TWI721161B - Silane isocyanate compound and composition containing the compound - Google Patents

Abstract

The subject of the present invention is to provide a compound that can form a film that can have both water repellency, droplet slippage, and substrate adhesion.

The silane isocyanate compound of the present invention is a trialkylsilyloxy group with an alkyl group of 1 to 4 carbon atoms, and the silicon atom bonded to the isocyanate group is linked by a polysilyloxy group.

Description

Silane isocyanate compound and composition containing the compound

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 components, semiconductor components, construction materials, automotive parts, nanoimprint technology, etc., because droplets will adhere to the surface of the substrate, sometimes the substrate may be contaminated or corroded. Problems such as degradation of pollution or corrosion performance. Therefore, in these fields, the water repellency of the substrate surface is required to be good.

For such a coating film, Patent Document 1 has proposed a use of (CH ₃ ) ₃ SiO-(Si(CH ₃ ) ₂ O) ₄₆ -Si(CH ₃ ) ₂ -(CH ₂ ) ₂ -Si(NCO) ₃ , (CH ₃ ) ₃ SiO-(Si(CH ₃ ) ₂ O) ₁₀ -Si(CH ₃ ) ₂ -(CH ₂ ) ₂ -Si(NCO) ₃ and the like are used as a surface treatment layer formed by a surface treatment agent.

[Prior technical literature] 〔Patent Literature〕

[Patent Document 1] JP 2002-166506 A

In the conventionally known film, the adhesion of the substrate may be insufficient. The present invention has been made in view of such facts, and its subject is to provide a compound that can form a film that can have both water repellency, droplet slippage, and substrate adhesion.

In order to solve the above-mentioned problems, the inventors have conducted intensive research and found that if a compound in which an isocyanate group is bonded to a specific group at the center silicon atom is used, a compound that can make water repellency, droplet slippery, and substrate dense can be formed. It is a compound that has both the characteristics of the film.

The present invention includes the following inventions.

[1] A silane isocyanate compound, which is a trialkylsilyloxy group with an alkyl group of 1 to 4 carbon atoms, and the silicon atom bonded to the isocyanate group is formed by connecting a polysilyloxy group.

[2] The silane isocyanate compound of item [1], which is represented by formula (I);

[In the formula (I), R ^s1 represents a hydrocarbon group having 1 to 4 carbon atoms or of _{^{(R s3) 3 SiO-, R}} s2 and R ^s3 each independently represent a carbon-based alkyl group of 1 to 4, in which R ^s1 of Hydrocarbon groups and ^{the hydrogen atoms contained in the alkyl group of R s3} may be substituted by fluorine atoms. However, ^{when all of R s1} are hydrocarbon groups, R ^s1 is an alkyl group; X ^s1 represents a hydrolyzable group other than an isocyanate group, a hydrocarbon group, or contains silicon The group of the oxy group, the _{-CH 2} -contained in the hydrocarbon group of ^{X s1} can be substituted into -O-, but the -CH ₂ -adjacent to the Si atom is not substituted into -O-, and two consecutive- CH ₂ -is not substituted with -O- at the same time; n1 represents an integer of 1 or more; p1 and p2 are each 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 comprising the silane isocyanate compound of any one of [1] to [3] and a solvent.

[5] The coating composition according to [4], which further contains a metal compound in which at least one hydrolyzable group is bonded to a central metal atom.

[6] A method for producing the compound of any one of items [1] to [3], characterized in that the compound represented by formula (I-X1) is reacted with the compound represented by formula (I-X2) ；

[In formula (I-X1), R ^s1 represents a hydrocarbon group with 1 to 4 carbons or (R ^s3 ) ₃ SiO-, R ^s2 and R ^s3 each independently represent an alkyl group with 1 to 4 carbons, in the R ^{The hydrogen atoms contained in the hydrocarbon group of s1 and} the alkyl group of R ^s3 may be substituted by fluorine atoms. However, ^{when all of R s1} are hydrocarbon groups, R ^s1 is an alkyl group; n1 represents an integer of 1 or more; in formula (I-X2) , X ^s1 represents a hydrolyzable group other than an isocyanate group, a hydrocarbon group, or a group containing a silyloxy group. The _{-CH 2} -contained in the hydrocarbon group of ^{X s1} can be substituted with -O-, but-adjacent to the Si atom CH ₂ -is not substituted into -O-, and two consecutive -CH ₂ -are not substituted into -O- at the same time; p3 represents an integer of 2 to 4].

The silane isocyanate compound (a) of the present invention is a water-repellent film formed from the silane isocyanate compound (a) because the silicon atom bonding the trialkylsilyloxy group and the isocyanate group is linked by a polysilyloxy group The water repellency, droplet slip and substrate adhesion are good.

[Figure 1] Figure 1 shows the emission spectrum of "SP-9 250DB" manufactured by Ushio Electric Co., Ltd.

The silane isocyanate compound (a) of the present invention is a silicon atom (silicone isocyanate) bonded between a trialkyl silyl group and an isocyanate group. Oxy link. Therefore, the silane isocyanate compound (a) can form a film that has both water repellency, droplet slippage, and substrate adhesion. In particular, in the silane isocyanate compound (a) of the present invention, the molecular chain in which the trialkylsilyloxy group and the isocyanate group are bonded to the silicon atom is formed of polysilyloxy group and does not contain carbon-carbon bonds Therefore, a film with good light resistance can be formed.

The aforementioned trialkylsilyloxy group may be independently bonded to the aforementioned polysilyloxy group, or a group formed by multiple bonding to one silyloxy group (hereinafter, sometimes referred to as a composite group) is bonded to The aforementioned polysilyloxy. These single trialkylsilyl groups and composite groups are preferably groups represented by formula (s1).

[In formula (s1), R ^s1 represents a hydrocarbon group or (R ^s3 ) ₃ SiO-, and R ^s3 represents an alkyl group with 1 to 4 carbon atoms. The ^{hydrogen atoms contained in the hydrocarbon group of R s1 and} the alkyl group of R ^s3 may be substituted by fluorine atoms. However, ^{when all of R s1} are hydrocarbon groups, R ^s1 is an alkyl group. ＊Indicating the bonding hand with polysilyloxy group].

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

The hydrocarbon group of R ^s1 is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. Examples of the alkyl group include methyl, ethyl, propyl, and butyl. The plural R ^s1 may be the same or different, and the same is preferred.

The carbon number of the alkyl group of the aforementioned R ^s3 is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2. The alkyl group of R ^{s3 includes} , for example, methyl, ethyl, propyl, butyl, etc., methyl or ethyl is preferred, and methyl is particularly preferred.

In addition, ^{hydrogen atoms contained in the hydrocarbon group of R s1 and} the alkyl group of R ^s3 may be substituted with fluorine atoms. When the number of substitution of fluorine atoms is such that the number of carbon atoms is A, 1 or more is preferable, 3 or more is more preferable, and 2×A+1 or less is more preferable. Contained in the hydrogen atom or a hydrocarbon group of R ^s1 R ^s3 of alkyl substituted by fluorine atoms, or R ^s1 coefficient R ^s3 silicon atoms bonded to the hydrocarbyl group or alkyl substituted with R ^s3 of the each one of R ^s1 Choose appropriately in the range of 1~3.

^{(R s1} ) ₃ SiO- or (R ^s3 ) ₃ SiO- (any of these systems are trialkylsilyloxy groups) in which all R ^s1 are hydrocarbon groups (alkyl groups), the best examples include the following The base shown in the formula and so on. In the formula, * represents the bond hand.

In addition, ^{the total carbon number of R s1} or R ^{s3 contained in (R s1} ) ₃ SiO- or (R ^s3 ) ₃ SiO- in which ^{all of R s1} is a hydrocarbon group (alkyl) is preferably 9 or less, more preferably It is 6 or less, more preferably 4 or less. Furthermore, ^{among the R s1} or R ^{s3 contained in (R s1} ) ₃ SiO- or (R ^s3 ) ₃ SiO- in which ^{all of R s1} is a hydrocarbon group (alkyl), at least one is preferably a methyl group, and two or more of R ^s1 to R ^s3 preferably methyl, to the 3 or R ^s1 to R ^s3 all methyl tertiary good.

Moreover, the group system in which at least one of ^{R s1 is (R s3} ) ₃ SiO-(trialkylsilyloxy) can be, for example, a group represented by the following formula.

The aforementioned polysilyloxy group may be a straight-chain divalent group or a branched-chain trivalent or higher group. A polydialkylsiloxy group is more preferred. good. The aforementioned polysilyloxy group is preferably a group represented by formula (s2).

