WO2023058621A1

WO2023058621A1 - Coating-forming composition, coating, and chemical liquid

Info

Publication number: WO2023058621A1
Application number: PCT/JP2022/037026
Authority: WO
Inventors: 僚井上; みちる賀川; 央基山口; 浩治久保田
Original assignee: ダイキン工業株式会社
Priority date: 2021-10-08
Filing date: 2022-10-03
Publication date: 2023-04-13
Also published as: JP2023164657A; TW202323450A; JP2023057045A; JP7440793B2

Abstract

The present disclosure provides: a coating-forming composition from which a coating having excellent water repellency and excellent wear resistance can be formed; a coating; and a chemical liquid.　The composition comprises inorganic fine particles, a polymerizable component, and a water-repellent component, wherein: the inorganic fine particles comprise first inorganic fine particles having an average particle diameter of 1-100 nm and second inorganic fine particles having an average particle diameter of 500 nm to 5 μm; the content of the first inorganic fine particles is 3-25 parts by mass with respect to 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component, and the water-repellent component; the content of the second inorganic fine particles is 12-27 parts by mass with respect to 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component, and the water-repellent component; and the water-repellent component is a polymer having at least a structural unit based on a specific compound.

Description

Film-forming composition, film, and chemical solution

The present disclosure relates to a film-forming composition, a film, and a chemical solution.

Conventionally, various coatings have been proposed that can impart super water repellency to the surface of objects. For example, Patent Document 1 discloses that a super water-repellent film having both super water repellency and abrasion resistance can be formed by using fine particles having a polymerizable group and a compound having two or more polymerizable groups in the molecule. is disclosed. Patent Document 2 discloses a technique for forming a super water-repellent film that is a film containing fluorine atoms and has both super water repellency and abrasion resistance by appropriately controlling various properties of the film. .

Further, Patent Document 3 discloses a film-forming composition containing a fluorine-based copolymer containing a fluoroolefin, a perfluoroalkyl group-containing monomer, and a hydroxyl group-containing unsaturated monomer, and silica fine powder. It is Such a composition is said to be capable of forming a film having excellent water and oil repellency, releasability, releasability, and storage stability.

WO2016/056663 WO2017/179678 JP 2011-84745 A

An object of the present disclosure is to provide a film-forming composition, a film, and a chemical solution capable of forming a film having excellent water repellency and excellent abrasion resistance.

That is, the present disclosure encompasses subject matter described in, for example, the following sections.
Item 1
including inorganic fine particles, a polymerizable component, and a water-repellent component,
The inorganic fine particles include first inorganic fine particles having an average particle size of 1 nm or more and 100 nm or less, and second inorganic fine particles having an average particle size of 500 nm or more and 5 μm or less,
The content of the first inorganic fine particles is 3 to 25 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component,
The content of the second inorganic fine particles is 12 to 27 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component,
The total content of the first inorganic fine particles and the second inorganic fine particles per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component, 20 parts by mass or more,
The water-repellent component has the following general formula (1):

(Wherein, X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (wherein X ¹ and X ² are the same or different and are a hydrogen atom, a fluorine atom or a chlorine atom ), a cyano group, a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a straight chain having 1 to 20 carbon atoms is a straight or branched alkyl group, Y is a direct bond, a hydrocarbon group having 1 to 10 carbon atoms which may have an oxygen atom, a —CH ₂ CH ₂ N(R ¹ )SO ₂ — group (with the proviso that , R ¹ is an alkyl group having 1 to 4 carbon atoms, and the right end of the formula is bonded to R ^a and the left end is bonded to O.), —CH ₂ CH(OY ¹ )CH ₂ — group (provided that Y ¹ is a hydrogen atom or an acetyl group, and the right end of the formula is bonded to R ^a and the left end is bonded to O.), or a —(CH ₂ ) _n SO ₂ — group (where n is 1 to 10). , The right end of the formula is bonded to ^Ra , and the left end is bonded to O.), where ^Ra is a linear or branched alkyl group having 20 or less carbon atoms, a linear or branched alkyl group having 6 or less carbon atoms, or A branched fluoroalkyl group, a polysiloxane with a molecular weight of 300 to 50,000, a polyether group with a molecular weight of 400 to 5,000, or a fluoropolyether group with a molecular weight of 400 to 5,000.). A film-forming composition, which is a polymer.
Item 2
The content of the second inorganic fine particles is 15 to 27 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component,
In the above formula (1), R ^a is a linear or branched alkyl group having 20 or less carbon atoms, a linear or branched fluoroalkyl group having 6 or less carbon atoms, or a polyether group having a molecular weight of 400 to 5000 Item 2. The film-forming composition according to Item 1, which is a fluoropolyether group having a molecular weight of 400 to 5,000.
Item 3
The content of the water-repellent component is 0.1 to 30 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component. Item 3. The film-forming composition according to Item 1 or 2.
Item 4
4. The film-forming composition according to any one of Items 1 to 3, wherein the polymerizable component is a polymer having a crosslinkable functional group and a curing agent.
Item 5
A film comprising a cured product of the film-forming composition according to any one of Items 1 to 4.
Item 6
including inorganic fine particles, a binder component, and a water-repellent component,
The inorganic fine particles include first inorganic fine particles having an average particle size of 1 nm or more and 100 nm or less, and second inorganic fine particles having an average particle size of 500 nm or more and 5 μm or less,
The content of the first inorganic fine particles is 3 to 25 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component,
The content of the second inorganic fine particles is 12 to 27 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component,
The total content of the first inorganic fine particles and the second inorganic fine particles is 20 parts per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component. Part by mass or more,
The water-repellent component has the following general formula (1):

(Wherein, X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (wherein X ¹ and X ² are the same or different and are a hydrogen atom, a fluorine atom or a chlorine atom ), a cyano group, a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a straight chain having 1 to 20 carbon atoms is a straight or branched alkyl group, Y is a direct bond, a hydrocarbon group having 1 to 10 carbon atoms which may have an oxygen atom, a —CH ₂ CH ₂ N(R ¹ )SO ₂ — group (with the proviso that , R ¹ is an alkyl group having 1 to 4 carbon atoms, and the right end of the formula is bonded to R ^a and the left end is bonded to O.), —CH ₂ CH(OY ¹ )CH ₂ — group (provided that Y ¹ is a hydrogen atom or an acetyl group, and the right end of the formula is bonded to R ^a and the left end is bonded to O.), or a —(CH ₂ ) _n SO ₂ — group (where n is 1 to 10). , The right end of the formula is bonded to ^Ra , and the left end is bonded to O.), where ^Ra is a linear or branched alkyl group having 20 or less carbon atoms, a linear or branched alkyl group having 6 or less carbon atoms, or A branched fluoroalkyl group, a polysiloxane with a molecular weight of 300 to 50,000, a polyether group with a molecular weight of 400 to 5,000, or a fluoropolyether group with a molecular weight of 400 to 5,000.). A coating that is a polymer.
Item 7
The content of the second inorganic fine particles is 15 to 27 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component,
In the above formula (1), R ^a is a linear or branched alkyl group having 20 or less carbon atoms, a linear or branched fluoroalkyl group having 6 or less carbon atoms, or a polyether group having a molecular weight of 400 to 5000 Alternatively, the coating according to item 6, which is a fluoropolyether group having a molecular weight of 400 to 5,000.
Item 8
The content of the water-repellent component is 0.1 to 30 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component. The coating according to 6 or 7.
Item 9
In a coating containing inorganic fine particles,
The inorganic fine particles include first inorganic fine particles having an average particle size of 1 nm or more and 100 nm or less, and second inorganic fine particles having an average particle size of 500 nm or more and 5 μm or less,
The contact angle of water is 150° or more,
A film having a water contact angle of 150° or more after being rubbed with a paper waste cloth at least 50 times with a load of 100 g/cm ² .
Item 10
The coating according to any one of claims 5 to 9, wherein the snow accretion start time measured by the following snow accretion test is 5 minutes or longer.
<Snow accretion test>
A coating is placed on a test stand in a test room kept at a constant temperature in the range of 1 to 2 ° C so that the snow-covered surface is vertical to the ground, and the coating is subjected to a wind speed of 10 m / sec and a collision amount of 110 kg /. Pre-made artificial snow is blown under the condition of m ² /h. This blowing causes the artificial snow to impinge on the covering surface. From the start of this spraying, a video was taken of the entire sprayed surface of the sample, and the presence or absence of snow accretion on the film surface was visually confirmed from the video obtained after the test was completed. Measured as the start time (no snow accretion time).
Item 11
A chemical solution comprising the film-forming composition according to any one of Items 1 to 4.

According to the film-forming composition of the present disclosure, a film having excellent water repellency and excellent abrasion resistance can be formed.

Although conventional super water-repellent coatings have excellent water repellency, they often lack sufficient abrasion resistance. I was having problems with the drop. From this point of view, the superhydrophobic coating has been required to improve abrasion resistance while maintaining high water repellency.

In view of these circumstances, the present inventors have conducted extensive research with the aim of forming a film that has excellent water repellency and excellent abrasion resistance. As a result, by combining specific inorganic fine particles, a polymerizable component and a water-repellent component, in particular, by using two types of fine particles having different average particle sizes as inorganic fine particles in combination, abrasion resistance can be improved while maintaining high water repellency. It has been found that an improved coating can be formed, and the above objects can be achieved. In addition, we have found that such a coating can also have excellent anti-snow accretion performance. Hereinafter, embodiments of the present disclosure will be described in detail.

Hereinafter, embodiments of the present invention will be described in detail. In this specification, the expressions "contain" and "include" include the concepts of "contain", "include", "substantially consist of" and "consist only of".

In this specification, the numerical range indicated using "-" indicates the range including the numerical values before and after "-" as the minimum and maximum values, respectively. In the numerical ranges described stepwise in this specification, the upper limit value or lower limit value of the numerical range in one step can be arbitrarily combined with the upper limit value or lower limit of the numerical range in another step. In the numerical ranges described herein, the upper and lower limits of the numerical ranges may be replaced with values shown in Examples or values that can be uniquely derived from Examples.

1. Film-Forming Composition The film-forming composition of the present disclosure contains at least inorganic fine particles, a polymerizable component, and a water-repellent component. First, each of these components will be described in detail.

(Inorganic fine particles)
The inorganic fine particles include first inorganic fine particles having an average particle size of 1 nm or more and 100 nm or less and second inorganic fine particles having an average particle size of 500 nm or more and 5 μm or less. By including two types of inorganic fine particles having different sizes in the film-forming composition of the present disclosure, the first inorganic fine particles are not embedded in the coating, and a unique fine uneven structure can be formed on the surface. As a result, water repellency and anti-adhesion properties are remarkably improved. In addition, since the film-forming composition of the present disclosure contains inorganic fine particles, the strength of the film is improved, and the second inorganic fine particles prevent the first inorganic fine particles from sliding down during abrasion, so the abrasion resistance of the film is improved. improves.

