CN111918927A - Mixed composition - Google Patents

Abstract

The objective of this invention is to provide the composition which can form the film which has favorable hot water resistance. The present invention relates to a composition, characterized in that it is an organosilicon compound (a) in which at least one molecular chain containing a trialkylsilyl group and at least one hydrolyzable group are bonded to a silicon atom, at least one hydrolyzable group A mixed composition of a metal compound (b) group-bonded to a metal atom, a solvent (c2) having a vapor pressure of 0.032kPa to 10kPa at 20° C. and a sp value of 11 (cal/cm ³ ) ^1/2 or less, the above three The hydrogen atom contained in the alkylsilyl group may be replaced by a fluorine atom, the total amount of the organosilicon compound (a) and the metal compound (b) in the composition is 0.5% by mass or more, and the above-mentioned solvent (c2) in the composition The amount is 5 mass % or more.

Description

mixed composition

technical field

The present invention relates to mixed compositions of organosilicon compounds and metal compounds.

Background technique

In various display devices, optical elements, semiconductor elements, building materials, automobile parts, nanoimprint technology, etc., the contamination and corrosion of the substrate may occur due to the adhesion of droplets to the surface of the substrate, and the contamination and corrosion may lead to performance degradation and other issues. Therefore, in these fields, good water repellency of the surface of the substrate is required.

As such a composition having water repellency, Patent Document 1 discloses a solution containing an organosilane such as an alkylalkoxysilane having 3 to 18 carbon atoms, a metal alkoxide, an organic solvent, water, and a catalyst, as Examples of the organic solvent include methanol, ethanol, isopropanol, and tetrahydrofuran, which have a higher vapor pressure than water. In addition, Patent Document 2 discloses a mixed composition which is an organosilicon compound, a metal compound, satisfies at least any one of the conditions of a vapor pressure at 20°C of 1000 Pa or less and a boiling point of 120°C or more, and a solubility parameter of 8.0 (cal/cm ³ ) ^1/2 or more of a high-boiling point solvent (C) and a mixed composition of a low-boiling-point solvent (D) having a vapor pressure at 20° C. greater than 1000 Pa and a boiling point of less than 120° C., the above-mentioned high-boiling point solvent (C ) is 0.088 parts by mass or more and less than 1.74 parts by mass with respect to 100 parts by mass of the composition.

prior art literature

Patent Literature

Patent Document 1: WO2014/136275

Patent Document 2: Japanese Patent Laid-Open No. 2017-201008

SUMMARY OF THE INVENTION

However, the water-repellent film may be exposed to harsh environments such as ultraviolet rays and rainwater depending on applications such as outdoors, and it is preferable to maintain good performance even after exposure to the harsh environment. It is known that when an organosilicon compound is used in a water-repellent film, the stability to light is very high, but on the other hand, it has a siloxane bond, so it is not easy to have durability against water or hot water. Therefore, in order to maintain a good performance of a film having water repellency of an organosilicon compound even after being exposed to a severe environment, a film with high hot water resistance is an important performance for maintaining performance even in an actual use environment .

Patent Document 2 discloses an organosilicon compound having a molecular chain containing a trialkylsilyl group as an organosilicon compound, and the total amount of the organosilicon compound and the metal compound is about 0.3% with respect to 100% by mass of the composition However, considering the adhesiveness of the film, etc., it is desired to further increase the total amount of the organosilicon compound and the metal compound. According to the study by the present inventors, in the composition of Patent Document 2, when the concentration of the organosilicon compound and the metal compound is increased, the durability against hot water (hot water resistance) tends to deteriorate.

Therefore, an object of the present invention is to provide a composition capable of forming a film having favorable hot water resistance with a high total concentration of the organosilicon compound having a trialkylsilyl group-containing molecular chain and the metal compound.

As a result of studies conducted by the present inventors, it was found that by mixing a solvent satisfying predetermined requirements in a mixed composition in which the total concentration of the organosilicon compound having a trialkylsilyl group-containing molecular chain and the metal compound is 0.5 mass % or more, The above-mentioned subject can be achieved, and the present invention has been completed. The present invention is as follows.

[1] A mixed composition, characterized in that it is a mixed composition of an organosilicon compound (a), a metal compound (b) and a solvent (c2), wherein the organosilicon compound (a) is at least one compound containing a trialkyl group A compound in which the molecular chain of a silyl group and at least one hydrolyzable group are bonded to a silicon atom, the metal compound (b) is a compound in which at least one hydrolyzable group is bonded to a metal atom, and the solvent (c2) is at 20° C. The vapor pressure is 0.032kPa～10kPa and the sp value is 11(cal/cm ³ ) ^1/2 or less,

The hydrogen atom contained in the above-mentioned trialkylsilyl group may be substituted by a fluorine atom,

The total amount of the organosilicon compound (a) and the metal compound (b) in the composition is 0.5% by mass or more,

The quantity of the said solvent (c2) in a composition is 5 mass % or more.

[2] The composition according to [1], wherein the amount of the solvent (c2) in the composition is 30% by mass or more.

[3] The composition according to [1] or [2], wherein a solvent (c1) having a solubility in water at 20°C of 231 g/L or more and an sp value of 20 or less is mixed.

[4] The composition according to [1] or [2], wherein a solvent (c1) having an sp value of more than 11 (cal/cm ³ ) ^1/2 is mixed.

[5] The composition according to [1] or [2], wherein at least one solvent (c1) selected from isopropanol, ethanol, methanol, and methyl ethyl ketone is mixed.

[6] The composition according to any one of [1] to [5], wherein the water content in the composition is 0.5 mass % or less.

[7] The composition according to any one of [1] to [6], wherein the organosilicon compound (a) is a compound represented by the following formula (A1).

[In the above formula (A1), R ^a1 represents a molecular chain containing a trialkylsilyl group,

A plurality of A ^a1 each independently represents a hydrolyzable group,

Z ^a1 represents a molecular chain containing a trialkylsilyl group, a group containing a siloxane skeleton, or a group containing a hydrocarbon chain,

The hydrogen atom contained in the trialkylsilyl group in R ^a1 and Z ^a1 may be substituted by a fluorine atom,

x is either 0 or 1. ]

[8] The composition according to any one of [1] to [7], wherein the metal compound (b) is a compound represented by the following formula (B1).

M(Z ^b1 ) _r (A ^b1 ) _mr (B1)

[In the above formula (B1), M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr or Ta,

Z ^b1 represents a group containing a siloxane skeleton, a group containing a hydrocarbon chain, or a hydrogen atom,

A plurality of A ^b1 each independently represents a hydrolyzable group,

m represents an integer of 3 to 5 based on the metal atom,

r is 0 or 1. ]

[9] The composition according to any one of [1] to [8], wherein the organosilicon compound (a) is a compound represented by the following formula (A2).

[In the above formula (A2),

A plurality of A ^a1 each independently represents a hydrolyzable group,

Z ^a1 represents a molecular chain containing a trialkylsilyl group, a group containing a siloxane skeleton, or a group containing a hydrocarbon chain, and the hydrogen atom contained in the trialkylsilyl group may be substituted by a fluorine atom,

A plurality of R ^s1 each independently represent a hydrocarbon group or a trialkylsiloxy group, and the hydrogen atom contained in the hydrocarbon group or the trialkylsiloxy group may be substituted with a fluorine atom,

A plurality of R ^s2 each independently represents an alkyl group having 1 to 10 carbon atoms,

Z ^s1 represents -O- or a divalent hydrocarbon group, and -CH ₂ - contained in the divalent hydrocarbon group may be substituted with -O-.

