KR20200140841A - Mixed composition - Google Patents

Abstract

An object of the present invention is to provide a composition capable of realizing a film having excellent water repellency, oil repellency and sulfuric acid resistance. The present invention is a mixture of at least one trialkylsilyl group-containing molecular chain and an organosilicon compound (a), an organic polysilazane (b), and a solvent (c) in which at least one hydrolyzable group is bonded to a silicon atom. The composition relates to a composition wherein the total concentration of the organosilicon compound (a) and the organopolysilazane (b) is 0.2 mass% or more and less than 2.6 mass% with respect to 100 mass% of the mixed composition.

Description

Mixed composition

The present invention relates to a mixed composition of an organosilicon compound and an organopolysilazane.

In various display devices, optical devices, semiconductor devices, building materials, automobile parts, nanoimprint technology, etc., problems such as contamination or corrosion of the base material due to the adhesion of droplets to the surface of the base material, and performance degradation resulting from this contamination or corrosion May occur. Therefore, in these fields, it is desired to have good water repellency and oil repellency on the surface of the substrate.

As a composition having such water and oil repellency, Patent Documents 1 and 2 disclose coating agents containing polysilazane and silicone oil.

Japanese Unexamined Patent Application Publication No. 2014-139301 Japanese Unexamined Patent Application Publication No. 2012-153849

The water-repellent and oil-repellent film may be exposed to harsh environments such as ultraviolet rays or rain, depending on applications such as outdoors, and it is desirable that good performance can be maintained even after exposure to harsh environments. In the outdoors it is that the sulfuric acid and nitric acid generated by the reaction SO _X and NO _X, and moisture in the air, resulting in deterioration of the film has been apparent review. Therefore, a coating having good acid resistance (especially strong deterioration factor, sulfuric acid resistance) is required. However, the film obtained by using the coating agent disclosed in Patent Documents 1 and 2 leaves room for examination in terms of abrasion resistance, sulfuric acid resistance, appearance, and the like.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition capable of realizing a film having excellent water and oil repellency and at least excellent in sulfuric acid resistance.

The film obtained from the composition of the present invention is also preferably excellent in at least one or more of droplet sliding properties, abrasion resistance, appearance, and hot water resistance, and more preferably excellent in both droplet sliding properties, abrasion resistance, appearance, and hot water resistance.

The present inventors, as a result of repeated intensive research in order to solve the above problems, by mixing an organosilicon compound in which a trialkylsilyl group-containing molecular chain and a hydrolyzable group are bonded to a silicon atom and an organopolysilazane at a predetermined concentration, The present invention was completed by finding that a film having excellent water/oil repellency and sulfuric acid resistance, preferably excellent in droplet sliding properties, abrasion resistance, appearance, and hot water resistance, can be obtained. The present invention is as follows.

[1] Mixed composition of an organosilicon compound (a), an organic polysilazane (b), and a solvent (c) having at least one trialkylsilyl group-containing molecular chain and at least one hydrolyzable group bonded to a silicon atom as,

The hydrogen atom contained in the trialkylsilyl group may be substituted with a fluorine atom,

A mixed composition wherein the total concentration of the organosilicon compound (a) and the organopolysilazane (b) is 0.2% by mass or more and less than 2.6% by mass based on 100% by mass of the composition.

[2] The composition according to [1], wherein the organic polysilazane (b) has a structural unit represented by the following formula (B2).

[Formula 1]

[In the formula (B2), R ^p21 , R ^p22 , and R ^p23 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. However, at least one of R ^p21 and R ^p22 represents a hydrocarbon group having 1 to 10 carbon atoms.]

[3] The composition according to [1] or [2], wherein the organosilicon compound (a) is a compound represented by the following formula (A1).

[Formula 2]

[In the 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, a siloxane skeleton-containing group, or a hydrocarbon chain-containing group,

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

x is 0 or 1.]

[4] The composition according to any one of [1] to [3], wherein the organosilicon compound (a) is a compound represented by the following formula (A2).

[Formula 3]

[In the formula (A2), a plurality of ^Rs1 each independently represents a hydrocarbon group or a trialkylsilyloxy group, and the hydrogen atom contained in the hydrocarbon group or trialkylsilyloxy 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,

n1 represents an integer of 1 or more,

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 -, the L ^s1 represents a divalent hydrocarbon group, and -CH ₂ -contained in the divalent hydrocarbon group is substituted with -O- You may have it.

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

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

The hydrogen atom contained in the trialkylsilyl group for Z ^a1 may be substituted with a fluorine atom,

x is 0 or 1.]

[5] The composition according to any of [2] to [4], wherein the organic polysilazane (b) further has a structural unit represented by the following formula (B1).

[Formula 4]

[In the formula (B1), R ^p10 and R ^p11 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms,

Y represents a C1-C10 divalent hydrocarbon group,

Each of a plurality of Xs independently represents a hydrolyzable group.]

[6] The composition according to [5], wherein the organic polysilazane (b) contains 2% by mass to 50% by mass of the SiX ₃ group represented by the formula (B1).

[7] The composition according to any of [1] to [6], wherein the mass ratio (a/b) of the organosilicon compound (a) and the organic polysilazane (b) is 0.2 or more.

[8] A film which is a cured product of the composition according to any one of [1] to [7].

[9] A coating body in which the film according to [8] is coated on a base material, wherein the density of the film on the side of the base material determined by the X-ray reflectance method is 0.9 g/cm 3 or more.

According to the present invention, it is possible to provide a composition capable of realizing a film having excellent water/oil repellency and sulfuric acid resistance by mixing an organosilicon compound and an organic polysilazane at a predetermined concentration. Therefore, the film obtained from the composition of the present invention tends to be able to maintain water and oil repellency for a long time even outdoors. The film obtained from the composition of the present invention is also preferably excellent in at least one or more of droplet sliding properties, abrasion resistance, appearance, and hot water resistance, and more preferably excellent in all of droplet sliding properties, abrasion resistance, appearance, and hot water resistance.

1 is a graph showing an example of a fitting process in XRR measurement.

