si atom is not replaced by -O-, and two consecutive -CH _2- are not replaced by -O- at the same time.
In formula (IIB3), R ^f2 represents a hydrolyzable silane oligomer residue. Z ^f3 represents a fluoroalkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a hydroxy group or −O−. ]

Silyloxy group-containing group R ^b2 or Z ^f2, hydrocarbon groups R ^b2 or Z ^f2, and the number of atoms of the hydrolyzable silane oligomer residue of R ^f2, rather than the number of atoms of the trialkylsilyl group containing molecular chain It is preferable that the amount is small. This facilitates the structure (B) to act as a spacer in the coating.
Silyloxy group-containing group R ^b2 or Z ^f2, and the hydrocarbon group of R ^b2 or Z ^f2, silyloxy group-containing group Z ^a1, and include hydrocarbon groups and each similar group.

As R ^b2 , a silyloxy group-containing group, a hydroxy group or —O— is preferable, and a hydroxy group or —O− is more preferable. As Z ^f2 , a silyloxy group-containing group, a hydroxy group or —O— is preferable, and a hydroxy group or —O− is more preferable. As Z ^f3 , a fluoroalkyl group, a hydroxy group or —O— is preferable.

As the structure (B), when M is a silicon atom, a structure represented by the following formula can be mentioned. In the formula, L ^f2 represents an alkanediyl group having 5 to 20 carbon atoms. r8 is 1 to 20 (preferably 1 to 10), r9 is 1 to 10 (preferably 1 to 5), and r10 is 1 to 10 (preferably 1 to 5).

In the film formed from the composition of the present invention, the abundance ratio of the structure (B) to the structure (A) (structure (B) / structure (A)) is preferably 1/10 or more on a molar basis. It is more preferably 1/1 or more, still more preferably 2/1 or more, preferably 100/1 or less, more preferably 50/1 or less, still more preferably 30/1 or less, and even more preferably 25 /. It is 1 or less.

The film can be formed by bringing the composition into contact with the base material. Examples of the method for bringing the composition into contact with the substrate include a spin coating method, a dip coating method, a spray coating method, a roll coating method, a bar coating method, a die coating method and the like, and a spin coating method and a spray coating method are preferable. According to the spin coating method and the spray coating method, the film thickness can be easily adjusted.

At this time, the composition may be further diluted if necessary. The dilution ratio is preferably 2 to 100 times, more preferably 5 to 50 times, that of the composition before dilution. As the diluting solvent, the solvent exemplified as the solvent (c) can be appropriately used.

By allowing the composition of the present invention in contact with the substrate and allowing it to stand in the air, the hydrolyzable groups are hydrolyzed by taking in the moisture in the air to form a siloxane skeleton, and a film is formed. Will be done. When allowed to stand, it may be held at 40 to 250 ° C.

Further, a film-treated substrate in which the film of the present invention is formed on the substrate is also included in the scope of the present invention. The shape of the base material may be either a flat surface or a curved surface, or may be a three-dimensional structure in which a large number of surfaces are combined. The base material may be composed of either an organic material or an inorganic material, and the organic material includes acrylic resin, polycarbonate resin, polyester resin, styrene resin, acrylic-styrene copolymer resin, and cellulose. Thermoplastic resins such as resins, polyolefin resins and polyvinyl alcohols; thermocurable resins such as phenolic resins, urea resins, melamine resins, epoxy resins, unsaturated polyesters, silicone resins and urethane resins; etc. are mentioned as inorganic materials. Examples include ceramics; glass; metals such as Fe, Si, Cu, and All ; alloys containing the above metals; and the like.
The base material may be subjected to an easy-adhesion treatment in advance. Examples of the easy-adhesion treatment include a hydrophilization treatment such as corona treatment, plasma treatment, and ultraviolet treatment. Further, a primer treatment with a resin, a silane coupling agent, a tetraalkoxysilane, or the like may be used.

As the primer layer, a layer formed from a composition for forming a primer layer containing a component (P) capable of forming a siloxane skeleton (hereinafter, may be referred to as a component (P)) is preferable. The composition for forming a primer layer comprises a compound represented by the following formula (Pa) as a component (P) (hereinafter, may be referred to as a compound (Pa)) and / or a partially hydrolyzed condensate thereof (P1). It preferably contains an ingredient.
Si (X ^P2 ) ₄ … (Pa)
[In formula (Pa), ^XP2 represents a halogen atom, an alkoxy group or an isocyanato group. ]

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

As the compound (Pa), one kind or two or more kinds can be used, and Si (NCO) ₄ , Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) _{4, and the} like are preferable.