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

The carbon number of the aforementioned R ^s2 alkyl group is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2. The alkyl group of R ^s2 may be, for example, methyl, ethyl, propyl, butyl, etc., methyl or ethyl is preferred, and methyl is particularly preferred.

The n1 series is preferably 1~100, more preferably 1~80, even more preferably 1~50, particularly preferably 1~30.

The aforementioned isocyanate group-bonded silicon atom only needs to have more than one isocyanate group, one isocyanate group-bonded silicon atom (monoisocyanate silicon atom), two isocyanate group-bonded silicon atoms (diisocyanate silicon atom), Either three isocyanate group-bonded silicon atoms (triisocyanate silicon atom) or four isocyanate group-bonded silicon atoms (tetraisocyanate silicon atom) can be used. In the case of mono-, di-, or triisocyanate silicon atoms, the silicon atom can be bonded to hydrolyzable groups other than isocyanate groups, hydrocarbyl groups, or silyloxy-containing groups, and the -CH ₂ -contained in the hydrocarbyl group can be Replaced by -O-. _{However, -CH 2} -adjacent to the Si atom is not substituted with -O-, and two consecutive -CH ₂ -s are not substituted with -O- at the same time.

The silicon atom system to which such an isocyanate group is bonded can be, for example, a group represented by formula (s3).

[In formula (s3), X ^s1 represents a hydrolyzable group other than an isocyanate group, a hydrocarbon group, or a group containing a silyloxy group, and _{the -CH 2} -system contained in the hydrocarbon group of ^{X s1} can be substituted with -O- . _{However, the -CH 2} -adjacent to the Si atom is not substituted with -O-, and two consecutive -CH ₂ -s are not substituted with -O- at the same time. The p1 and p2 systems are each independently 1 to 3, and the total is 4 or less. ＊Denotes the bonding hands with polysilyloxy].

For p1, 1~3 is preferred, 1~2 is more preferred, and 1 is particularly preferred. P2 is preferably 1 to 3, more preferably 2 to 3, particularly preferably 3. 4-p1-p2 is preferably 0 to 1, and more preferably 0.

Examples of hydrolyzable groups other than the aforementioned isocyanate group include alkoxy, ethoxy, propoxy, butoxy and other alkoxy groups having 1 to 4 carbon atoms; acetoxy groups; chlorine atoms; etc., An alkoxy group having 1 to 4 carbon atoms is preferred, and an alkoxy group having 1 to 2 carbon atoms is more preferred.

The silane isocyanate compound (a) is preferably a compound represented by formula (I).

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

The compound represented by the aforementioned formula (I) has the group represented by the aforementioned formula (s1) as a trialkylsilyloxy group, and the group represented by the aforementioned formula (s2) as a polysilyloxy group, and has the aforementioned formula ( The group shown in s3) is used as an isocyanate group to bond to a silicon atom. The preferred aspect of (s1) this part, (s2) this part, and (s3) this part in formula (I) is the same as the above formula ( s1), (s2), and (s3) are the same.

The aforementioned silyloxy-containing group is a monovalent group containing silyloxy (-Si-O-), which is a structure enclosed by p1 of formula (I) (hereinafter sometimes referred to as "containing three Alkylsilyloxy group") is preferably composed of a few atoms.

The aforementioned silyloxy group-containing group is preferably a group represented by the following formula (s4).

[In formula (s4), R ^s2 has the same meaning as above. R ^s5 represents a hydrocarbon group with 1 to 4 carbon atoms or a hydroxyl group, the -CH ₂ -contained 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 -contained in the divalent hydrocarbon group may be substituted with -O-. _{However, -CH 2} -adjacent to the Si atom is not substituted with -O-, and two consecutive -CH ₂ -s are not substituted with -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, and -CH ₂ -contained in the divalent hydrocarbon group may be substituted with -O-. _{However, -CH 2} -adjacent to the Si atom is not substituted with -O-, and two consecutive -CH ₂ -s are not substituted with -O- at the same time. n2 represents an integer from 0 to 5. ＊Denotes the bonding hands with silicon atoms].

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

The hydrocarbon group of X ^s1 is preferably an alkyl group such as a methyl group, an ethyl group, and a propyl group. _{Examples of the group system in which -CH 2} -contained in the hydrocarbon group is substituted with -O- can be exemplified by 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 above, respectively].

The silane isocyanate compound (a) is particularly preferably a compound represented by the following formula. In the formula, n10 represents an integer from 1 to 30.

The silane isocyanate compound (a) can be produced by reacting a compound in which a trialkylsilyloxy group and a hydroxyl group are linked by a polysilyloxy group with a silicon isocyanate compound, for example, the compound represented by the aforementioned formula (I) It can be produced by reacting a compound represented by formula (I-X1) with a compound represented by formula (I-X2).

[In formula (I-X1), R ^s1 represents a hydrocarbon group or (R ^s3 ) ₃ SiO-, and R ^s2 and R ^s3 each independently represent an alkyl group with 1 to 4 carbon atoms. The ^{hydrogen atoms contained in the hydrocarbon group of R s1 and} the alkyl group of R ^s3 may be substituted by fluorine atoms. However, ^{when all of R s1} are hydrocarbon groups, 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 other than an isocyanate group, a hydrocarbyl group, or a group containing a silyloxy group. The _{-CH 2} -contained in the hydrocarbyl group of ^{X s1} can be substituted with -O- . However, -CH ₂ -of adjacent Si atoms is not substituted with -O-, and two consecutive -CH ₂ -s are not substituted with -O- at the same time. p3 represents an integer of 2 or more].

Compound (I-X2) is 1 mol or more of compound (I-X1), preferably 1 mol or more, more preferably 1.5 mol, and even more preferably 2 mol or more, and 5 mol or less More preferably, it is more preferably 3 mol or less.

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

The aforementioned compound (I-X1) is a compound in which a halogen atom is bonded to both ends of the dialkylsiloxane chain (hereinafter, "dihalogenated dialkylsiloxane") or a cyclic dialkyl group Silicone, ginseng (trialkylsiloxy) silyl, and M ¹ O- group (M ¹ represents an alkali metal.) bonded compound (hereinafter, "alkali metal silyl oxide") is produced by reacting .

The halogen atom system contained in the aforementioned dihalogenated dialkylsiloxane includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a chlorine atom is preferred. In addition, lithium is preferred as the alkali metal system.

In addition, the number of silicon atoms contained in the aforementioned cyclic dialkylsiloxane is preferably 2 or more and 10 or less, more preferably 2 or more and 5 or less, and still more preferably 2 or more and 4 or less.

Alkali metal silicon-based oxides can be ^{produced by reacting a compound represented by (R s1} ) ₃ Si-OH with an alkali metal alkyl. Alkali metal alkyls include, for example, alkyl lithiums such as n-butyllithium, second-butyllithium, and tertiary-butyllithium, and n-butyllithium is particularly preferred.

The composition containing the above-mentioned 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 isocyanate group bonded to the central silicon atom, it has good adhesion to various substrates and can form a film that has both water repellency, droplet slippage, and light resistance.

The content of the silane isocyanate compound (a) is based on 100% by mass of the composition, preferably 0.001% by mass or more, more preferably 0.1% by mass or more, still more preferably 1% by mass or more, and more preferably 50% by mass or less More preferably, it is 30% by mass or less, and even more preferably, it is 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 within 100% by mass of the composition, preferably 0.01% by mass or more, more preferably 0.05% by mass or more .

In addition, when the metal compound (b) described later is contained in the composition, the content of the silane isocyanate compound (a) is within 100% by mass of the composition, preferably 10% by mass or less, and more preferably 5% by mass or less .

The aforementioned composition may further include a metal compound (b) having at least one hydrolyzable group bonded to a metal atom, and the aforementioned silyloxy group-containing group or the aforementioned hydrocarbon chain-containing group can be bonded to the aforementioned metal atom. The number of atoms of the aforementioned silyloxy group and the number of carbons of the hydrocarbon chain portion of the aforementioned hydrocarbon chain-containing group are respectively less than those bonded to the silane isocyanate compound (a) The central silicon atom has the number of atoms of the molecular chain containing the trialkylsilyl group, so the film formed by the composition of the present invention can form a part with the function of a spacer. As a result, the molecular chain containing the trialkylsilyl group can improve the water repellency enhancing effect. The group bonded to the metal atom is preferably a group containing a silyloxy group.