The composition of the present invention is an organosilicon in which at least one trialkylsilyl group-containing molecular chain and at least one hydrolyzable group are bonded to a silicon atom (hereinafter, this silicon atom may be referred to as a ``center silicon atom''). It is obtained by mixing the compound (a) and the organic polysilazane (b) at a predetermined concentration, and when it is formed into a film, the water/oil repellency and sulfuric acid resistance (preferably, in addition to the water/oil repellency and sulfuric acid resistance) It was found to be excellent in slip properties, abrasion resistance, appearance and hot water resistance).

In addition, the composition of the present invention includes those in which the reaction proceeds after mixing, for example, during storage.

In the organosilicon compound (a) in the present invention, at least one trialkylsilyl group-containing molecular chain and at least one hydrolyzable group are bonded to a central silicon atom.

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

The hydrolyzable group may be a group that provides a hydroxy group (silanol group) by hydrolysis, and examples thereof include alkoxy groups having 1 to 6 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group; Hydroxy group; Acetoxy group; Chlorine atom; Isocyanate group; Etc. are mentioned preferably. Especially, it is preferable that it is a C1-C6 alkoxy group, it is more preferable that it is a C1-C4 alkoxy group, and it is still more preferable that it is a C1-C2 alkoxy group.

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 3 or less.

In addition, as described later, the organosilicon compound (a) of the present invention has a plurality of silicon atoms, and the hydrolyzable group may be bonded to two or more silicon atoms, but it is only bonded to the one central silicon atom. It is particularly preferred.

In the central silicon atom of the organosilicon compound (a), in addition to the trialkylsilyl group-containing molecular chain and the hydrolyzable group, a siloxane skeleton-containing group having fewer elements than the number of elements constituting the molecular chain of the trialkylsilyl group-containing molecular chain, Alternatively, a hydrocarbon chain-containing group containing a hydrocarbon chain having fewer carbon atoms than the number of elements constituting the molecular chain of the trialkylsilyl group-containing molecular chain may be bonded.

In the composition of the present invention, two or more kinds of the organosilicon compounds (a) may be mixed.

It is preferable that the said organosilicon compound (a) is a compound specifically represented by following formula (A1).

[Formula 5]

In formula (A1), R ^a1 represents a trialkylsilyl group-containing molecular chain, a plurality of A ^a1 each independently represents a hydrolyzable group, and Z ^a1 represents a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, Or a group containing a hydrocarbon chain, and 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.

The trialkylsilyl group-containing molecular chain of R ^a1 is a monovalent group having a structure in which the trialkylsilyl-containing group is bonded to the end of the molecular chain, and formed from the composition of the present invention by the trialkylsilyl-containing group bonded to the molecular chain. The water repellency and oil repellency of the resulting film are improved. In addition, the presence of the trialkylsilyl group-containing molecular chain reduces the resistance between the droplet (water droplets, oil droplets, etc.) and the film, so that the droplet is liable to move. In the case where the alkyl group of the trialkylsilyl-containing group is substituted with a fluoroalkyl group, the water and oil repellency of the film interface (surface) can be similarly improved. Further, when the trialkylsilyl group is unevenly distributed on the surface of the film, diffusion of sulfuric acid or hot water into the film is prevented, a film having high sulfuric acid resistance is obtained, and preferably a film having high temperature water resistance is obtained.

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

[Formula 6]

In formula (s1), a plurality of ^Rs1 each independently represents a hydrocarbon group or a trialkylsilyloxy group, and the hydrogen atom contained in the hydrocarbon group or trialkylsilyloxy group may be substituted with a fluorine atom. * Represents a bonding hand.

In the formula (s1), with at least one of R ^s1 or tree silyloxy alkyl, it is preferred that R ^s1 are both an alkyl group;

When R ^s1 is a hydrocarbon group, the number of carbon atoms is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2. When R ^s1 is a hydrocarbon group, an aliphatic hydrocarbon group is preferable, and an alkyl group is more preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. A plurality of ^Rs1 may be the same or different, and the same is preferable. When all of R ^s1 are hydrocarbon groups (especially alkyl groups), the total number of carbon atoms of the three R ^s1s is preferably 9 or less, more preferably 6 or less, and still more preferably 4 or less. It is preferable that at least one of the three R ^s1 is a methyl group, more preferably at least two of the three R ^s1 are methyl groups, and it is particularly preferable that all of the three R ^s1 are methyl groups.

^Examples of the group (trialkylsilyl group) in which all of R ^s1 are hydrocarbon groups (alkyl groups) include groups specifically represented by the following formulas. In the formula, * represents a bond hand.

[Formula 7]

Further, in the above formula (s1), when R ^s1 is a trialkylsilyloxy group, it is preferable that at least one of R ^s1 is a trialkylsilyloxy group. Examples of the trialkylsilyloxy group include a group in which an oxygen atom is bonded to a silicon atom of a group (trialkylsilyl group) in which all ^Rs1 is a hydrocarbon group (alkyl group). In the above formula (s1), more preferably two or more, still more preferably three R ^s1 are trialkylsilyloxy groups.

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

[Formula 8]

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

The molecular chain to which the trialkylsilyl-containing group is bonded is preferably linear or branched, and preferably linear. The molecular chain preferably includes a dialkylsiloxane chain, and preferably includes a linear dialkylsiloxane chain. Further, the molecular chain may contain a divalent hydrocarbon group. Even if a part of the molecular chain is a divalent hydrocarbon group, since the remainder is a dialkylsiloxane chain, the chemical and physical durability of the resulting film is good.

It is preferable that the molecular chain is a group represented by formula (s2).

[Formula 9]

In formula (s2), a plurality of ^Rs2 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-. * On the left represents a hand bonded to a central silicon atom, and * on the right represents a hand bonded to a trialkylsilyl-containing group. n1 represents an integer of 1 or more.

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

n1 is preferably 1 to 100, more preferably 1 to 80, more preferably 1 to 60, particularly preferably an integer of 1 to 45, and particularly preferably 1 to 30.

The number of carbon atoms of the divalent hydrocarbon group in Z ^s1 and L ^s1 is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4. It is preferable that the said divalent hydrocarbon group is chain, and when it is a chain, either linear or branched chain may be sufficient. Further, the divalent hydrocarbon group is preferably a divalent aliphatic hydrocarbon group, and preferably an alkanediyl group. Examples of the divalent hydrocarbon group include a methylene group, an ethylene group, a propylene group, and a butylene group.

