JP7557136B2 - Coating and composition for forming coating - Google Patents

Description

This disclosure relates to coatings and compositions for forming coatings.

Various coatings that can impart super-liquid repellency to the surface of an object have been proposed (note that in this specification, a coating that can impart super-liquid repellency to the surface of an object may be referred to as a "super-liquid repellent coating").

For example, Patent Document 1 discloses that a super-liquid-repellent coating that combines super-liquid repellency and abrasion resistance can be formed by using fine particles with polymerizable groups and a compound that has two or more polymerizable groups in the molecule. Patent Document 2 discloses a technology that can form a super-liquid-repellent coating that combines super-liquid repellency and abrasion resistance by appropriately controlling the various properties of a coating that contains fluorine atoms.

International Publication No. 2016/056663 International Publication No. 2017/179678

The present disclosure aims to provide a coating that has excellent liquid repellency and abrasion resistance while also having high hardness, and a coating-forming composition capable of forming such a coating.

That is, the present disclosure includes, for example, the subject matter described in the following sections:
Item 1
The composite particle includes a fine particle coated with a first polymer and a second polymer,
At least one of the first polymer and the second polymer has an alkyl group or a fluoroalkyl group, and
the second polymer includes a polymer having a structural unit based on a compound having two or more polymerizable groups in the molecule,
The fine particles have an average particle size of 1 μm or more.
Item 2
2. The coating according to item 1, wherein the fine particles have a specific surface area of 30 to 700 m ² /g.
Item 3
The first polymer is represented by the following general formula (1):

（式中、Ｘは、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ＣＦＸ^１Ｘ^２基（但し、Ｘ^１およびＸ^２は、同一又は異なって、水素原子、フッ素原子又は塩素原子である。）、シアノ基、炭素数１～６の直鎖状又は分岐状のフルオロアルキル基、置換又は非置換のベンジル基、置換又は非置換のフェニル基、若しくは炭素数１～２０の直鎖状又は分岐状アルキル基を示し、Ｙは、直接結合、酸素原子を有していてもよい炭素数１～１０の炭化水素基、－ＣＨ_２ＣＨ_２Ｎ（Ｒ^１）ＳＯ_２－基（但し、Ｒ^１は炭素数１～４のアルキル基であり、式の右端がＲ^ａに、左端がＯにそれぞれ結合している。）、－ＣＨ_２ＣＨ（ＯＹ^１）ＣＨ_２－基（但し、Ｙ^１は水素原子またはアセチル基であり、式の右端がＲ^ａに、左端がＯにそれぞれ結合している。）、又は－（ＣＨ_２）_ｎＳＯ_２－基（ｎは１～１０であり、式の右端がＲ^ａに、左端がＯにそれぞれ結合している。）を示し、Ｒ^ａは炭素数２０以下の直鎖状又は分岐状のアルキル基、炭素数６以下の直鎖状又は分岐状のフルオロアルキル基、若しくは分子量４００～５０００のポリエーテル基又は分子量４００～５０００のフルオロポリエーテル基を示す。）で表される化合物に基づく構造単位を有する重合体を含む、項１又は２に記載の被膜。
項４
少なくとも一種の微粒子を含む被膜であって、
水の接触角が、１５０°以上であり、
紙製ウエスを荷重１００ｇで１００回塗擦した後の水の接触角が１５０°以上であり、鉛筆硬度が２Ｂ以上である、被膜。
項５
前記微粒子の平均粒子径が１μｍ以上である、項４に記載の被膜。
項６
前記微粒子の比表面積が３０～７００ｍ^２／ｇである、項４又は５に記載の被膜。
項７
被膜形成用組成物であって、
微粒子が第１の重合体で被覆されてなる複合粒子；及び
分子内に２つ以上の重合性基を有する、少なくとも一種の化合物を含み、
前記微粒子の平均粒子径が１μｍ以上である、被膜形成用組成物。
項７－１
前記第１の重合体は、上述の一般式（１）で表される化合物に基づく構造単位を有する重合体を含む、項７に記載の被膜形成用組成物。
項８
前記微粒子の比表面積が３０～７００ｍ^２／ｇである、項７に記載の被膜形成用組成物。項９
硬化後の被膜は、
水の接触角が、１５０°以上であり、
紙製ウエスを荷重１００ｇで１００回塗擦した後の水の接触角が、１５０°以上であり、鉛筆硬度が２Ｂ以上である、項７又は８に記載の被膜形成用組成物。

(wherein X represents 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 represent 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 linear or branched alkyl group having 1 to 20 carbon atoms; Y represents 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 (wherein R ¹ represents 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), or a -CH ₂ CH(OY ¹ )CH ₂ - group (wherein Y ¹ represents a hydrogen atom or an acetyl group, and the right end of the formula is bonded to R ^a , and the left end of the formula is bonded to O.), or a -(CH ₂ ) _n SO ₂ - group (n is 1 to 10, the right end of the formula is bonded to R ^a , and the left end is bonded to O), and R ^a represents 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 polyether group having a molecular weight of 400 to 5000, or a fluoropolyether group having a molecular weight of 400 to 5000.
Item 4
A coating comprising at least one type of particulate,
The contact angle of water is 150° or more,
A coating having a water contact angle of 150° or more after rubbing 100 times with a paper cloth under a load of 100 g and a pencil hardness of 2B or more.
Item 5
Item 5. The coating according to item 4, wherein the fine particles have an average particle size of 1 μm or more.
Item 6
Item 6. The coating according to item 4 or 5, wherein the fine particles have a specific surface area of 30 to 700 m ² /g.
Item 7
A coating composition comprising:
Composite particles in which fine particles are coated with a first polymer; and at least one compound having two or more polymerizable groups in the molecule,
The coating composition, wherein the fine particles have an average particle size of 1 μm or more.
Item 7-1
Item 8. The coating composition according to Item 7, wherein the first polymer comprises a polymer having a structural unit based on the compound represented by the general formula (1).
Item 8
Item 8. The coating composition according to item 7, wherein the fine particles have a specific surface area of 30 to 700 m ² /g.
After hardening, the coating is
The contact angle of water is 150° or more,
Item 9. The coating composition according to item 7 or 8, wherein the water contact angle after rubbing a paper cloth with a load of 100 g 100 times is 150° or more and the pencil hardness is 2B or more.