In the film-forming composition of the present disclosure, the average particle size of the first inorganic fine particles can be measured by the following method. First, the volatile components of the film-forming composition are removed by heat treatment (300° C., 3 hours). The microparticles thus obtained are directly observed with a scanning electron microscope, and 200 microparticles in the photographed image are selected. However, in this selection, fine particles having an equivalent circle diameter of 450 nm or more should not be selected. The average value of the equivalent circle diameters of the selected 200 fine particles is calculated, and this value is taken as the average particle size of the first inorganic fine particles in the film-forming composition.

In the film-forming composition of the present disclosure, the average particle size of the second inorganic fine particles can be measured by the following method. First, the volatile components of the film-forming composition are removed by heat treatment (300° C., 3 hours). The microparticles thus obtained are directly observed with a scanning electron microscope, and 200 microparticles in the photographed image are selected. However, in this selection, fine particles having an equivalent circle diameter of 450 nm or more are selected. The average value of the equivalent circle diameters of the selected 200 fine particles is calculated, and this value is taken as the average particle size of the first inorganic fine particles in the film-forming composition.

When the average particle diameter of the first inorganic fine particles is less than 1 nm, aggregation tends to occur, and the water repellency and abrasion resistance of the coating of the coating composition tend to decrease. In addition, when the average particle diameter of the first inorganic fine particles exceeds 100 nm, the difference between the average particle diameter of the second inorganic fine particles and the average particle diameter of the second inorganic fine particles becomes small, and the effect of using different average particle diameters together cannot be sufficiently obtained. As a result, it becomes difficult to improve the abrasion resistance of the film of the film-forming composition.

The average particle size of the first inorganic fine particles is preferably 2 nm or more, more preferably 3 nm or more, even more preferably 4 nm or more, and particularly preferably 5 nm or more. The average particle size of the first inorganic fine particles is preferably 80 nm or less, more preferably 60 nm or less, even more preferably 50 nm or less, and particularly preferably 30 nm or less.

When the average particle diameter of the second inorganic fine particles is less than 500 nm, the difference from the average particle diameter of the first inorganic fine particles becomes small, and the effect of using different average particle diameters together cannot be sufficiently obtained. As a result, it becomes difficult to improve the abrasion resistance of the film of the film-forming composition, and the anti-snow accretion performance is also deteriorated. If the average particle diameter of the second inorganic fine particles exceeds 5 µm, high water repellency cannot be obtained, and the particles tend to fall off the coating, resulting in poor abrasion resistance of the coating of the coating composition. difficult to improve.

The average particle diameter of the second inorganic fine particles is preferably 800 nm or more, more preferably 1 µm or more, even more preferably 1.5 µm or more, and particularly preferably 2 µm or more. The average particle size of the second inorganic fine particles is preferably 4.5 μm or less, more preferably 4 μm or less, still more preferably 3.5 μm or less, and particularly preferably 3 μm or less.

The types of the first inorganic fine particles and the second inorganic fine particles are not particularly limited as long as they satisfy the aforementioned average particle diameter, and for example, a wide range of known metal oxide fine particles can be exemplified. Specific examples of metal oxides include silica, alumina, titanium oxide, zirconia, and the like, and the first inorganic fine particles and the second inorganic fine particles are silica in that the hardness and water resistance of the coating are likely to increase. is preferably The types of the first inorganic fine particles and the second inorganic fine particles may be the same or different, preferably the first inorganic fine particles and the second inorganic fine particles are the same, more preferably , both the first inorganic fine particles and the second inorganic fine particles are silica.

The specific surface areas of the first inorganic fine particles and the second inorganic fine particles are not particularly limited. For example, the specific surface area is preferably 30 to 700 m ² /g, more preferably 80 to 330 m ² in terms of easily improving the hardness of the obtained coating. /g is more preferred. In the film-forming composition of the present disclosure, the specific surface area of the fine particles means a value measured by the BET method (so-called BET specific surface area).

The surfaces of the first inorganic fine particles and the second inorganic fine particles may be hydrophilic or hydrophobic. The first inorganic fine particles and the second inorganic fine particles may be a mixture of hydrophilic and hydrophobic properties. The first inorganic fine particles and the second inorganic fine particles may be treated with a surface treatment agent to control wettability. The first inorganic fine particles and the second inorganic fine particles preferably do not have a radically polymerizable reactive group (for example, a polymerizable double bond such as an acryloyl group) on the surface, that is, the first inorganic fine particles And it is preferable that the polymer is not covalently bonded to the surface of the second inorganic fine particles. As a result, the wear resistance of the coating is improved, and particularly the snow accretion prevention performance is likely to be enhanced.

The shape of the first inorganic fine particles and the second inorganic fine particles is also not particularly limited, and examples thereof include spherical, ellipsoidal and the like, and may be amorphous particles such as irregular shaped particles. The first inorganic fine particles and the second inorganic fine particles can also form aggregates. Aggregates may be spherical or non-spherical, and may be chain-like.

The inorganic fine particles contained in the film-forming composition of the present disclosure can contain 80% by mass or more of the first inorganic fine particles and the second inorganic fine particles, preferably 90% by mass or more, and more preferably 95% by mass or more. , more preferably 99% by mass or more. The inorganic fine particles contained in the film-forming composition of the present disclosure may be only the first inorganic fine particles and the second inorganic fine particles, and particularly the first inorganic fine particles and the second inorganic fine particles. preferable.

In the film-forming composition of the present disclosure, the content ratio of both the first inorganic fine particles and the second inorganic fine particles is not particularly limited. The film-forming composition of the present disclosure has excellent water repellency and easily forms a film having excellent abrasion resistance and snow accretion prevention performance. The first inorganic fine particles are preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more of the total mass. Further, the first inorganic fine particles are preferably 90% by mass or less, more preferably 80% by mass or less, and 60% by mass or less with respect to the total mass of the first inorganic fine particles and the second inorganic fine particles. More preferably, the content is particularly preferably 50% by mass or less.

(Water repellent component)
In the film-forming composition of the present disclosure, the water-repellent component is a component capable of imparting water repellency to the film when the film is formed, and is based on a compound represented by the following general formula (1). It is a polymer having structural units.

In the above formula (1), X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (provided that X ¹ and X ² are the same or different, a hydrogen atom, a fluorine atom, or chlorine atom.), a cyano group, a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a 1 to 20 carbon atoms represents a linear or branched alkyl group. When X is an alkyl group having 3 or more carbon atoms or a fluoroalkyl group, these may be either cyclic or acyclic. When X is an alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 2 carbon atoms. The fluoroalkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 to 2 carbon atoms.

In the above formula (1), Y is a direct bond, a hydrocarbon group having 1 to 10 carbon atoms optionally having an oxygen atom, a —CH ₂ CH ₂ N(R ¹ )SO ₂ — group (where R ¹ is an alkyl group having 1 to 4 carbon atoms, and the right end of the formula is bonded to R ^a and the left end is bonded to O.), —CH ₂ CH(OY ¹ )CH ₂ — group (with the proviso that Y ¹ is a hydrogen atom or an acetyl group, and the right end of the formula is bonded to R ^a and the left end is bonded to O.), or a —(CH ₂ ) _n SO ₂ — group (where n is 1 to 10, and the formula The right end of is bound to ^Ra , and the left end is bound to O.). "Direct bond" means that R ^a and O at both ends of Y are directly bonded in the above formula (1), that is, Y does not contain an element. When Y is a hydrocarbon group having 1 to 10 carbon atoms, it is specifically an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, more preferably 1 to 2 carbon atoms. is an alkylene group of

In the above formula (1), R ^a is a linear or branched alkyl group having 20 or less carbon atoms, a linear or branched fluoroalkyl group having 6 or less carbon atoms, a polysiloxane having a molecular weight of 300 to 50,000, or It represents a polyether group with a molecular weight of 400-5000 or a fluoropolyether group with a molecular weight of 400-5000. The fluoroalkyl group is preferably, for example, a perfluoroalkyl group. The polysiloxane is preferably polydimethylsiloxane, more preferably R ² —(Si(CH ₃ ) ₂ O) _n —. In R ² —(Si(CH ₃ ) ₂ O) _n —, R ² is a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and 1 to 6 carbon atoms. is more preferred. In R ² —(Si(CH ₃ ) ₂ O) _n —, n is 3-680, preferably 10-500, more preferably 100-400. The fluoropolyether group is preferably, for example, a perolopolyether group.

Specific examples of the compound represented by Formula (1) include a wide range of acrylic acid esters disclosed in Patent Document 1 described above.

Among them, the compound represented by the formula (1) has a hydrogen atom, a chlorine atom, a fluorine atom, or a methyl Y is a direct bond or an alkylene group having 1 to 10 carbon atoms (preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 2 carbon atoms), and R ^a is 1 carbon atom -20 linear or branched alkyl groups, C1-6 linear or branched fluoroalkyl groups, polysiloxanes with molecular weights of 300 to 50,000, or polyether groups with molecular weights of 400 to 5,000, or molecular weights of 400 Combinations of ˜5000 fluoropolyether groups can be mentioned. A more preferred compound represented by formula (1) has X being a hydrogen atom or a methyl group, Y being an alkylene group having 1 to 2 carbon atoms, and R ^a being a linear or branched fluoroalkyl having 1 to 6 carbon atoms. It is a polysiloxane with a group or molecular weight of 300-50,000. A combination in which X is a hydrogen atom or a methyl group, Y is a direct bond, and R ^a is a linear or branched alkyl group having 1 to 20 carbon atoms or polysiloxane having a molecular weight of 300 to 50,000 is also preferred.

Specific compounds of the compound represented by formula (1) include fluoroalkyl (meth)acrylates having a fluoroalkyl group having 1 to 6 carbon atoms and alkyl groups having 1 to 20 carbon atoms (preferably 1 to 18). of alkyl (meth)acrylates. Moreover, the compound represented by Formula (1) can also be obtained from a commercial item. For example, in the compound represented by the formula (1), examples of compounds in which ^Ra is a polysiloxane having a molecular weight of 300 to 50000 include JNC's product names "Silaplane (registered trademark) FM-0711" and "Silaplane (registered trademark) FM-0721”, “Silaplane (registered trademark) FM-0725”, and “Silaplane (registered trademark) FM-0701T”.

In addition to the compound represented by the formula (1), the water-repellent component is a structural unit based on a (meth)acrylate having an epoxy site, or a (meth)acrylate having an amide bond (for example, Y in the formula (1) is compound replaced with a functional group having an amide bond). For example, the (meth)acrylate having an epoxy moiety can be glycidyl (meth)acrylate, and the (meth)acrylate having an amide bond can be stearamidoethyl (meth)acrylate.