The aforementioned metal compound (b) is preferably a compound represented by formula (II-1), (II-2) or (II-3). These compounds can be used individually or in combination of multiple types. In addition, the compound represented by formula (II-1), (II-2) or (II-3) may be its hydrolysis condensate. Here, the hydrolysis condensate means a compound in which all or a 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 that can form a metal alkoxide. R ^b1 represents a silyloxy-containing group, a hydrocarbyl group, or a hydrolyzable group, and _{the -CH 2} -contained in the hydrocarbyl group of ^{R b1} may be substituted with -O-. _{However, -CH 2} -adjacent to the silicon atom is not substituted with -O-, and two consecutive -CH ₂ -s are not substituted with -O- at the same time. A ^b1 represents a hydrolyzable group. k is 2 less than the price of M.

In the formula (II-2), R ^f1 represents a fluorinated carbon-containing group. A ^f1 represents a hydrolyzable group. Z ^f1 represents a group containing a silyloxy group, a hydrocarbyl group or a hydrolyzable group, and the _{-CH 2} -contained in the hydrocarbyl group of ^{Z f1} may be substituted with -O-. _{However, -CH 2} -adjacent to the silicon atom is not substituted with -O-, and two consecutive -CH ₂ -s are not substituted with -O- at the same time.

In the formula (II-3), R ^f2 represents a hydrolyzable silane oligomer residue. A ^f2 each independently represents a hydrolyzable group, a fluoroalkyl group having 1 to 12 carbons, or an alkyl group having 1 to 4 carbons].

M is a metal atom that can bond with an alkoxy group to form a metal alkoxide, and the metal atom also includes semi-metals such as Si and Ge. The M series may include, for example, trivalent metals such as Al, Fe, and In; tetravalent metals such as Hf, Si, Ti, Sn, Zr, etc.; and the like, preferably Si.

The hydrolyzable group of R ^b1 , A ^b1 , A ^f1 , Z ^f1 or A ^f2 includes, for example, the same groups and isocyanate groups as the hydrolyzable groups in the silane isocyanate compound (a), and an alkane with 1 to 4 carbon atoms An oxy group is preferred, and an alkoxy group having 1 to 2 carbon atoms is more preferred.

The ^{silyloxy-containing group or hydrocarbyl group of R b1} or Z ^{f1 For} the silyloxy-containing group or hydrocarbyl group of X ^s1 , it can be appropriately selected from the ranges described separately, and the number is less than 1 Good, 0 is particularly good.

The ^{fluorinated carbon-containing group of R f1} is a monovalent group having 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 preferred. The group containing fluorinated carbon is preferably the group represented by formula (f1).

[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. The L system represents any of -O-, -COO-, -OCO-, -NR ^f5 -, -NR ^f5 CO-, and -CONR ^f5 -. R ^f5 represents a hydrogen atom or an alkyl group with 1 to 4 carbons or a fluoroalkyl group with 1 to 4 carbons. h1~h5 are integers from 0 to 100, and the total value of h1 to h5 is 100 or less. In addition, when the order of each repeating unit in the parentheses of h1 to h5 is attached, it can be any (position) in the formula. ＊Denotes the bond hand].

The carbon number of the fluoroalkyl group of R ^f3 or R ^f4 ranges from 1 to 20, preferably from 1 to 12, more preferably from 1 to 10, and even more preferably from 1 to 5. In addition, ^{when the number of substitutions of fluorine atoms in the fluoroalkyl group of R f3} or R ^{f4 is} the number of carbon atoms contained in the fluoroalkyl group as A, it is 1 or more and 2A+1 or less, which is 2A+1, That is, 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.} L ^f1 is preferably -O-, -COO-, or -OCO-.

For h1, 1~30 is preferred, 1~25 is more preferred, 1~10 is even more preferred, 1~5 is particularly preferred, and the best is 1~2. The h2 series is preferably 0-15, more preferably 0-10. The h3 series is preferably 0~5, more preferably 0~2. The h4 system is preferably 0~4, more preferably 0~2. For h5, 0~4 is better, even better Department 0~2. 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, and even more preferably 20 or less.

In particular, R ^f3 is a perfluoroalkyl group with 1 to 5 carbons, R ^f4 is a fluorine atom or a perfluoroalkyl group with 1 to 5 carbons, R ^b4 is a hydrogen atom, and h3, h4 and h5 are any of them 0, h1 is 1~5, h2 is 0~5 preferably.

Examples of the aforementioned fluorocarbon-containing group include groups represented by the following formula. In the formula, R ^f3 and R ^{b4 have} the same meanings as above, R ^{f3 is} preferably a perfluoroalkyl group with 1 to 12 carbon atoms, and R ^{b4 is} preferably a hydrogen atom. Also, r2 is 5~20 (preferably 8~15), r3 is 1~7 (preferably 2~6), r4 is 1~10 (preferably 3~7), r5 is 1~6 ( Preferably it is 2~4).

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

The group represented by the formula (f1-2) may be, for example, a group represented by the following formula. However, L ^f2 represents an alkanediyl group having 5 to 20 carbon atoms.

[Chemical formula 18] F ₃ COL ^f2 -* F ₃ CF ₂ COL ^f2 -* F ₃ C(F ₂ C) ₂ -OL ^f2 -* F ₃ C(F ₂ C) ₃ -OL ^f2 -*

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

The group represented by the formula (f1-4) includes, for example, the group represented by the following formula. However, L ^f2 represents an alkanediyl group having 5 to 20 carbon atoms.

The group represented by the formula (f1-5) includes, for example, the group represented by the following formula. However, L ^f3 represents an alkanediyl group having 1 to 6 carbon atoms.

[Chemical formula 21] F ₃ CL ^f3 -* F ₃ CF ₂ CL ^f3 -* F ₃ C(F ₂ C) ₂ -L ^f3 -* F ₃ C(F ₂ C) ₃ -L ^f3 -* F ₃ C( F ₂ C) ₄ -L ^f3 -* F ₃ C(F ₂ C) ₅ -L ^f3 -* F ₃ C(F ₂ C) ₆ -L ^f3 -* F ₃ C(F ₂ C) ₇ -L ^f3 -*

The base system containing fluorocarbon may be fluoroalkylaryl, fluoroalkylalkenyl, fluoroalkylalkynyl and the like. Examples of the fluoroalkyl aryl group include (C _1-8 fluoroalkyl) phenyl and (C _1-8 fluoroalkyl) naphthyl, and the fluoroalkyl alkenyl group includes, for example, (C _1-17 fluoroalkyl). ) Vinyl and fluoroalkylalkynyl groups include, for example, (C _1-17 fluoroalkyl)ethynyl.

In the formula (II-3), ^{the hydrolyzable silane oligomer residue of R f2} means a compound derived from a silicon atom and a hydrolyzable group bonded to the silicon atom (hereinafter, sometimes referred to as "hydrolyzable The monovalent group of the hydrolysis condensate of silane monomer"). The number of silicon atoms contained in the residue of the hydrolyzable silane oligomer is preferably 3 or more, more preferably 5 or more, and still more preferably 7 or more. The number of silicon atoms contained in the residue of the hydrolyzable silane oligomer is preferably 15 or less, more preferably 13 or less, and still more preferably 10 or less.

In addition, when the hydrolyzable silane oligomer residue has an alkoxy group, the alkoxy group may include, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc., preferably a methoxy group, Ethoxy and so on. The aforementioned hydrolyzable silane oligomer residue may have one or two or more of these alkoxy groups, and preferably one.

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

[In the above formula (f2), A ^f3 represents a hydrolyzable group, an alkyl group with 1 to 4 carbons, or a fluoroalkyl group with 1 to 4 carbons. h6 is an integer from 0 to 100. ＊Denotes the bond with Si].

The hydrolyzable group of A ^{f3 includes , for example, the same groups as the hydrolyzable group of R b1} . Alkoxy is preferred, and carbon numbers such as ethoxy and methoxy are 1-4 (preferably 1~ 2) Alkoxy; isocyanate group is preferred.

The h6 system is preferably 0 or more and 10 or less, and more preferably 0 or more and 7 or less. A ^f3 is preferably a hydrolyzable group or a fluoroalkyl group having 1 to 4 carbons, and it is preferable ^{that at least one of A f3} is a fluoroalkyl group having 1 to 4 carbons. In addition, ^{at least one of A f3} is preferably a hydrolyzable group (especially a methoxy group and an ethoxy group).

The hydrolyzable silane oligomer residue is preferably a group represented by the following formula.