The coating of the present disclosure has excellent super-liquid repellency and abrasion resistance, while also having high hardness. Furthermore, the coating composition of the present disclosure can form a coating that has excellent super-liquid repellency and abrasion resistance, while also having high hardness.

In recent years, there has been a demand for super-liquid-repellent coatings to have high hardness in addition to super-liquid-repellency and abrasion resistance. This is because by increasing the hardness, the coating becomes less likely to peel off even if it is worn away, improving the durability of the super-liquid-repellent coating. In this regard, while conventional super-liquid-repellent coatings have excellent super-liquid-repellency and abrasion resistance, their hardness is relatively low, and no detailed study has been conducted on the perspective of increasing hardness.

In view of the above circumstances, the present inventors have conducted extensive research with the aim of forming a coating that has excellent super-liquid repellency and abrasion resistance while also having high hardness. As a result, they have found that the above-mentioned object can be achieved by including at least fine particles with an average particle size of 1 μm or more as a component in the coating. It is generally recognized that the performance of a coating is improved by reducing the average particle size of the fine particles contained in the coating (for example, by making the average particle size of the fine particles smaller, on the nano-order of 1 μm or less). However, the present inventors have found that, conversely, increasing the average particle size of the fine particles leads to improved hardness while maintaining super-liquid repellency and abrasion resistance.

Embodiments of the present disclosure are described in detail below. In this specification, the expressions "contain" and "include" include the concepts of "contain," "include," "consist essentially of," and "consist only of."

In this specification, a numerical range indicated using "~" indicates a range that includes the numerical values before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this specification, the upper limit or lower limit of a numerical range in a certain stage can be arbitrarily combined with the upper limit or lower limit of a numerical range in another stage. In the numerical ranges described in this specification, the upper limit or lower limit of the numerical range may be replaced with a value shown in an example or a value that can be unambiguously derived from an example.

The coatings disclosed herein can be broadly divided into two types: Coating A and Coating B. Both Coating A and Coating B have excellent super-liquid repellency and abrasion resistance, while also having high hardness. Coating A and Coating B will be described in turn below.

1. Coating A
Coating A of the present disclosure includes at least a composite particle in which a fine particle is coated with a first polymer, and a second polymer, wherein at least one of the first polymer and the second polymer has an alkyl group or a fluoroalkyl group, and the second polymer includes a polymer having a structural unit based on a compound having two or more polymerizable groups in the molecule, and the fine particles have an average particle size of 1 μm or more.

(Composite particles)
In the coating A of the present disclosure, the composite particle is formed by coating a fine particle with a first polymer. In particular, in the composite particle, the surface of the fine particle and the first polymer form a chemical bond. Examples of the chemical bond include a covalent bond, a coordinate bond, an ionic bond, a hydrogen bond, and a van der Waals force, and the like, and a covalent bond is preferable.

The type of fine particles is not particularly limited, and examples include silica fine particles, other metal oxide fine particles, carbon black, fullerenes, and carbon nanotubes. Since coating A tends to become hard, it is preferable that the fine particles are silica.

The average particle diameter of the microparticles is 1 μm or more. If the average particle diameter of the microparticles is less than 1 μm, the coating will not have the desired hardness. It is more preferable that the average particle diameter of the microparticles is 2 μm or more. There is no particular upper limit to the average particle diameter of the microparticles, and for example, it is preferably 5 μm or less, and more preferably 3 μm or less.

In the coating A of the present disclosure, the method for measuring the average particle diameter of the fine particles follows the procedure shown below. First, the coating is heat-treated to burn off the organic components in the coating, thereby separating the fine particles in coating A. The heat treatment is performed at 300°C for 3 hours in a nitrogen gas atmosphere. The obtained fine particles are directly observed with a scanning electron microscope, and 200 fine particles in the captured image are selected and their circle-equivalent diameters are measured. The arithmetic mean value is taken as the average particle diameter of the fine particles in coating A. In this specification, the average particle diameter of the fine particles refers to the average particle diameter of the primary particles of the fine particles.

The specific surface area of the fine particles is not particularly limited, and is preferably from 30 to 700 m ² /g, and more preferably from 100 to 300 m ² /g, in that the hardness of the coating is easily improved.

In the coating A of the present disclosure, the specific surface area of the fine particles refers to a value measured by the BET method (so-called BET specific surface area). The method for isolating the fine particles from coating A to measure the specific surface area is the same as the method for isolating the fine particles in the method for measuring the average particle size of the fine particles in coating A described above.

The shape of the microparticles is not particularly limited, and may be, for example, spherical, elliptical, or irregularly shaped.

The type of the first polymer that coats the fine particles is not particularly limited, and for example, a wide variety of known polymer compounds can be used. The first polymer may, for example, contain fluorine atoms or may not contain fluorine atoms.

The first polymer may include, for example, a polymer having a structural unit based on a compound represented by the following formula (1). As a precautionary note, in this specification, "structural unit based on a compound" refers to a repeating constituent unit formed when such a compound is polymerized, and does not refer to the compound itself.

In the formula (1), X represents 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 linear or branched alkyl group having 1 to 20 carbon atoms. When X is an alkyl group having 3 or more carbon atoms, it may be either cyclic or non-cyclic, and the number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 2. When X is a fluoroalkyl group, it may be either cyclic or non-cyclic. In addition, the number of carbon atoms of both the alkyl group and the fluoroalkyl group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2.

In the formula (1), Y represents a direct bond, a _{hydrocarbon group having 1 to 10 carbon atoms which may have an oxygen atom, a -CH2CH2N (} ^R1 ) _SO2- group (wherein ^R1 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), a _-CH2CH ( ^OY1 ) _CH2- group (wherein ^Y1 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 -( _CH2 ) _nSO2- group (n is 1 to 10, and the right end of the formula is bonded to _R ^a and the left end is bonded to O). A "direct bond" means that in the formula (1), R ^a and O at both ends of Y are directly bonded, which means that 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, and more preferably an alkylene group having 1 to 2 carbon atoms.