In addition, the polymer having at least a structural unit based on the compound represented by formula (1) can contain a structural unit based on a compound other than the compound represented by formula (1). Examples of such structural units include structural units based on hydroxyalkyl (meth)acrylates, structural units based on (meth)acrylates having an epoxy site, and (meth)acrylates having an amide bond (for example, Y in the formula (1) is amide a compound substituted with a functional group having a bond), a structural unit based on a chlorine-containing vinyl monomer, a structural unit based on a chlorine-containing vinylidene monomer, a structural unit based on an acrylamide monomer, etc. can be done. For example, structural units based on hydroxyalkyl (meth)acrylates include 2-hydroxyethyl methacrylate and the like, and (meth)acrylates having an epoxy moiety include glycidyl (meth)acrylate and the like. Examples of (meth)acrylates having an amide bond include stearamidoethyl (meth)acrylate. Examples of chlorine-containing vinyl monomers include vinyl chloride. Examples of chlorine-containing vinylidene monomers include vinylidene chloride. and the acrylamide monomer can include N-methylolacrylamide.

The polymer having at least structural units based on the compound represented by formula (1) may further contain other structural units. Monomers for forming other structural units may include one or more of various monofunctional monomers and/or polyfunctional monomers. Such monomers have ethylenically unsaturated double bonds and include acid group-containing monomers, hydroxyl group-containing monomers, chlorine-containing monomers, nitrogen-containing monomers, alkylene glycol group-containing Examples include monomers, alkoxyalkyl group-containing monomers, carbonyl group-containing monomers, silane group-containing monomers, ring structure-containing monomers, etc., but the present invention is not limited thereto. .

Acid group-containing monomers include (meth)acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monobutyl ester, itaconic acid monomethyl ester, Itaconic acid monobutyl ester, vinyl benzoic acid and the like can be mentioned.

Examples of hydroxyl group-containing monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) ) acrylates and the like.

　Chlorine-containing monomers include vinyl chloride and vinylidene chloride.

Nitrogen-containing monomers include (meth)acrylamide, N-monomethyl(meth)acrylamide, N-monoethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, Nn-propyl(meth)acrylamide, N - isopropyl (meth)acrylamide, methylenebis (meth)acrylamide, N-methylol (meth)acrylamide, N-butoxymethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropylacrylamide, diacetoneacrylamide , dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, stearamidoethyl (meth)acrylate, N-vinylpyrrolidone, (meth)acrylonitrile and the like.

Examples of alkylene glycol group-containing monomers include ethylene glycol (meth)acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, and diethylene glycol methoxy (meth) acrylate.
Examples of alkoxyalkyl group-containing monomers include methoxyethyl (meth)acrylate, methoxybutyl (meth)acrylate, ethoxybutyl (meth)acrylate, and trimethylolpropane tripropoxy (meth)acrylate.
Carbonyl group-containing monomers include acrolein, bomylstyrene, vinyl ethyl ketone, (meth)acryloxyalkylpropenal, acetonyl (meth)acrylate, diacetone (meth)acrylate, 2-hydroxypropyl (meth)acrylate acetylacetate. , butanediol-1,4-acrylate acetylacetate, 2-(acetoacetoxy)ethyl (meth)acrylate and the like.

Silane group-containing monomers include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(methoxyethoxy)silane, γ-(meth)acryloyloxypropyltrimethoxysilane, 2-styrylethyltrimethoxysilane, vinyltrichlorosilane, γ-(meth)acryloyloxypropylhydroxysilane, γ-(meth)acryloyloxypropylmethylhydroxysilane and the like.

Ring structure-containing monomers include glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, glycidyl allyl ether, benzyl (meth)acrylate, phenylethyl (meth)acrylate, methylbenzyl (meth)acrylate, naphthylmethyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, styrene, α-methylstyrene, p-methylstyrene, tert-methylstyrene, chlorostyrene, (meth)acryloylaziridine, (meth)acrylic acid 2- aziridinylethyl, vinyltoluene, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (Meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloyl-1-methoxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4-( meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino- 2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4-(meth)acryloylamino-2,2, 6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-cyano-4-(meth)acryloylamino-2,2,6 ,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine and the like.

Examples of polyfunctional monomers include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene oxide-modified 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, propylene oxide-modified neopentyl glycol di(meth)acrylate, Di(meth)acrylates of polyhydric alcohols having 1 to 10 carbon atoms, such as tripropylene glycol di(meth)acrylate; Alkyl di(meth)acrylates having 2 to 50 moles of alkylene oxide groups having 2 to 4 carbon atoms, such as polypropylene glycol di(meth)acrylate having 2 to 50 and tripropylene glycol di(meth)acrylate; ethoxylation Glycerin tri(meth)acrylate, propylene oxide-modified glycerol tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol monohydroxy tri(meth)acrylate, trimethylolpropane Tri(meth)acrylates of polyhydric alcohols having 1 to 10 carbon atoms such as triethoxytri(meth)acrylate; pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate Tetra (meth) acrylate of polyhydric alcohol having 1 to 10 carbon atoms such as; Penta(meth)acrylate; hexa(meth)acrylate of polyhydric alcohol having 1 to 10 carbon atoms such as pentaerythritol hexa(meth)acrylate; bisphenol A di(meth)acrylate, 2-(2'-vinyloxyethoxyethyl) Epoxy group-containing (meth)acrylates such as (meth)acrylates and epoxy (meth)acrylates; polyfunctional (meth)acrylates such as urethane (meth)acrylates;

The polymer having at least a structural unit based on the compound represented by formula (1) contains 40% by mass or more of the structural unit based on the compound represented by formula (1) with respect to the total mass of the water-repellent component. is preferable, more preferably 60% by mass or more, more preferably 80% by mass or more, and particularly preferably 95% by mass or more. A polymer having at least structural units based on the compound represented by formula (1) can also be formed only with structural units based on the compound represented by formula (1). The water-repellent component can contain one or more structural units based on the compound represented by formula (1).

The water repellent component can also be obtained from commercial products, for example, the product name "Unidyne (registered trademark) TG series" manufactured by Daikin Industries, Ltd., the product name "Scotchguard (registered trademark)" manufactured by 3M, Toagosei trade names "Symac (registered trademark) US-270", "Symac (registered trademark) US-350", "Symac (registered trademark) US-352", "Symac (registered trademark) US-380" manufactured by Japan A trade name “SG-204” manufactured by Catalyst Co., Ltd. can be mentioned.

(Polymerizable component)
In the film-forming composition of the present disclosure, the polymerizable component is a component that becomes a binder component when the film is formed, and can be called a binder component precursor. In other words, the polymerizable component is a component that can be cured (eg, a polymerization reaction or a curing reaction) and that, after curing, forms the binder component of the coating. However, the polymerizable component excludes the polymer of the compound represented by the formula (1).

The type of the polymerizable component is not particularly limited as long as it can form a binder component, and a wide range of known materials can be used. For example, the polymerizable component contained in the film-forming composition is a component that can give a cured product by the progress of a curing reaction by applying heat, or can give a cured product by irradiation with light such as UV. is an ingredient. A component that can give a cured product as a result of the curing reaction progressing by applying heat is called a “thermosetting resin component”, and a component that can give a cured product by light irradiation is called a “photocurable resin component”. do. The polymerizable component is preferably at least one of a thermosetting resin component and a photocurable resin component.

The type of thermosetting resin component is not particularly limited, and for example, it can be a mixture of a known polymer and a curing agent that is included as necessary. Such a polymer preferably has, for example, a crosslinkable functional group, and in this case, for example, thermal curing facilitates the progress of the crosslinking reaction. From this point of view, the polymerizable component (thermosetting resin component) is preferably a polymer having a crosslinkable functional group and a curing agent. Hereinafter, a polymer having a crosslinkable functional group is abbreviated as "crosslinkable polymer".

The crosslinkable polymer may or may not have a fluorine atom (fluoroalkyl group). However, from the viewpoint that the water repellency of the film is likely to be improved, the crosslinkable polymer preferably has a fluoroalkyl group.

The crosslinkable polymer having no fluorine atom can be obtained from commercial products. (registered trademark) UWS-2740”, “Halshybrid Udable (registered trademark) UWS-2841”, “Halshybrid Udable (registered trademark) UWS-2818”, “Halshybrid Udable (registered trademark) UWS-2816” , "Hals Hybrid Udable (registered trademark) UWH-4818", "Hals Hybrid UV-G (registered trademark) UV-G12", "Hals Hybrid UV-G (registered trademark) UV-G13", "Hals Hybrid UV- G (registered trademark) UV-G101”, “Hals Hybrid UV-G (registered trademark) UV-G301”, “Hals Hybrid UV-G (registered trademark) UV-G137”, “Acryset (registered trademark) ATH-2060 ”, “Acryset (registered trademark) ATH-2070”, “Acryset (registered trademark) ATH-2077CR”, and “Acryset (registered trademark) ATH-2088CR”.

In the crosslinkable polymer, the crosslinkable functional group is preferably, for example, a hydroxyl group, a carboxyl group, an amino group, a thiol group, an isocyanate group, or the like. In this case, such compounds preferably further have a fluoroalkyl group. The crosslinkable functional groups are preferably covalently bonded, for example, to the side chains of the crosslinkable polymer.

When the crosslinkable polymer has a fluoroalkyl group, examples of the crosslinkable polymer include fluorine-containing polymers having various crosslinkable functional groups.
(a) tetrafluoroethylene structural units and/or chlorotrifluoroethylene structural units,
(b) a non-aromatic vinyl ester monomer structural unit containing no hydroxyl group or carboxyl group;
(c) a hydroxyl group-containing vinyl monomer structural unit that does not contain an aromatic group and a carboxyl group;
(e) carboxyl group-containing monomer structural units that do not contain hydroxyl groups and aromatic groups and (f) other monomer structural units (provided that (d) does not contain aromatic group-containing monomer structural units that do not contain hydroxyl groups and carboxyl groups) )
A polymer consisting of can be mentioned. Hereinafter, this polymer is referred to as "Polymer F". When the thermosetting resin is polymer F, the water resistance of the coating is particularly improved.

The content of the (a) tetrafluoroethylene structural unit and/or chlorotrifluoroethylene structural unit has a lower limit of 20 mol%, preferably 30 mol%, more preferably 40 mol%, particularly It is preferably 42 mol %, and the upper limit is 49 mol %, preferably 47 mol %.

Examples of the monomer that provides the non-aromatic vinyl ester monomer structural unit (b) include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, and lauric acid. One or more of vinyl, vinyl stearate, vinyl cyclohexylcarboxylate and the like can be mentioned. These monomers are non-aromatic monomers containing no hydroxyl group or carboxyl group. Monomers that give a particularly preferred non-aromatic vinyl ester monomer structural unit (b) are selected from the group consisting of vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexylcarboxylate and vinyl acetate from the viewpoint of excellent weather resistance. It is the one of choice. Among these, non-aromatic carboxylic acid vinyl esters, particularly carboxylic acid vinyl esters having 6 or more carbon atoms, more preferably vinyl carboxylates having 9 or more carbon atoms, are preferred from the viewpoint of chemical resistance. Esters are preferred. The upper limit of the carbon number of the carboxylic acid in the carboxylic acid vinyl ester is preferably 20 or less, more preferably 15 or less. As a specific example, vinyl versatate is most preferable.