R ^b1 is preferably a silyloxy group-containing group or a hydrolyzable group, and more preferably a hydrolyzable group. When a plural number of R ^b1 is contained, any one of them is preferably a hydrolyzable group. In this case, it ^{is preferable that R b1} and A ^{b1 have the} same hydrolyzable group. Z ^f1 is preferably a silyloxy-containing group or a hydrolyzable group, and more preferably a hydrolyzable group. A ^f2 is preferably a fluoroalkyl group or a hydrolyzable group.

The compound (II-1) includes, for example, a compound having only a hydrolyzable group; a compound having a silyloxy group and a hydrolyzable group; a compound having two silyloxy group and a hydrolyzable group ; A compound with a hydrocarbyl group and a hydrolyzable group; a compound with two hydrocarbyl groups and a hydrolyzable group; etc.

Examples of compounds with only hydrolyzable groups include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc.; triethoxyaluminum, tripropane Trialkoxy aluminum such as aluminum oxide and tributoxide aluminum; trialkoxy iron such as triethoxy iron; trimethoxy indium, triethoxy indium, tripropoxy indium, tributoxide Trialkoxy indium such as indium; tetraalkoxy hafnium such as tetramethoxy hafnium, tetraethoxy hafnium, tetrapropoxy hafnium, tetrabutoxy hafnium, etc.; tetramethoxy titanium, tetraethoxy Base titanium, tetrapropoxy titanium, tetrabutoxy Tetraalkoxide titanium such as titanium base; tetramethoxide tin, tetraethoxytin, tetrapropoxytin, tetrabutoxytin, etc. tetraalkoxide tin; tetramethoxyzirconium, tetraethoxy Tetraalkoxy zirconium such as base zirconium, tetrapropoxy zirconium, tetrabutoxy zirconium, etc.; etc.

The compound system having a group containing a silyloxy group and a hydrolyzable group includes, for example, trimethylsilyloxytrimethoxysilane, trimethylsilyloxytriethoxysilane, and trimethylsilyloxytripropoxy Trimethylsilyloxytrialkoxysilane such as silyl silane; etc.

The compound system having two silyloxy-containing groups and hydrolyzable groups includes, for example, bis(trimethylsilyloxy)dimethoxysilane and bis(trimethylsilyloxy)diethoxysilane , Bis(trimethylsilyloxy)dipropoxysilane, etc. bis(trimethylsilyloxy)dialkoxysilane; etc.

The compound system having a hydrocarbon group and a hydrolyzable group includes, for example, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, methyltripropoxysilane, etc. Alkyl trialkoxy silane; vinyl trimethoxy silane, vinyl triethoxy silane and other alkenyl trialkoxy silane; etc.

Compounds having two hydrocarbon groups and hydrolyzable groups include, for example, dimethyldimethoxysilane, diethyldimethoxysilane, dimethyldiethoxysilane, and diethyldiethoxysilane The dialkyl dialkoxysilanes; etc.

The compound (II-2) is a compound represented by the following formula, for example. In the formula, r2 is 5~20 (preferably 8~15), r3 is 1~7 (preferably 2~6), r4 is 1~10 (preferably 2~8, more preferably 2~5 ), r5 is 1~5 (preferably 2~4), r6 is 2~10 (preferably 2~8), r7 is 2~10 (preferably 3~7).

Compound (II-3) may be, for example, a compound represented by the following formula Things.

When the metal compound (b) is contained in the composition, its content is in 100% by mass of the composition, preferably 0.02% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more , 20% by mass or less is preferable, 10% by mass or less is more preferable, and 7% by mass or less is still more preferable.

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)/silicone isocyanate compound (a)) is based on a molar basis and is 1 /10 or more is better, more preferably 1/1 or more, still more preferably 2/1 or more, more preferably 100/1 or less, more preferably 50/1 or less, and even more preferably 40/1 or less, More preferably, it is 30/1 or less.

The composition of the present invention preferably contains the solvent (c). Examples of the solvent (c) include water; hydrophilic organic solvents such as alcohol-based solvents, ether-based solvents, ketone-based solvents, ester-based solvents, and amide-based solvents; and hydrophobicity of aromatic hydrocarbon-based solvents, saturated hydrocarbon-based solvents, etc. The organic solvent may be used alone or in combination of two or more kinds.

烷等，酮系溶劑係可舉例如丙酮、甲乙酮等，酯系溶劑係可舉例如乙酸乙酯、乙酸丁酯等，醯胺系溶劑係可舉例如二甲基甲醯胺等，芳香族烴系溶劑係可舉例如苯、甲苯、二甲苯等，飽和烴系溶劑係可舉例如己烷、環己烷等。 Examples of the aforementioned alcohol-based solvent systems include methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, and diethylene glycol, and examples of the aforementioned ether-based solvent systems include dimethoxyethane and tetrahydrofuran. ,two

Alkanes, etc., ketone-based solvents, for example, acetone, methyl ethyl ketone, etc., ester-based solvents, for example, ethyl acetate, butyl acetate, etc., amide-based solvents, for example, dimethylformamide, etc., aromatic hydrocarbons Examples of the solvent system include benzene, toluene, and xylene, and examples of the saturated hydrocarbon solvent system include hexane and cyclohexane.

Among them, ether solvents and saturated hydrocarbon solvents are preferred.

The solvent (c) is based on 1 part by mass of the silane isocyanate compound (a) (when the metal compound (b) is included, the total of the silane isocyanate compound (a) and the metal compound (b)), preferably 0.1 parts by mass or more , More preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, particularly preferably 12 parts by mass or more, preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 50 parts by mass the following. If the amount of solvent (c) is in this range, it is easy to control the thickness of the film.

The composition system of the present invention may not contain the catalyst (d), but may also contain the catalyst (d) as needed. The catalyst (d) may act as a hydrolysis catalyst for isocyanate groups and other hydrolyzable groups bonded to silicon atoms, and examples thereof include acidic compounds; basic compounds; organometallic compounds; and the like. Examples of the aforementioned acidic compounds include inorganic acids such as hydrochloric acid and nitric acid; organic acids such as acetic acid; and the like. The aforementioned basic compound system includes, for example, ammonia; amine; and the like. The aforementioned organometallic compounds include organometallic compounds with metal elements such as Al, Fe, Zn, and Sn as the central metal, and organoaluminum compounds such as aluminum acetylacetone complexes, aluminum ethyl acetylacetone complexes, etc. Compounds; organic iron compounds such as iron octoate; organic zinc compounds such as zinc acetylacetone monohydrate, zinc naphthenate, zinc octoate, etc.; dibutyl tin two Organotin compounds such as acetate complexes; etc.

When the catalyst (d) is contained, its content is relative to 100 parts by mass of the silane isocyanate compound (a) (when the metal compound (b) is contained, the total of the silane isocyanate compound (a) and the metal compound (b)) is 100 parts by mass, More preferably 0.0001 parts by mass or more, more preferably 0.0002 parts by mass or more, still more preferably 0.001 parts by mass or more, more preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass the following.

Furthermore, the composition of the present invention may contain antioxidants, rust inhibitors, ultraviolet absorbers, light stabilizers, anti-fungal agents, antibacterial agents, anti-biological adhesion agents, and deodorizing agents within a range that does not hinder the effects of the present invention. Various additives such as agents, pigments, flame retardants, antistatic agents, etc.

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

The aforementioned phenolic antioxidant system may include, for example, n-octadecyl-3-(4-hydroxy-3,5-di-tertiary-butylphenyl) propionate, 2,6-di-tertiary- Butyl-4-methylphenol, 2,2-sulfur-diethylene-bis-[3-(3,5-di-tertiary-butyl-4-hydroxyphenyl)propionate], tri-ethyl Diol-bis-[3-(3-tertiary-butyl-5-methyl-4-hydroxyphenyl)propionate], 3,9-bis[2-{3-(3-third- Butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxspiro[5‧5]undecane Alkane, four {3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid} neopentylerythritol ester, 2-tert-butyl-6-(3-third -Butyl-2-hydroxy-5-methyldibenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tertiary-pentylbenzene Yl)ethyl]-4,6-di-tertiary-pentyl phenyl acrylate, 1,3,5-trimethyl-2,4,6-ginseng (3,5-di-tertiary-butan 4-hydroxydi Benzoyl)benzene, ginseng (3,5-di-tertiary-butyl-4-hydroxydibenzyl) isocyanate, 1,3,5-ginseng (4-tert-butyl- 3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 2,2'-methylene Bis(6-tertiary-butyl-4-methylphenol), 4,4'-butylene bis(6-tertiary-butyl-3-methylphenol), 4,4'-thiobis( 6-tert-butyl-3-methylphenol) and so on.