The component (P1) contained in the composition for forming a primer layer may be a partially hydrolyzed condensate of the compound (Pa). The partial hydrolysis condensation product of compound (Pa) can be produced by a general hydrolysis condensation method using an acid catalyst or a base catalyst. The degree of condensation (degree of polymerization) of the partially hydrolyzed condensate is preferably such that the product dissolves in the solvent. The component (Pa) may be compound (Pa) or a partially hydrolyzed condensate of compound (Pa), and is a mixture of compound (Pa) and its partially hydrolyzed condensate, unreacted. It may be a partially hydrolyzed condensate of compound (Pa) containing compound (Pa). Commercially available products can also be used as the compound (Pa) and its partially hydrolyzed condensate.

Further, the composition for forming a primer layer further comprises, as a component (P), a compound represented by the formula (Pb) (hereinafter, may be referred to as a compound (Pb)) and / or a partially hydrolyzed condensate thereof (hereinafter, may be referred to as a compound (Pb)). P2) It may contain a component.
(X ^P3 ) ₃ Si- (CH ₂ ) _p- Si (X ^P3 ) ₃ ... (Pb)
[However, in the formula (Pb), ^XP3 independently represents a hydrolyzable group or a hydroxyl group, and p is an integer of 1 to 8. ]

Wherein (Pb), the hydrolyzable group represented by X ^P3, include the same groups or atoms as the X ^P2. From the compound (Pb) of the balance between stability and hydrolysis ease point, the X ^P3, preferably an alkoxy group and an isocyanato group, an alkoxy group is particularly preferred. As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable. The X ^P3 to a plurality present in the compound (Pb) may be different groups in the same group, it is preferable in terms of ease availability of the same group.

As the compound (Pb), one kind or two or more kinds can be used, and (CH ₃ O) ₃ SCH ₂ CH ₂ Si (OCH ₃ ) ₃ , (OCN) ₃ SCH ₂ CH ₂ Si (NCO) ₃ , Cl ₃ SCH ₂ CH ₂ SiCl ₃ , (C ₂ H ₅ O) ₃ SCH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ , (CH ₃ O) ₃ SCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (CH 2 H 5 O) OCH ₃ ) ₃ etc. can be mentioned.

The component (P2) may be a partially hydrolyzed condensate of the compound (Pb). The partially hydrolyzed condensate of compound (Pb) can be obtained in the same manner as described in the production of the partially hydrolyzed condensate of compound (Pa). The degree of condensation (degree of polymerization) of the partially hydrolyzed condensate is preferably such that the product dissolves in the solvent. The component (P2) may be a compound (Pb) or a partially hydrolyzed condensate of the compound (Pb), and is a mixture of the compound (Pb) and the partially hydrolyzed condensate thereof, unreacted. It may be a partially hydrolyzed condensate of compound (Pb) containing compound (Pb). Commercially available products can also be used as the compound (Pb) and its partially hydrolyzed condensate. Further, the composition for forming a primer layer may contain a co-hydrolyzed condensate obtained by co-hydrolysis of the compound (Pb) and the compound (Pa) as a component (P), and contains various polysilazanes. May be good.

The composition for forming a primer layer preferably contains an organic solvent in consideration of economy, workability, ease of controlling the thickness of the obtained primer layer, and the like, in addition to the solid content as a layer constituent component. .. The organic solvent preferably dissolves the solid content contained in the primer layer forming composition, and examples thereof include the same solvent as the solvent (c) used in the composition. The organic solvent is not limited to one type, and two or more types of solvents having different polarities, evaporation rates, etc. may be mixed and used. When the composition for forming a primer layer contains a partially hydrolyzed condensate or a partially hydrolyzed cocondensate, the solvent used for producing these may be contained.

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

As a method for forming the base layer using the primer layer forming composition, a method to which an organosilane compound-based surface treatment agent can be applied can be used. The composition for forming a primer layer is applied to the surface of the substrate by a method such as brush coating, flow coating, rotary coating, dip coating, squeegee coating, spray coating, hand coating, etc., and if necessary, in an air atmosphere or a nitrogen atmosphere. The base layer can be formed by curing after drying. The curing conditions are appropriately controlled depending on the type and concentration of the primer layer forming composition used. The curing of the primer layer forming composition may be performed at the same time as the curing of the composition.
The thickness of the primer layer is not particularly limited as long as it can impart moisture resistance, adhesion, and barrier properties such as alkali from the substrate to the film formed on the primer layer.