The content of the non-aromatic vinyl ester monomer structural unit (b) has a lower limit of 25 mol%, preferably 30 mol%, and an upper limit of 69.9 mol%, preferably 69.9 mol%, based on the total amount of the polymer F. 60 mol %, more preferably 43 mol %, particularly preferably 40 mol %.

The monomer that gives the hydroxyl group-containing vinyl monomer structural unit (c) is a non-aromatic monomer containing no carboxyl group, and examples thereof include hydroxyalkyl vinyl ethers and hydroxyalkyl allyl ethers represented by formula (2).
_CH2 = ^CHR10 (2)

Here, in formula (2), R ¹⁰ represents —OR ²⁰ or —CH ₂ OR ²⁰ (where R ²⁰ is an alkyl group having a hydroxyl group). R ²⁰ is, for example, a linear or branched alkyl group having 1 to 8 carbon atoms to which 1 to 3, preferably 1 hydroxyl group is bonded. Examples of formula (2) include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methyl One or more of butyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether and the like can be used. Among them, 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether are preferable as the monomer that provides the hydroxyl group-containing vinyl monomer structural unit (c).

The presence of this hydroxyl group-containing vinyl monomer structural unit (c) can improve the workability, impact resistance, and stain resistance of the film.

The content of the hydroxyl group-containing vinyl monomer structural unit (c) has a lower limit of 8 mol%, preferably 10 mol%, more preferably 15 mol%, and an upper limit of 30 mol%, preferably 30 mol%, based on the total amount of the polymer F. 20 mol %.

Polymer F can be basically composed of (a), (b) and (c) (however, two or more of each unit may be copolymerized), but up to 10 mol % Other copolymerizable monomeric units (f) may be included. Other copolymerizable monomer structural units (f) are the above (a), (b) and (c), aromatic group-containing monomer structural units (d) and carboxyl group-containing monomer structural units other than (e). It is a monomer structural unit.

Examples of monomers that give other copolymerizable monomer structural units (f) include alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; non-fluorine olefins such as ethylene, propylene, n-butene and isobutene. . When other copolymerizable monomer structural units (f) are included, the content in polymer F is 10 mol % or less, preferably less than 5 mol %, more preferably 4 mol % or less.

Polymer F can further contain (d) aromatic group-containing monomer structural units that do not contain hydroxyl groups and carboxyl groups. (d) The aromatic group-containing monomer structural unit that does not contain a hydroxyl group and a carboxyl group includes, for example, one or more vinyl benzoate monomers such as vinyl benzoate and vinyl para-t-butylbenzoate. para-t-butyl vinyl benzoate, and vinyl benzoate is particularly preferred.

The content of the aromatic group-containing monomer structural unit (d) in the polymer F has a lower limit of 2 mol%, preferably 4 mol%, and an upper limit of 15 mol%, preferably 10 mol%, more preferably 8. in mol %.

Polymer F can further contain (e) a carboxyl group-containing monomer structural unit that does not contain a hydroxyl group and an aromatic group. Examples of carboxyl group-containing monomers include acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, and maleic anhydride. , fumaric acid, fumaric acid monoester, vinyl phthalate, vinyl pyromellitic acid, and the like. Among them, crotonic acid, itaconic acid, maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoester, and 3-allyloxypropionic acid, which have low homopolymerizability, are preferred.

The content of the carboxyl group-containing monomer structural unit (e) in the polymer F has a lower limit of 0.1 mol%, preferably 0.4 mol%, and an upper limit of 2.0 mol%, preferably 1.5. in mol %.

Polymer F has a number average molecular weight of, for example, 1,000 to 1,000,000, preferably 3,000 to 50,000 as measured by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent. The glass transition temperature (2nd run) of polymer F determined by a differential scanning calorimeter (DSC) is, for example, 10 to 60°C, preferably 20 to 40°C. The method for producing the polymer F is also not particularly limited, and a wide range of known production methods can be employed. In addition, the polymer F can be obtained from commercial products and the like.

Specific examples of the polymer F include Zeffle (registered trademark) GK series manufactured by Daikin Industries, Ltd., Lumiflon (registered trademark) LF series manufactured by Asahi Glass Co., Ltd., Fluorate (registered trademark) series manufactured by DIC Corporation, and Kyner manufactured by Arkema. Examples include Aquatec (registered trademark) and KYNAR 500 Plus.

The thermosetting resin component contains a curing agent as described above in addition to the crosslinkable polymer. The curing agent is not particularly limited, and for example, compounds used as curing agents for thermosetting resins can be widely applied. In particular, the curing agent is preferably a compound having two or more polymerizable groups in the molecule described above.

A specific example of the curing agent is an isocyanate curing agent. Examples of isocyanate-based curing agents include compounds having an isocyanate group (hereinafter simply referred to as isocyanate compounds). Examples of isocyanate compounds include those represented by the following general formula (20).

In formula (20), Z ⁶ has at least one terminal isocyanate group, at least one carbon atom may be substituted with a hetero atom, and at least one hydrogen atom may be substituted with a halogen atom. It is preferably a linear or branched monovalent hydrocarbon group or carbonyl group which may have a carbon-carbon unsaturated bond. In R ³ , at least one carbon atom may be substituted with a hetero atom, at least one hydrogen atom may be substituted with a halogen atom, or at least one carbon atom may be substituted with a hetero atom. It is preferably a branched or cyclic hydrocarbon group having a valence of 2 or more or a carbonyl group, which may have a carbon-carbon unsaturated bond. o in the formula (20) is an integer of 2 or more.

R ³ preferably has 1 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and still more preferably 3 to 10 carbon atoms.

Z ⁶ preferably has 1 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and still more preferably 3 to 10 carbon atoms.

The isocyanate compound may be used singly or in combination.

Examples of isocyanate compounds include polyisocyanates. As used herein, polyisocyanate means a compound having two or more isocyanate groups in the molecule. The isocyanate compound may be a polyisocyanate obtained by trimerizing a diisocyanate. Polyisocyanates obtained by trimerizing such diisocyanates may be triisocyanates. Polyisocyanate, which is a trimer of diisocyanate, may exist as a polymer obtained by polymerizing these.

The diisocyanate is not particularly limited, but isocyanate groups such as trimethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate are bonded to aliphatic groups. Diisocyanate; diisocyanates in which an isocyanate group is bonded to an aromatic group, such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolidine diisocyanate, and naphthalene diisocyanate.

Specific polyisocyanates include, but are not limited to, compounds having the following structures.

These polyisocyanates may exist as polymers. For example, in the case of an isocyanurate-type polyisocyanate of hexamethylene diisocyanate, they may have a polymer having the following structure.

In a preferred embodiment, the isocyanate compound is an isocyanurate-type polyisocyanate.

The above isocyanurate-type polyisocyanate may be a polymer obtained by polymerizing these. The isocyanurate-type polyisocyanate may be a monocyclic compound having only one isocyanurate ring, or may be a polycyclic compound obtained by polymerizing this monocyclic compound.

In one embodiment using two or more isocyanate compounds, a mixture containing monocyclic compounds having only one isocyanurate ring can be used.

In another embodiment using two or more isocyanate compounds, a mixture containing an isocyanate compound that is an isocyanurate-type polyisocyanate can be used. The isocyanurate-type polyisocyanate may be, for example, a triisocyanate, specifically a triisocyanate obtained by trimerizing a diisocyanate.

Specific examples of isocyanate compounds include 2,4-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene. Diisocyanate, n-pentane-1,4-diisocyanate, trimers thereof, adducts thereof, burettes and isocyanurates, polymers thereof having two or more isocyanate groups, further blocked Isocyanates and the like can be mentioned. Specific examples of more detailed curing agents include Sumidule (registered trademark) N3300 (manufactured by Sumika Covestro Urethane Co., Ltd.), Desmodur (registered trademark) N3600 (manufactured by Sumika Covestro Urethane Co., Ltd.), Desmodur T, L, IL, HL series (manufactured by Sumika Covestro Urethane Co., Ltd.), Desmodur (registered trademark) 2460M (manufactured by Sumika Covestro Urethane Co., Ltd.), Sumidule (registered trademark) 44 series (Sumika Covestro Urethane Co., Ltd.) company), SBU isocyanate series (manufactured by Sumika Covestro Urethane Co., Ltd.), Desmodur (registered trademark) E, M series (manufactured by Sumika Covestro Urethane Co., Ltd.), Sumidule HT (Sumika Covestro Urethane Co., Ltd.) ), Desmodur N series (manufactured by Sumika Covestro Urethane Co., Ltd.), Desmodur Z4470 series (manufactured by Sumika Covestro Urethane Co., Ltd.), Duranate TPA-100 (manufactured by Asahi Kasei Corporation), Duranate TKA-100 (Asahi Kasei Corporation), Duranate 24A-100 (manufactured by Asahi Kasei Corporation), Duranate 22A-75P (manufactured by Asahi Kasei Corporation) and Duranate P301-75E (manufactured by Asahi Kasei Corporation), Duranate MF-K60B (manufactured by Asahi Kasei Corporation), Duranate SBB-70P (manufactured by Asahi Kasei Corp.), Duranate SBN-70D (manufactured by Asahi Kasei Corp.), Duranate MF-B60B (manufactured by Asahi Kasei Corp.), Duranate 17B-60P (manufactured by Asahi Kasei Corp.), Duranate TPA-B80E (manufactured by Asahi Kasei Corp.) (manufactured by Asahi Kasei Corp.), Duranate E402-B80B (manufactured by Asahi Kasei Corp.), and Duranate WM44-L70G (manufactured by Asahi Kasei Corp.).

In the thermosetting resin component, the content of the curing agent can be 10 to 100% by mass, preferably 15 to 35% by mass, based on the total mass of the crosslinkable polymer and the curing agent.

On the other hand, when the polymerizable component is a photocurable resin component, a monomer that undergoes a polymerization reaction upon irradiation with light such as UV can be used. A wide range of known photopolymerizable monomers can be employed. When the polymerizable component is a photocurable resin component, for example, it is also preferable to use a known photopolymerization initiator. The type of photopolymerization initiator is also not particularly limited, and for example, a wide range of known photopolymerization initiators used for forming water-repellent coating films can be employed.

(Coating film-forming composition)
In the film-forming composition of the present disclosure, the content ratios of the inorganic fine particles, the polymerizable component and the water-repellent component are not particularly limited as long as the effects of the present disclosure are not impaired.