In addition, some -CH ₂ -contained in the divalent hydrocarbon group may be substituted with -O-. In this case, two consecutive -CH ₂ -s are not simultaneously substituted with -O-, and -CH ₂ -adjacent to the Si atom is not substituted with -O-. When two or more -CH ₂ -are substituted with -O-, the number of carbon atoms between -O- and -O- is preferably 2 to 4, and more preferably 2 to 3. As a group in which part of the divalent hydrocarbon group is substituted with -O-, specifically, a group having a (poly)ethylene glycol unit, a group having a (poly)propylene glycol unit, and the like can be exemplified.

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

Examples of the molecular chain included in the trialkylsilyl group-containing molecular chain include molecular chains represented by the following formulas. In the formula, q1 represents an integer of 1 to 60, * on the left represents a bond with a central silicon atom, and * on the right represents a bond with a trialkylsilyl-containing group. It is preferable that q1 is an integer of 1 to 45, More preferably, it is an integer of 1 to 30.

[Formula 10]

[Formula 11]

[Formula 12]

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

It is preferable that the trialkylsilyl group-containing molecular chain is a group represented by the following formula (s3).

[Formula 13]

In formula (s3), R ^s1 , R ^s2 , Z ^s1 , Y ^s1 , and n1 are synonymous with the above. * Represents a bond hand with a central silicon atom.

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

[Formula 14]

In formulas (s3-1) and (s3-1-1), R ^s2 , Y ^s1 , Z ^s1 , and n1 have the same meaning as above. Each of R ^s3 independently represents an alkyl group having 1 to 4 carbon atoms. * Represents a bond hand with a central silicon atom.

The number of carbon atoms in the alkyl group represented by R ^s3 is preferably 1 to 3, more preferably 1 to 2. In addition, in formulas (s3-1) and (s3-1-1), 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, further It is preferably 4 or less. _{^{Also, -Si (R s3) 3 R}} s3 of, R ^s3 is preferably at least one is the methyl group, and two or more R ^s3 is preferably a methyl group, and three R ^s3 are all a methyl group is particularly included in the desirable.

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

[Formula 15]

In formulas (s3-2) and (s3-2-1), R ^s2 , Y ^s1 , Z ^s1 , and n1 are the same as above. R ^s4 each independently represents an alkyl group having 1 to 4 carbon atoms. * Represents a bond hand with a central silicon atom.

Examples of the C1-C4 alkyl group represented by R ^s4 include the groups described for R ^s3 , and the preferred range thereof is also the same.

As the trialkylsilyl group-containing molecular chain, a group represented by formula (s3-I) can be mentioned. In formula (s3-I), * represents a bond with a central silicon atom.

[Formula 16]

[Table 1]

[Table 2]

It is preferable that n30 shown in Tables 1 and 2 is 1 to 30.

Next, A ^a1 in Formula (A1) will be described. Each of the plurality of A ^a1 is independently a hydrolyzable group, and may be a group that provides a hydroxy group (silanol group) by hydrolysis, for example, carbon number such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. 1 to 6 alkoxy groups; Hydroxy group; Acetoxy group; Chlorine atom; Isocyanate group; Etc. are mentioned preferably. Especially, it is preferable that it is a C1-C6 alkoxy group, it is more preferable that it is a C1-C4 alkoxy group, and a C1-C2 alkoxy group is still 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 trialkylsilyl group-containing molecular chain, the same thing as R ^a1 is mentioned.

Further, when Z ^a1 is a siloxane skeleton-containing group, the siloxane skeleton-containing group is a monovalent group containing a siloxane unit (Si-O-), and is less than the number of elements constituting the trialkylsilyl group-containing molecular chain of R ^a1 . It is preferred that it is composed of a number of elements. Thereby, the siloxane skeleton-containing group becomes a group having a shorter length than a trialkylsilyl group-containing molecular chain or a three-dimensional area (increase in volume). The divalent hydrocarbon group may be contained in the siloxane skeleton-containing group.

It is preferable that the siloxane skeleton-containing group is a group represented by the following formula (s4).

[Formula 17]

In formula (s4), R ^s2 , Z ^s1 , and Y ^s1 are the same as above. R ^s5 represents a hydrocarbon group or a hydroxy 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 the integer of 0-5. * Represents a bond hand with a central silicon atom.

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

It is preferable that n3 is 1-5, More preferably, it is 1-3.

The sum of the number of elements in the siloxane skeleton-containing group is preferably 100 or less, more preferably 50 or less, still more preferably 30 or less, and preferably 10 or more. In addition, the R ^a1 trialkylsilyl group containing preferably a molecular chain and Z or more siloxane skeleton-containing groups of the original small number of cars 10 of the ^a1 of, more preferably at least 20, as is preferred, more preferably not more than 1000, 500 Or less, more preferably 200 or less.

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

[Formula 18]

When Z ^a1 is a hydrocarbon chain-containing group, the number of carbon atoms in the hydrocarbon chain portion may be smaller than the number of elements constituting the molecular chain of the trialkylsilyl group-containing molecular chain. Further, it is preferable that the number of carbon atoms in the longest linear chain of the hydrocarbon chain is smaller than the number of elements constituting the longest linear chain of the trialkylsilyl group-containing molecular chain. The hydrocarbon chain-containing group is usually composed of only a hydrocarbon group (hydrocarbon chain), but if necessary, a part of the methylene group (-CH ₂ -) of the hydrocarbon chain may be substituted with an oxygen atom. Further, 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 simultaneously substituted with an oxygen atom.

In addition, the number of carbon atoms in the hydrocarbon chain portion means the number of carbon atoms constituting a hydrocarbon group (hydrocarbon chain) in an oxygen-unsubstituted hydrocarbon chain-containing group, and in an oxygen-substituted hydrocarbon chain-containing group, an oxygen atom is a methylene group. Assuming that it is (-CH ₂ -), it means the number of strong carbon atoms.

Hereinafter, unless otherwise specified, an oxygen-unsubstituted hydrocarbon chain-containing group (i.e., a monovalent hydrocarbon group) is used as an example to describe a hydrocarbon chain-containing group, but in any description, among the methylene groups (-CH ₂ -) It is possible to replace some with oxygen atoms.