The aforementioned sulfur-based antioxidant system can include, for example, 3,3'-thiodipropionate di-n-dodecyl ester, 3,3'-thiodipropionate di-n-tetradecyl ester, 3,3 '-Di-n-octadecyl thiodipropionate, 4-(3-dodecylthiopropionate) neopentyl erythritol ester, etc.

The aforementioned phosphorus-based antioxidants may include, for example, ginseng (2,4-di-tertiary-butylphenyl) phosphite, bis(2,4-di-tertiary-butylphenyl) neopentaerythritol Phosphite, bis(2,6-di-tertiary-butyl-4-methylphenyl) neopentylerythritol diphosphite, bis(2,4-di-cumylphenyl) new Pentaerythritol diphosphite, Si (2,4-di-tertiary-butylphenyl)-4,4'-biphenylene diphosphate, bis-[2,4-di-tertiary- Butyl, (6-methyl)phenyl]ethyl phosphite, etc.

-2,4-二基}{(2,2,6,6-四甲基-4-哌啶基)亞胺基}-1,6-六亞甲基{(2,2,6,6-四甲基-4-哌啶基)亞胺基}〕等。 Examples of the aforementioned hindered amine antioxidants include bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (melting point 81~86℃), 2,2,6,6 -Tetramethyl-4-piperidinyl methacrylate (melting point 58℃), poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5- three

-2,4-Diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imino}-1,6-hexamethylene{(2,2,6,6 -Tetramethyl-4-piperidinyl)imino}] etc.

Examples of the aforementioned rust inhibitor are alkanolamines such as triethanolamine; quaternary ammonium salts; alkanethiols; imidazolines, imidazoles, alkylimidazoline derivatives, benzimidazoles, 2-hydrothiobenzimidazoles Azoles such as benzotriazole Class; sodium metavanadate; bismuth citrate; phenol derivatives; aliphatic amines, aromatic amines, ethoxylated amines such as alkylamines or polyalkenyl amines, cyanoalkylamines, cyclohexylamine benzoate, Amine compounds such as aliphatic diamines such as alkylene diamines and aromatic diamines; amides of the aforementioned amine compounds and carboxylic acids; alkyl esters; pyrimidines; naphthenic acids; sulfonic acid complexes; calcium nitrite, Nitrite such as sodium nitrite and dicyclohexylamine nitrite; polyol compounds such as polyalcohol and polyphenol; heteropolymer of sodium molybdate, sodium tungstate, sodium phosphonate, sodium chromate, sodium silicate, etc. Acid salts; gelatin; polymers of carboxylic acids; nitro compounds; formaldehyde; acetylene alcohols; thiol compounds such as aliphatic thiols, aromatic thiols, and acetylene thiols; aliphatic thioethers, aromatic thioethers, and acetylenes Sulfide compounds such as sulfides; sulfinium compounds, benzhydryl sulfide compounds, etc.; thiourea; combination of amine or quaternary ammonium salt and halogen ion; combination of alkylamine and potassium iodide; tannin Combination with sodium phosphate; combination of triethanolamine and lauryl sarcosine; combination of triethanolamine and lauryl sarcosine and benzotriazole; combination of alkylamine and benzotriazole and sodium nitrite and sodium phosphate ;Wait.

-2-基)-5〔(己基)氧〕-酚、2-乙氧基-2’-乙基-草酸雙醯胺苯等。 Examples of the aforementioned ultraviolet absorber/light stabilizer system include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethyl Benzyl dibenzyl) phenyl]-2H-benzotriazole, 2-(3-tertiary-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2 -(2'-Hydroxy-5'-tertiary-octylphenyl)benzotriazole, methyl-3-[3-tertiary-butyl-5-(2H-benzotriazol-2-yl) )-4-hydroxyphenyl]propionate-polyethylene glycol (molecular weight about 300) condensate, hydroxyphenyl benzotriazole derivative, 2-(4,6-diphenyl-1,3, 5-Three

-2-yl)-5[(hexyl)oxy]-phenol, 2-ethoxy-2'-ethyl-diaminobenzene oxalate and the like.

The antifungal agent/antibacterial agent system includes, for example, 2-(4-thiazolyl)benzimidazole, sorbic acid, 1,2-benzisothiazolin-3-one, (2-pyridylsulfur-1-oxide) ) Sodium, dehydroacetic acid, 2-methyl-5-chloro-4-isothiazolone complex, 2,4,5,6-tetrachlorophthalonitrile, methyl 2-benzimidazole carbamate, 1- (Butylaminomethyl)-2-benzimidazole carbamic acid methyl ester, mono- or dibromocyanoacetamide, 1,2-dibromo-2,4-dicyanobutane, 1,1-di Bromo-1-nitropropanol and 1,1-dibromo-1-nitro-2-acetoxypropane, etc.

、4,5-二氯-2-正-辛基-4-異噻唑啉-3-酮、呋喃酮類、烷基吡啶化合物、Gramine系化合物、異腈化合物等。 The aforementioned anti-biological adhesion agent system may include, for example, tetramethylthiuram (thiuram) disulfide, bis(N,N-dimethyldiamine ethyl thioformate) zinc, 3-(3,4-dichlorobenzene) Yl)-1,1-dimethylurea, dichloro-N-((dimethylamino)sulfonyl)fluoro-N-(P-tolyl)methanesulfonamide, pyridine-triphenyl Borane, N,N-dimethyl-N'-phenyl-N'-(fluorodichloromethylsulfur)sulfonamide, cuprous thiocyanate (1), cuprous oxide, tetrabutyl thiuram Disulfide, 2,4,5,6-tetrachloroisophthalonitrile, zinc ethylene bisdithiocarbamate, 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine , N-(2,4,6-trichlorophenyl)maleimide, bis(2-pyridinethiol-1-oxide) zinc salt, bis(2-pyridinethiol-1-oxide) Copper salt, 2-methylsulfide-4-tert-butylamino-6-cyclopropylamino-s-tri

, 4,5-Dichloro-2-n-octyl-4-isothiazolin-3-one, furanones, alkylpyridine compounds, Gramine compounds, isonitrile compounds, etc.

The aforementioned deodorant system can include, for example, lactic acid, succinic acid, malic acid, citric acid, maleic acid, malonic acid, ethylenediamine polyacetic acid, alkane-1,2-dicarboxylic acid, and alkene-1,2-dicarboxylic acid. Organic acids such as carboxylic acid, cycloalkane-1,2-dicarboxylic acid, cycloolefin-1,2-dicarboxylic acid, naphthalenesulfonic acid, etc.; zinc undecylenate, zinc 2-ethylhexanoate, castor Fatty acid metals such as zinc sesame oil; iron oxide, iron sulfate, oxygen Zinc, 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.) four Metal compounds such as sulfonic phthalocyanine, titanium dioxide, visible light-sensitive titanium dioxide (nitrogen doped type, etc.); α-, β- or γ-cyclodextrin, its methyl derivatives, hydroxypropyl derivatives, glucoside derivatives Cyclodextrins such as porous methacrylic acid polymer, porous acrylic polymer, porous divinylbenzene polymer, porous styrene-divinylbenzene-vinyl Aromatic polymers such as pyridine polymer, porous divinylbenzene-vinylpyridine polymer, and their copolymers, chitin, chitosan, activated carbon, silica gel, activated alumina, zeolite , Ceramics and other porous bodies.

系顏料、雙偶氮縮合系顏料或苯並咪唑酮系顏料等。 The aforementioned pigments include, for example, carbon black, titanium oxide, phthalocyanine-based pigments, quinacridone-based pigments, isoindolinone-based pigments, perylene or pyrene-based pigments, quinoline yellow-based pigments, and diketopyrrole-pyrrole-based pigments ,two

Series pigments, bis-azo condensation series pigments, or benzimidazolone series pigments, etc.

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

The aforementioned antistatic agent may include, for example, a quaternary ammonium salt type cationic surfactant, a betaine type amphoteric surfactant, an alkyl phosphate type anionic surfactant, a first amine salt, a second amine salt, Cationic surfactants such as tertiary amine salts, tertiary amine salts or pyridine derivatives, sulfated oils, soaps, sulfated ester oils, sulfated amide oils, sulfated ester salts of olefins, fatty alcohol sulfuric acid Ester salts, alkyl sulfate ester salts, fatty acid ethyl sulfonate, alkyl naphthalene sulfonate, alkyl benzene sulfonate, succinate sulfonate Anionic surfactants such as acid salts or phosphate salts, fatty acid esters of polyhydric alcohols, ethylene oxide adducts of fatty alcohols, ethylene oxide adducts of fatty acids, fatty amine groups or fatty acid amides The ethylene oxide adduct of alkylphenol, the ethylene oxide adduct of alkylphenol, the ethylene oxide adduct of fatty acid ester of polyhydric alcohol, or nonionic surfactants such as polyethylene glycol, Amphoteric surfactants such as carboxylic acid derivatives or imidazoline derivatives.