In the film-forming composition of the present disclosure, the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component (hereinafter referred to as "total mass (S1)") The content of the first inorganic fine particles per 100 parts by mass is 3 to 25 parts by mass. When the content of the first inorganic fine particles is less than 3 parts by mass per 100 parts by mass of the total mass (S1), the effect of the first inorganic fine particles cannot be sufficiently exhibited, and the desired water repellency and abrasion resistance are not achieved. is not obtained, and the anti-snow accretion performance is lowered, and even if the amount exceeds 25 parts by mass, the desired water repellency and abrasion resistance cannot be obtained, and not only is it difficult to form a coating. The content of the first inorganic fine particles is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, and 10 parts by mass or more per 100 parts by mass of the total mass (S1). is more preferred. In addition, the content of the first inorganic fine particles is preferably 23 parts by mass or less, more preferably 22 parts by mass or less, and 20 parts by mass or less per 100 parts by mass of the total mass (S1). It is even more preferable to have

In addition, in the film-forming composition of the present disclosure, the content of the second inorganic fine particles per 100 parts by mass of the total mass (S1) is 12 to 27 parts by mass. When the content of the second inorganic fine particles is less than 12 parts by mass per 100 parts by mass of the total mass (S1), the effect of the second inorganic fine particles cannot be sufficiently exhibited, and the desired water repellency and abrasion resistance are not achieved. is not obtained, the anti-snow accretion performance is lowered, and even if it exceeds 27 parts by mass, the desired water repellency and abrasion resistance cannot be obtained, and not only is it difficult to form a coating. The content of the second inorganic fine particles is preferably 15 parts by mass or more, more preferably 16 parts by mass or more, and 18 parts by mass or more per 100 parts by mass of the total mass (S1). is more preferably 26 parts by mass or less, and more preferably 25 parts by mass or less.

The total content of the first inorganic fine particles and the second inorganic fine particles is 20 parts by mass or more per 100 parts by mass of the total mass (S1). As a result, desired water repellency and abrasion resistance can be obtained, excellent film-forming property can be achieved, and snow accretion prevention performance can be easily improved. The total content of the first inorganic fine particles and the second inorganic fine particles per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component, It is preferably 25 parts by mass or more, more preferably 30 parts by mass or more, preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and 40 parts by mass or less. is more preferred.

In the film-forming composition of the present disclosure, the “total mass (S1) of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component” is calculated as solid content. It means mass and does not include volatile components such as solvents. Further, when the polymerizable component is the thermosetting resin component, the mass of the polymerizable component in the total mass (S1) is the total mass of the polymer having a crosslinkable functional group and the curing agent. When the polymerizable component is the photocurable resin component, it means the total mass of the photopolymerizable monomer and the photopolymerization initiator. When the polymerizable component is both the thermosetting resin component and the photocurable resin component, the mass of the polymerizable component in the total mass (S1) is a polymer having a crosslinkable functional group and a curing is the total weight of the agent and the photopolymerizable monomer and photoinitiator.

The content of the water-repellent component (polymer having a structural unit based on the compound represented by formula (1)) in the film-forming composition of the present disclosure has excellent water repellency and abrasion resistance. It is preferably 0.1 to 30 parts by mass per 100 parts by mass of the total mass (S1) in terms of easy formation of a coating excellent in the above. The content of the water-repellent component is more preferably 1 part by mass or more, more preferably 15 parts by mass or less, and 10 parts by mass or less per 100 parts by mass of the total mass (S1). is more preferred.

In the film-forming composition of the present disclosure, the content of the polymerizable component is preferably 40 to 90 parts by mass per 100 parts by mass of the total mass (S1). In this case, the hardness of the film is less likely to decrease, and the water repellency and water resistance are likely to be improved. The content of the polymerizable component is more preferably 50 to 90 parts by mass, more preferably 60 to 80 parts by mass, per 100 parts by mass of the total mass (S1).

More specifically, when the polymerizable component is the thermosetting resin component, the content of the thermosetting resin component is 40 to 90 parts by mass per 100 parts by mass of the total mass (S1). , more preferably 50 to 90 parts by mass, even more preferably 60 to 80 parts by mass. As a result, the hardness of the film is less likely to decrease, and the water repellency and water resistance are likely to be improved. When the polymerizable component is the photocurable resin component, the content of the photocurable resin component is preferably 40 to 90 parts by mass per 100 parts by mass of the total mass (S1), and 50 to It is more preferably 90 parts by mass, and even more preferably 60 to 80 parts by mass. As a result, the hardness of the film is less likely to decrease, and the water repellency and water resistance are likely to be improved.

In the film-forming composition of the present disclosure, at least one of the polymerizable component and the water-repellent component preferably has a fluorine atom (that is, a fluoroalkyl group) or polysiloxane, and more preferably has a fluorine atom, Among them, it is particularly preferable that the polymerizable component has a fluorine atom. As a result, the film formed from the film-forming composition has excellent water repellency, high hardness, excellent water resistance, and improved abrasion resistance. Of course, both the polymerizable component and the water-repellent component may have a fluorine atom (fluoroalkyl group), or both the polymerizable component and the water-repellent component may have no fluorine atom. good. An example of the case where the polymerizable component has a fluoroalkyl group is the case where the crosslinkable polymer contained in the thermosetting resin component is the polymer F. An example of the case where the water-repellent component has a fluoroalkyl group is a polymer that is a fluoroalkyl (meth)acrylate in which the fluoroalkyl group has 1 to 6 carbon atoms in the compound represented by formula (1). .

When the water-repellent component contained in the film-forming composition of the present disclosure does not have a fluorine atom (especially a fluoroalkyl group), the abrasion resistance of the film is likely to be further improved. Among them, when the water-repellent component is a compound represented by the formula (1), and R ^a is a linear or branched alkyl group having 20 or less carbon atoms, the abrasion resistance of the coating is more likely to be improved. . Examples of such compounds include saturated fatty acids contained in known lubricating oils, examples of which include caprylic acid, capric acid, Structures having straight-chain alkyl groups with the same number of carbon atoms as those of lauric acid, myristic acid, palmitic acid, stearic acid, or these saturated fatty acids can be mentioned.

The film-forming composition of the present disclosure may contain other components as long as it contains the first inorganic fine particles, the second inorganic fine particles, the polymerizable component, and the water-repellent component. For example, the film-forming composition can contain a component capable of exhibiting water repellency in addition to the polymer having a structural unit based on the compound represented by formula (1). A specific example of such a component is a polymer having a (meth)acrylate as a main skeleton and having a fluoroalkyl group or an alkyl group at its side chain site.

The film-forming composition can also contain a solvent, if necessary. The type of solvent is not limited, and for example, a wide range of solvents that are used to form a film can be used. Examples include fluorine-based solvents such as hydrofluoroethers, ester compounds, alcohol compounds, and the like. can.

The content of the solvent contained in the film-forming composition is not particularly limited. It can be 200 to 2000 parts by mass.

The film-forming composition can also contain additives other than a component capable of exhibiting water repellency and a solvent. When the film-forming composition contains other additives, the content ratio thereof is 5% by mass or less with respect to the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component, and the water-repellent component. is desirable.

The method for preparing the film-forming composition of the present disclosure is not particularly limited. For example, first inorganic fine particles, second inorganic fine particles, a polymerizable component (for example, a thermosetting resin component containing the polymer F and a curing agent), and a water-repellent component (represented by formula (1) It can be prepared by mixing with a predetermined compounding amount. The mixing method is also not particularly limited, and for example, a wide range of known mixers and the like can be used.

The method of forming a film using the film-forming composition of the present disclosure is not particularly limited. For example, a film can be formed by applying the film-forming composition to a substrate for forming a film to form a coating film, and curing the coating film. Such a coating is a cured product of the coating-forming composition of the present disclosure.

The coating method of the film-forming composition is not particularly limited, and a wide range of known coating film-forming methods can be employed. For example, it can be applied by a method such as brush coating, spray coating, spin coating, or dispenser. The type of base material for forming the coating film of the film-forming composition is not particularly limited. material can be mentioned.

The method of curing the film-forming composition is also not particularly limited, and for example, various methods such as heat curing and photo-curing can be employed, and heat-curing and photo-curing can be combined. When heat curing is employed, it is preferable to heat the coating film of the film-forming composition to 60 to 150 ° C. In this case, the film of the film-forming composition is easily formed, has high hardness, and is also water resistant. Excellent. The heating time is not particularly limited, and can be appropriately set according to the heating temperature.

A chemical solution can be prepared using the film-forming composition of the present disclosure. Since such a chemical solution contains the film-forming composition of the present disclosure, it is suitable for use in forming a film. The chemical solution can be composed only of the film-forming composition, or other additives (for example, film-forming solvent known additives used as drugs).

2. Coating The coating of the present disclosure can be formed, for example, using the coating composition of the present disclosure described above, or the coating of the present disclosure can be formed using the chemical solution. In this case, the film of the present disclosure is a cured product of the film-forming composition or chemical solution of the present disclosure.

Therefore, the coating of the present disclosure includes first inorganic fine particles, second inorganic fine particles, a binder component, and a water-repellent component. Here, the binder component is a component formed by polymerizing the polymerizable component.

In the film of the present disclosure, the first inorganic fine particles and the second inorganic fine particles are respectively the same as the first inorganic fine particles and the second inorganic fine particles contained in the film-forming composition of the present disclosure. Therefore, the average particle size of the first inorganic fine particles contained in the coating is 1 nm or more and 100 nm or less, and the average particle size of the second inorganic fine particles contained in the coating is 500 nm or more and 5 μm or less.

The specific surface areas of the first inorganic fine particles and the second inorganic fine particles are not particularly limited. For example, the specific surface area is preferably from 30 to 700 m ² /g, more preferably from 800 to 330 m ² , from the viewpoint of easily improving the hardness of the resulting coating. /g is more preferred. In the film-forming composition of the present disclosure, the specific surface area of the fine particles means a value measured by the BET method (so-called BET specific surface area).

The surfaces of the first inorganic fine particles and the second inorganic fine particles may be hydrophilic or hydrophobic. The first inorganic fine particles and the second inorganic fine particles may be a mixture of hydrophilic and hydrophobic properties. The shapes of the first inorganic fine particles and the second inorganic fine particles are also not particularly limited, and examples thereof include spherical, ellipsoidal and the like, and may be amorphous particles such as irregular shaped particles. The first inorganic fine particles and the second inorganic fine particles preferably do not have a radically polymerizable reactive group (for example, a polymerizable double bond such as an acryloyl group) on the surface, that is, the first inorganic fine particles And it is preferable that no polymer (for example, a binder component and a water-repellent component) is covalently bonded to the surface of the second inorganic fine particles. As a result, the wear resistance of the coating is improved, and particularly the snow accretion prevention performance is likely to be enhanced.

The inorganic fine particles contained in the coating of the present disclosure can contain 80% by mass or more of the first inorganic fine particles and the second inorganic fine particles, preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably It is 99% by mass or more. The inorganic fine particles contained in the film of the present disclosure may be only the first inorganic fine particles and the second inorganic fine particles, and are particularly preferably only the first inorganic fine particles and the second inorganic fine particles.