When the hydrocarbon chain-containing group is a hydrocarbon group, the carbon number is preferably 1 or more and 3 or less, and more preferably 1. Further, the hydrocarbon chain-containing group may be branched or linear. The 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 saturated aliphatic hydrocarbon chain-containing group is more preferably a saturated aliphatic hydrocarbon group. The saturated aliphatic hydrocarbon group includes, for example, a methyl group, an ethyl group, and a propyl group.

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

X in formula (A1) is 0 or 1, Preferably it is 0.

It is preferable that the organosilicon compound (a) represented by the formula (A1) is a compound represented by the following formula (A2).

[Formula 19]

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

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

[Formula 20]

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

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

[Formula 21]

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

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

[Formula 22]

[Table 3-1]

[Table 3-2]

[Table 4-1]

[Table 4-2]

The n10 shown in Table 3-1, Table 3-2, Table 4-1, and Table 4-2 is preferably 1 to 30.

Among the above formulas (A-I), those represented by (A-I-26) are more preferable. That is, as the organosilicon compound (a) represented by the formula (A2), it is preferably represented by the following formula (A2-26).

[Formula 23]

In formula (A2-26), n is 1 to 60, and preferably 1 to 30.

The amount of the organosilicon compound (a) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.3% by mass or more in 100% by mass of the composition. Moreover, as an upper limit, it is preferable that it is less than 2.6 mass %, More preferably, it is 2.0 mass% or less, More preferably, it is 1.5 mass% or less, Especially preferably, it is 1.0 mass% or less. It is preferable that the amount of the organosilicon compound (a) above satisfies the above range in any of the compounding amount at the time of preparation of the composition and the value calculated from the analysis result of the composition. In addition, in the present specification, when the range of the amount (concentration) or mass ratio of each component is described, similarly to the above, any of the compounding amount at the time of preparation of the composition and the value calculated from the analysis result of the composition is the range It is desirable to satisfy.

As an example of the method for synthesizing the organosilicon compound (a), the method described in Japanese Unexamined Patent Application Publication No. 2017-201009 can be mentioned.

It is preferable that the organic polysilazane (b) in this invention has a structural unit represented by following formula (B2).

[Formula 24]

In formula (B2), R ^p21 , R ^p22 and R ^p23 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. However, at least one of R ^p21 and R ^p22 represents a hydrocarbon group having 1 to 10 carbon atoms.

When R ^p21 , R ^p22 and R ^p23 are a hydrocarbon group, the number of carbon atoms is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2. The hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and among them, a methyl group is preferable.

R ^p23 is more preferably a hydrogen atom.

It is preferable that the said organic polysilazane (b) further has a structural unit represented by following formula (B1).

[Formula 25]

In formula (B1), R ^p10 and R ^p11 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, Y represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and a plurality of X's are each independently And a hydrolyzable group.

The number of carbon atoms in the hydrocarbon group for R ^p10 and R ^p11 is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2. As the hydrocarbon group for R ^p10 and R ^p11 , an aliphatic hydrocarbon group is preferable, and an alkyl group is more preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and among them, a methyl group is preferable.

As the divalent hydrocarbon group of Y, the number of carbon atoms is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2. It is preferable that the said divalent hydrocarbon group is chain, and when it is a chain, either linear or branched chain may be sufficient. Further, the divalent hydrocarbon group is preferably a divalent aliphatic hydrocarbon group, and preferably an alkanediyl group. Examples of the divalent hydrocarbon group include a methylene group, an ethylene group, a propylene group, and a butylene group.

In addition, some -CH ₂ -contained in the divalent hydrocarbon group may be substituted with -O-. In this case, two consecutive -CH ₂ -s are not simultaneously substituted with -O-, and -CH ₂ -adjacent to the Si atom is not substituted with -O-. When two or more -CH ₂ -are substituted with -O-, the number of carbon atoms between -O- and -O- is preferably 2 to 4, and more preferably 2 to 3. As a group in which part of the divalent hydrocarbon group is substituted with -O-, specifically, a group having a (poly)ethylene glycol unit, a group having a (poly)propylene glycol unit, and the like can be exemplified.

The hydrolyzable group of X may be a group that provides a hydroxy group (silanol group) by hydrolysis, and examples thereof include alkoxy groups having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group; Hydroxy group; Acetoxy group; Chlorine atom; Isocyanate group; Etc. are mentioned preferably. Among these, an alkoxy group having 1 to 4 carbon atoms is preferable, and an alkoxy group having 1 to 2 carbon atoms is more preferable. A plurality of Xs may be the same or different, and the same is preferable.

In the composition of the present invention, two or more kinds of the organic polysilazane (b) may be mixed.

The organic polysilazane (b) preferably contains at least 2% by mass, more preferably 5% by mass of the SiX ₃ group of the formula (B1) with respect to 100% by mass of the organic polysilazane (b). Or more, more preferably 8% by mass or more. The upper limit is not limited, but may be 50% by mass or less, 40% by mass or less, or 30% by mass or less.

The total concentration of the organosilicon compound (a) and the organopolysilazane (b) is 0.2 mass% or more and less than 2.6 mass% with respect to 100 mass% of the composition of the present invention. The lower limit is preferably 0.3% by mass or more, and more preferably 0.5% by mass or more. The upper limit is preferably 2.0% by mass or less, more preferably 1.8% by mass or less, still more preferably 1.3% by mass or less, and particularly preferably 1.0% by mass or less. By adjusting the total concentration of the organosilicon compound (a) and the organopolysilazane (b) within the above range, when a film is formed, sulfuric acid resistance can be improved. In addition, abrasion resistance, hot water resistance, and the like can be improved, and the appearance can be improved, such as no white turbidity or uneven coating.

In the composition of the present invention, the mass ratio (a/b) of the organosilicon compound (a) and the organopolysilazane (b) is preferably 0.2 or more, more preferably 0.4 or more, and even more preferably 0.5 or more. to be. The upper limit is preferably 100 or less, more preferably 50 or less, more preferably 10 or less, and particularly preferably 8 or less.

The content ratio of the hydrogen atom of Si-H and the hydrocarbon group having 1 to 10 carbon atoms bonded to Si in the organic polysilazane (b) can be appropriately selected, but for example, the molar ratio of the hydrocarbon group/hydrogen atom is It is 0.1-50, preferably 0.2-10. In addition, these molar ratios can be calculated from NMR measurement or the like.