In the formula (1), R ^a represents 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 5000. The fluoroalkyl group is preferably, for example, a perfluoroalkyl group, and the fluoropolyether group is preferably, for example, a perfluoropolyether group.

Specific examples of the compound represented by formula (1) include the acrylic acid esters disclosed in the above-mentioned Patent Document 1.

Among these, from the viewpoint of excellent water repellency and oil repellency, the compound represented by formula (1) may be a combination in which X is a hydrogen atom or a fluorine atom, Y is 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 a linear or branched alkyl group having 2 to 20 carbon atoms, a linear or branched fluoroalkyl group having 2 to 6 carbon atoms, or a polyether group or fluoropolyether group having a molecular weight of 400 to 5000. More preferred compounds represented by formula (1) are those in which X is a hydrogen atom, Y is an alkylene group having 1 to 2 carbon atoms, and R ^a is a linear or branched fluoroalkyl group having 2 to 6 carbon atoms.

Specific examples of compounds represented by formula (1) include fluoroalkyl (meth)acrylates in which the fluoroalkyl group has 1 to 6 carbon atoms.

When the first polymer contains a polymer having a structural unit based on a compound represented by formula (1), the structural unit based on the compound represented by formula (1) contained in the polymer may be of one type alone or two or more types.

The molecular weight of the first polymer is not particularly limited, and can be, for example, within the range of mass average molecular weight formed by known radical polymerization. The first polymer may be a homopolymer formed of only one type of structural unit, or a copolymer formed of two or more structural units. If it is a copolymer, it may be in any form, such as a random copolymer or a block copolymer.

The first polymer may be formed only of a polymer having a structural unit based on the compound represented by formula (1), or may have structural units other than the structural unit based on the compound represented by formula (1). The total content of structural units based on the compound represented by formula (1) contained in the first polymer is, for example, 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 99% by mass or more.

The method for producing the composite particles is not particularly limited, and for example, a wide variety of known methods can be used. For example, as described below, the composite particles can be produced using fine particles having polymerizable groups or functional groups involved in polymerization on the surface and a compound represented by formula (1).

(Second Polymer)
In the coating A of the present disclosure, the second polymer is a component that can act as a binder for the coating. The second polymer includes a polymer having a structural unit based on a compound having two or more polymerizable groups in the molecule. As long as the second polymer has such a structural unit, the type of the second polymer is not particularly limited, and a wide variety of known polymers can be used.

The type of compound having two or more polymerizable groups in the molecule is not particularly limited, and for example, known compounds can be widely used. The compound having two or more polymerizable groups in the molecule may have, for example, a fluoroalkyl group, or may not have a fluoroalkyl group. The polymerizable group is not particularly limited, and for example, the sequential polymerizable group may be an isocyanate group, a hydroxyl group, an amine group, a carboxyl group, etc., and the chain polymerizable group may be a radical polymerizable group, a cationic polymerizable group, and an anionic polymerizable group, etc., and specific examples of the most commonly used radical polymerizable group include a vinyl group, a (meth)acrylic group, a styryl group, and a maleimide group. In particular, the compound having two or more polymerizable groups in the molecule is preferably a curing agent described later. In the compound having two or more polymerizable groups in the molecule, the upper limit of the polymerizable group may be, for example, 6.

The second polymer may be, for example, a polymer having a structure in which various thermosetting resins are crosslinked with a curing agent. Thermosetting resins and curing agents are described below.

<Thermosetting resin>
The thermosetting resin may or may not have a fluoroalkyl group. From the viewpoint of easily improving the water repellency of the coating, it is preferable that the thermosetting resin has a fluoroalkyl group.

The thermosetting resin is preferably a compound that reacts with a curing agent (described later) by heat to cause a curing reaction. Therefore, the thermosetting resin is preferably a compound that has a reactive functional group in the molecule, such as a hydroxyl group, a carboxyl group, an amino group, a thiol group, or an isocyanate group. In this case, it is preferable that such a compound further has a fluoroalkyl group.

From this viewpoint, it is preferable to use a fluorine-containing polymer having a reactive functional group as the thermosetting resin. Examples of the fluorine-containing polymer include
(a) a tetrafluoroethylene structural unit,
(b) a non-aromatic vinyl ester monomer structural unit not containing a hydroxyl group or a carboxyl group;
(c) a hydroxyl group-containing vinyl monomer structural unit not containing an aromatic group or a carboxyl group,
(e) a carboxyl group-containing monomer structural unit not containing a hydroxyl group or an aromatic group, and (f) other monomer structural units (excluding (d) an aromatic group-containing monomer structural unit not containing a hydroxyl group or a carboxyl group).
Hereinafter, this polymer will be referred to as "Polymer F." When the thermosetting resin is Polymer F, the water resistance of the coating is particularly improved.

The content ratio of the (a) tetrafluoroethylene structural unit in the total amount of polymer F has a lower limit of 20 mol%, preferably 30 mol%, more preferably 40 mol%, and particularly preferably 42 mol%, and an upper limit of 49 mol%, preferably 47 mol%.

Examples of monomers that provide the non-aromatic vinyl ester monomer structural unit (b) include one or more of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, and vinyl cyclohexylcarboxylate. These monomers are non-aromatic monomers that do not contain hydroxyl groups and carboxyl groups. A particularly preferred monomer that provides the non-aromatic vinyl ester monomer structural unit (b) is one selected from the group consisting of vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexylcarboxylate, and vinyl acetate, in terms of excellent weather resistance, etc. Among these, non-aromatic vinyl carboxylates, particularly vinyl carboxylates having 6 or more carbon atoms in the carboxylic acid, and more preferably vinyl carboxylates having 9 or more carbon atoms in the carboxylic acid, are preferred in terms of chemical resistance. The upper limit of the number of carbon atoms in the carboxylic acid in the vinyl carboxylate is 20 or less, and more preferably 15 or less. As a specific example, vinyl versatate is the most preferred.