In the coating of the present disclosure, the content ratio of both the first inorganic fine particles and the second inorganic fine particles is not particularly limited. In that the film of the present disclosure has excellent water repellency and excellent abrasion resistance, the first inorganic fine particles are 5 masses with respect to the total mass of the first inorganic fine particles and the second inorganic fine particles. % or more, more preferably 10 mass % or more, and even more preferably 20 mass % or more. Further, the first inorganic fine particles are preferably 90% by mass or less, more preferably 80% by mass or less, and 60% by mass or less with respect to the total mass of the first inorganic fine particles and the second inorganic fine particles. More preferably, the content is particularly preferably 50% by mass or less.

In the film of the present disclosure, the binder component is a component formed by curing the polymerizable component described above. For example, when the polymerizable component is the aforementioned thermosetting resin component, the polymer F is a polymer cured (crosslinked) with the curing agent. The binder component may contain an uncured polymerizable component as long as the performance of the film of the present disclosure is not impaired.

In the film of the present disclosure, the water-repellent component is the same as the water-repellent component contained in the above-described film-forming composition of the present disclosure. Therefore, the water-repellent component in the film is a polymer having a structural unit derived from the compound represented by formula (1).

In the coating of the present disclosure, the polymer having structural units derived from the compound represented by formula (1) can contain structural units other than the compound represented by formula (1). Examples of such structural units include structural units based on hydroxyalkyl (meth)acrylates, structural units based on (meth)acrylates having an epoxy site, and (meth)acrylates having an amide bond (for example, Y in the formula (1) is amide a compound substituted with a functional group having a bond), a structural unit based on a chlorine-containing vinyl monomer, a structural unit based on a chlorine-containing vinylidene monomer, a structural unit based on an acrylamide monomer, etc. can be done. For example, structural units based on hydroxyalkyl (meth)acrylates include 2-hydroxyethyl methacrylate and the like, and (meth)acrylates having an epoxy moiety include glycidyl (meth)acrylate and the like. Examples of (meth)acrylates having an amide bond include stearamidoethyl (meth)acrylate. Examples of chlorine-containing vinyl monomers include vinyl chloride. Examples of chlorine-containing vinylidene monomers include vinylidene chloride. and the acrylamide monomer can include N-methylolacrylamide.

In the coating of the present disclosure, the polymer having at least structural units based on the compound represented by formula (1) may further contain other structural units. Monomers for forming other structural units may include one or more of various monofunctional monomers and/or polyfunctional monomers. Such monomers include the aforementioned acid group-containing monomers, hydroxyl group-containing monomers, chlorine-containing monomers, nitrogen-containing monomers, alkylene glycol group-containing monomers, alkoxyalkyl group-containing monomers, A carbonyl group-containing monomer, a silane group-containing monomer, and a ring structure-containing monomer can be mentioned, and the respective types are the same as those described above.

In the coating film of the present disclosure, the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component (hereinafter referred to as “total mass (S2)”) per 100 parts by mass The content of the first inorganic fine particles is 3 to 25 parts by mass. When the content of the first inorganic fine particles is less than 3 parts by mass per 100 parts by mass of the total mass (S2), the effect of the first inorganic fine particles cannot be sufficiently exhibited, and the desired water repellency and abrasion resistance are not achieved. is not obtained, and the anti-snow accretion performance is lowered, and even if the amount exceeds 25 parts by mass, the desired water repellency and abrasion resistance cannot be obtained, and not only is it difficult to form a coating. The content of the first inorganic fine particles is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, and 10 parts by mass or more per 100 parts by mass of the total mass (S2). is more preferred. In addition, the content of the first inorganic fine particles is preferably 23 parts by mass or less, more preferably 22 parts by mass or less, and 20 parts by mass or less per 100 parts by mass of the total mass (S2). It is even more preferable to have

Further, in the coating of the present disclosure, the content of the second inorganic fine particles per 100 parts by mass of the total mass (S2) is 12 to 27 parts by mass. When the content of the second inorganic fine particles is less than 12 parts by mass per 100 parts by mass of the total mass (S2), the effect of the second inorganic fine particles cannot be sufficiently exhibited, and the desired water repellency and abrasion resistance are not achieved. is not obtained, the anti-snow accretion performance is lowered, and even if it exceeds 27 parts by mass, the desired water repellency and abrasion resistance cannot be obtained, and not only is it difficult to form a coating. The content of the second inorganic fine particles is preferably 15 parts by mass or more, more preferably 16 parts by mass or more, and 18 parts by mass or more per 100 parts by mass of the total mass (S2). is more preferably 26 parts by mass or less, and more preferably 25 parts by mass or less.

The total content of the first inorganic fine particles and the second inorganic fine particles is 20 parts by mass or more per 100 parts by mass of the total mass (S2). As a result, desired water repellency and abrasion resistance can be obtained, excellent film-forming property can be achieved, and snow accretion prevention performance can be easily improved. The total content of the first inorganic fine particles and the second inorganic fine particles is preferably 25 parts by mass or more, more preferably 30 parts by mass or more, per 100 parts by mass of the total mass (S2). Also, it is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less.

In the "total mass (S2) of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component" of the coating of the present disclosure, the binder component is a cured product of the thermosetting resin , the mass of the binder component in the total mass (S2) means the total mass of the cured product of the polymer having a crosslinkable functional group and the curing agent, and the binder component is the photocurable In the case of a cured product of a flexible resin, it means the total mass of the photopolymerizable monomer and the photopolymerization initiator. When the binder component is both the thermosetting resin and the cured product of the photocurable resin, the mass of the polymerizable component in the total mass (S2) includes a polymer having a crosslinkable functional group and a cured product. It means the total mass of the cured product of the agent and the cured product of the photopolymerizable monomer and the photopolymerization initiator.

The content of the water-repellent component in the coating film of the present disclosure is 0.00% per 100 parts by mass of the total mass (S2), since a coating film having excellent water repellency and excellent wear resistance can be easily formed. 1 to 30 parts by mass. The content of the water-repellent component is preferably 1 part by mass or more, more preferably 15 parts by mass or less, and 10 parts by mass or less per 100 parts by mass of the total mass (S2). is more preferred.

In the coating of the present disclosure, the content of the binder component is preferably 40 to 90 parts by mass per 100 parts by mass of the total mass (S2). In this case, the hardness of the film is less likely to decrease, and the water repellency and water resistance are likely to be improved. The content of the binder component is more preferably 50 to 90 parts by mass, more preferably 60 to 80 parts by mass, per 100 parts by mass of the total mass (S2).

More specifically, when the binder component is a cured product of the thermosetting resin, the content of the cured product of the thermosetting resin is 40 to 90 mass parts per 100 parts by mass of the total mass (S2). parts, more preferably 50 to 90 parts by mass, and more preferably 60 to 80 parts by mass. As a result, the hardness of the film is less likely to decrease, and the water repellency and water resistance are likely to be improved. When the binder component is a cured product of the photocurable resin, the content of the cured product of the photocurable resin is preferably 40 to 90 parts by mass per 100 parts by mass of the total mass (S2). , more preferably 50 to 90 parts by mass, more preferably 60 to 80 parts by mass. As a result, the hardness of the film is less likely to decrease, and the water repellency and water resistance are likely to be improved.

In the film of the present disclosure, at least one of the binder component and the water-repellent component preferably has a fluorine atom (that is, a fluoroalkyl group) or polysiloxane, and more preferably has a fluorine atom. It is more preferable to have a fluorine atom. As a result, the coating has excellent water repellency, high hardness, excellent water resistance, and even improved abrasion resistance. Of course, both the binder component and the water repellent component may have fluorine atoms (fluoroalkyl groups), or both the binder component and the water repellent component may not have fluorine atoms. An example of the binder component having a fluoroalkyl group is polymer F or a crosslinked product thereof. When the water-repellent component has a fluoroalkyl group, the polymer represented by the formula (1) is a fluoroalkyl (meth)acrylate in which the fluoroalkyl group has 1 to 6 carbon atoms.

In the film of the present disclosure, the binder component and the water-repellent component can coat the first inorganic fine particles and the second inorganic fine particles, but are not covalently bonded, for example, preferably physically adsorbed. . This makes it possible to improve both the wear resistance and the anti-snow accretion performance, which have conventionally been in a trade-off relationship.

When the water-repellent component contained in the coating of the present disclosure does not have a fluorine atom (especially a fluoroalkyl group), the abrasion resistance of the coating is likely to be further improved. Among them, when the water-repellent component is a compound represented by the formula (1), and R ^a is a linear or branched alkyl group having 20 or less carbon atoms, the abrasion resistance of the coating is more likely to be improved. . Examples of such compounds include saturated fatty acids contained in known lubricating oils, examples of which include caprylic acid, capric acid, Structures having straight-chain alkyl groups with the same number of carbon atoms as those of lauric acid, myristic acid, palmitic acid, stearic acid, or these saturated fatty acids can be mentioned.

In addition, the coating of the present disclosure can contain a component other than the compound represented by formula (1), which is a component capable of imparting water repellency to the coating when the coating is formed. A specific example of such a component is a polymer having a (meth)acrylate as a main skeleton and having a fluoroalkyl group or an alkyl group at its side chain site.

The coating of the present disclosure has, for example, a water contact angle of 150° or more. This allows the coating of the present disclosure to exhibit excellent water repellency.

The coating of the present disclosure has a surface with a water contact angle of 150° or more after rubbing at least 50 times with a paper waste cloth under a load of 100 g/cm ² .

In the snow accretion test of the coating described later, the coating of the present disclosure preferably has a snow accretion start time of, for example, 5 minutes or longer, more preferably 7 minutes or longer, and even more preferably 10 minutes or longer.

The coating of the present disclosure has, for example, an average thickness of 10 nm to 100 μm, a minimum local thickness of 5 nm to 50 μm, and a maximum local thickness of 15 nm to 150 μm, preferably an average thickness of 15 nm to 95 μm, and a minimum local thickness of The thickness is 10 nm to 45 μm, the maximum local thickness is 20 nm to 145 μm, more preferably the average thickness is 20 nm to 90 μm, the minimum local thickness is 15 nm to 40 μm, and the maximum local thickness is 25 nm to 140 μm. The average film thickness can be calculated from, for example, the amount of applied coating film, the solid content concentration, and the dry film thickness calculated from the density of the composition. The minimum local film thickness and the maximum local film thickness can be calculated using a device capable of measuring three-dimensional shapes. An example of such a device is a shape analysis laser microscope VK-X1000 manufactured by KEYENCE.

The coating of the present disclosure can be formed on various substrates. Examples of the substrate include known resin substrates such as acrylic resins and polycarbonate resins, metals such as aluminum, and various substrates such as inorganic substrates.