The composition of the present invention contains a solvent (c).

Examples of the solvent (c) include alcohol-based solvents, ether-based solvents, ketone-based solvents, ester-based solvents, amide-based solvents, aliphatic hydrocarbon-based solvents, and aromatic hydrocarbon-based solvents.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, 1-propoxy 2-propanol, and the like, and examples of the ether solvent include dimethoxyethane, tetrahydrofuran, and di- Oxane, dibutyl ether, etc. are mentioned, Acetone, methyl ethyl ketone (2-butanone) etc. are mentioned as a ketone solvent, Ethyl acetate, butyl acetate, etc. are mentioned as ester solvent, An amide solvent Examples of the solvent include dimethylformamide, and examples of the aliphatic hydrocarbon solvent include pentane, hexane, heptane, octane, isooctane, cyclopentane, cyclohexane, cycloheptane, methylcyclohexane, mineral spirit, and the like, and aromatic hydrocarbon solvents As examples, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, and the like can be mentioned. Among them, ketone solvents, ether solvents, ester solvents, and aliphatic hydrocarbon solvents are preferred, and aliphatic hydrocarbon solvents are more preferred. One type of these solvents may be used, or two or more types may be appropriately mixed and used. It is preferable that the solvent (c) does not contain moisture because the stability of the coating solution is increased, and coating shake and foreign matter during coating can be reduced.

The concentration of the solvent (c) relative to 100% by mass of the composition is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by mass or more. The upper limit is set according to the amount of the organosilicon compound (a), organopolysilazane (b), and additional components other than these (hereinafter referred to as the third component (d)), and the organosilicon compound (a), organic The solvent (c) may be other than the polysilazane (b) and the third component (d).

The composition of the present invention may coexist with a catalyst. In the present invention, the catalyst is not particularly limited as long as it is a catalyst capable of curing organic polysilazane, for example, 1-methylpiperazine, 1-methylpiperidine, 4,4'-trimethylenedipiperi Dean, 4,4'-trimethylenebis(1-methylpiperidine), diazabicyclo-[2,2,2]octane, cis-2,6-dimethylpiperazine, 4-(4-methylpiperidine Din)pyridine, pyridine, dipyridine, α-picoline, β-picoline, γ-picoline, piperidine, lutidine, pyrimidine, pyridazine, 4,4'-trimethylenedipyridine, 2-( N-heterocyclic compounds such as methylamino) pyridine, pyrazine, quinoline, quinoxaline, triazine, pyrrole, 3-pyrroline, imidazole, triazole, tetrazole, and 1-methylpyrrolidine, for example methyl Amine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tributylamine, pentylamine, dipentylamine, tripentyl Amines such as amine, hexylamine, dihexylamine, trihexylamine, heptylamine, diheptylamine, octylamine, dioctylamine, trioctylamine, phenylamine, diphenylamine, and triphenylamine, for example 1 ,8-diazabicyclo[5,4,0]7-undecene (DBU), 1,5-diazabicyclo[4,3,0]5-nonene (DBN), 1,5,9-triaza Cyclododecane, 1,4,7-triazacyclononane, etc. are mentioned.

Moreover, as a catalyst, in addition to the said catalyst, For example, an acidic compound; Basic compounds; Organometallic compounds; And the like. Examples of the acidic compound include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrogen peroxide, chloric acid, and hypochlorous acid; Organic acids such as acetic acid, propionic acid, butyric acid, valeric acid, maleic acid and stearic acid; And the like. Examples of the basic compound include ammonia. Examples of the organometallic compound include organometallic compounds containing metal elements such as Al, Fe, Zn, and Sn as a central metal, and organic aluminum compounds such as aluminum carboxylic acid, aluminum acetylacetone complex, and aluminum ethylacetoacetate complex; Organic iron compounds such as iron carboxylate (iron octylate, etc.); Organic zinc compounds such as zinc acetylacetonatomonohydrate, zinc naphthenate, and zinc octylate; Organotin compounds such as dibutyltin diacetate complex; In addition, examples of the organometallic compound include metal carboxates including Ni, Ti, Pt, Rh, Co, Ru, Os, Pd, Ir, and the like; Acetylacetona complexes including Ni, Pt, Pd, Rh, and the like; Metal fine particles such as Au, Ag, Pd, Ni, Zn, and Ti; Metal peroxide; Metal chloride; And cyclopentadienyl complexes of metals such as ferrocene and zirconocene.

The composition of the present invention may coexist various additives such as antioxidants, rust inhibitors, ultraviolet absorbers, light stabilizers, mold inhibitors, antibacterial agents, bioadhesive inhibitors, deodorants, pigments, flame retardants, and antistatic agents within the range that does not impair the effect. do.

The coating, which is a cured product of the above composition, and a coating body coated with the coating on a substrate are also included in the present invention.

The film obtained from the composition of the present invention is usually formed on a substrate, and as a method of contacting the substrate, for example, a method of coating the composition on the substrate, spin coating method, dip coating method, spray Coating method, roll coating method, bar coating method, hand coating (a method of soaking the liquid in a cloth and painting it on the substrate), sprinkling (a method of applying the liquid directly to the substrate using a dropper, etc.), spraying (spraying A method of applying to a substrate using ), and the like.

The composition brought into contact with the substrate as described above is allowed to stand in air at room temperature (for example, 1 hour to 48 hours) or by heating (for example, 300°C or less) to react with moisture in the air, Decomposition and siloxy vaporization proceed, and a Si-O skeleton-containing film can be formed on the substrate. The film thickness of the film can be, for example, about 0.1 to 500 nm. It is preferably 0.2 to 200 nm, more preferably 0.3 to 100 nm. By adjusting to these film thicknesses, a film uniformly cured to the inside of the film can be obtained, and a film having good wear resistance can be obtained.

The contact angle of the droplets on the film of the present invention is preferably 90° or more, more preferably 98° or more, and still more preferably 100° or more. This contact angle can be determined according to the measurement method of Examples described later.

The sliding speed of the droplets on the film of the present invention is preferably 10 mm/sec or more, more preferably 25 mm/sec or more, still more preferably 30 mm/sec or more, and particularly preferably 45 mm/sec or more. This sliding speed can be determined according to the measurement method of Examples to be described later.