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

The monomer which gives the hydroxyl group-containing vinyl monomer structural unit (c) is a non-aromatic monomer which does not contain a carboxyl group, and examples thereof include hydroxyalkyl vinyl ethers or hydroxyalkyl allyl ethers represented by the formula (2).
CH ₂ =CHR ¹⁰ (2)

Here, in formula (2), R ¹⁰ represents -OR ²⁰ or -CH ₂ OR ²⁰ (wherein 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 groups are bonded. Examples include one or more of 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-methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether. Among these, the monomer that provides the hydroxyl group-containing vinyl monomer structural unit (c) is preferably 4-hydroxybutyl vinyl ether or 2-hydroxyethyl vinyl ether.

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

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

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

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

Polymer F may further contain (d) an aromatic group-containing monomer structural unit that does not contain a hydroxyl group or a carboxyl group. (d) Examples of aromatic group-containing monomer structural units that do not contain a hydroxyl group or a carboxyl group include one or more types of vinyl benzoate monomers such as vinyl benzoate and vinyl para-t-butylbenzoate, with vinyl para-t-butylbenzoate and vinyl benzoate being particularly preferred.

The content of aromatic group-containing monomer structural unit (d) in 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 mol%.

Polymer F may further contain (e) a carboxyl group-containing monomer structural unit that does not contain a hydroxyl group or an aromatic group. Examples of the carboxyl group-containing monomer include one or more of acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, maleic acid anhydride, fumaric acid, fumaric acid monoester, vinyl phthalate, and vinyl pyromellitic acid. Among these, 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 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 mol%.

The number average molecular weight of polymer F, as measured by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent, is, for example, 1,000 to 1,000,000, preferably 3,000 to 50,000. The glass transition temperature (2nd run) of polymer F, as measured by differential scanning calorimetry (DSC), is, for example, 10 to 60°C, preferably 20 to 40°C. The method for producing polymer F is not particularly limited, and a wide variety of known production methods can be used. Polymer F can also be obtained commercially.

Specific examples of polymer F include the Zeffle (registered trademark) GK series manufactured by Daikin Industries, Ltd.

<Curing Agent>
The type of the curing agent is not particularly limited, and for example, a wide variety of compounds used as curing agents for thermosetting resins can be used. In particular, the curing agent is preferably a compound having two or more polymerizable groups in the molecule.

Specific examples of curing agents include isocyanate-based curing agents. 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), ^Z6 is a linear or branched monovalent hydrocarbon group or carbonyl group which has an isocyanate group at at least one terminal, at least one carbon atom which may be substituted with a heteroatom, at least one hydrogen atom which may be substituted with a halogen atom, and which may have a carbon-carbon unsaturated bond; ^R3 is a branched or cyclic divalent or higher hydrocarbon group or carbonyl group which has at least one carbon atom which may be substituted with a heteroatom, at least one hydrogen atom which may be substituted with a halogen atom, at least one carbon atom which may be substituted with a heteroatom, and which may have a carbon-carbon unsaturated bond; and o is an integer of 2 or greater.

^R3 preferably has 1 to 20 carbon atoms, more preferably has 2 to 15 carbon atoms, and even more preferably has 3 to 10 carbon atoms.

^Z6 preferably has 1 to 20 carbon atoms, more preferably has 2 to 15 carbon atoms, and further preferably has 3 to 10 carbon atoms.

The isocyanate compound may be used alone or in combination.

An example of an isocyanate compound is polyisocyanate. In this specification, 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. Such a polyisocyanate obtained by trimerizing a diisocyanate may be a triisocyanate. A polyisocyanate that is a trimer of a diisocyanate may exist as a polymer obtained by polymerization of these.

Diisocyanates include, but are not limited to, diisocyanates in which an isocyanate group is bonded to an aliphatic group, such as trimethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and norbornane diisocyanate; and 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 examples of 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, the polymer may have the following structure:

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

The above-mentioned isocyanurate-type polyisocyanates may be polymers formed by polymerization of these. The isocyanurate-type polyisocyanates may be monocyclic compounds having only one isocyanurate ring, or may be polycyclic compounds obtained by polymerization of the monocyclic compounds.

In one embodiment in which two or more isocyanate compounds are used, a mixture containing a monocyclic compound 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 polyisocyanate can be used. The isocyanurate polyisocyanate may be, for example, a triisocyanate, specifically a triisocyanate obtained by trimerizing a diisocyanate.

Specific examples of isocyanate compounds include Sumidur (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, and HL series (manufactured by Sumika Covestro Urethane Co., Ltd.), Desmodur (registered trademark) 2460M (manufactured by Sumika Covestro Urethane Co., Ltd.), Sumidur (registered trademark) 44 series (manufactured by Sumika Covestro Urethane Co., Ltd.), SBU Isocyanate series (manufactured by Sumika Covestro Urethane Co., Ltd.), and Desmodur (registered trademark) E and M series. Commercially available products such as Sumidurse (manufactured by Sumika Covestro Urethane Co., Ltd.), Sumidur HT (manufactured by 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 (manufactured by 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) can be used.

When the thermosetting resin component contains a curing agent, its content can be 10 to 30 mass % based on the total mass of the thermosetting resin.

(Constitution and properties of coating A)
As described above, the coating A of the present disclosure contains at least a composite particle in which a fine particle is coated with a first polymer, and a second polymer. The content ratio of both in the coating is not particularly limited and can be any. For example, in order that the coating has excellent super-liquid repellency and abrasion resistance while being likely to have high hardness, it is preferable that the composite particle is contained in an amount of 30 to 70 mass% based on the total mass of the composite particle and the second polymer.

In the coating A of the present disclosure, at least one of the first polymer and the second polymer that coat the fine particles has an alkyl group or a fluoroalkyl group, preferably a fluoroalkyl group, and more preferably a perfluoroalkyl group. In this case, the coating A is likely to have excellent super-liquid repellency and abrasion resistance. In particular, both the first polymer and the second polymer have an alkyl group or a fluoroalkyl group, preferably a fluoroalkyl group, and more preferably both have a perfluoroalkyl group. In this case, the coating A is likely to have even more excellent super-liquid repellency and abrasion resistance.

When the first polymer has a perfluoroalkyl group, for example, in the compound represented by formula (1), R ^a is a perfluoroalkyl group. When the second polymer has a perfluoroalkyl group, for example, the thermosetting resin has a perfluoroalkyl group.