Y ^s1 represents a single bond or -Si(R ^s2 ) ₂ -L ^s1 -, this L ^s1 represents a divalent hydrocarbon group, and -CH ₂ - contained in the divalent hydrocarbon group may be substituted with -O-.

n1 represents an integer greater than 1,

x is either 0 or 1. ]

According to the mixed composition of the present invention, the obtained film has good hot-water properties as evaluated by the sliding-off speed after the hot-water test.

Detailed ways

In the composition of the present invention, the total amount of the organosilicon compound (a) and the metal compound (b) is 0.5% by mass or more, and the solvent (c2) satisfying the predetermined requirements is mixed, so that the obtained film has good hot water resistance, It is also preferable that the transparency of the film can also be made good. Hereinafter, the organosilicon compound (a), the metal compound (b), and the solvent (c2) will be described in order. In addition, the said mixed composition also includes the thing which reacted after mixing, for example, during storage.

1. Organosilicon compound (a)

In the organosilicon compound (a) of the present invention, at least one trialkylsilyl group-containing molecular chain and at least one hydrolyzable group are bonded to a silicon atom (hereinafter, the silicon atom may be referred to as "central silicon atom"). .

The molecular chain containing a trialkylsilyl group refers to a monovalent group having a structure in which a group containing a trialkylsilyl group is bonded to the end of the molecular chain. The water-repellent property of the film formed from the mixed composition of the present invention is improved by combining with the molecular chain. Moreover, by making the molecular chain containing a trialkylsilyl group exist, the resistance between a droplet (water droplet etc.) and this film|membrane reduces, and a droplet moves easily. Even when the alkyl group of the trialkylsilyl group-containing group is substituted with a fluoroalkyl group, the water repellency of the film interface (surface) can be similarly improved.

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

As said hydrolyzable group, what is necessary is just to provide a hydroxyl group by hydrolysis (bonded with silicon atom to become a silanol group) group, for example, methoxy group, ethoxy group, propoxy group, An alkoxy group having 1 to 6 carbon atoms such as a butoxy group; a hydroxyl group; an acetoxy group; a chlorine atom; an isocyanate group and the like. Among them, an alkoxy group having 1 to 6 carbon atoms is preferable, an alkoxy group having 1 to 4 carbon atoms is more preferable, and an alkoxy group having 1 to 2 carbon atoms is still more preferable.

In the organosilicon compound (a), the number of hydrolyzable groups bonded to the central silicon atom is 1 or more, preferably 2 or more, and usually preferably 3 or less.

To the central silicon atom of the organosilicon compound (a), in addition to a trialkylsilyl group-containing molecular chain and a hydrolyzable group, a siloxane skeleton-containing group (preferably a ratio of the number of elements) may be bonded. A siloxane skeleton-containing group with a small number of elements constituting a molecular chain containing a trialkylsilyl group) or a group containing a hydrocarbon chain (preferably containing more carbon atoms than constituting a molecular chain containing a trialkylsilyl group) The number of elements in the molecular chain is less than the hydrocarbon chain containing hydrocarbon chain group).

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

[In the above formula (A1), R ^a1 represents a trialkylsilyl group-containing molecular chain, a plurality of A ^a1 each independently represents a hydrolyzable group, Z ^a1 represents a trialkylsilyl group-containing molecular chain, In the siloxane skeleton group or the group containing a hydrocarbon chain, the hydrogen atom contained in the trialkylsilyl group in R ^a1 and Z ^a1 may be substituted with a fluorine atom, and x is 0 or 1. ]

R ^a1 is a molecular chain containing a trialkylsilyl group, and as described above, is a monovalent group having a structure in which a group containing a trialkylsilyl group is bonded to the terminal of the molecular chain.

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

In formula (s1), a plurality of R ^s1 each independently represents a hydrocarbon group or a trialkylsiloxy group, and the hydrogen atom contained in the hydrocarbon group or the trialkylsiloxy group may be substituted with a fluorine atom. * indicates the binding site. In the above formula (s1), it is preferable that at least one of R ^s1 is a trialkylsiloxy group, or all of R ^s1 are an alkyl group.

When R ^s1 is a hydrocarbon group, the number of carbon atoms is preferably 1-4, more preferably 1-3, and still more preferably 1-2. When R ^s1 is a hydrocarbon group, an aliphatic hydrocarbon group is preferable, and an alkyl group is more preferable. As this alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, etc. are mentioned. A plurality of R ^s1 may be the same or different, but preferably the same. When all R ^s1 are hydrocarbon groups (especially alkyl groups), the total number of carbon atoms of three R ^s1 is preferably 9 or less, more preferably 6 or less, and further preferably 4 or less. Preferably, at least one of the three R ^s1 is a methyl group, more preferably at least two are a methyl group, and particularly preferably all the three R ^s1 are a methyl group.

As a group (trialkylsilyl group) in which all R ^s1 are a hydrocarbon group (alkyl group), the group etc. which are represented by the following formula are mentioned specifically,. In the formula, * represents a binding site.

In the above formula (s1), at least one of R ^s1 is preferably a trialkylsiloxy group. As said trialkylsilyloxy group, the group which an oxygen atom couple|bonded with the silicon atom of the group (trialkylsilyl group) in which all R ^s1 is a hydrocarbon group (alkyl group) is mentioned. In the above formula (s1), preferably two or more R ^s1 are trialkylsiloxy groups, and more preferably three R ^s1 are trialkylsiloxy groups.

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

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

The molecular chain to which the trialkylsilyl group-containing group is bonded is preferably linear or branched, and preferably linear. The above-mentioned molecular chain preferably contains a dialkylsiloxane chain, preferably a linear dialkylsiloxane chain. The above-mentioned molecular chain further containing a dialkylsiloxane chain may contain a divalent hydrocarbon group. Even if a part of the molecular chain is a divalent hydrocarbon group, the remaining part is a dialkylsiloxane chain, so that the obtained film has good chemical and physical durability.

The molecular chain described above is preferably a group represented by the formula (s2).

In formula (s2), a plurality of R ^s2 each independently represents an alkyl group having 1 to 10 carbon atoms. Z ^s1 represents -O- or a divalent hydrocarbon group, and -CH ₂ - contained in the divalent hydrocarbon group may be substituted with -O-. Y ^s1 represents a single bond or -Si(R ^s2 ) ₂ -L ^s1 -. L ^s1 represents a divalent hydrocarbon group, and -CH ₂ - contained in the divalent hydrocarbon group may be substituted with -O-. The * on the left side represents the bonding site with the central silicon atom, and the * on the right side represents the bonding site with the trialkylsilyl group-containing group.

The number of carbon atoms of R ^s2 is preferably 1-4, more preferably 1-3, still more preferably 1-2.

n1 is preferably 1-100, more preferably 1-80, still more preferably 1-60, still more preferably 1-45, particularly preferably 1-30.

The number of carbon atoms of the divalent hydrocarbon group represented by Z ^s1 or L ^s1 is preferably 1-10, more preferably 1-6, and still more preferably 1-4. The above-mentioned divalent hydrocarbon group is preferably in the form of a chain, and when it is in the form of a chain, it may be either a straight chain or a branched chain. Moreover, it is preferable that the said divalent hydrocarbon group is a divalent aliphatic hydrocarbon group, and it is preferable that it is an alkanediyl group. As a divalent hydrocarbon group, a methylene group, an ethylene group, a propylene group, a butylene group, etc. are mentioned.