The film of the present disclosure has excellent water repellency and excellent abrasion resistance, so it is easy to maintain its performance over the long term. In addition, the film formed from the film-forming composition of the present disclosure is excellent in anti-snow accretion performance, and even when exposed to snow, snow accretion is unlikely to occur for a long period of time. For example, even in areas with heavy snowfall, the coating of the present disclosure can exhibit snow accretion prevention performance for a long period of time.

Therefore, the coating of the present disclosure is suitably used for imparting water repellency and/or oil repellency to the surface to be treated, and can be suitably used for various articles that require super liquid repellency. Applications of the coating of the present disclosure are not particularly limited, and examples include water and oil repellent agents, frost retardation applications, anti-icing agents, snow-resistant agents, anti-fingerprint agents, anti-fingerprint agents, low-friction agents, and lubricants. , a protein adhesion control agent, a cell adhesion control agent, a microorganism adhesion control agent, a scale adhesion inhibitor, an antifungal agent, an antibacterial agent, and the like. In addition, the film of the present disclosure can be suitably used for various articles and the like that require a function to prevent snow accretion. For example, the base material on which the film is formed can be suitably used as an antenna cover. can.

3. Other Aspects of the Coating As another aspect of the coating of the present disclosure (hereinafter referred to as another coating of the present disclosure), first inorganic fine particles containing inorganic fine particles and having an average particle diameter of 1 nm or more and 100 nm or less, and an average It contains second inorganic fine particles having a particle diameter of 500 nm or more and 5 μm or less, and has a water contact angle of 150° or more, and the water contact angle after rubbing at least 50 times with a paper waste cloth with a load of 100 g/cm ^{2 .} is 150° or more. The method of forming other coatings of the present disclosure is not particularly limited. For example, even when the film-forming composition or chemical liquid of the present disclosure is used, the other forms of the film can be formed.

The inorganic fine particles contained in the other coating of the present disclosure are the same as the inorganic fine particles contained in the aforementioned coating of the present disclosure. Therefore, the inorganic fine particles contained in the other coating of the present disclosure include first inorganic fine particles having an average particle size of 1 nm or more and 100 nm or less and second inorganic fine particles having an average particle size of 500 nm or more and 5 μm or less. . In addition, the content ratio of the first inorganic fine particles and the second inorganic fine particles contained in the other coating of the present disclosure is also the same as that of the coating of the present disclosure.

Other coatings of the present disclosure can contain a binder component and a water-repellent component in the same manner as the coating of the present disclosure, and their types and content ratios can also be the same as the coating of the present disclosure. Other coatings of the present disclosure may have thicknesses in similar ranges as the coatings of the present disclosure.

Other coatings of the present disclosure can exhibit excellent water repellency by having a water contact angle of 150° or more. The contact angle of water can be adjusted, for example, by appropriately selecting the types and contents of the inorganic fine particles, the binder component, and the water-repellent component. Another coating of the present disclosure has a water contact angle of 150 ° or more after rubbing with a paper waste cloth at least 50 times (preferably 50 times) with a load of 100 g / cm ² . can have

Applications of other coatings of the present disclosure are not particularly limited, and examples thereof include uses similar to those to which the coating of the present disclosure can be applied.

(Method for measuring various physical properties of the coating of the present disclosure)
A method for measuring various physical properties of the coating of the present disclosure (including coatings of the other forms described above) will be described.

<Water contact angle (static contact angle)>
The contact angle of water is the static contact angle of water. The contact angle of water is measured using a contact angle meter (Kyowa Interface Science Co., Ltd. “Drop Master 701”). is done. If the static contact angle is 150° or more, the liquid may not be able to stand on its own on the substrate surface. In such a case, the static contact angle is measured using the syringe needle as a support, and the value obtained at that time is defined as the static contact angle.

<Snow accretion test>
A coating is placed on a test stand in a test room kept at a constant temperature in the range of 1 to 2 ° C so that the snow-covered surface is vertical to the ground, and the coating is subjected to a wind speed of 10 m / sec and a collision amount of 110 kg /. Pre-made artificial snow is blown under the condition of m ² /h. This blowing causes the artificial snow to impinge on the covering surface. From the start of this spraying, a video was taken of the entire sprayed surface of the sample, and the presence or absence of snow accretion on the film surface was visually confirmed from the video obtained after the test was completed. Measured as the start time (no snow accretion time).

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the embodiments of these examples.

(Example 1)
3 parts by mass of silica fine particles (“Aerosil 300” manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 300 m ² /g and an average particle diameter of 7 nm as the first inorganic fine particles, and a specific surface area of 300 m ² as the second inorganic fine particles. / g, and 27 parts by mass of silica fine particles (“Sylysia 310P” manufactured by Fuji Silysia Chemical) having an average particle diameter of 2.7 μm, and tetrafluoroethylene and a hydroxyl group-containing thermosetting resin corresponding to the polymer F. 55 parts by mass of a vinyl monomer copolymer (in terms of solid content), 12 parts by mass of "Sumidule N-3300" (manufactured by Sumitomo Covestro Urethane) as a curing agent, and a water-repellent component (represented by formula (1) 3 parts by mass (in terms of solid content) of the fluorine-containing copolymer described in Preparation Example 2 of Patent No. 5831599 as a polymer containing a structural unit based on a compound) and butyl acetate as a solvent are prepared and blended. A film-forming composition was prepared in a vial. After applying the film-forming composition to a polycarbonate substrate by a spray method, the polycarbonate substrate was treated at 130° C. for 10 minutes to form a film.
The fluorine-containing copolymer (water-repellent component) described in Preparation Example 2 of Japanese Patent No. 5831599 was prepared as follows. A 300 ml reactor equipped with a stirrer, thermometer, reflux condenser, dropping funnel, nitrogen inlet and heating device was prepared, and 45 parts by mass of isopropyl alcohol (IPA) as a solvent was added. Subsequently, (CF ₂ ) ₆ CH ₂ CH ₂ OCOC(CH ₃ )=CH ₂ (C6FMA) 65 parts by mass, isobornyl methacrylate (IBMA) 20 parts by mass, and 2-hydroxyethyl methacrylate (HEMA) 15 parts by mass under stirring. 5 parts by mass of lauryl mercaptan (L-SH) as a chain transfer agent was added to monomers (total of 100 parts by mass of monomers) consisting of parts by mass, and 1 part by mass of t-butyl perpivalate as an initiator was added in this order. , and this mixture was mixed and stirred for 12 hours under a nitrogen atmosphere at 60°C to carry out copolymerization. Next, this reaction mixture was cooled to room temperature to obtain a fluorine-containing copolymer solution. The solid content concentration of this solution was 70% by mass. The monomer composition of the fluorine-containing copolymer almost matched the charged monomer composition, and the weight average molecular weight was 9,000.

(Example 2)
A film was formed with the same formulation as in Example 1, except that the first inorganic fine particles were 9 parts by mass and the second inorganic fine particles were 21 parts by mass.

(Example 3)
A film was formed with the same formulation as in Example 1, except that the first inorganic fine particles were 15 parts by mass and the second inorganic fine particles were 15 parts by mass.

(Example 4)
20 parts by mass of the first inorganic fine particles, 20 parts by mass of the second inorganic fine particles, 46 parts by mass of a copolymer of tetrafluoroethylene and a hydroxyl group-containing vinyl monomer (in terms of solid content), 10 parts by mass of Sumidule N-3300 A film was formed with the same formulation as in Example 1, except that the fluorine-containing copolymer described in Preparation Example 2 of Japanese Patent No. 5831599 was changed to 4 parts by mass (in terms of solid content).

(Example 5)
25 parts by mass of the first inorganic fine particles, 25 parts by mass of the second inorganic fine particles, 37 parts by mass of a copolymer of tetrafluoroethylene and a hydroxyl group-containing vinyl monomer (in terms of solid content), 8 parts by mass of Sumidur N-3300 A film was formed with the same formulation as in Example 1, except that the fluorine-containing copolymer described in Preparation Example 2 of Japanese Patent No. 5831599 was changed to 5 parts by mass (in terms of solid content).

(Example 6)
19 parts by mass of silica fine particles (“Aerosil 300” manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 300 m ² /g and an average particle diameter of 7 nm as the first inorganic fine particles, and a specific surface area of 300 m ² as the second inorganic fine particles. / g, and 11 parts by mass of silica fine particles having an average particle diameter of 2.7 μm (“Silysia 310P” manufactured by Fuji Silysia Chemical), and 44 parts of “Udable UWS-2816 (manufactured by Nippon Shokubai Co., Ltd.)” as a thermosetting resin. Parts by mass (in terms of solid content), 20 parts by mass of "Sumidule N-3300" (manufactured by Sumitomo Covestro Urethane) as a curing agent, and 6 parts by mass of "Symac US-352" (manufactured by Toagosei Co., Ltd.) as a water-repellent component. (Converted to solid content), butyl acetate was prepared as a solvent, and these were blended to prepare a film-forming composition in a vial. After applying the film-forming composition to a polycarbonate substrate by a spray method, the polycarbonate substrate was treated at 130° C. for 10 minutes to form a film.

(Example 7)
16 parts by mass of silica fine particles (“Aerosil 300” manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 300 m ² /g and an average particle diameter of 7 nm as the first inorganic fine particles, and a specific surface area of 300 m ² as the second inorganic fine particles. / g, and 14 parts by mass of silica fine particles having an average particle diameter of 2.7 μm (“Sylysia 310P” manufactured by Fuji Silysia Chemical), and 38 parts of “Udable UWS-2816 (manufactured by Nippon Shokubai Co., Ltd.)” as a thermosetting resin. Parts by mass (in terms of solid content), 20 parts by mass (in terms of solid content) of “Duranate E402-B80B” (manufactured by Asahi Kasei Co., Ltd.) as a curing agent, and 12 parts of “Cymac US-380” (manufactured by Toagosei Co., Ltd.) as a water-repellent component. Parts by mass (in terms of solid content) and butyl acetate as a solvent were prepared and blended to prepare a film-forming composition in a vial. After applying the film-forming composition to a polycarbonate substrate by a spray method, the polycarbonate substrate was treated at 130° C. for 10 minutes to form a film.

(Example 8)
8 parts by mass of silica fine particles ("Aerosil 300" manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 300 m ² /g and an average particle diameter of 7 nm as the first inorganic fine particles, and a specific surface area of 300 m ² as the second inorganic fine particles. / g, and 20 parts by mass of silica fine particles having an average particle diameter of 2.7 μm ("Sylysia 310P" manufactured by Fuji Silysia Chemical), and 25 parts of "Udable UWS-2818 (manufactured by Nippon Shokubai Co., Ltd.)" as a thermosetting resin. Parts by mass (in terms of solid content), 15 parts by mass (in terms of solid content) of “Duranate E402-B80B” (manufactured by Asahi Kasei Co., Ltd.) as a curing agent, and “Cymac US-352” (manufactured by Toagosei Co., Ltd.) as a water-repellent component 32. Parts by mass (in terms of solid content) and butyl acetate as a solvent were prepared and blended to prepare a film-forming composition in a vial. After applying the film-forming composition to a polycarbonate substrate by a spray method, the polycarbonate substrate was treated at 130° C. for 10 minutes to form a film.