Coating A may, for example, have a fluorine content of 80% by mass or less. Alternatively, coating A may not contain fluorine. The fluorine content in coating A is preferably 1 to 75% by mass, and more preferably 5 to 70% by mass. With a fluorine content in the above range, coating A can exhibit stronger liquid repellency and abrasion resistance.

In this disclosure, the fluorine content in the coating is defined as the content of F element in the elemental composition obtained by X-ray photoelectron spectroscopy (XPS) measurement. XPS measurement is performed using a commercially available device [e.g., ESCA3400 (product name) (SHIMADZU), PHI5000 VersaProbe II (product name) (UlVAC-PHI)].

The average surface roughness Ra of the surface of the coating A can be 0.5 to 20 μm, more preferably 0.6 to 17.5 μm, and even more preferably 0.7 to 15 μm. By having the average surface roughness Ra within the above range, the coating A can exhibit stronger liquid repellency and abrasion resistance.

Coating A can have a water contact angle of 150° or more. This allows coating A to exhibit excellent water repellency.

The contact angle of coating A with n-hexadecane can be 80° or more. This allows coating A to exhibit excellent oil repellency.

The water contact angle of coating A is 150° or more after rubbing a paper cloth 100 times with a load of 100 g. This allows coating A to have abrasion resistance. In this disclosure, paper cloth refers to "Kimwipe" (registered trademark) manufactured by Nippon Paper Crecia Co., Ltd.

The pencil hardness of coating A can be 2B or more. This allows coating A to exhibit excellent hardness. The pencil hardness of coating A is preferably 2B or more, more preferably B or more.

Coating A may also contain other components in addition to the composite particles and the second polymer. When coating A contains other components, the content of the other components may be 5% by mass or less, preferably 1% by mass or less, more preferably 0.1% by mass or less, and particularly preferably 0.05% by mass or less, based on the total mass of the composite particles and the second polymer. Coating A may be formed only from the composite particles and the second polymer.

Coating A has excellent super-liquid repellency and abrasion resistance, and also has high hardness, so it is less likely to peel off than conventional coatings and has excellent durability. Therefore, coating A is used to impart water repellency and/or oil repellency to the treated surface, and can be suitably used for various articles that require super-liquid repellency.

The applications of the coating A of the present disclosure are not particularly limited, and the coating A of the present disclosure can be suitably used, for example, as a water and oil repellent, for retarding frost formation, an anti-icing agent, an anti-snow agent, an agent for preventing fingerprint adhesion, an agent for making fingerprints unrecognizable, a low-friction agent, a lubricant, an agent for controlling protein adhesion, an agent for controlling cell adhesion, an agent for controlling microbial adhesion, an agent for inhibiting scale adhesion, an antifungal agent, an antibacterial agent, etc.

(Method of forming coating A)
The method for forming the coating A is not particularly limited, and for example, a known method using the following coating-forming composition can be adopted.

<Film-forming composition>
The coating composition may, for example, comprise a composite particle in which a fine particle is coated with a first polymer, and at least one compound A2 having two or more polymerizable groups in the molecule (hereinafter, simply referred to as “compound A2”). "). Here, the composite particles in which the fine particles are coated with the first polymer are the same as the composite particles contained in the above-mentioned coating A. Compound A2 can also contain For example, the curing agent is the same as the above-mentioned curing agent, and an example is the above-mentioned isocyanate compound. The coating composition can further contain the above-mentioned thermosetting resin.

The composite particles can be produced, for example, by using fine particles having polymerizable groups or functional groups involved in polymerization on the surface and a compound represented by formula (1).

As for the fine particles having a polymerizable group or a functional group involved in polymerization on the surface, the fine particles can be, as described above, silica fine particles, other metal oxide fine particles, carbon black, fullerene, carbon nanotubes, etc. The fine particles are preferably silica, since the coating A tends to become hard and the surface can be easily modified with a polymerizable group-containing compound or a polymerization initiator group-containing compound.

The polymerizable group on the surface of the fine particles is not particularly limited, and examples thereof include radical polymerizable groups, cationic polymerizable groups, and anionic polymerizable groups. In terms of versatility and reactivity, radical polymerizable groups are preferred, and examples thereof include vinyl groups, (meth)acrylic groups, styryl groups, and maleimide groups. The method for producing fine particles having polymerizable groups on the surface is not particularly limited, and for example, known production methods can be widely adopted. Fine particles having polymerizable groups on the surface can also be obtained from commercial products. Examples of functional groups involved in polymerization on the surface of the fine particles include groups based on radical polymerization initiators or groups based on chain transfer agents. Examples of groups based on radical polymerization initiators include azo groups and peroxy groups, and a specific example of a group based on a chain transfer agent is a thiol group.

The average particle diameter of the microparticles having polymerizable groups on the surface is 1 μm or more. If the average particle diameter of the microparticles is less than 1 μm, the coating will not have the desired hardness. It is more preferable that the average particle diameter of the microparticles is 2 μm or more. There is no particular upper limit to the average particle diameter of the microparticles, and for example, it is preferably 5 μm or less, and more preferably 3 μm or less.

The method for measuring the average particle size of the microparticles having polymerizable groups on the surface in the composition for forming a film follows the procedure shown below. The volatile components of the composition for forming a film are removed by heat treatment (300°C, 3 hours), and the obtained microparticles are directly observed under a scanning electron microscope. 200 microparticles in the captured image are selected, and the circle equivalent diameters of these are measured. The arithmetic mean value is the average particle size of the microparticles in the composition for forming a film. In the composition of the present disclosure, the average particle size of the microparticles can be regarded as the average particle size of the composite particles.

The specific surface area of the fine particles having polymerizable groups on the surface is not particularly limited, and is preferably 30 to 700 m ² /g, more preferably 100 to 300 m ² /g, in that the hardness of the resulting coating is easily improved.

In the film-forming composition, the specific surface area of the fine particles refers to a value measured by the BET method (so-called BET specific surface area). The fine particles in the film-forming composition can be obtained by removing the volatile components of the film-forming composition by heat treatment.