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

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

As a molecular chain contained in the molecular chain containing a trialkylsilyl group, the molecular chain represented by the following formula is mentioned. In the formula, q1 represents an integer of 1 to 60, and * represents a bonding site to a central silicon atom or a trialkylsilyl group-containing group. q1 may be in the same numerical range as the above-mentioned n1, but is preferably an integer of 1-30.

In addition, the total number of elements constituting the trialkylsilyl group-containing molecular chain is preferably 24 or more, more preferably 40 or more, and still more preferably 50 or more. In addition, it is preferably 5000 or less, more preferably 4000 or less, still more preferably 2000 or less, particularly preferably 1200 or less, still more preferably 700 or less, and particularly preferably 250 or less.

The molecular chain containing a trialkylsilyl group is preferably a group represented by the following formula (s3).

In the above formula (s3), R ^s1 , R ^s2 , Z ^s1 , Y ^s1 , and n1 have the same meanings as described above. * indicates the bonding site to the central silicon atom.

The molecular chain containing a trialkylsilyl group is preferably a group represented by the following formula (s3-1) or the following formula (s3-2), and more preferably a group represented by the following formula (s3-2).

When the molecular chain containing a trialkylsilyl group is represented by the following formula (s3-1), it is more preferably a group represented by the following formula (s3-1-1).

In formula (s3-1) and formula (s3-1-1), R ^s2 , Y ^s1 , Z ^s1 , and n1 have the same meanings as described above. R ^s3 represents an alkyl group having 1 to 4 carbon atoms. * indicates the bonding site to the central silicon atom.

The number of carbon atoms of the alkyl group represented by R ^s3 is preferably 1-3, and more preferably 1-2. In addition, in the formula (s3-1) and the formula (3-1-1), the total number of carbon atoms of R ^s3 contained in *-Si(R ^s3 ) ₃ is preferably 9 or less, more preferably 6 or less, and still more preferably 4 or less. In addition, among R ^s3 contained in *-Si(R ^s3 ) ₃ , at least one is preferably a methyl group, preferably two or more R ^s3 are methyl groups, and particularly preferably all three R ^s3 are methyl groups.

Moreover, when the molecular chain containing a trialkylsilyl group is represented by following formula (s3-2), it is more preferable that it is a group represented by following formula (s3-2-1).

In formulas (s3-2) and (s3-2-1), R ^s2 , Y ^s1 , Z ^s1 , and n1 have the same meanings as described above. R ^s4 represents an alkyl group having 1 to 4 carbon atoms. * indicates the bonding site to the central silicon atom.

As a molecular chain containing a trialkylsilyl group, the group represented by formula (s3-I) is mentioned.

In formula (s3-I), * represents a bonding site with the central silicon atom.

[Table 1]

[Table 2]

In the above formula (a1), n10 is preferably 1-30.

Next, A ^a1 in the formula (A1) will be described. A plurality of A ^a1 are each independently a hydrolyzable group, as long as it is a group that provides a hydroxyl group (silanol group) by hydrolysis, for example, a methoxy group, an ethoxy group, a propoxy group, a butyl group, and a butyl group are preferably used. An alkoxy group having 1 to 4 carbon atoms such as an oxy group; a hydroxyl group; an acetoxy group; a chlorine atom; an isocyanate group and the like. Among them, an alkoxy group having 1 to 4 carbon atoms is preferable, and an alkoxy group having 1 to 2 carbon atoms is more preferable.

Z ^a1 in formula (A1) represents a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, or a hydrocarbon chain-containing group. When Z ^a1 is a molecular chain containing a trialkylsilyl group, the same example as the above-mentioned R ^a1 can be given.

In addition, when Z ^a1 is a group containing a siloxane skeleton, the group containing a siloxane skeleton is a monovalent group containing a siloxane unit (Si—O—), and it is preferable that R ^a1 is constituted by a quantitative ratio. The molecular chain containing a trialkylsilyl group is composed of elements with a small number of elements. Therefore, the group containing a siloxane skeleton is a group having a shorter length or smaller steric breadth (volume size) than a molecular chain containing a trialkylsilyl group. A divalent hydrocarbon group may be contained in the group containing a siloxane skeleton.

The group containing a siloxane skeleton is preferably a group represented by the following formula (s4).

In formula (s4), R ^s2 , Z ^s1 and Y ^s1 have the same meanings as described above. R ^s5 represents a hydrocarbon group or a hydroxyl group, -CH ₂ - contained in the hydrocarbon group may be substituted with -O-, and a hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom. n3 represents an integer of 0-5. * indicates the bonding site to the central silicon atom.

Examples of the hydrocarbon group represented by R ^s5 include the same groups as the hydrocarbon group represented by R ^s1 , and an aliphatic hydrocarbon group is preferable, and an alkyl group is more preferable. The number of carbon atoms is preferably 1-4, more preferably 1-3, still more preferably 1-2.

n3 is preferably 1-5, more preferably 1-3.

The total number of elements of the siloxane skeleton-containing group is preferably 600 or less, more preferably 500 or less, still more preferably 350 or less, still more preferably 100 or less, still more preferably 50 or less, particularly preferably 30 or less , and preferably 10 or more. The difference in the number of elements of the trialkylsilyl group-containing molecular chain of R ^a1 and the siloxane skeleton-containing group of Z ^a1 is preferably 10 or more, more preferably 20 or more, preferably 1000 or less, and more preferably 500 or less, more preferably 200 or less.

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

When Z ^a1 is a group containing a hydrocarbon chain, it is preferable that the number of carbon atoms in the hydrocarbon chain part is smaller than the number of elements constituting the molecular chain containing the trialkylsilyl group. In addition, it is preferable that the number of carbon atoms in the longest straight chain of the hydrocarbon chain is smaller than the number of elements constituting the longest straight chain of the trialkylsilyl group-containing molecular chain. The hydrocarbon chain-containing group is usually composed of only a hydrocarbon group (hydrocarbon chain), but may be a group in which a part of methylene groups (—CH ₂ —) of the hydrocarbon chain is substituted with an oxygen atom as necessary. In addition, the methylene group (-CH ₂ -) adjacent to the Si atom is not substituted with an oxygen atom, and two consecutive methylene groups (-CH ₂ -) are not substituted with an oxygen atom at the same time.

It should be noted that the number of carbon atoms in the hydrocarbon chain portion refers to the number of carbon atoms constituting a hydrocarbon group (hydrocarbon chain) in the case of an oxygen-unsubstituted hydrocarbon chain-containing group, and in the case of an oxygen-substituted hydrocarbon chain-containing group. In the case of a group, it means the number of carbon atoms counted assuming that the oxygen atom is a methylene group (-CH ₂ -).

Hereinafter, unless otherwise specified, an oxygen-unsubstituted hydrocarbon chain-containing group (ie, a monovalent hydrocarbon group) will be used as an example to describe the hydrocarbon chain-containing group. In any description, the methylene group may be A part of the group (-CH ₂ -) is replaced with an oxygen atom.

When the above-mentioned hydrocarbon chain-containing group is a hydrocarbon group, the number of carbon atoms is preferably 1 to 3, and more preferably 1. In addition, the above-mentioned hydrocarbon chain-containing group may be branched or linear. The above-mentioned hydrocarbon chain-containing group is preferably a saturated or unsaturated aliphatic hydrocarbon chain-containing group, and more preferably a saturated aliphatic hydrocarbon chain-containing group. The above-mentioned saturated aliphatic hydrocarbon chain-containing group is more preferably a saturated aliphatic hydrocarbon group. The saturated aliphatic hydrocarbon group includes, for example, methyl, ethyl, propyl and the like.