In addition, as for additives, lubricants, fillers, plasticizers, nucleating agents, anti-compressive agents, foaming agents, emulsifiers, gloss agents, binding agents, etc. may be further coexisted.

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

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

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

The film of the present invention makes the initial contact angle of water to the film θ ₀₁ , and when the contact angle after immersing in ion-exchanged water at 70°C for 12 hours is θ _w2 , the contact angle change rate d _w2 shown in the following formula is -10% or more is preferable, more preferably -5% or more, still more preferably -1% or more, and 0% is more preferable, but 2% or less, and further 5% or less is also allowed.

Contact angle change rate d _w2 (%)=(θ _w2 -θ ₀₁ )/θ ₀₁ ×100

_{The initial contact angle θ 01} of the water 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 may be 130° or less.

The aforementioned contact angle means the value measured by the θ/2 method using 3.0 μL of water.

_{The drop angle α w} of the water to 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 may be 5° or more, and further It can also be 10° or more.

_{In addition, the contact angle retardation Δθ w} of water to 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 lag Δθ _w and the drop angle α _w of the aforementioned water can be measured by the sliding method using 6.0 μL of water.

The sliding speed in 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, particularly preferably 20 mm/sec or more.

The aforementioned sliding speed is a value obtained by dividing the moving distance when a 50 μL droplet (water) is dropped by the time required for the movement when the substrate with the film of the present invention is inclined at 20°. Specifically, it can be measured by the dynamic sliding method using a contact angle meter made by Kyowa Interface System.

The film of the present invention makes the initial contact angle of water to the film A ₁ , and the light intensity of the mercury lamp with a bright line in the region below 300nm is 200±10mW/cm ² , at a temperature of 20-40℃, In an atmospheric environment with a humidity of 30~75%, when the contact angle after 6 hours of irradiation is set to B _Z , the change rate of the contact angle before and after the irradiation calculated according to the following formula is preferably -10% or more, more preferably -4.5% or more, more preferably -4% or more, such as 0% or less, and further -1% or less are also allowed.

Contact angle change rate (%)=((B _Z -A ₁ )/A ₁ )×100(%)

The structure (A) derived from the silane isocyanate compound (a) is preferably a trialkylsilyloxy group having an alkyl group with a carbon number of 1 to 4, and a polysilyloxy group bonded structure (containing a trialkyl group) The base of silyloxy group) and the structure shown in formula (IA).

[In formula (IA), R ^s1 , R ^s2 and n1 have the same meaning as above. Z ^a1 means (R ^s1 ) ₃ Si-O-(Si(R ^s2 ) ₂ -O-) _n1 -, a group containing a silyloxy group, a hydrocarbyl group or -O-, which is contained in the hydrocarbyl group of ^{Z a1} CH ₂ -can be substituted into -O-. _{However, the -CH 2} -adjacent to the Si atom is not substituted with -O-, and two consecutive -CH ₂ -s are not simultaneously substituted with -O-].

In the formula (IA), the ^{silyloxy-containing group and the hydrocarbyl group of Z a1 may} be a silyloxy-containing group and a hydrocarbyl group, respectively, and are appropriately selected from the range described above. Z ^a1 is preferably a group containing a silyloxy group or -O-, more preferably -O-.

The structure (A) is preferably the structure shown in formula (IA-1).

[In formula (IA-1), R ^s1 , R ^s2 and n1 have the same meaning as above].

The structure (A) is particularly preferably the structure shown by the following formula. In the formula, n10 represents an integer from 1 to 30.

In addition, the film formed from the composition of the present invention preferably has a structure derived from the metal compound (b). The structure (B) derived from the metal compound (b) is bonded to a metal atom (However, when the metal atom is a silicon atom, it is different from the silicon atom bonded to a molecular chain containing a trialkylsilyl group) The group (hydrocarbyl group, silyloxy group-containing group, hydroxyl group, etc.) is because the number of constituent elements is less than the molecular chain containing trialkylsilyl group, so the structure (B) functions as As a result of the spacer, the water repellency improvement effect caused by the molecular chain containing the trialkylsilyl group is easily improved.

The structure (B) derived from the metal compound (b) is preferably the 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 group containing a silyloxy group, a hydrocarbyl group, a hydroxyl group or an -O- group, and the _{-CH 2} -contained in the hydrocarbyl group of ^{R b2} can be substituted with -O-. _{However, -CH 2} -adjacent to the silicon atom is not substituted with -O-, and two consecutive -CH ₂ -s are not substituted with -O- at the same time. k is an integer of 1 or 2 according to the valence of M.

In the formula (IIB2), R ^f1 represents a fluorinated carbon-containing group. Z ^f2 represents a group containing a silyloxy group, a hydrocarbyl group, a hydroxyl group or -O-, and the _{-CH 2} -contained in the hydrocarbyl group of ^{Z f2} can be substituted with -O-. _{However, the -CH 2} -adjacent to the Si atom is not substituted with -O-, and two consecutive -CH ₂ -s are not substituted with -O- at the same time.

In the formula (IIB3), R ^f2 represents a hydrolyzable silane oligomer residue. Z ^f3 represents a fluoroalkyl group with 1 to 12 carbons, an alkyl group with 1 to 4 carbons, a hydroxyl group or -O-].

R ^b2 or Z ^f2 of the group of silicon-based group-containing, R Z ^{f2 b2} of hydrocarbyl or hydrolyzable atoms and R ^f2 of alkoxy silicon oligomer residues than the system containing a molecular chain of trialkyl silicon based The smaller number of atoms is better. This makes it easier for the structure (B) to act as a spacer in the film.

R ^b2 or Z ^f2 of the group containing a group of silicon-based, or a hydrocarbon group and R ^b2 may be the line Z ^f2 such as for example silicon based group Z ^a1 of the group, and the hydrocarbon group containing the same respectively.

R ^b2 is preferably a group containing a silyloxy group, a hydroxyl group or -O-, and more preferably a hydroxyl group or -O-. Z ^f2 is preferably a group containing a silyloxy group, a hydroxyl group or -O-, and more preferably a hydroxyl group or -O-. Z ^f3 is preferably a fluoroalkyl group, a hydroxyl group or -O-.

When the structure (B) is a silicon atom, the structure shown in 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 existence ratio of structure (B) to structure (A) (structure (B)/structure (A)) is preferably 1/10 or more on a molar basis, more preferably More than 1/1, more preferably more than 2/1, more preferably less than 100/1, more preferably less than 50/1, more preferably less than 30/1, and even more preferably less than 25/1 .

By bringing the aforementioned composition into contact with the substrate, the aforementioned film can be formed. The method of bringing the composition into contact with the substrate can be, for example, spin coating, dip coating, spray coating, roll coating, rod coating, die coating, etc., such as spin coating, spray coating, etc. The coating method is preferred. According to the spin coating method and spray coating method, it is easy to adjust the thickness of the film.

At this time, the composition system can be further diluted as needed. The dilution ratio can be 2~100 times for the composition before dilution, more preferably It is 5-50 times. As the dilution solvent system, the solvent exemplified as the solvent (c) can be suitably used.

When the composition of the present invention is in contact with the substrate, it is allowed to stand still in the air, and the moisture in the air is taken in to hydrolyze the hydrolyzable group to form a siloxane skeleton and form a film. When standing still, it can be kept at 40~250℃.

Furthermore, a film-treated substrate in which the film of the present invention is formed on a substrate is also included in the scope of the present invention. The shape of the base material can be any one of a plane or a curved surface, and can also be a three-dimensional structure composed of a plurality of surfaces. In addition, the base material can be composed of any of organic materials and inorganic materials. Examples of the aforementioned organic materials include acrylic resins, polycarbonate resins, polyester resins, styrene resins, and acrylic-styrene copolymer resins. , Cellulose resin, polyolefin resin, polyvinyl alcohol and other thermoplastic resins; phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester, silicone resin, urethane resin, etc. thermosetting For example, the inorganic materials include ceramics; glass; metals such as Fe, Si, Cu, An, and Al; alloys containing the foregoing metals; and the like.

The aforementioned substrate can be pre-applied for easy bonding treatment. Examples of easy adhesion treatment include corona treatment, plasma treatment, ultraviolet treatment and other hydrophilization treatments. In addition, primer treatment with resin, silane coupling agent, tetraalkoxysilane, etc. can also be used.