Composite particles can be produced by a polymerization reaction between fine particles having polymerizable groups on their surfaces and a compound represented by formula (1). As a result, the polymerizable groups on the surface of the fine particles undergo a polymerization reaction with the compound represented by formula (1), and the fine particle surface and the compound represented by formula (1) are chemically bonded (covalently bonded). An example of the polymerization reaction is radical polymerization.

The conditions for the polymerization reaction between the fine particles having polymerizable groups on the surface and the compound represented by formula (1) are not particularly limited, and a wide variety of known methods can be used. This polymerization reaction can be carried out in a polymerization solvent. A polymerization initiator can also be used in the polymerization reaction. The types of polymerization solvent and polymerization initiator are not particularly limited, and a wide variety of known solvents and polymerization initiators used in polymerization reactions can be used. For example, examples of the polymerization solvent include fluorine-based solvents such as hydrofluoroethers, as well as alcohol compounds, water, and mixtures thereof.

The film-forming composition may contain a solvent as necessary. The type of solvent is not limited, and a wide variety of solvents that are used to form films can be used, including, for example, fluorine-based solvents such as hydrofluoroethers, alcohol compounds, ester compounds (e.g., ethyl acetate), ether compounds, and the like.

The content of the solvent in the coating composition is not particularly limited, and can be, for example, 80 to 95% by mass relative to the total mass of the composite particles, the thermosetting resin, and the compound A2.

The film-forming composition may also contain other additives in addition to the composite particles and compound A2, as well as the polymerization initiator and the solvent. When the film-forming composition contains other additives, the content ratio of the other additives may be, for example, 5% by mass or less, preferably 1% by mass or less, more preferably 0.1% by mass or less, and particularly preferably 0.05% by mass or less, based on the total mass of the composite particles and compound A2.

The method for preparing the coating composition is not particularly limited. For example, the composite particles, the thermosetting resin, and the compound A2 (e.g., a curing agent) can be prepared using an appropriate mixing means. In this preparation, the composite particles may be mixed in the form of a dispersion. The solids concentration of the dispersion can be, for example, 5 to 20% by mass.

The method for forming the coating A using the coating composition is not particularly limited. For example, the coating can be formed by applying the coating composition to a substrate on which the coating is to be formed to form a coating film, and then polymerizing the coating film.

The type of substrate for forming the coating of the coating composition is not particularly limited, and a wide variety of substrates can be used that can be coated with the coating composition. Examples of substrates include various substrates such as plastics, metals, ceramics, and fibers, and more specifically, acrylic resin substrates and polycarbonate resin substrates. The substrate may be made of a single material or a composite of two or more materials. If necessary, various primer treatments can be applied to the substrate to facilitate coating.

There are no particular limitations on the method of applying the composition for forming a coating film, and any known coating film forming method can be widely used. Examples of methods for applying the composition for forming a coating film include brush coating, spray coating, spin coating, and using a dispenser. After application, appropriate processing can be performed as necessary to form the desired coating film on the substrate.

The method for curing the composition for forming the film is not particularly limited, and various methods such as heat curing can be used. When heat curing is used, the coating of the composition for forming the film can be heated to 20 to 200°C, and the preferred heating temperature range is 60 to 150°C.

As described above, coating A can be formed by using the coating composition.

A chemical solution can be prepared using the film-forming composition. Since such a chemical solution contains the film-forming composition, it is suitable for use in forming a film. The chemical solution can be composed of only the film-forming composition, or can contain other additives (for example, known additives used as film-forming solvents) to the extent that the intended performance of the film-forming composition of the present disclosure is not impaired.

2. Coating B
The coating B of the present disclosure is a coating containing at least one type of fine particle,
The contact angle of water is 150° or more,
After rubbing the surface with a paper cloth 100 times under a load of 100 g, the water contact angle is 150° or more and the pencil hardness is 2B or more.

Coating B has a water contact angle of 150° or more, which allows coating B to exhibit excellent water repellency.

Coating B has a water contact angle of 150° or more after rubbing 100 times with a paper rag under a load of 100 g, meaning that the coating has excellent hardness and abrasion resistance, improving the durability of the coating.

Coating B has a pencil hardness of 2B or more. This allows coating B to exhibit excellent hardness. The pencil hardness of coating B is preferably 2B or more, more preferably B or more.

Coating B has the above physical properties, and therefore has excellent super-liquid repellency and abrasion resistance, while also having high hardness, making it less likely to peel off than conventional coatings and providing excellent durability. Therefore, coating B is used to impart water and/or oil repellency to the treated surface, and can be suitably used for various articles that require super-liquid repellency.

In addition, it is also preferable that coating B has the following physical properties:

Coating B may have a fluorine content of, for example, 80% by mass or less. For example, the fluorine content in coating B is 1 to 75% by mass, and more preferably 2 to 70% by mass. With a fluorine content in the above range, coating B can exhibit stronger liquid repellency and abrasion resistance.

Coating B may have an average surface roughness Ra of 0.5 to 20 μm, more preferably 0.6 to 17.5 μm, and even more preferably 0.7 to 15 μm. By having the average surface roughness Ra within the above range, it is possible to exhibit stronger liquid repellency and abrasion resistance.

The contact angle of coating B with n-hexadecane can be 80° or more. This allows coating B to exhibit excellent oil repellency.

As long as coating B has the above-mentioned physical properties, other configurations and physical properties are not particularly limited. Coating B preferably contains the composite particles contained in coating A described above. In this case, coating B is more likely to have the above-mentioned physical properties and is more likely to have improved hardness.

The types of composite particles contained in coating B are the same as those in coating A, such as silica particles, other metal oxide particles, carbon black, fullerenes, and carbon nanotubes. Since coating B tends to become hard, it is preferable that the particles are silica.

The average particle diameter of the microparticles is 1 μm or more. If the average particle diameter of the microparticles is less than 1 μm, the coating will not have the desired hardness. It is more preferable that the average particle diameter of the microparticles is 2 μm or more. There is no particular upper limit to the average particle diameter of the microparticles, and for example, it is preferably 5 μm or less, and more preferably 3 μm or less.

In the coating B of the present disclosure, the method for measuring the average particle size of the microparticles is the same as the method for measuring the average particle size of the microparticles contained in the coating A.