The film formed from the composition containing the compound of the present invention can achieve both water repellency, slipperiness of droplets, and light resistance, and can be used for display devices such as touch panel displays, optical elements, semiconductor elements, building materials, and automobile parts. , Useful as a base material in nanoimprint technology and the like. The film formed from the composition containing the compound of the present invention is suitably used as an article such as a body, window glass (windshield, side glass, rear glass), mirror, bumper, etc. in transportation equipment such as trains, automobiles, ships, and aircraft. Be done. It can also be used for outdoor applications such as building outer walls, tents, photovoltaic modules, sound insulation boards, and concrete. It can also be used for fishing nets, insect nets, aquariums, etc. Furthermore, it can be used for kitchens, bathrooms, wash basins, mirrors, articles for each member around the toilet, ceramics such as chandeliers and tiles, artificial marble, and various indoor equipment such as air conditioners. It can also be used as an antifouling treatment for jigs, inner walls, pipes, etc. in factories. It is also suitable for goggles, eyeglasses, helmets, pachinko, textiles, umbrellas, playsets, soccer balls, and the like. Further, it can also be used as an adhesion preventive agent for various packaging materials such as food packaging materials, cosmetic packaging materials, and the inside of pots.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples as well as the present invention, and appropriate modifications are made to the extent that it can be adapted to the gist of the above and the following. Of course, it is possible to carry out, and all of them are included in the technical scope of the present invention. In the following, unless otherwise specified, "part" means "part by mass" and "%" means "% by mass".
The measurement method used in the examples is as follows.

(Contact angle evaluation)
A contact angle measuring device (DM700, manufactured by Kyowa Interface Science Co., Ltd.) was used. The contact angle was measured by the θ / 2 method using ion-exchanged water having a liquid volume of 3 μL.
(Dynamic water repellency evaluation)
Using DM700 manufactured by Kyowa Interface Science Co., Ltd., sliding method (analysis method: contact method, liquid volume: 6.0 μL, inclination method: continuous inclination, slide detection: after sliding, movement judgment: forward angle, sliding judgment distance: 0. The dynamic water repellency property (contact angle hysteresis, fall angle) of the transparent film surface with respect to water was measured by 25 mm).

(Adhesion evaluation)
The sample was immersed in ion-exchanged water at 70 ° C. for 12 hours to perform a hot water test, and the water contact angle before and after immersion was measured.

(Evaluation of droplet slipperiness)
Dynamic water repellency property of transparent film surface against water by dynamic sliding method (analysis method: liquid volume: 50.0 μL, inclination method: sample inclination, inclination angle: 20 °) using DM700 manufactured by Kyowa Interface Science Co., Ltd. (Water droplet slipperiness) was measured.

(Light resistance evaluation)
A uniform light irradiation unit (manufactured by Ushio) was attached to a mercury lamp (“SP-9 250DB” manufactured by Ushio, Inc.), and a sample was placed at a distance of 17.5 cm from the lens. When the light intensity of 200-800 nm was measured using an intensity meter (“VEGA” manufactured by OPHIL), it was ^{200 mW / cm 2.} The sample was irradiated with a mercury lamp for 6 hours in an air atmosphere having a temperature of 20 to 40 ° C. and a humidity of 30 to 75%. The initial contact angle of the droplet (ion-exchanged water with a liquid volume of 3 μL) on the transparent film is A ₁ , and the contact angle of the droplet after irradiation is B _Z. The rate of change is shown in Table 2.
Contact angle change rate (%) = {(B _Z −A ₁ ) / A ₁ } × 100 (%)
The spectral irradiance of the mercury lamp (“SP-9 250DB” manufactured by Ushio, Inc.) is as shown in FIG. 1, and has a bright line in a region of 300 nm or less.

Example 1-1
1.6 g of trimethylsilanol and 8 mL of tetrahydrofuran (THF) were placed in a four-necked flask and stirred. The mixture was cooled to −40 ° C., and 11.1 mL of an n-BuLi hexane solution (1.6 mol / L) was added dropwise. The temperature was raised to 0 ° C., 31.68 g of hexamethylcyclotrisiloxane dissolved in 28 mL of THF was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 17 hours. THF, ion-exchanged water, and hexane were sequentially added to the reaction solution and separated to separate the organic layer. The mixture was washed with ion-exchanged water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 32 g of a colorless and transparent intermediate 1 represented by the following formula. In the formula, the average number of repetitions n of the units enclosed in parentheses was 8. Hereinafter, the average number of repetitions was calculated from the NMR spectrum.