The coating of the present invention preferably exhibits abrasion resistance of 3000 times or more, more preferably 5000 times or more, and still more preferably 8000 times or more in the measurement of the abrasion resistance of the examples described later.

It is preferable that the appearance of the film of the present invention is free from foreign matter, white ae, etc. that can be seen with the naked eye after film formation. If there is foreign matter or white dust, when the droplet is slid, the droplet may be caught and not slipped, or the active ingredient may flow along with the droplet, resulting in loss of performance. If foreign matter or white dust occurs, the film may be wiped off with a cloth, etc., but the components contributing to water and oil repellency are removed too much by the wiping operation, resulting in deterioration of performance or non-uniformity of performance within the surface of the film. In some cases, it is preferable to express the removal performance without wiping off.

The contact angle of the droplets on the film of the present invention after the hot water test is preferably 90° or more, more preferably 97° or more, and still more preferably 102° or more. The contact angle after this hot water test can be determined according to the measurement method of Examples described later.

The sliding speed of the droplets on the film of the present invention after the hot water test is preferably 20 mm/sec or more, more preferably 25 mm/sec or more, and still more preferably 27 mm/sec or more. The sliding speed after this hot water test can be determined according to the measurement method of Examples to be described later.

In the evaluation of the sulfuric acid resistance test of Examples described later, the coating of the present invention is preferably wiped off at least one point, more preferably at least two points, and particularly preferably wiped off all three points.

If the film thickness of the film of the present invention is too thick, since the film of the present invention has moisture-absorbing curing properties, curing does not sufficiently proceed to the inside, and the film becomes soft, resulting in poor wear resistance. Therefore, it is preferable that the film has an appropriate film thickness. Further, when the film is too thick, the surface of the film tends to become cloudy due to irregularities or bleed components on the surface of the film, resulting in poor appearance. As a criterion for whether or not curing has progressed to the extent that the coating exhibits wear resistance, it can be evaluated by measuring the density of the coating. In particular, the density of the film in the vicinity of the substrate is preferably 0.90 g/cm 3 or more, and more preferably 0.95 g/cm 3 or more. The upper limit is not particularly limited, but is, for example, about 2.2 g/cm 3. The density of the film in the vicinity of the substrate refers to the density of the film on the substrate side in the film in a coating body coated with the film of the present invention on the substrate. As a method of measuring the density of the film, for example, an X-ray reflectance method can be used.

The X-ray reflectance method is used as a means of measuring the lamination structure, film thickness, or density of a multilayer thin film whose composition or film structure is unknown. This X-ray reflectance method is to measure by using the interference vibration of X-rays reflected at the interface where layers of different densities are in contact. For example, measurement of the thickness of an oxide film formed on an electrode or a stacked structure of a spin valve film. Is used in the interpretation of

In such X-ray reflectance measurement (XRR), by observing the phenomenon that the X-rays reflected from each interface of the film interfere as described above, and fitting this measurement result using simulation calculation data, the density of each layer and the film It becomes possible to analyze the thickness and roughness. The above-described density of the film on the substrate side refers to a value obtained by fitting treatment, and when the film is fitted to a plurality of layers by performing a fitting treatment, the density of the layer closest to the substrate becomes the density of the film on the substrate side. In addition, when the film is fitted to a single layer, the density is adopted as the density of the film on the substrate side. Here, fitting means correcting the difference between the theoretical calculated value of the spectral intensity and the measured intensity with respect to the X-ray spectrum detected when X-ray measurement is performed.

Fig. 1 shows an example in which the XRR measurement result of the film is fitted. The density of a thin film having a film thickness of several tens of nm from the outermost surface can be calculated from the critical angle of total reflection, and the density of other layers can be calculated from the amplitude of the interference fringes.

In addition, the film thickness of each layer can be calculated from the period of vibration. In addition, roughness can be calculated from the attenuation rate of the entire reflectance measurement data and the amplitude of the interference fringes on the high angle side, as described in Japanese Unexamined Patent Application Publication No. 2001-349849, for example. have.

The procedure of the fitting process will be described in detail below. First, measurement data is obtained by incidence of X-rays from an angle near the critical angle with respect to the surface of a film sample made of a single layer film or a multilayer film. When the number of measurement points of the data is Np and the angle of the incident X-ray at a certain measurement point n is α(n), for example, α(n) is the reflected X-ray intensity at 0.05° to 5°, respectively. By observation and normalizing to the intensity of the incident X-ray, the reflectance R{α(n)} of the X-ray at the incident angle α(n) is obtained. The correlation of α(n) with R{α(n)} is called the XRR profile. Depending on the substrate or film thickness of the sample, it is necessary to measure under appropriate conditions. Specifically, the appropriate conditions are the measurement range of the angle α(n) of the incident X-ray and the divergence angle [°] of the incident X-ray.

In α(n), the angle at which the measurement starts is required to satisfy the condition that the incident X-rays are totally reflected. In general, the condition for total reflection of X-rays can be estimated from the element species and density, and it is said that the critical angle of total reflection is 0.23° for a glass substrate or a Si substrate. In addition, it is preferable that the measurement end angle is an angle at which the signal strength is equal to that of the background.

With respect to the divergence angle of incident X-rays, it is known that the thicker the film on the substrate, the shorter the period of X-ray interference [°], and the thicker the film, the smaller the divergence angle [°] of incident X-rays. Needs to be. In general, it is said that if the thickness of the film is 100 nm or more, the divergence angle needs to be 0.015° or less, and if the film thickness is 300 nm or more, it is necessary to set the divergence angle to 0.003° or less. In order to set the divergence angle to be 0.015° or less, there is a method such as reflecting once by a spectroscopic crystal such as Ge (110). Moreover, in order to make the divergence angle 0.003° or less, there is a method such as reflecting twice by a spectroscopic crystal such as Ge (110). When these spectral crystals reflect X-rays, the incident intensity decreases sharply. Therefore, it is better not to introduce the spectral crystal more than necessary.