The specific surface area of the fine particles is not particularly limited, and is preferably 30 to 700 m ² /g, and more preferably 100 to 300 m ² /g, in that the hardness of the coating is easily improved. In the coating B of the present disclosure, the method for measuring the specific surface area of the fine particles is the same as the method for measuring the specific surface area of the fine particles contained in the coating A.

The method for forming the coating B of the present disclosure is not particularly limited, and any known method can be widely adopted as long as the above-mentioned physical properties are obtained. Among them, the method for forming the coating B using the above-mentioned coating-forming composition is preferable.

Coating B has excellent super-liquid repellency and abrasion resistance, and also has a high hardness, so it is less likely to peel off than conventional coatings and has excellent durability. Therefore, coating B is used to impart water repellency and/or oil repellency to the treated surface, and can be used effectively for various articles that require super-liquid repellency.

The applications of the coating B of the present disclosure are not particularly limited, and it can be suitably used for applications similar to those of the coating A described above, for example.

(Methods for measuring various physical properties of the coating of the present disclosure)
Methods for measuring various physical properties of the coating of the present disclosure will be described. Note that, just for the sake of clarity, the coating of the present disclosure includes the above-mentioned coating A and coating B.

<Average surface roughness Ra>
The average surface roughness Ra is measured using a color 3D laser microscope (KEYENCE VK-X1000 and its accessory microscope unit).

<Water 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"). Specifically, five measurements are performed for one sample using water (2 μL droplets). When the static contact angle is 150° or more, the liquid may not be able to stand on the substrate surface. In such a case, the static contact angle is measured using a syringe needle as a support, and the value obtained at that time is taken as the static contact angle.

<Contact angle of n-hexadecane>
The contact angle of n-hexadecane (abbreviated as n-HD) is the static contact angle of n-HD. The contact angle of n-HD is measured using a contact angle meter (Kyowa Interface Science Co., Ltd. "Drop Master 701"); specifically, five measurements are taken for one sample using n-HD (2 μL droplets). When the static contact angle is 150° or more, the liquid may not be able to stand on the substrate surface independently. In such a case, the static contact angle is measured using a syringe needle as a support, and the value obtained at that time is taken as the static contact angle.

<Contact angle of water after rubbing paper cloth 100 times with a load of 100 g>
The water contact angle after rubbing a paper cloth (Kimwipe (registered trademark) manufactured by Nippon Paper Crecia Co., Ltd.) with the coating 100 times at a load of 100 g is measured using an abrasion resistance tester (Rubbing Tester (3-unit model) 151E manufactured by Imoto Seisakusho Co., Ltd.). The paper cloth is attached to the tester, and the surface of the sample (coating) is wiped a certain number of times (100 times) at a load of 100 g, and then the water contact angle is measured using the water contact angle measurement method described above. The area of the paper cloth in contact with the sample is 1 ^cm2 .

<Pencil hardness>
The pencil hardness is measured in accordance with JIS K 5600-5.

The present disclosure will be explained in more detail below with reference to examples, but the present disclosure is not limited to the aspects of these examples.

Example 1
[Rf(C6) methacrylate/fine particles] copolymer/(Zeffle GK-570+Sumidur N3300)=50/50 (w/w) thin film preparation)
<Preparation of [Rf(C6) methacrylate/fine particle] copolymer solution>
In a 200 mL four-neck flask, 3 g of silica fine particles with an average particle size of 2.7 μm (Fuji Silysia Chemical, Silica 310P, specific surface area 300 m ² /g), 0.06 g of 3-mercaptopropyltrimethoxysilane (Shin-Etsu Chemical), and 60 g of perfluorobutyl ethyl ether were charged and heated at 70° C. for 2 hours. Next, 6 g of C ₆ F ₁₃ CH ₂ CH ₂ OCOC(CH ₃ )═CH ₂ [hereinafter abbreviated as Rf(C6) methacrylate] and 0.3 g of azobisisobutyronitrile (hereinafter abbreviated as AIBN) were added and reacted for 6 hours to obtain a dispersion of composite particles. After polymerization, the solid content concentration of the composite particles in the dispersion was calculated.
<Preparation of Coating Fluid>
Next, the composite particle dispersion, Zeffle GK-570 (product name) (manufactured by Daikin Industries, Ltd. (copolymer of tetrafluoroethylene and hydroxyl group-containing vinyl monomer)) corresponding to polymer F as a thermosetting resin, Sumidur N3300 (Sumika Covestro Urethane Co., Ltd.) as a curing agent (isocyanate compound), and butyl acetate were mixed to obtain a coating composition for forming a film as a coating liquid. In this composition for forming a film, the composite particles were blended so that the ratio of (mass of the composite particles in the dispersion):(total mass of Zeffle GK-570 (in terms of solid content) and Sumidur N3300)=50:50.
<Preparation of coating film>
The above coating liquid was applied to an acrylic substrate by spraying, and the substrate was then heat-treated at 130° C. for 10 minutes to obtain a desired coating film.

Example 2
A coating was prepared in the same manner as in Example 1, except that 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was replaced with 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.).

Example 3
A coating was prepared in the same manner as in Example 1, except that the composition for forming the coating was mixed so that the ratio of the composite particles in the dispersion to the total weight of Zeffle GK-570 (solid content equivalent) and Sumidur N3300 was 40:60.

Example 4
A coating was prepared in the same manner as in Example 2, except that the composition for forming the coating was mixed so that the ratio of the composite particles in the dispersion to the total weight of Zeffle GK-570 (solid content equivalent) and Sumidur N3300 was 40:60.

Example 5
A coating was prepared in the same manner as in Example 1, except that the silica fine particles were changed to silica fine particles having an average particle size of 2.7 μm (manufactured by Fuji Silysia Chemical, Silisia 530, specific surface area 500 m ² /g).

(Comparative Example 1)
A coating was prepared in the same manner as in Example 1, except that the silica fine particles were changed to R711 (manufactured by Nippon Aerosil) having an average primary particle diameter of 12 nm, and 3-mercaptopropyltrimethoxysilane was not used.