When a part of methylene groups (—CH ₂ —) in the saturated aliphatic hydrocarbon group is substituted with an oxygen atom, specifically, a group having a (poly)ethylene glycol unit, etc. can be exemplified.

x in formula (A1) is 0 or 1, preferably 0.

The hydrolyzable group represented by A ^a1 is, as explained as the hydrolyzable group possessed by the above-mentioned organosilicon compound (a), a group that provides a hydroxyl group by hydrolysis (bonded to a silicon atom to form a silanol group) , the examples exemplified above can be used.

The organosilicon compound (a) represented by the formula (A1) is preferably a compound represented by the following formula (A2).

In the above formula (A2), R ^s1 , R ^s2 , Z ^s1 , Y ^s1 , n1 , A ^a1 , Z ^a1 , and x have the same meanings as described above, respectively.

The organosilicon compound (a) represented by the above formula (A2) is preferably represented by the following formula (A2-1) or the following formula (A2-2), more preferably by the following formula (A2-2).

When the organosilicon compound (a) represented by the above formula (A2) is represented by the following formula (A2-1), it is more preferably a compound represented by the formula (A2-1-1).

In the above formula (A2-1) and the above formula (A2-1-1), R ^s2 , R ^s3 , Y ^s1 , Z ^s1 , n1 , and A ^a1 have the same meanings as described above.

When the organosilicon compound (a) represented by the above formula (A2) is a compound represented by the following formula (A2-2), it is more preferably a compound represented by the following formula (A2-2-1).

In the above formula (A2-2) and the above formula (A2-2-1), R ^s2 , R ^s4 , Y ^s1 , Z ^s1 , n1 and A ^a1 have the same meanings as above.

As an organosilicon compound (a) represented by the said formula (A2), the compound represented by formula (A-I) is mentioned specifically,.

[Table 3-1]

It is preferable that n10 in all of (A-I-1) to (A-I-25) of the said Table 3-1 is 1-30.

[Table 3-2]

It is preferable that n10 in all of (A-I-26) to (A-I-50) of the said Table 3-2 is 1-30.

[Table 4-1]

[Table 4-2]

In Table 4-1 and Table 4-2 above, n10 in (A-I-51) to (A-I-100) is preferably 1 to 30.

In the above formula (A-I), the compound represented by (A-I-26) is more preferable. That is, as the organosilicon compound (a) represented by formula (A2), a compound represented by the following formula is preferable.

In the said formula (A-I-26), n10 is 1-60, Preferably it is 1-50, More preferably, it is 1-30.

As an example of the synthesis method of the said organosilicon compound (a), the method described in Unexamined-Japanese-Patent No. 2017-201009 is mentioned.

In 100 mass % of the composition, the amount of the organosilicon compound (a) is, for example, 0.2 mass % or more, more preferably 0.3 mass % or more, and preferably 3.0 mass % or less, and more preferably 2.0 mass % or less. As for the amount of the above-mentioned organosilicon compound (a), it is preferable that any one of the value calculated from the compounding amount at the time of composition preparation and the analysis result of the composition satisfies the above-mentioned range. It should be noted that, when describing the range of the amount, mass ratio or molar ratio of each component in this specification, in the same manner as above, it is preferable to use the value calculated from the compounding amount at the time of composition preparation and the analysis result of the composition. Either one satisfies this range.

The mixed composition of this invention can use 2 or more types of organosilicon compounds (a). In addition, the organosilicon compound (a) may be a condensate in the composition.

2. Metal compound (b)

The metal compound (b) is a compound in which at least one hydrolyzable group is bonded to a metal atom (hereinafter sometimes referred to as a metal atom M). The metal atom M of the metal compound (b) may be any metal atom capable of bonding with an alkoxy group to form a metal alkoxide, and the metal atom in this specification is used to include metalloids such as Si and Ge. Specifically, trivalent metals such as Al, Fe, and In; tetravalent metals such as Ge, Hf, Si, Ti, Sn, Zr; pentavalent metals such as Ta, etc., are preferably trivalent metals or tetravalent metals. Trivalent metals such as Al or tetravalent metals such as Si, Ti, Zr, and Sn are more preferred, Al, Si, Ti, and Zr are further preferred, and Si is most preferred.

Examples of the hydrolyzable group of the metal compound (b) include the same groups as the hydrolyzable groups exemplified in the above-mentioned organosilicon compound (a), preferably an alkoxy group having 1 to 4 carbon atoms, and more Preferably, it is an alkoxy group having 1 to 2 carbon atoms. The hydrolyzable groups of the organosilicon compound (a) and the metal compound (b) may be the same or different, and both are preferably alkoxy groups having 1 to 4 carbon atoms.

In the metal atom M of the metal compound (b), it is possible to bond at a bonding site other than the bonding site to which the hydrolyzable group is bonded: it is possible to bond with the central silicon atom of the above-mentioned organosilicon compound (a) A combined siloxane skeleton-containing group (preferably a siloxane skeleton-containing group having a smaller number of elements than the number of elements constituting the molecular chain of the trialkylsilyl group-containing molecular chain of the organosilicon compound (a)) ; a hydrocarbon chain-containing group that can be bonded to the central silicon atom of the above-mentioned organosilicon compound (a) (preferably a constituent molecule that contains more carbon atoms than the trialkylsilyl group-containing molecular chain of the organosilicon compound (a) A hydrocarbon chain-containing group of a hydrocarbon chain with a small number of elements in the chain); a hydrogen atom can be appropriately selected from the range described in the above-mentioned organosilicon compound (a), and the number of bonds is preferably 1 or less, particularly preferably 0 .

In the metal compound (b), the number of hydrolyzable groups is preferably 2 or more, more preferably 3 or more, and further preferably 4 or less.

Examples of the metal compound (b) include a compound having only a hydrolyzable group; a compound having a siloxane skeleton-containing group and a hydrolyzable group; a compound having two siloxane skeleton-containing groups and a hydrolyzable group group compound; compound with hydrocarbon chain-containing group and hydrolyzable group; compound with two hydrocarbon chain-containing groups and hydrolyzable group; compound with hydrogen atom and hydrolyzable group; hydrogen atom Atoms, hydrocarbon chain-containing groups and compounds with hydrolyzable groups, etc.

Examples of compounds having only a hydrolyzable group include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane; Trialkoxyaluminum such as propoxyaluminum and tributoxidealuminum; Trialkoxyiron such as triethoxyiron; trimethoxyindium, triethoxyindium, tripropoxyindium, tributoxide Trialkoxy indium such as indium; tetraalkoxy hafnium such as tetramethoxyhafnium, tetraethoxyhafnium, tetrapropoxyhafnium, tetrabutoxyhafnium; tetramethoxytitanium, tetraethoxytitanium, Tetraalkoxytitanium such as tetrapropoxytitanium, tetrabutoxytitanium; tetraalkoxytin such as tetramethoxytin, tetraethoxytin, tetrapropoxytin, tetrabutoxytin; tetramethoxytin Tetraalkoxy zirconium such as zirconium oxide, zirconium tetraethoxide, zirconium tetrapropoxide, zirconium tetrabutoxide; tantalum pentamethoxy, tantalum pentaethoxide, tantalum pentapropoxide, tantalum pentabutoxide Tantalum and other pentaalkoxy tantalum, etc.

Examples of compounds having a siloxane skeleton-containing group and a hydrolyzable group include trimethylsiloxytrimethoxysilane, trimethylsiloxytriethoxysilane, and trimethylmethylsilane. Trimethylsiloxytrialkoxysilane, such as siloxytripropoxysilane, etc., etc..