For the measured profile obtained by measuring in this way, the parameters of the film thickness, density, and roughness (the interface between the air and the film, the interface between the film, and the interface between the film and the substrate) were initially set for each of the substrate and film or multilayer film. It is called a simulation calculation profile obtained by setting and changing at least one or more of these parameters by simulation calculation. The density of the film sample is determined by fitting this simulation calculation profile to be close to the measured profile.

As the procedure of the fitting process, for example, an analysis by the least squares method is used. A parameter such as minimizing the sum of 2 powers of the residuals between the simulation calculation profile and the measured profile is determined. This is the one set of parameters that best fits the measurement data.

The residual squared sum (χ ² ) is the difference between the calculated reflectance (Ical) of the spectral intensity and the experimental reflectance (Iexp), expressed by the formula (Y), and is preferably 0.01 or less. Here, Np is the number of data points within the fitting range. α _i is the angle of the incident X-ray.

[Equation 1]

···(Y)

The above fitting process can be analyzed by using Rigaku's analysis software (GlobalFit) or the like.

The substrate to which the composition of the present invention is brought into contact is not particularly limited, and the shape of the substrate may be either a flat surface or a curved surface, or a three-dimensional structure in which a plurality of surfaces are combined. Moreover, the material of the base material is also not limited, and may be composed of either an organic material or an inorganic material. Examples of the organic material include thermoplastic resins such as acrylic resin, polycarbonate resin, polyester resin, styrene resin, acrylic-styrene copolymer resin, cellulose resin, and polyolefin resin; Thermosetting resins such as phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester, silicone resin, and urethane resin; And the like, and examples of the inorganic material include ceramics; Glass; Metals such as iron, silicon, copper, zinc, and aluminum; An alloy containing the metal; And the like.

The substrate may be subjected to an easily bonding treatment in advance. Examples of the easy adhesion treatment include hydrophilic treatment such as corona treatment, plasma treatment, and ultraviolet treatment. Further, a primer treatment with a resin, a silane coupling agent, tetraalkoxysilane, or the like may be performed, or a glass film such as polysilazane may be applied to the substrate in advance.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not originally limited by the following examples, and it is also carried out with appropriate changes within the range suitable for the purpose of the above and later. Of course it is possible, and they are all included in the technical scope of the present invention.

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

Measurement of contact angle

Using "DM700" manufactured by Kyowa Interface Chemical Co., Ltd., the liquid volume was 3 μL, and the contact angle of the transparent film surface with respect to water was measured by the θ/2 method.

Measurement of slide speed

The sliding property of the water droplet was evaluated by the sliding speed when the water droplet was dropped on the surface of the film. Specifically, using a contact angle measuring device (DM700) manufactured by Kyowa Interface Science Co., Ltd., 50 μL of water droplets are dropped onto the film on a glass substrate tilted at 20°, until the water droplets slide 15 mm from the initial drop position. The time of was measured, and the sliding speed (mm/sec) of water droplets on the coating surface was calculated.

Measurement of wear resistance

With a load of 1000 g/cm 3 and a reciprocating speed of 1600 mm per minute, a distance of 20 mm was rubbed 2000 times with Sabina MX (registered trademark), and then rubbed in units of 1000 times. Each contact angle was measured, and the number of times until two of the three points decreased to 90° or less was measured.

Appearance evaluation

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

○: No contamination at all

△: Partial contamination of the membrane can be confirmed

×: Overall contamination of the membrane can be confirmed

Measurement of hot water resistance

The sample was immersed in ion-exchanged water at 70°C for 12 hours, and the water contact angle and sliding speed before and after immersion were measured.

Measurement of sulfuric acid resistance and oil repellency

On the film, 0.035 g of 0.1M sulfuric acid was added dropwise to each of three places, and left to stand at room temperature for 12 hours to evaporate moisture. After evaporation of water, a circle was drawn on the area where sulfuric acid was dropped using a magic (Sakura pen-touch oily core), and then wiped with Sabina (registered trademark) of wiping cloth. When all three points of the magic mark were wiped off, it was indicated as ◯, and when there was a point that was not wiped off, it was indicated as x. Moreover, the fact that the magic mark is wiped off indicates that the oil repellency is also good.

Measurement of film density

For the measurement of the film density, an X-ray reflectance measuring apparatus (SmartLab) manufactured by Rigaku Corporation was used. As the X-ray source, a 45 kW X-ray generator, a wavelength of CuKα ray by a Cu target λ=0.15418 nm or a wavelength of CuKα1 ray λ=0.15406 nm is used, and a monochromator is not used or a Ge(220) monochromatic Crystal was used. As setting conditions, the sampling width was set to 0.01° or 0.002°, and the investigation range was set to 0.0 to 2.5° or 0.0 to 1.6°. And it measured under the said setting conditions, and obtained the reflectance measurement value. The obtained measured values were analyzed using the company's analysis software (GlobalFit).

Example 1

0.03 g of compound (1) having an average of 24 n in the above formula (A2-26), and 0.03 g of Durazane (registered trademark) 1500 slow cure (manufactured by MRCK) were dissolved in 9.94 g of isooctane, and at room temperature For 1 minute, the mixture was mixed using a vortex to obtain a coating solution. The coating solution was formed into a film on an alkali-free glass (Eagle XG) subjected to plasma treatment with a spin coater (manufactured by MIKASA) under conditions of a rotation speed of 3000 rpm and 20 sec, followed by heat treatment at 200°C for 3 hours. A film was obtained on the phase. Thereafter, the coating was evaluated by the above measurement method. In addition, Durazane (registered trademark) 1500 slow cure has a structural unit represented by the following formula (B3).

[Formula 26]

In formula (B3), R represents a hydrogen atom or a methyl group.

Examples 2 to 11, Comparative Examples 1 to 2

A film was produced in the same manner as in Example 1, except that the types and/or amounts of the organosilicon compound (a), organopolysilazane (b), and solvent (c) were changed in the proportions shown in Table 5. Further, Durazane (registered trademark) 1500 rapid cure (made by MRCK) also has the same structural unit as in (B3) above. Durazane (registered trademark) 1500 slow cure and Durazane (registered trademark) 1500 rapid cure have 9 to 27 mass% of Si(OC ₂ H ₅ ) ₃ groups, and in the structure in (B3), The molar ratios (methyl group/hydrogen atom) of the hydrogen atom of the SiH group and the methyl group of the Si-CH ₃ group were all 1.5 to 3.0.