(Comparative Example 2)
A coating was prepared using a super water-repellent material HIREC100 (NTT Advanced Technologies).

(Evaluation of the coating)
The test pieces of the coatings obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were subjected to the following tests.

<Contact angle measurement (water)>
Using a contact angle meter Drop Master 701 (manufactured by Kyowa Interface Science Co., Ltd.), a water droplet volume of 2 μL was used, and measurements were taken at five points for one sample. When the static contact angle becomes 150° or more, depending on the conditions, In such a case, the liquid cannot stand on the surface of the substrate by itself, so the static contact angle was measured using the needle of a syringe as a support, and the obtained value was taken as the static contact angle. Here, a falling angle of 0° means that a 20 μL droplet cannot be landed on the substrate from the needle, or even if it can be landed, the droplet falls between 0° and 1° before or during the measurement. This means that the droplets fall and cannot be measured with the equipment used.

<Contact angle measurement (n-HD)>
The static contact angle of n-hexadecane (abbreviated as n-HD) was measured using a contact angle meter (Kyowa Interface Science Co., Ltd. "Drop Master 701"). When the static contact angle is 150° or more, the liquid may not be able to stand on the substrate surface. The static contact angle was measured using a syringe needle as a support, and the value obtained at that time was taken as the static contact angle.

<Pencil hardness>
The pencil hardness was measured according to JIS K 5600-5.

<Contact angle of water after rubbing paper cloth 100 times with a load of 100 g>
The contact angle of water after rubbing a paper cloth 100 times with a load of 100 g was measured using an abrasion resistance tester (Imoto Manufacturing Co., Ltd. "Rubbing Tester (triple type) 151E"). A paper cloth was attached to the tester, and the sample (coating) surface was wiped a certain number of times (100 times) with a load of 100 g (contact area: 1 ^cm2 ), and then the water contact angle was measured using the water contact angle measurement method described above.

<Number of wear tests>
The number of abrasion tests was performed using an abrasion resistance tester (Imoto Manufacturing Co., Ltd. "Rubbing Tester (3-unit type) 151E"). A paper cloth (Nippon Paper Crecia Co., Ltd. "Kimwipe" (registered trademark)) was attached to the tester, and the sample (coating) surface was wiped with a load of 100 g (contact area: 1 ^cm2 ) until the static contact angle became 150° or less. The abrasion resistance performance here was defined as the number of abrasion tests that could maintain a super-water-repellent state (average static contact angle of 5 times 150° or more, or an average of 140° or more with an average of 150° or more, with a standard deviation of 150° or more).

Table 1 shows the results of the static contact angle of water (20 μL of water), sliding angle, static contact angle with n-hexadecane (n-HD), pencil hardness, contact angle of water after loading with a paper cloth (contact angle of water after rubbing 100 times with a paper cloth under a load of 100 g), and number of abrasion tests for the coatings obtained in each example and comparative example.

The results in Table 1 show that the coatings obtained in each Example had excellent super-liquid repellency and abrasion resistance, while also having high hardness. On the other hand, in Comparative Example 1, since the average particle size of the microparticles was small, the coating had super-liquid repellency, but did not have excellent abrasion resistance or hardness.

Claims (8)

The composite particle includes a fine particle coated with a first polymer and a second polymer,
At least one of the first polymer and the second polymer has an alkyl group or a fluoroalkyl group, and
the second polymer includes a polymer having a structural unit based on a compound having two or more polymerizable groups in the molecule,
The first polymer is represented by the following general formula (1):

(wherein X represents 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 represent 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 linear or branched alkyl group having 1 to 20 carbon atoms; Y represents 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 (wherein R ¹ represents 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), or a -CH ₂ CH(OY ¹ )CH ₂ - group (wherein Y ¹ represents 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 (n is 1 to 10, the right end of the formula is bonded to R ^a , and the left end is bonded to O; R ^a represents 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 polyether group having a molecular weight of 400 to 5000, or a fluoropolyether group having a molecular weight of 400 to 5000;
The fine particles have an average particle size of 1 μm or more. The coating according to claim 1, wherein the fine particles have a specific surface area of 30 to 700 m ² /g. A coating comprising at least one type of particulate,
the fine particles are composite particles coated with a first polymer,
The first polymer is represented by the following general formula (1):

(wherein X represents 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 represent 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 linear or branched alkyl group having 1 to 20 carbon atoms; Y represents 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 (wherein R ¹ represents 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), or a -CH ₂ CH(OY ¹ )CH ₂ - group (wherein Y ¹ represents 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 (n is 1 to 10, the right end of the formula is bonded to R ^a , and the left end is bonded to O; R ^a represents 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 polyether group having a molecular weight of 400 to 5000, or a fluoropolyether group having a molecular weight of 400 to 5000;
The contact angle of water is 150° or more,
A coating having a water contact angle of 150° or more after rubbing 100 times with a paper cloth under a load of 100 g and a pencil hardness of 2B or more. The coating according to claim 3 , wherein the fine particles have an average particle size of 1 μm or more. The coating according to claim 3 or 4 , wherein the fine particles have a specific surface area of 30 to 700 m ² /g. A coating composition comprising:
Composite particles in which fine particles are coated with a first polymer; and at least one compound having two or more polymerizable groups in the molecule,
The first polymer is represented by the following general formula (1):

(wherein X represents 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 represent 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 linear or branched alkyl group having 1 to 20 carbon atoms; Y represents 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 (wherein R ¹ represents 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), or a -CH ₂ CH(OY ¹ )CH ₂ - group (wherein Y ¹ represents 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 (n is 1 to 10, the right end of the formula is bonded to R ^a , and the left end is bonded to O; R ^a represents 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 polyether group having a molecular weight of 400 to 5000, or a fluoropolyether group having a molecular weight of 400 to 5000;
The coating composition, wherein the fine particles have an average particle size of 1 μm or more. 7. The coating composition according to claim 6 , wherein the fine particles have a specific surface area of 30 to 700 m ² /g. After hardening, the coating is
The contact angle of water is 150° or more,
8. The coating composition according to claim 6 , which has a water contact angle of 150° or more after rubbing 100 times with a paper cloth under a load of 100 g, and a pencil hardness of 2B or more.