As a compound having two siloxane skeleton-containing groups and a hydrolyzable group, bis(trimethylsiloxy)dimethoxysilane, bis(trimethylsiloxy)di Di(trimethylsiloxy) dialkoxysilanes, such as ethoxysilane and bis(trimethylsiloxy)dipropoxysilane, etc. are mentioned.

Examples of compounds having a hydrocarbon chain-containing group and a hydrolyzable group include methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, and methyltrimethoxysilane. Alkyltrialkoxysilanes such as vinyltripropoxysilane; alkenyltrialkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, and the like.

Examples of compounds having two hydrocarbon chain-containing groups and hydrolyzable groups include dimethyldimethoxysilane, diethyldimethoxysilane, dimethyldiethoxysilane, and diethyl Dialkyldialkoxysilanes such as alkyldiethoxysilanes and the like.

Trimethoxysilane, triethoxysilane, tripropoxysilane, etc. are mentioned as a compound which has a hydrogen atom and a hydrolyzable group.

As a compound which has a hydrogen atom, a hydrocarbon chain containing group, and a hydrolyzable group, dimethoxymethylsilane, diethoxymethylsilane, etc. are mentioned.

Specifically, the metal compound (b) is preferably a compound represented by the following formula (B1).

M(Z ^b1 ) _r (A ^b1 ) _mr (B1)

[In the above formula (B1), M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr or Ta,

Z ^b1 represents a group containing a siloxane skeleton, a group containing a hydrocarbon chain, or a hydrogen atom,

A plurality of A ^b1 each independently represents a hydrolyzable group,

m represents an integer of 3 to 5 based on the metal atom,

r is 0 or 1. ]

The siloxane skeleton-containing group, the hydrocarbon chain-containing group, and the hydrolyzable group of A ^b1 in Z ^b1 in the above formula (B1) can be selected from the siloxane-containing groups described in the above-mentioned organosilicon compound (a). The group of the skeleton, the group containing a hydrocarbon chain, and the hydrolyzable group are appropriately selected, and the preferred range is also the same.

m represents an integer of 3 to 5 based on the metal atom, that is, represents the valence of the metal atom M. r is preferably zero. Particularly preferably, M is Si, r is 0, and A ^b1 is an alkoxy group having 1 to 4 carbon atoms, that is, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, or tetrabutoxysilane is preferred , particularly preferably tetramethoxysilane or tetraethoxysilane.

In 100 mass % of the composition, the amount of the metal compound (b) is, for example, 0.3 mass % or more, more preferably 0.5 mass % or more, and preferably 5 mass % or less, and more preferably 3 mass % or less.

The mixed composition of this invention can use 2 or more types of metal compounds (b). In addition, the metal compound (b) may be a condensate in the composition.

The total amount of the organosilicon compound (a) and the metal compound (b) is 0.5% by mass or more, preferably 0.8% by mass or more, more preferably 1.0% by mass or more, and preferably 5% by mass relative to 100% by mass of the composition Below, it is more preferable that it is 4 mass % or less, and it is still more preferable that it is 3 mass % or less.

The molar ratio ((b)/(a)) of the metal compound (b) to the organosilicon compound (a) is preferably 5 or more, more preferably 10 or more, still more preferably 15 or more, and more preferably 40 or less, more preferably 35 or less, more preferably 30 or less.

3. Solvent

3-1. Solvent (c2)

The vapor pressure at 20°C of the solvent (c2) is 0.032 kPa to 10 kPa, and the sp value is 11 (cal/cm ³ ) ^1/2 or less. The composition of the present invention contains 5% by mass or more of such a solvent (c2) in the composition. The solvent (c2) having such characteristics is characterized in that it has good compatibility with components such as the organosilicon compound (a) and the metal compound (b), and evaporates appropriately during film formation. With this feature, the film composition distribution of the obtained coating film becomes appropriate, and the residual solvent is reduced, whereby the hot water resistance can be improved.

The vapor pressure (20° C.) of the solvent (c2) is preferably 0.05 kPa or more, more preferably 0.1 kPa or more, and preferably 8 kPa or less, more preferably 6 kPa or less. In particular, when the vapor pressure is 6 kPa or less, the appearance of the film becomes favorable, and the sliding property after film formation is also favorable. For example, the sliding speed at the time of evaluating the sliding property after film formation can be performed in the same manner as in the method of the examples described later. 10 mm/sec or more.

In addition, the sp value of the solvent (c2) is 11 (cal/cm ³ ) ^1/2 or less. In this manual, the sp value (Solubility Parameter) is a value calculated by the method described in "RFFedors, Polym. Eng. Sci., 14[2], 147-154 (1974)". In the Fedors method, the sp value is defined by the square root of the cohesive energy density. Specifically, the sp value is defined by the following formula.

δ=(ΔE/V) ^1/2 (1)

In the above formula (1), δ represents the sp value ((cal/cm ³ ) ^1/2 ), ΔE represents the cohesive energy (cal/mol), and V represents the molar molecular volume of the solvent (cm ³ /mol).

It is considered that in the Fedors method, the above-mentioned cohesive energy and molar molecular volume depend on the kind and number of substituents contained in the solvent. Therefore, the cohesive energy was calculated based on the cohesive energy and molecular volume (shown in the following Table 5) possessed by each substituent and in consideration of the number of substituents.

[table 5]

For example, butyl acetate used as a preferred solvent (c2) in the present invention is a solvent having 2 -CH ₃ , 3 -CH ₂ -, 1 -COO-.

The cohesive energy ΔE of butyl acetate is calculated as:

ΔE (cal/mol)=1125×2+1180×3+4300×1.

In addition, the molar molecular volume V of butyl acetate is calculated as:

V(cm ³ /mol)=33.5×2+16.1×3+18×1.

Therefore, by using these values in the above formula (1), the sp value of butyl acetate can be calculated to be 8.70 (cal/cm ³ ) ^1/2 .

The sp value of the solvent (c2) is preferably 10.5 (cal/cm ³ ) ^1/2 or less, more preferably 10 (cal/cm ³ ) ^1/2 or less, and more preferably 5 (cal/cm ³ ) ^1/2 or more , more preferably 6 (cal/cm ³ ) ^1/2 or more.

The boiling point of the solvent (c2) under atmospheric pressure is, for example, 85°C or higher, preferably 90°C or higher, more preferably 100°C or higher, and preferably 190°C or lower, more preferably 180°C or lower.

In addition, the solubility of the solvent (c2) in water at 20° C. is, for example, 230 g/L or less, and the lower limit is not particularly limited, but may be 1 g/L or more.

As a solvent (c2), isopropyl acetate, butyl acetate, 2-ethoxyethyl acetate, etc. are mentioned.

When the amount of the solvent (c2) is 5 mass % or more with respect to 100 mass % of the composition, the hot water resistance of the film obtained thereby becomes favorable. The amount of the solvent (c2) is preferably 23.0% by mass or more, whereby the hot water resistance can be further improved. The amount of (c2) is more preferably 30% by mass or more, still more preferably 40% by mass or more, still more preferably 50% by mass or more, particularly preferably 55% by mass or more, and the upper limit is, for example, 98% by mass or less. In particular, by setting the amount of the solvent (c2) to be 55% by mass or more, the appearance of the film can be improved, which is preferable.

The mixed composition of this invention can use 2 or more types of solvent (c2).