After dissolving 0.98 g of tetraisocyanate silane in 8 mL of diethyl ether, the mixture was cooled to 0 ° C., 9.35 g of intermediate 1 dissolved in 40 mL of diethyl ether was added dropwise, and the mixture was stirred at 35 ° C. for 2 hours. The solvent was distilled off at 3 hPa and 35 ° C. to obtain 9.6 g of Compound 1 represented by the following formula. In the formula, the average number of repetitions n of the units enclosed in parentheses was 8.

^{The measurement results of 29} Si-NMR (400 MHz, reference: CDCl ₃ (= 7.24 ppm) relaxation reagent: acetylacetone chromium, 10% added to the solute) of the obtained compound (1) are shown below.
²⁹ Si-NMR (solvent: CDCl ₃ ) δ (ppm): 8.20-8.80 ((CH ₃ ) ₃ -Si), -22.50--21.00 ((CH ₃ ) _2- Si) , -106.50--105.4 (Si-NCO)

Example 1-2
6.25 g of tris (trimethylsiloxy) silanol and 28 g of THF were placed in a three-necked flask and stirred. The mixture was cooled to −40 ° C., and 12.5 mL of an n-BuLi hexane solution (1.6 mol / L) was added dropwise. The temperature was raised to 0 ° C., 35.59 g of hexamethylcyclotrisiloxane dissolved in 28 g of THF was added dropwise, and the mixture was stirred for 17 hours. The mixture was cooled to −40 ° C., THF, ion-exchanged water, and hexane were sequentially added to the reaction solution, and the mixture was separated to separate the organic layer. The mixture was washed with ion-exchanged water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a colorless and transparent intermediate 2 represented by the following formula. In the formula, the average number of repetitions n of the units enclosed in parentheses was 8.

After dissolving 0.98 g of tetraisocyanate silane in 8 mL of diethyl ether, the mixture was cooled to 0 ° C., 9.90 g of the intermediate 2 dissolved in 40 mL of diethyl ether was added dropwise, and the mixture was stirred at 35 ° C. for 2 hours. The solvent was distilled off at 3 hPa and 35 ° C. to obtain 10.0 g of Compound 2 represented by the following formula. In the formula, the average number of repetitions n of the units enclosed in parentheses was 8.
^{The measurement results of 29} Si-NMR (400 MHz, reference: CDCl ₃ (= 7.24 ppm) relaxation reagent: acetylacetone chromium, 10% added to the solute) of the obtained compound (2) are shown below.
²⁹ Si-NMR (solvent: CDCl ₃ ) δ (ppm): 8.20-8.80 ((CH ₃ ) ₃ -Si), -22.50--21.00 ((CH ₃ ) _2- Si) , -106.50--105.4 (Si-NCO)

Comparative Example 1-1
0.45 g of trimethylsilanol and 5.1 mL of tetrahydrofuran (THF) were placed in a four-necked flask and stirred. The mixture was cooled to −40 ° C., and 3.13 mL of an n-BuLihexane solution (1.6 mol / L) was added dropwise. The temperature was raised to 0 ° C., 16.68 g of hexamethylcyclotrisiloxane dissolved in 11.9 mL of THF was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 17 hours. The mixture was concentrated under reduced pressure to obtain a colorless and transparent intermediate 3. The mixture was cooled to −40 ° C., and 0.99 g of chlorotriethoxysilane was added dropwise. 100 mL of hexane was added and filtered. The filtrate was concentrated at 130 hPa and 25 ° C. to obtain 16.33 g of Compound 3 represented by the following formula. In the formula, the average number of repetitions n of the units enclosed in parentheses was 8.

Comparative Example 1-2
4.8 g of tetramethyl orthosilicate and 56 mg of tert-butylamine were charged in 10.0 g of Intermediate 1, and the mixture was stirred at 30 ° C. for 5 hours under a nitrogen atmosphere. After returning to room temperature, the mixture was concentrated under reduced pressure to obtain 10.6 g of Compound 4 represented by the following formula. In the formula, the average number of repetitions n of the units enclosed in parentheses was 15.

Examples 2-1 and 2-2
Compounds 1 and 2 as the silane isocyanate compound (a) and methyl ethyl ketone were mixed to obtain coating solutions 1 and 2 as shown in Table 1.

Examples 2-3, 2-4
Compounds 1 and 2 as the silane isocyanate compound (a), tetraethoxysilane (TEOS) as the metal compound (b) and methyl ethyl ketone were mixed at the compositions shown in Table 1 and stirred for 1 hour to prepare a sample solution. .. The obtained sample solution was further diluted with methyl ethyl ketone (MEK) to prepare coating solutions 3 and 4.