The primer layer is preferably a layer formed of a primer layer forming composition containing a component (P) capable of forming a silicone skeleton (hereinafter, sometimes referred to as component (P)). The composition for forming a primer layer contains a compound represented by the following formula (Pa) as a component (P) (hereinafter, sometimes referred to as a compound (Pa). ) And/or the (P1) component composed of a partially hydrolyzed condensate thereof is preferable.

Si(X ^P2 ) ₄ …(Pa)

[In the formula (Pa), X ^P2 represents a halogen atom, an alkoxy group, or an isocyanate group].

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

The compound (Pa) can be used in one type or two or more types, preferably Si(NCO) ₄ , Si(OCH ₃ ) ₄ , Si(OC ₂ H ₅ ) _4, etc.

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 condensate of the compound (Pa) uses an acid catalyst or an alkali catalyst, and can be produced by a general hydrolysis condensation method. The degree of condensation (degree of multimerization) of the partially hydrolyzed condensate is preferably based on the degree to which the product is dissolved in the solvent. The component (Pa) may be compound (Pa) or a partially hydrolyzed condensate of compound (Pa). A mixture of a compound (Pa) and its partially hydrolyzed condensate, and a partially hydrolyzed condensate of a compound (Pa) containing unreacted compound (Pa). Commercial products can also be used for the compound (Pa) or its partial hydrolysis-condensation product.

In addition, the composition system for forming a primer layer may further include a compound represented by formula (Pb) (hereinafter, sometimes referred to as compound (Pb)) and/or a partially hydrolyzed condensate thereof as component (P) The (P2) component.

(X ^P3 ) ₃ Si-(CH ₂ ) _p -Si(X ^P3 ) ₃ …(Pb)

[However, in the formula (Pb), X ^P3 each independently represents a hydrolyzable group or a hydroxyl group, and p is an integer of 1 to 8].

In the formula (Pb), ^{the hydrolyzable group system represented by X P3} includes, for example, the same groups or atoms ^{as the above-mentioned X P2.} In terms of the balance between the stability of the compound (Pb) and the ease of hydrolysis, X ^P3 is preferably an alkoxy group and an isocyanate group, and particularly preferably an alkoxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group. There are a plurality of X ^P3 groups in the compound (Pb), which may be the same group or different groups, and the same group can be easily obtained, which is preferable.

The compound (Pb) can be used in one type or two or more types, for example (CH ₃ O) ₃ SiCH ₂ CH ₂ Si(OCH ₃ ) ₃ , (OCN) ₃ SiCH ₂ CH ₂ Si(NCO) ₃ , Cl ₃ SiCH ₂ CH ₂ SiCl ₃ , (C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ Si(OC ₂ H ₅ ) ₃ , (CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ etc.

The component (P2) may be a partial hydrolysis condensate of the compound (Pb). The partially hydrolyzed condensate of the compound (Pb) can be obtained by the same method as explained in the production of the partially hydrolyzed condensate of the compound (Pa). The degree of condensation (degree of multimerization) of the partially hydrolyzed condensate is preferably based on the degree to which the product is dissolved in the solvent. Component (P2) may be compound (Pb), or a partial hydrolysis condensate of compound (Pb), a mixture of compound (Pb) and its partial hydrolysis condensate, compound (Pb) containing unreacted compound (Pb) The partial hydrolysis condensate. Commercial products can also be used for the compound (Pb) or its partial hydrolysis-condensation product. In addition, the composition for forming a primer layer may include a co-hydrolysis condensate resulting from the co-hydrolysis of the compound (Pb) and the compound (Pa) as the component (P), and may also include various polysilazanes.

In addition to the solid content of the layer constituents, the composition for forming the primer layer should include an organic solvent in consideration of economy, workability, and ease of thickness control of the resulting primer layer. The organic solvent is preferably one that dissolves the solid content contained in the composition for forming a primer layer, and examples thereof include the same solvent as the solvent (c) used in the composition. The organic solvent system is not limited to one type, and two or more types of solvents having different polarities and evaporation speeds may be mixed and used. When the composition for forming a primer layer contains a partially hydrolyzed condensate or a partially hydrolyzed co-condensate, it may also include a solvent used for the production of these.

Furthermore, even if the composition for forming a primer layer does not contain a partial hydrolysis condensate or a partial hydrolysis co-condensate, in order to promote the hydrolysis co-condensation reaction, pre-preparation and the partial hydrolysis condensation reaction are generally the same as those used in the reaction. Catalysts such as acid catalysts are also preferable. Even when it contains a partially hydrolyzed condensate or a partially hydrolyzed co-condensate, when the catalyst used in the production thereof does not remain in the primer layer forming composition, it is preferable to prepare the catalyst. The composition system for forming a primer layer may contain water for the hydrolysis condensation reaction or the hydrolysis-cocondensation reaction.

The method of forming the base layer using the composition for forming a primer layer can be a method applicable to an organosilane compound-based surface treatment agent. Apply the primer layer forming composition to the surface of the substrate by brush coating, vertical flow coating, spin coating, dip coating, blade coating, spray coating, hand coating, etc. In the atmosphere or in a nitrogen environment, after drying as needed, it is hardened to form a base layer. The curing conditions can be appropriately controlled according to the type and concentration of the primer layer forming composition used. Again, the bottom The hardening of the composition for forming the lacquer layer can be performed simultaneously with the hardening of the composition.

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

The film formed from the composition containing the compound of the present invention can have both water repellency and droplet slippage and light resistance, and can be used as display devices such as touch panel displays, optical elements, semiconductor elements, and buildings. Substrates for materials, auto parts, nano-imprint technology, etc. The film formed by the composition containing the compound of the present invention can be suitably used as a body, windshield (front glass, side glass, rear glass), mirrors, etc. in transportation equipment such as trains, automobiles, ships, airplanes, etc. Anti-collision bars and other items. In addition, it can also be used for outdoor applications such as building exterior walls, tents, solar power modules, sound insulation boards, and cement. It can also be used in fishing nets, insect nets, water tanks, etc. Furthermore, it can also be used in various indoor equipment such as flow counters, bathrooms, washstands, mirrors, and various components around the toilet, chandeliers, ceramics such as tiles, artificial marbles, and air conditioners. In addition, it can also be used as an antifouling treatment for fixtures, inner walls, and piping in the factory. It is also suitable for goggles, glasses, helmets, pinball machines, fibers, umbrellas, game equipment, footballs, etc. Furthermore, it can also be used as an anti-adhesion agent for various packaging materials such as packaging materials for food, packaging materials for cosmetics, and the inside of thermos flasks.

[Example]

The following examples are given to illustrate the present invention in more detail, but the present invention is of course not limited by the following examples, and is applicable to the pre/postscript Of course, the scope of the intention can be implemented by adding appropriate changes, and any of them are included in the technical scope of the present invention. In addition, in the following, as long as there is no special statement, "part" means "mass part", and "%" means "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. Use 3μL of ion-exchanged water to measure the contact angle by the θ/2 method.

(Evaluation of dynamic water repellency characteristics)

Using DM700 manufactured by Kyowa Interface Science Co., Ltd., using the sliding method (analysis method: contact method, liquid volume: 6.0μL, tilt method: continuous tilt, sliding detection: after sliding, movement determination: forward angle, sliding determination distance: 0.25mm) , To measure the dynamic water repellency characteristics of the transparent film surface to water (contact angle hysteresis, drop angle).

(Adhesion evaluation)

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

(Evaluation of droplet slippage)

Use DM700 made by Concord Interface Science Company, with dynamic sliding method (Analysis method: liquid volume: 50.0μL, tilt method: sample tilt, tilt angle: 20°), to measure the dynamic water repellency characteristics (water drop slippery) of the transparent film surface to water.

(Evaluation of light resistance)

A uniform light irradiation unit (manufactured by Ushiro Corporation) was installed on a mercury lamp ("SP-9 250DB" manufactured by Ushiro Electric Co., Ltd.), and the sample was set at a distance of 17.5 cm from the lens. An intensity meter ("VEGA" manufactured by OPHIL) was used to measure the light intensity at 200-800 nm, and the result was 200 mW/cm ² . In an atmospheric environment with a temperature of 20-40°C and a humidity of 30-75%, irradiate the sample with mercury lamps for 6 hours. Set the initial contact angle of the droplet on the transparent film (liquid volume 3μL ion-exchanged water) as A ₁ , and set the contact angle of the droplet after irradiation as B _Z , and calculate the contact before and after irradiation according to the following formula The rate of change of the angle is shown in Table 3.