3-2. Solvent (c1)

In order to make the obtained film more favorable in hot water resistance (preferably for the transparency of the film to be favorable), the composition of the present invention is preferably mixed with the solvent (c2) and has a solubility in water at 20°C of 231 g/L or more and A solvent (c1) having an sp value of 20 or less. The solubility of the solvent (c1) in water at 20°C is preferably 250 g/L or more, more preferably 300 g/L or more, and the upper limit is not particularly limited, but the solvent (c1) and water are preferably mixed in any ratio. The sp value of the solvent (c1) is preferably 18 (cal/cm ³ ) ^1/2 or less, more preferably 16 (cal/cm ³ ) ^1/2 or less, and more preferably more than 11 (cal/cm ³ ) ^1/2 .

The boiling point of the solvent (c1) under atmospheric pressure is, for example, less than 85°C, preferably 83°C or less, and the lower limit is, for example, 60°C or more.

As a solvent (c1), isopropanol, ethanol, methanol, methyl ethyl ketone, etc. are mentioned.

The amount of the solvent (c1) is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 5% by mass or more, preferably 50% by mass or less, and more preferably 45% by mass relative to 100% by mass of the composition. % or less, more preferably 40% by mass or less.

The mass ratio (c2/c1) of the solvent (c2) to the solvent (c1) is preferably 1 or more, more preferably 3 or more, still more preferably 10 or more, and preferably 45 or less, more preferably 40 or less.

When a solvent (c1) is mixed with the composition of this invention, 2 or more types of solvent (c1) can be used.

The composition of the present invention may be mixed with any of acid catalysts, base catalysts, and organometallic catalysts commonly used in sol-gel methods. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; and organic acids such as citric acid, oxalic acid, and acetic acid. As a base catalyst, ammonia, amines, etc. are mentioned. Examples of the organometallic catalyst include organometallic compounds having metal elements such as Al, Fe, Zn, Sn, and Zr as the central metal, and examples include organoaluminum such as acetylacetonate aluminum complexes and ethyl acetoacetate aluminum complexes. Compounds; organic iron compounds such as iron octoate; organic zinc compounds such as zinc acetylacetonate monohydrate, zinc naphthenate, zinc octoate; organic tin compounds such as dibutyltin diacetate complex, etc. The catalyst is preferably an acid catalyst, and particularly preferably an organic acid catalyst such as acetic acid. The amount of the catalyst is, for example, 0.1 to 0.5% by mass in 100% by mass of the composition.

In addition, the composition of the present invention may be mixed with water, and the amount of water may be arbitrarily selected as long as it is in a range capable of uniformly dissolving in the solvent. For example, in 100 mass % of the composition, it is preferably 0.5 mass % or less. By appropriately controlling the amount of water, it is expected that the uniformity of the reaction solution will be improved, and the reproducibility of the preparation solution will be improved. The amount of water is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and may be 0.01% by mass or more. In addition, the ratio of water to 100 parts by mass of the total of the solvents (c1) and (c2) (when the solvent (c1) is not used only the amount of the solvent (c2)) is preferably 0.01 part by mass or more, and preferably 0.3 parts by mass or less.

The amount of water is also preferably adjusted relative to the total amount of the organosilicon compound (a) and the metal compound (b), and the ratio of the molar amount of water to the total molar amount of the organosilicon compound (a) and the metal compound (b) is preferably It is 0.1 or more, more preferably 0.12 or more, still more preferably 0.2 or more, and also preferably 10 or less, more preferably 5 or less, still more preferably 3 or less, and particularly preferably 2 or less.

The composition of the present invention may contain antioxidants, rust inhibitors, ultraviolet absorbers, light stabilizers, antifungal agents, antibacterial agents, biofouling inhibitors, deodorants, Various additives such as pigments, flame retardants, antistatic agents, etc.

The preparation procedure of the mixed composition of this invention is as follows, for example. First, the organosilicon compound (a) and the metal compound (b) are dissolved in a solvent. At this time, it is preferable to stir for about 5 to 30 minutes. Next, after adding a catalyst (preferably an acid catalyst) as necessary, the mixture is stirred for about 1 to 24 hours (preferably, stirring is performed while heating at about 40 to 70°C). As a result, a part of the hydrolyzable groups contained in the organosilicon compound (a) and the metal compound (b) undergo a hydrolysis/dehydration condensation reaction using moisture in the air or moisture contained in a catalyst used as needed. As a solvent (hereinafter sometimes referred to as a "reaction solvent") for dissolving the organosilicon compound (a) and the metal compound (b), the solvent (c1) described above is preferably used. By using the solvent (c1), a homogeneous solution can be prepared. Furthermore, the above-mentioned solvent (c2) was added and diluted to the obtained solution, and the coating solution (mixed composition of this invention) was produced. By mixing the solvent (c2) with the coating solution, the volatilization of the solvent after coating on the substrate can be appropriately adjusted, and the transparency and hot water resistance of the obtained film can be improved. The dilution solvent may be mixed with other solvents as long as the solvent (c2) is mixed, and the dilution solvent may be a solvent in which the solvent (c2) and the solvent (c1) are mixed.

In addition, as a method of bringing the mixed composition of the present invention into contact with a substrate, for example, a method of applying the composition to a substrate includes spin coating, dip coating, spray coating, roll coating, Bar coating, hand coating (a method of infiltrating a liquid into a cloth, etc. and coating it on a substrate), flushing (a method of applying a liquid directly to a substrate using a dropper, etc.), spraying (using a spray and the method of coating on the substrate), etc. In the state where the mixed composition of the present invention is in contact with the substrate, it is allowed to stand in the air at room temperature (for example, 0.5 to 48 hours, preferably 10 to 48 hours) or heated for about 1 to 10 hours (for example, 300 °C or lower), the hydrolysis and polycondensation of the hydrolyzable group are accelerated, and a film can be formed on the substrate.

The film thickness of the film formed from the mixed composition of the present invention varies depending on the coating method, but can be, for example, about 0.5 to 100 nm. Moreover, the contact angle of the water droplet evaluated by the method of the Example mentioned later about this film is 95 degrees - 110 degrees (preferably 98 degrees - 108 degrees), for example. In addition, the haze of the film evaluated by the method of the examples described later is, for example, 1.4% or less, preferably 1.0% or less, more preferably 0.8% or less, still more preferably 0.6% or less, and particularly preferably 0.3% or less. The lower limit is not particularly limited, but is, for example, about 0.01%. Moreover, the contact angle of the water droplet of the film after the hot water test evaluated by the method mentioned later is 95°-113° (preferably 98°-110°), for example. In addition, the sliding speed of the film after the hot water test is, for example, 5 mm/sec or more, preferably 10 mm/sec or more, more preferably 15 mm/sec or more, still more preferably 20 mm/sec or more, and the upper limit is not particularly limited, for example, 100 mm/sec. seconds or less.

The base material to be in contact with the mixed composition of the present invention is not particularly limited, and the shape of the base material may be either a plane or a curved surface, or may be a three-dimensional structure in which a plurality of surfaces are combined. In addition, the material of the base material is not limited, either, and may be composed of either an organic material or an inorganic material. Examples of the organic material include thermoplastic resins such as acrylic resins, polycarbonate resins, polyester resins, styrene resins, acrylic-styrene copolymer resins, cellulose resins, and polyolefin resins; phenolic resins, urea resins, and melamine resins. Thermosetting resins such as resins, epoxy resins, unsaturated polyesters, silicone resins, urethane resins, and the like, and inorganic materials include ceramics; glass; metals such as iron, silicon, copper, zinc, and aluminum; Metal alloys, etc.