Comparative Examples 2-1, 2-2, 2-3
Compounds 3 to 5 and methyl ethyl ketone were mixed to obtain coating solutions 5, 6 and 7 as shown in Table 1.

Compound 5 means a compound represented by the following formula.

Examples 3-1 to 3-4, Comparative Examples 3-1 to 3-3
The alkali-cleaned glass substrate (EAGLE XG, manufactured by Corning) was coated with the coating solutions 1 to 4 and the comparative coating solution at 3000 rpm for 20 seconds using a spin coater (manufactured by MIKASA), and allowed to stand at room temperature. The initial contact angle, droplet slipperiness, adhesion, and light resistance of the obtained film were evaluated. The results are shown in Table 2.

The film formed from the composition containing the compound of the present invention can achieve both water repellency, slipperiness of droplets, and adhesion, and can be used for display devices such as touch panel displays, optical elements, semiconductor elements, building materials, and automobile parts. , Useful as a base material in nanoimprint technology and the like. The film formed from the composition containing the compound of the present invention is suitably used as an article such as a body, window glass (windshield, side glass, rear glass), mirror, bumper, etc. in transportation equipment such as trains, automobiles, ships, and aircraft. Be done. It can also be used for outdoor applications such as building outer walls, tents, photovoltaic modules, sound insulation boards, and concrete. It can also be used for fishing nets, insect nets, aquariums, etc. Furthermore, it can be used for kitchens, bathrooms, wash basins, mirrors, articles for each member around the toilet, ceramics such as chandeliers and tiles, artificial marble, and various indoor equipment such as air conditioners. It can also be used as an antifouling treatment for jigs, inner walls, pipes, etc. in factories. It is also suitable for goggles, eyeglasses, helmets, pachinko, textiles, umbrellas, playsets, soccer balls, and the like. Further, it can also be used as an adhesion preventive agent for various packaging materials such as food packaging materials, cosmetic packaging materials, and the inside of pots.

Claims (6)

A trialkylsilyloxy group having 1 to 4 carbon atoms (however, the hydrogen atom contained in the alkyl group is not substituted with a fluorine atom) and an isocyanate group-bonded silicon atom are linked by a polysilyloxy group. Silane isocyanate compound. The silane isocyanate compound according to claim 1, which is represented by the formula (I).

[In the formula (I), R ^s1 represents a hydrocarbon group having 1 to 4 carbon atoms or (R ^s3 ) ₃ SiO−, and R ^s2 and R ^s3 are independently alkyl groups having 1 to 4 carbon atoms. Represents. The hydrogen atom contained in the hydrocarbon group of ^{R s1 and the alkyl group of R s3} is not substituted with a fluorine atom. However, if R ^s1 is all hydrocarbon groups, then R ^s1 is an alkyl group.
X ^s1 is a hydrolyzable group other than isocyanate group, a hydrocarbon group or a silyloxy group-containing group, -CH ₂ contained in the hydrocarbon group of the X ^s1 - may be replaced to -O-. _{However, -CH 2-} adjacent to the Si atom is not replaced by -O-, and two consecutive -CH _2- are not replaced by -O- at the same time.
n1 represents an integer of 1 or more.
p1 and p2 are independently 1 to 3, and the total is 4 or less. ] The silane isocyanate compound according to claim 2, wherein R ^s1 represents (R ^s3 ) _{3 SiO−.} A coating composition containing the silane isocyanate compound according to any one of claims 1 to 3 and a solvent. The coating composition according to claim 4, further comprising a metal compound in which at least one hydrolyzable group is bonded to a central metal atom. The method for producing a compound according to any one of claims 1 to 3, wherein the compound represented by the formula (IX1) is reacted with the compound represented by the formula (IX2).

[In the formula (IX1),
R ^s1 represents a hydrocarbon group having 1 to 4 carbon atoms or (R ^s3 ) ₃ SiO−, and R ^s2 and R ^s3 independently represent an alkyl group having 1 to 4 carbon atoms. The hydrogen atom contained in the hydrocarbon group of ^{R s1 and the alkyl group of R s3} is not substituted with a fluorine atom. However, if R ^s1 is all hydrocarbon groups, then R ^s1 is an alkyl group.
n1 represents an integer of 1 or more.
In formula (IX2),
X ^s1 is a hydrolyzable group other than isocyanate group, a hydrocarbon group, or a silyloxy group-containing group, -CH ₂ contained in the hydrocarbon group of the X ^s1 - may be replaced to -O-.
_{However, -CH 2-} adjacent to the Si atom is not replaced by -O-, and two consecutive -CH _2- are not replaced by -O- at the same time.
p3 represents an integer of 2-4. ]

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