The mass ratio of the Si(OC ₂ H ₅ ) ₃ group and the molar ratio of the hydrogen atom and the methyl group were determined based on the integral value of ¹ H-NMR (400 MHz, standard: CDCl ₃ (=7.24 ppm)). That is, the molar ratio of SiH, SiCH ₃ , and Si(OCH ₂ CH ₃ ) _{3 in} the organic polysilazane was calculated from the integral value, and the molar ratio of the hydrogen atom and the methyl group was calculated. Moreover, each was converted into a mass ratio, and the mass% of the Si(OC ₂ H ₅ ) ₃ group contained in the organic polysilazane was calculated.

As the compound (2) used in Comparative Example 1, a piece-terminated reactive silicone oil (X-24-9011, manufactured by Shin-Etsu Chemical Industries Co., Ltd.) was used.

[Table 5]

The evaluation results of the obtained film are shown in Tables 6 and 7.

[Table 6]

[Table 7]

In Examples 1 to 11, in which an organosilicon compound (a) and an organopolysilazane (b) are mixed at a predetermined concentration, water and oil repellency, droplet slipping, abrasion resistance, sulfuric acid resistance and hot water resistance, and appearance are excellent. I was able to create a film. Although the organosilicon compound has very high stability to light, on the other hand, since it has a siloxane bond, it has been found that it is not easy to provide a film obtained from a composition in which the organosilicon compound is mixed has durability against water or hot water. Therefore, in a film obtained from a composition in which an organosilicon compound is mixed, in order to maintain good performance even after exposure to a harsh environment, a film having high warm water resistance is said to be an important performance in order to maintain performance even in an actual use environment. can do. In addition, under general specification conditions, if the film is peeled off by rubbing against various objects or rain, or colliding with them, it becomes difficult to maintain the water/oil repellency performance, so abrasion resistance is also important as a characteristic of the film. Therefore, it is also preferable that it is a film having warm water resistance and abrasion resistance.

Industrial availability

The film obtained from the composition of the present invention is excellent in water/oil repellency and sulfuric acid resistance (preferably, in addition to water/oil repellency and sulfuric acid resistance, droplet sliding properties, abrasion resistance, appearance and hot water resistance). Therefore, it is useful as a substrate in a display device such as a touch panel display, an optical element, a semiconductor element, a building material, an automobile part, and a nanoimprint technology. In addition, it is suitably used as an article such as a body, window glass (front glass, side glass, rear glass), mirror, and bumper in transport equipment such as tanks, automobiles, ships, and aircraft. In addition, it can be used for outdoor applications such as exterior walls of buildings, tents, solar power modules, sound insulation panels, and concrete. It can also be used for fishing nets, insect control nets, and fish tanks. In addition, it can be used for various indoor facilities such as kitchens, baths, sinks, mirrors, articles of each member around the toilet, ceramics such as chandeliers and tiles, artificial marble, and air conditioners. In addition, it can be used as an antifouling treatment for jigs, inner walls, and pipes in factories. It is also suitable for goggles, glasses, helmets, pachinko, textiles, umbrellas, toys, soccer balls, etc. In addition, it can be used as an agent for preventing adhesion of various packaging materials, such as a food packaging material, a cosmetic packaging material, and an interior of a pot.

Claims (9)

A mixed composition of an organosilicon compound (a), an organic polysilazane (b), and a solvent (c) in which at least one trialkylsilyl group-containing molecular chain and at least one hydrolyzable group are bonded to a silicon atom,
The hydrogen atom contained in the trialkylsilyl group may be substituted with a fluorine atom,
A mixed composition wherein the total concentration of the organosilicon compound (a) and the organopolysilazane (b) is 0.2% by mass or more and less than 2.6% by mass based on 100% by mass of the composition. The method of claim 1,
The composition wherein the organic polysilazane (b) has a structural unit represented by the following formula (B2).
[Formula 1]

[In the formula (B2), R ^p21 , R ^p22 , and R ^p23 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. However, at least one of R ^p21 and R ^p22 represents a hydrocarbon group having 1 to 10 carbon atoms.] The method according to claim 1 or 2,
The composition wherein the organosilicon compound (a) is a compound represented by the following formula (A1).
[Formula 2]

[In the 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, a siloxane skeleton-containing group, or a hydrocarbon chain-containing group,
The hydrogen atom contained in the trialkylsilyl group in R ^a1 and Z ^a1 may be substituted with a fluorine atom,
x is 0 or 1.] The method according to any one of claims 1 to 3,
The composition wherein the organosilicon compound (a) is a compound represented by the following formula (A2).
[Formula 3]

[In the formula (A2), a plurality of ^Rs1 each independently represents a hydrocarbon group or a trialkylsilyloxy group, and the hydrogen atom contained in the hydrocarbon group or trialkylsilyloxy 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,
n1 represents an integer of 1 or more,
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 -, the L ^s1 represents a divalent hydrocarbon group, and -CH ₂ -contained in the divalent hydrocarbon group is substituted with -O- do.
A plurality of A ^a1 each independently represents a hydrolyzable group,
Z ^a1 represents a trialkylsilyl group-containing molecular chain, a siloxane skeleton-containing group, or a hydrocarbon chain-containing group,
The hydrogen atom contained in the trialkylsilyl group for Z ^a1 may be substituted with a fluorine atom,
x is 0 or 1.] The method according to any one of claims 2 to 4,
The composition wherein the organic polysilazane (b) further has a structural unit represented by the following formula (B1).
[Formula 4]

[In the formula (B1), R ^p10 and R ^p11 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms,
Y represents a C1-C10 divalent hydrocarbon group,
Each of a plurality of Xs independently represents a hydrolyzable group.] The method of claim 5,
The composition in which the organic polysilazane (b) contains 2% by mass to 50% by mass of SiX ₃ groups represented by the formula (B1). The method according to any one of claims 1 to 6,
The composition in which the mass ratio (a/b) of the organosilicon compound (a) and the organic polysilazane (b) is 0.2 or more. A film which is a cured product of the composition according to any one of claims 1 to 7. A coating formed by coating the coating according to claim 8 on a substrate, wherein the density of the coating on the substrate side determined by the X-ray reflectance method is 0.9 g/cm 3 or more.

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