The above-mentioned base material may be subjected to an easy-adhesion treatment in advance. Examples of the adhesion-facilitating treatment include hydrophilization treatments such as corona treatment, plasma treatment, and ultraviolet treatment. In addition, undercoating treatment can be performed using resins, silane coupling agents, tetraalkoxysilanes, or the like. In addition, a primer treatment may be performed with a resin, a silane coupling agent, a tetraalkoxysilane, or the like, or a glass coating such as polysilazane may be preliminarily coated on the substrate.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to the following examples, and it goes without saying that appropriate modifications can be made within the scope suitable for the gist described above and later, and these are included in the technical scope of the present invention.

The following Examples and Comparative Examples were evaluated by the following methods.

(1) Measurement of contact angle

The contact angle of the film surface was measured by the droplet method (analysis method: θ/2 method, amount of water droplet: 3.0 μL) using a contact angle measuring apparatus (DM700, manufactured by Kyowa Interface Science Co., Ltd.).

(2) Measurement of haze

The haze (Haze) of the film surface was measured using a haze meter HZ-2 (Suga Test Instruments) with a D65 light source (average sunlight).

(3) Hot water resistance test

The sample was immersed in ion-exchanged water at 70°C for 12 hours, the contact angle was measured in the same manner as in the above (1), and the sliding property of the water drop was evaluated by the sliding speed when the water drop was dropped on the film surface. The sliding speed was calculated by dropping 50 μL of water droplets on the film surface on a substrate inclined at 20° using a contact angle measuring device (DM700, manufactured by Kyowa Interface Science Co., Ltd.), and measuring the time for the water droplets to slide off 1.5 cm from the initial drop position. of.

Example 1

0.29 g of compound (1) and 0.71 g of tetraethoxysilane in which the average value of n10 in the above formula (A-I-26) was 24 were dissolved in 2.13 g of isopropanol. After adding dropwise 0.0008 g of acetic acid and 0.14 g of water as catalysts to the obtained solution, the solution was stirred at 65° C. for 4 hours to prepare a sample solution. The above-mentioned sample solution 1 was diluted with 66.88 g of butyl acetate to prepare a coating solution 1.

Using a spin coater (manufactured by MIKASA Co., Ltd.), the coating solution 1 was formed into a film on an alkali-free glass (EAGLE XG) subjected to plasma treatment under the conditions of a rotational speed of 3000 rpm and 20 seconds, and then heat-treated at 200° C. for 3 hours to obtain a film. sample.

Example 2

Except having diluted the said sample solution with 2-ethoxyethyl acetate 74.10g, and except having produced the coating solution 2, it carried out similarly to Example 1, and formed the film on the base material.

Example 3

Coating solution 3 was prepared by diluting the sample solution with a mixed solution of 23.74 g of isopropanol and 44.46 g of 2-ethoxyethyl acetate, except that the stirring time during the preparation of the above-mentioned sample solution was 6 hours. , and in the same manner as in Example 1, a film was formed on the substrate.

Example 4

Coating solution 4 was prepared by diluting the sample solution with a mixed solution of 11.87 g of isopropanol and 59.28 g of 2-ethoxyethyl acetate while setting the stirring time during the preparation of the above-mentioned sample solution to 6 hours. , and in the same manner as in Example 1, a film was formed on the substrate.

Example 5

0.21 g of compound (1) and 0.53 g of tetraethoxysilane having an average value of n10 of 24 in the above formula (A-I-26) were dissolved in 1.49 g of isopropanol, and the mixture was stirred at room temperature for 20 minutes. After adding dropwise 0.0008 g of acetic acid and 0.14 g of water as catalysts to the obtained solution, the solution was stirred at room temperature for 4 hours to prepare a sample solution. The above-mentioned sample solution was diluted with 55.58 g of 2-ethoxyethyl acetate to prepare coating solution 5. The coating solution 5 was coated on the substrate in the same manner as in Example 1, and a film was formed on the substrate.

Example 6

Coating solution 6 was prepared by diluting the sample solution with a mixed solution of 8.90 g of isopropanol and 44.46 g of 2-ethoxyethyl acetate while setting the stirring time during the preparation of the above-mentioned sample solution to 6 hours. , and in the same manner as in Example 5, a film was formed on the substrate.

Example 7

0.22 g of compound (1) and 0.55 g of tetraethoxysilane having an average value of n10 of 24 in the above formula (A-I-26) were dissolved in 1.34 g of isopropanol, and the mixture was stirred at room temperature for 20 minutes. After adding dropwise 0.0008 g of acetic acid and 0.14 g of water as catalysts to the obtained solution, the solution was stirred at room temperature for 6 hours to prepare a sample solution. The above-mentioned sample solution was diluted with 55.58 g of 2-ethoxyethyl acetate to prepare a coating solution 7. The coating solution 7 was coated on the substrate in the same manner as in Example 1, and a film was formed on the substrate.

Example 8

0.29 g of compound (1) and 0.71 g of tetraethoxysilane having an average value of n10 of 24 in the above formula (A-I-26) were dissolved in 2.13 g of isopropanol, and the mixture was stirred at room temperature for 20 minutes. After adding dropwise 0.0008 g of acetic acid and 0.14 g of water as catalysts to the obtained solution, the solution was stirred at room temperature for 4 hours to prepare a sample solution. The above-mentioned sample solution was diluted with 66.88 g of isopropyl acetate to prepare coating solution 8. The coating solution 8 was coated on the substrate in the same manner as in Example 1, and a film was formed on the substrate.

Example 9

Coating solution 9 was prepared by diluting the sample solution with a mixed solution of 29.68 g of isopropanol and 37.05 g of 2-ethoxyethyl acetate, except that the mixing time during the preparation of the above-mentioned sample solution was 6 hours. , and in the same manner as in Example 8, a film was formed on the substrate.

Example 10

The coating solution 10 was prepared by diluting the sample solution with a mixed solution of 47.48 g of isopropanol and 14.82 g of 2-ethoxyethyl acetate, except that the mixing time during the preparation of the above-mentioned sample solution was 6 hours. , and in the same manner as in Example 8, a film was formed on the substrate.

Example 11

0.43 g of compound (1) and 0.38 g of tetraethoxysilane having an average value of n10 of 24 in the above formula (A-I-26) were dissolved in 2.04 g of isopropanol, and the mixture was stirred at room temperature for 20 minutes. After adding dropwise 0.0008 g of acetic acid and 0.14 g of water as catalysts to the obtained solution, the solution was stirred at room temperature for 4 hours to prepare a sample solution. The above-mentioned sample solution was diluted with 84.90 g of 2-ethoxyethyl acetate to prepare a coating solution 11 . The coating solution 11 was coated on the substrate in the same manner as in Example 1 to form a film on the substrate.

Example 12

A coating solution 12 was prepared in the same manner as in Example 11 except that 84.39 g of 2-methoxy-1-methylethyl acetate was used instead of 84.90 g of 2-ethoxyethyl acetate. A film is formed on it.

Example 13

0.53 g of compound (2) and 0.29 g of tetraethoxysilane having an average value of n10 of 45 in the above formula (A-I-26) were dissolved in 2.07 g of isopropanol, and the mixture was stirred at room temperature for 20 minutes. After adding dropwise 0.0006 g of acetic acid and 0.10 g of water as catalysts to the obtained solution, the solution was stirred at room temperature for 4 hours to prepare a sample solution. The above-mentioned sample solution was diluted with 84.90 g of 2-ethoxyethyl acetate, and the coating solution 13 was prepared. The coating solution 13 was coated on the substrate in the same manner as in Example 1 to form a film on the substrate.