SYMAC US-352 and SYMAC US-380 used in Examples 6 to 8 are silicone-grafted acrylic polymers, and structural units based on compounds in which R ^a in formula (1) is polysiloxane having a molecular weight of 300 to 50,000. is a polymer having

(Comparative example 1)
A film was formed in the same manner as in Example 1, except that the first inorganic fine particles were not used and the second inorganic fine particles were 30 parts by mass.

(Comparative example 2)
A coating was formed with the same formulation as in Example 1, except that the first inorganic fine particles were 21 parts by mass and the second inorganic fine particles were 9 parts by mass.

(Comparative Example 3)
A film was formed with the same formulation as in Example 1, except that the first inorganic fine particles were 27 parts by mass and the second inorganic fine particles were 3 parts by mass.

(Comparative Example 4)
A film was formed with the same formulation as in Example 1, except that the first inorganic fine particles were 30 parts by mass and the second inorganic fine particles were 0 parts by mass.

(Comparative Example 5)
30 parts by mass of the first inorganic fine particles, 30 parts by mass of the second inorganic fine particles, 28 parts by mass of a copolymer of tetrafluoroethylene and a hydroxyl group-containing vinyl monomer (in terms of solid content), "Sumidule N-3300" 6 A film was formed with the same formulation as in Example 1, except that the fluorine-containing copolymer described in Preparation Example 2 of Japanese Patent No. 5831599 was changed to 6 parts by mass (in terms of solid content).

(Comparative Example 6)
10 parts by mass of the first inorganic fine particles, 10 parts by mass of the second inorganic fine particles, 64 parts by mass of a copolymer of tetrafluoroethylene and a hydroxyl group-containing vinyl monomer (in terms of solid content), 14 parts by mass of Sumidule N-3300 A film was formed with the same formulation as in Example 1, except that the fluorine-containing copolymer described in Preparation Example 2 of Japanese Patent No. 5831599 was changed to 2 parts by mass (on a solid content basis).

(Comparative Example 7)
5 parts by mass of first inorganic fine particles, 5 parts by mass of second inorganic fine particles, 73 parts by mass of copolymer of tetrafluoroethylene and hydroxyl group-containing vinyl monomer (converted to solid content), 16 parts by mass of Sumidule N-3300 A film was formed with the same formulation as in Example 1, except that the fluorine-containing copolymer described in Preparation Example 2 of Japanese Patent No. 5831599 was changed to 1 part by mass (in terms of solid content).

<Water contact angle (static contact angle)>
The contact angle of water was measured using a contact angle meter (Kyowa Interface Science Co., Ltd. "Drop Master 701"). Specifically, using water (droplet of 2 μL), 5 points were measured for one sample. When the static contact angle reaches 150° C. or more, the liquid cannot stand on its own and exist on the substrate surface. The value was taken as the static contact angle.

<Abrasion resistance evaluation>
Abrasion resistance was evaluated by a rubbing test described below. The initial contact angle was obtained by measuring the contact angle with water of the test piece of each coating obtained in Examples or Comparative Examples. After that, Kimwipe (trade name: Kimwipe, manufactured by Nippon Paper Crecia Co., Ltd.) as a paper waste was placed on the holder (area in contact with the sample: 1 cm ² ) of the rubbing tester (Imoto Seisakusho's rubbing tester "wear resistance tester 151E triple specification"). It was worn and rubbed a certain number of times with a load of 100 g/cm ² . After that, the water contact angle was measured to evaluate the abrasion resistance against wiping. Abrasion resistance here means the number of times of abrasion that can maintain a super water-repellent state (an average static contact angle value of 5 times is 150° or more, or an average of 140° or more and a standard deviation of 150° or more). Defined. In this test, the contact angle was measured in the same manner as <water contact angle (static contact angle)>.

<Snow accretion test>
An evaluation sample (film) is placed on a test stand in a test room kept at a constant temperature in the range of 1 to 2 ° C so that the snow-covered surface is vertical to the ground, and the sample is subjected to a wind speed of 10 m / sec, Artificial snow prepared in advance was blown under the condition of a collision amount of 110 kg/m ² /h. This blowing caused the artificial snow to impinge on the sample (coating) surface. From the start of this spraying, a video was taken of the entire sprayed surface of the sample, and the presence or absence of snow accretion on the film surface was visually confirmed from the video obtained after the test was completed. The start time (that is, the non-snow accretion time) was used.

Table 1 shows the results of the static contact angle of water (20 μL of water), wear resistance evaluation, and snow accretion start time. It was confirmed that all of the films obtained in Examples were excellent in both abrasion resistance and snow adhesion prevention performance. On the other hand, the coatings obtained in the comparative examples were formed from a composition in which the inorganic fine particles were not appropriately blended, so the wear resistance was remarkably deteriorated.

Claims

including inorganic fine particles, a polymerizable component, and a water-repellent component,
The inorganic fine particles include first inorganic fine particles having an average particle size of 1 nm or more and 100 nm or less, and second inorganic fine particles having an average particle size of 500 nm or more and 5 μm or less,
The content of the first inorganic fine particles is 3 to 25 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component,
The content of the second inorganic fine particles is 12 to 27 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component,
The total content of the first inorganic fine particles and the second inorganic fine particles per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component, 20 parts by mass or more,
The water-repellent component has the following general formula (1):

(Wherein, X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (wherein X 1 and X 2 are the same or different and are a hydrogen atom, a fluorine atom or a chlorine atom ), a cyano group, a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a straight chain having 1 to 20 carbon atoms is a straight or branched alkyl group, Y is a direct bond, a hydrocarbon group having 1 to 10 carbon atoms which may have an oxygen atom, a —CH 2 CH 2 N(R 1 )SO 2 — group (with the proviso that , R 1 is an alkyl group having 1 to 4 carbon atoms, and the right end of the formula is bonded to R a and the left end is bonded to O.), —CH 2 CH(OY 1 )CH 2 — group (provided that Y 1 is a hydrogen atom or an acetyl group, and the right end of the formula is bonded to R a and the left end is bonded to O.), or a —(CH 2 ) n SO 2 — group (where n is 1 to 10). , The right end of the formula is bonded to Ra , and the left end is bonded to O.), where Ra is a linear or branched alkyl group having 20 or less carbon atoms, a linear or branched alkyl group having 6 or less carbon atoms, or A branched fluoroalkyl group, a polysiloxane with a molecular weight of 300 to 50,000, a polyether group with a molecular weight of 400 to 5,000, or a fluoropolyether group with a molecular weight of 400 to 5,000.). A film-forming composition, which is a polymer.
The content of the second inorganic fine particles is 15 to 27 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component,
In the above formula (1), R a is a linear or branched alkyl group having 20 or less carbon atoms, a linear or branched fluoroalkyl group having 6 or less carbon atoms, or a polyether group having a molecular weight of 400 to 5000 or a fluoropolyether group having a molecular weight of 400 to 5,000.
The content of the water-repellent component is 0.1 to 30 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the polymerizable component and the water-repellent component. The film-forming composition according to claim 1 or 2.
The film-forming composition according to any one of claims 1 to 3, wherein the polymerizable component is a polymer having a crosslinkable functional group and a curing agent.
A film comprising a cured product of the film-forming composition according to any one of claims 1 to 4.
including inorganic fine particles, a binder component, and a water-repellent component,
The inorganic fine particles include first inorganic fine particles having an average particle size of 1 nm or more and 100 nm or less, and second inorganic fine particles having an average particle size of 500 nm or more and 5 μm or less,
The content of the first inorganic fine particles is 3 to 25 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component,
The content of the second inorganic fine particles is 12 to 27 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component,
The total content of the first inorganic fine particles and the second inorganic fine particles is 20 parts per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component. Part by mass or more,
The water-repellent component has the following general formula (1):

(Wherein, X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (wherein X 1 and X 2 are the same or different and are a hydrogen atom, a fluorine atom or a chlorine atom ), a cyano group, a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a straight chain having 1 to 20 carbon atoms is a straight or branched alkyl group, Y is a direct bond, a hydrocarbon group having 1 to 10 carbon atoms which may have an oxygen atom, a —CH 2 CH 2 N(R 1 )SO 2 — group (with the proviso that , R 1 is an alkyl group having 1 to 4 carbon atoms, and the right end of the formula is bonded to R a and the left end is bonded to O.), —CH 2 CH(OY 1 )CH 2 — group (provided that Y 1 is a hydrogen atom or an acetyl group, and the right end of the formula is bonded to R a and the left end is bonded to O.), or a —(CH 2 ) n SO 2 — group (where n is 1 to 10). , The right end of the formula is bonded to Ra , and the left end is bonded to O.), where Ra is a linear or branched alkyl group having 20 or less carbon atoms, a linear or branched alkyl group having 6 or less carbon atoms, or A branched fluoroalkyl group, a polysiloxane with a molecular weight of 300 to 50,000, a polyether group with a molecular weight of 400 to 5,000, or a fluoropolyether group with a molecular weight of 400 to 5,000.). A coating that is a polymer.
The content of the second inorganic fine particles is 15 to 27 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component,
In the above formula (1), R a is a linear or branched alkyl group having 20 or less carbon atoms, a linear or branched fluoroalkyl group having 6 or less carbon atoms, or a polyether group having a molecular weight of 400 to 5000 or a fluoropolyether group with a molecular weight of 400-5000.
The content of the water-repellent component is 0.1 to 30 parts by mass per 100 parts by mass of the total mass of the first inorganic fine particles, the second inorganic fine particles, the binder component and the water-repellent component. Item 8. The coating according to item 6 or 7.
In a coating containing inorganic fine particles,
The inorganic fine particles include first inorganic fine particles having an average particle size of 1 nm or more and 100 nm or less, and second inorganic fine particles having an average particle size of 500 nm or more and 5 μm or less,
The contact angle of water is 150° or more,
A film having a water contact angle of 150° or more after being rubbed with a paper waste cloth at least 50 times with a load of 100 g/cm 2 .
The coating according to any one of claims 5 to 9, wherein the snow accretion start time measured by the following snow accretion test is 5 minutes or longer.
<Snow accretion test>
A coating is placed on a test stand in a test room kept at a constant temperature in the range of 1 to 2 ° C so that the snow-covered surface is vertical to the ground, and the coating is subjected to a wind speed of 10 m / sec and a collision amount of 110 kg /. Pre-made artificial snow is blown under the condition of m 2 /h. This blowing causes the artificial snow to impinge on the covering surface. From the start of this spraying, a video was taken of the entire sprayed surface of the sample, and the presence or absence of snow accretion on the film surface was visually confirmed from the video obtained after the test was completed. Measured as the start time (no snow accretion time).
A chemical solution comprising the film-forming composition according to any one of claims 1 to 4.