Contact angle change rate (%)=((B _Z -A ₁ )/A ₁ )×100(%)

In addition, the spectral irradiance of the mercury lamp ("SP-9 250DB" manufactured by Ushiro Electric Co., Ltd.) is as shown in Fig. 1, and has a bright line in the region below 300 nm.

Example 1-1

1.6 g of trimethylsilanol and 8 mL of tetrahydrofuran (THF) were added to a four-necked flask and stirred. Cool to -40°C, drop 11.1 mL of n-BuLi hexane solution (1.6 mol/L). The temperature was raised to 0°C, 31.68 g of hexamethylcyclotrisiloxane dissolved in 28 mL of THF was dropped, and the temperature was raised to room temperature and stirred for 17 hours. Add THF, ion-exchanged water, and hexane in order to the reaction solution, The liquid was separated and the organic layer was taken out separately. It was washed with ion-exchanged water, dried with 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 repeating number n of the units in parentheses is 8. Hereinafter, the average repetition number is calculated from the NMR spectrum.

After dissolving 0.98 g of tetraisocyanate silane in 8 mL of diethyl ether, it was cooled to 0°C, 9.35 g of Intermediate 1 dissolved in 40 mL of diethyl ether was added dropwise, and 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 repeating number n of the units in parentheses is 8.

The 29Si-NMR (400MHz, standard: CDCl3 (=7.24ppm) mitigation reagent: Acetylacetone column, 10% added to the solute) of the obtained compound (1) measured results 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

In a three-necked flask, 6.25 g of ginseng (trimethylsiloxy) silanol and 28 g of THF were added and stirred. Cool to -40°C, drop 12.5 mL of n-BuLi hexane solution (1.6 mol/L). The temperature was raised to 0°C, 35.59 g of hexamethylcyclotrisiloxane dissolved in 28 g of THF was dropped, and the mixture was stirred for 17 hours. After cooling to -40°C, THF, ion-exchanged water, and hexane were sequentially added to the reaction solution for liquid separation, and the organic layer was taken out respectively. It was washed with ion-exchanged water, dried with anhydrous magnesium sulfate, and concentrated under reduced pressure to prepare a colorless and transparent intermediate 2 represented by the following formula. In the formula, the average repeating number n of the units in parentheses is 8.

After dissolving 0.98 g of tetraisocyanate silane in 8 mL of diethyl ether, it was cooled to 0°C, 9.90 g of Intermediate 2 dissolved in 40 mL of diethyl ether was added dropwise, and 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. Where The average number of repetitions of the units in brackets n is 8.

The 29Si-NMR (400MHz, standard: CDCl3 (=7.24ppm) mitigation reagent: Acetylacetone column, 10% added to the solute) of the obtained compound (2) measured results 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

In a four-necked flask, 0.45 g of trimethylsilanol and 5.1 mL of tetrahydrofuran (THF) were added and stirred. Cool to -40°C, drop 3.13 mL of n-BuLi hexane solution (1.6 mol/L). 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. Concentrate under reduced pressure to obtain colorless and transparent intermediate 3. After cooling to -40°C, 0.99 g of chlorotriethoxysilane was added dropwise. Add 100 mL of hexane and filter. Concentrate the filtrate at 130hPa and 25℃ to obtain below 16.33g The compound shown in the formula 3. In the formula, the average repeating number n of the units in parentheses is 8.

Comparative example 1-2

To 10.0 g of Intermediate 1, 4.8 g of tetramethyl orthosilicate and 56 mg of tertiary butylamine were added, and the mixture was stirred at 30° C. for 5 hours under a nitrogen environment. After returning to room temperature, it was concentrated under reduced pressure to obtain 10.6 g of compound 4 represented by the following formula. In the formula, the average repeating number n of the units in parentheses is 15.

Examples 2-1, 2-2

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

Examples 2-3, 2-4

Compounds 1, 2, tetraethoxysilane (TEOS) and methyl ethyl ketone, which are the silane isocyanate compound (a), which are the metal compound (b), were mixed with the composition 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) and used as coating solutions 3 and 4.

Comparative examples 2-1, 2-2, 2-3

Compounds 3 to 5 and methyl ethyl ketone were mixed with the composition shown in Table 1 to obtain coating solutions 5 and 6.

Compound 5 means a compound represented by the following formula.

Examples 3-1~3-4, Comparative Examples 3-1~3-2

The alkali-washed glass substrate (EAGLE XG, manufactured by Corning) was coated with the aforementioned coating solutions 1 to 4 and the comparative coating solution at 3000 rpm using a spin coater (manufactured by MIKASA) for 20 seconds and left at room temperature. Set. For the resulting film, the initial contact angle, droplet slippage, adhesion, and light resistance were evaluated. The results are shown in Table 2.

〔Possibility of industrial use〕

The film formed by the composition containing the compound of the present invention can have both water repellency and droplet slippage and adhesion, and can be used As a base material for display devices such as touch panel displays, optical components, semiconductor components, building materials, automotive parts, and nanoimprint technology. The film formed by the composition containing the compound of the present invention can be suitably used as a body, windshield (front glass, side glass, rear glass), mirrors, etc. in transportation equipment such as trains, automobiles, ships, airplanes, etc. Anti-collision bars and other items. In addition, it can also be used for outdoor applications such as building exterior walls, tents, solar power modules, sound insulation boards, and cement. It can also be used in fishing nets, insect nets, water tanks, etc. Furthermore, it can also be used in various indoor equipment such as flow counters, bathrooms, washstands, mirrors, and various components around the toilet, chandeliers, ceramics such as tiles, artificial marbles, and air conditioners. In addition, it can also be used as an antifouling treatment for fixtures, inner walls, and piping in the factory. It is also suitable for goggles, glasses, helmets, pinball machines, fibers, umbrellas, game equipment, footballs, etc. Furthermore, it can also be used as an anti-adhesion agent for various packaging materials such as packaging materials for food, packaging materials for cosmetics, and the inside of thermos flasks.

Claims (5)

A silane isocyanate compound, which is represented by formula (I):

[In the formula (I), R ^s1 represents a hydrocarbon group with 1 to 4 carbons or (R ^s3 ) ₃ SiO-, R ^s2 and R ^s3 each independently represent an alkyl group with 1 to 4 carbons, in the R ^s1 Hydrocarbon groups and ^{the hydrogen atoms contained in the alkyl group of R s3} may be substituted with fluorine atoms. However, ^{when all of R s1} are hydrocarbon groups, R ^s1 is an alkyl group not substituted with fluorine; X ^s1 represents a hydrolyzable group other than isocyanate , A hydrocarbon group or a group containing a silyloxy group, the _{-CH 2} -contained in the hydrocarbon group of ^{X s1} can be substituted into -O-, but the -CH ₂ -adjacent to the Si atom is not substituted into -O-, and Two consecutive -CH ₂ -are not replaced with -O- at the same time; n1 represents an integer of 1 or more; p1 and p2 are each independently 1 to 3, and the total is 4 or less]. For example, the silane isocyanate compound of the first item in the scope of patent application, wherein R ^s1 represents (R ^s3 ) ₃ SiO-. A coating composition comprising the silane isocyanate compound of the first or second item in the scope of patent application and a solvent. For example, the coating composition of item 3 of the scope of patent application, which further contains A metal compound in which at least one hydrolyzable group is bonded to the central metal atom. A method for manufacturing a compound as claimed in item 1 or 2 of the scope of patent application, characterized in that the compound represented by formula (I-X1) is reacted with the compound represented by formula (I-X2);

[In formula (I-X1), R ^s1 represents a hydrocarbon group with 1 to 4 carbons or (R ^s3 ) ₃ SiO-, R ^s2 and R ^s3 each independently represent an alkyl group with 1 to 4 carbons, in the R ^{The hydrogen atoms contained in the hydrocarbon group of s1 and} the alkyl group of R ^s3 may be substituted by fluorine atoms. However, ^{when all of R s1} are hydrocarbon groups, R ^s1 is an alkyl group; n1 represents an integer of 1 or more; in formula (I-X2) , X ^s1 represents a hydrolyzable group other than an isocyanate group, a hydrocarbon group, or a group containing a silyloxy group. The _{-CH 2} -contained in the hydrocarbon group of ^{X s1} can be substituted with -O-, but-adjacent to the Si atom CH ₂ -is not substituted into -O-, and two consecutive -CH ₂ -are not substituted into -O- at the same time; p3 represents an integer of 2 to 4].

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