Example 14

A coating solution 14 was prepared in the same manner as in Example 13, except that 84.39 g of 2-methoxy-1-methylethyl acetate was used instead of 84.90 g of 2-ethoxyethyl acetate. A film is formed on it.

Example 15

0.28 g of compound (2) and 0.54 g of tetraethoxysilane having an average value of n10 of 45 in the above formula (A-I-26) were dissolved in 2.01 g of isopropanol, and the mixture was stirred at room temperature for 20 minutes. To the obtained solution, 0.0011 g of acetic acid and 0.18 g of water were added dropwise as catalysts, and then stirred at room temperature for 4 hours to prepare a sample solution. The above-mentioned sample solution was diluted with 84.90 g of 2-ethoxyethyl acetate to prepare a coating solution 15 . The coating solution 15 was coated on the substrate in the same manner as in Example 1 to form a film on the substrate.

Example 16

A coating solution 16 was prepared in the same manner as in Example 15, except that 84.39 g of 2-methoxy-1-methylethyl acetate was used instead of 84.90 g of 2-ethoxyethyl acetate. A film is formed on it.

Comparative Example 1

0.29 g of compound (1) and 0.71 g of tetraethoxysilane having an average value of n10 of 24 in the above formula (A-I-26) were dissolved in 2.13 g of isopropanol, and the mixture was stirred at room temperature for 20 minutes. To the obtained solution, 0.17 g of acetic acid and 0.02 g of water were added dropwise as catalysts, followed by stirring at room temperature for 4 hours to prepare a sample solution. The above-mentioned sample solution was diluted with 71.44 g of 2-butoxyethyl acetate to prepare a coating solution a. The coating solution a was coated on the substrate in the same manner as in Example 1, and a film was formed on the substrate.

Comparative Example 2

Except having diluted the sample solution with 62.62 g of 1-octanol to prepare coating solution b, it carried out similarly to the comparative example 1, and formed the film on the base material.

Comparative Example 3

Except having diluted the sample solution with 59.36 g of isopropyl alcohol to prepare the coating solution c, it carried out similarly to the comparative example 1, and formed the film on the base material.

The results are shown in Table 6-1, Table 6-2 and Table 7. In addition, Table 8 shows the physical properties of the solvents used in Examples and Comparative Examples.

[Table 6-2]

[Table 7]

[Table 8]

※1 Mix in any ratio

*2 Regarding the solubility of isopropyl acetate in water, it shows the value at 27°C

*3 Regarding the solubility of 1-octanol in water, it shows the value at 25°C

^{Examples 1} to The film of 16 had good sliding properties of water droplets after the hot water test. On the other hand, the films of Comparative Examples 1 to 3 formed from the composition without the mixed solvent (c2) showed poor sliding properties after the hot water test.

Industrial Availability

The film obtained from the mixed composition of the present invention is excellent in water resistance, abrasion resistance, sulfuric acid resistance, and hot water resistance. Therefore, it is useful as a base material in display devices such as touch panel displays, optical elements, semiconductor elements, building materials, automobile parts, nanoimprint technology, and the like. In addition, it can be suitably used as the main body of transportation equipment such as trains, automobiles, ships, and airplanes, window glass (front glass, side glass, rear glass), rear view mirror, shock absorber, and the like. In addition, it can also be used in outdoor applications such as building outer walls, tents, solar power generation modules, sound insulation panels, and concrete. It can also be used for fishing nets, insect nets, sinks, etc. It can also be used for various indoor equipment such as kitchens, bathrooms, washstands, mirrors, various parts around toilets, chandeliers, ceramics such as tiles, artificial marble, and air conditioners. In addition, it is also suitable for use as an antifouling treatment for jigs in factories, inner walls, piping, and the like. Also suitable for goggles, glasses, protective caps, marbles, fibers, umbrellas, toys, soccer balls, etc. In addition, it can be used as an antiadhesion agent for various packaging materials such as food packaging materials, cosmetic packaging materials, and the inside of cans.

Claims (9)

1. a mixed composition is characterized in that, is the mixed composition of organosilicon compound a, metal compound b and solvent c2, and described organosilicon compound a is at least one molecular chain containing trialkylsilyl and at least one. A compound in which one hydrolyzable group is bonded to a silicon atom, the metal compound b is a compound in which at least one hydrolyzable group is bonded to a metal atom, the vapor pressure of the solvent c2 at 20°C is 0.032kPa～10kPa, and the solubility is 0.032kPa～10kPa The parameter value, that is, the sp value is 11(cal/cm ³ ) ^1/2 or less, The hydrogen atom contained in the trialkylsilyl group may be substituted by a fluorine atom, The total amount of the organosilicon compound a and the metal compound b in the composition is 0.5% by mass or more, The amount of the solvent c2 in the composition is 5% by mass or more. 2 . The composition according to claim 1 , wherein the amount of the solvent c2 in the composition is 30% by mass or more. 3 . 3 . The composition according to claim 1 , wherein a solvent c1 having a solubility in water at 20° C. of 231 g/L or more and an sp value of 20 or less is mixed. 4 . 4. The composition according to claim 1 or 2, wherein a solvent c1 having an sp value greater than 11 (cal/cm ³ ) ^1/2 is mixed. The composition according to claim 1 or 2, wherein at least one solvent c1 selected from isopropanol, ethanol, methanol, and methyl ethyl ketone is mixed. 6 . The composition according to claim 1 , wherein the water content in the composition is 0.5 mass % or less. 7 . 7 . The composition according to claim 1 , wherein the organosilicon compound a is a compound represented by the following formula (A1), 8 .

In the formula (A1), R ^a1 represents a molecular chain containing a trialkylsilyl group, A plurality of A ^a1 each independently represents a hydrolyzable group, Z ^a1 represents a molecular chain containing a trialkylsilyl group, a group containing a siloxane skeleton, or a group containing a hydrocarbon chain, The hydrogen atom contained in the trialkylsilyl group in R ^a1 and Z ^a1 may be substituted by a fluorine atom, x is either 0 or 1. 8 . The composition according to claim 1 , wherein the metal compound b is a compound represented by the following formula (B1), 9 . M(Z ^b1 ) _r (A ^b1 ) _mr (B1) In the formula (B1), M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr or Ta, Z ^b1 represents a group containing a siloxane skeleton, a group containing a hydrocarbon chain, or a hydrogen atom, A plurality of A ^b1 each independently represents a hydrolyzable group, m represents an integer of 3 to 5 based on the metal atom, r is 0 or 1. 9 . The composition according to claim 1 , wherein the organosilicon compound a is a compound represented by the following formula (A2), 10 .

In the formula (A2), A plurality of A ^a1 each independently represents a hydrolyzable group, Z ^a1 represents a molecular chain containing a trialkylsilyl group, a group containing a siloxane skeleton, or a group containing a hydrocarbon chain, and the hydrogen atom contained in the trialkylsilyl group may be substituted by a fluorine atom, A plurality of R ^s1 each independently represent a hydrocarbon group or a trialkylsiloxy group, and the hydrogen atom contained in the hydrocarbon group or the trialkylsiloxy group may be substituted by a fluorine atom, A plurality of R ^s2 each independently represents an alkyl group having 1 to 10 carbon atoms, Z ^s1 represents -O- or a divalent hydrocarbon group, and -CH ₂ - contained in the divalent hydrocarbon group can be replaced by -O-, Y ^s1 represents a single bond or -Si(R ^s2 ) ₂ -L ^s1 -, the L ^s1 represents a divalent hydrocarbon group, and -CH ₂ - contained in the divalent hydrocarbon group can be replaced by -O-, n1 represents an integer greater than 1, x is either 0 or 1.