WO2016056663A1

WO2016056663A1 - Coating film, coating method using same and article coated with same

Info

Publication number: WO2016056663A1
Application number: PCT/JP2015/078849
Authority: WO
Inventors: 央基山口; 翔英; 正道森田
Original assignee: ダイキン工業株式会社
Priority date: 2014-10-10
Filing date: 2015-10-09
Publication date: 2016-04-14
Also published as: TW201638292A

Abstract

Provided is a super-liquid-repellent coating film with improved abrasion resistance. A coating film contains a polymer having respective moieties based on: (1) at least one type of fine particles having a polymerizable group; and (2) at least one type of compound having a polymerizable group, wherein at least one type of the fine particles (1) and/or at least one type of the compound(s) (2) have a fluoroalkyl group, and at least one type of the compound(s) (2) is a compound having two or more polymerizable groups in the molecule.

Description

Coating, coating method thereby, and article coated thereby

The present invention relates to a coating, particularly a coating capable of imparting super-water repellency and super-oil repellency (hereinafter, collectively referred to as “super-liquid repellency”) to a surface, and further, a coating method using the coating and thereby It also relates to coated articles.

Various coatings capable of imparting super liquid repellency to the surface of an object (hereinafter sometimes referred to as “super liquid repellent coating”) have been proposed.

For example, there has been proposed a method of imparting super liquid repellency by chemically bonding a fluoroalkylsilane compound to a surface to be treated on which a cured coating film containing silica fine particles or the like is formed (Patent Document 1).

A method of forming a film by hydrolyzing alkoxysilane in a mixed state of alkoxysilane, perfluoroalkylsilane and silica fine particles has also been proposed (Patent Document 2).

In addition, a coating obtained by copolymerizing fine particles having radical polymerizable groups on the surface and a fluorine-containing monomer has been proposed (Non-patent Document 1).

JP 2001-131318 A JP 2010-89373 A

The present inventors have found that the conventional super-liquid-repellent coating has a problem that the abrasion resistance is not sufficient. The present invention aims to solve this new problem. In particular, an object of the present invention is to provide a super-liquid-repellent film that achieves both super-liquid repellency, which is the original performance, and wear resistance.

The inventors of the present invention have made extensive studies, and at least a structural unit based on a fine particle having a polymerizable group and a compound having two or more polymerizable groups in the molecule (however, at least one of them has a fluoroalkyl group). It has been found that the above-described problems can be solved by using the polymer having the coating as a coating. The fluoroalkyl group provides strong liquid repellency, and the copolymer may have a specific structure by copolymerization using a compound having two or more radical polymerizable groups in the molecule. It seems to have led to the acquisition of excellent wear resistance. The present invention has been completed by further trial and error, and includes the following embodiments.
Item 1.
(1) at least one kind of fine particles having a polymerizable group; and (2) a film containing a polymer each having a polymerizable group and a structural unit based on at least one compound,
At least one of the fine particles (1) and / or at least one of the compounds (2) has a fluoroalkyl group, and at least one of the compounds (2) has two or more polymerizations in the molecule. A film, which is a compound having a functional group.
Item 2.
The polymer contains the fine particles (1) and the compound (2).
It is a polymer that can be obtained by polymerizing at the same time or sequentially polymerizing in at least two stages.
Item 12. The coating according to Item 1.
Item 3.
Item 3. The coating according to Item 2, wherein the polymer is a polymer that can be obtained by polymerizing at least one of the compounds (2) having two or more polymerizable groups in the molecule in the second and subsequent stages. .
Item 4.
Item 4. The coating according to any one of Items 1 to 3, wherein the polymerizable groups are the same or different and are a vinyl group, a (meth) acryl group, a styryl group, or a maleimide group.
Item 5.
At least one of the compounds (2) is represented by the following general formula (1):

(In the formula, X represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX ¹ X ² group (where 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 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a straight chain having 1 to 20 carbon atoms Or 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 (provided that , R ¹ is an alkyl group having 1 to 4 carbon atoms, and the right end of the formula is bonded to Rf 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, the right end of the formula is R In, attached respectively left end to O), or _{_{-. (CH 2) n SO}} 2 - group (n is 1 to 10, the right end of the formula is Rf, the left end is attached respectively to the O And Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, or a fluoropolyether group having a molecular weight of 400 to 5,000). The coating according to any one of 1 to 4.
Item 6.
The compound (2) having two or more polymerizable groups in the molecule is represented by the following general formula (2):

(In the formula, X represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX ¹ X ² group (where 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 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a straight chain having 1 to 20 carbon atoms Or 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 (provided that , R ¹ is an alkyl group having 1 to 4 carbon atoms, and the right end of the formula is bonded to Z ¹ and the left end 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 Z ¹ and the left end is bonded to O.) or — (CH ₂ ) _n SO ₂ — group (n is 1 to 10, the right end of the formula is bonded to Z ¹ and the left end is bonded to O. Z ¹ is a residue obtained by removing m + 1 hydrogen atoms from a hydrocarbon optionally having an oxygen atom and / or a fluorine atom, or a carbon atom or an oxygen atom, and Z ² is A residue obtained by removing n hydrogen atoms from a hydrocarbon optionally having an oxygen atom and / or a fluorine atom, or a carbon atom or an oxygen atom, m is an integer of 1 to 3, and n is 1 to Item 6. The film according to any one of Items 1 to 5, wherein the film is a compound represented by an integer of 4 and a number obtained by multiplying m and n is 2 or more.
Item 7.
Item 7. The coating according to any one of Items 1 to 6, wherein the water has a static contact angle of 150 ° or more and n-hexadecane has a static contact angle of 90 ° or more.
Item 8.
Item 8. The coating according to any one of Items 1 to 7, wherein the falling angle of water during film formation is 10 ° or less.
Item 9.
Item 9. A coating method comprising a step of bringing an object to be treated into contact with the film according to any one of Items 1 to 8.
Item 10.
Item 9. A composition containing the fine particles (1), which is used for coating with the film according to any one of Items 1 to 8.
Item 11.
Item 9. A composition containing the compound (2), which is used for coating with the film according to any one of Items 1 to 8.
Item 12.
A coating composition comprising (A) at least one fine particle having a polymerizable group on the surface; and (B) at least one compound having two or more polymerizable groups in the molecule.
Item 13.
A coating composition comprising (1) at least one fine particle having a polymerizable group on the surface; and (2) a polymer having a polymerizable group and a structural unit based on at least one compound.
Item 14.
Item 14. The coating composition according to any one of Items 10 to 13, wherein when the composition is applied to a substrate, the static contact angle with respect to water on the coating surface is 150 ° or more, and n-hexadecane is used. A coating composition having a static contact angle of 90 ° or more.
Item 15.
Item 15. The coating composition according to any one of Items 10 to 14, wherein a falling angle with respect to water of an application surface when the composition is applied to a substrate is 10 ° or less.

According to the present invention, a coating film having excellent liquid repellency and wear resistance can be provided. Conventional super-liquid-repellent coatings could not be applied to the surface of articles that require wear resistance, but the scope of application can be extended to articles that require wear resistance by using the present invention.

18 is a graph showing the results of rubbing tests of Test Examples 13 to 17.

In the present invention, the “fluoroalkyl group” means an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and includes a fluoropolyether group unless otherwise specifically used.
1. Coating 1.1: Fine Particles Having Polymerizable Groups on the Surface The fine particles having polymerizable groups on the surface used in the present invention are not particularly limited, and examples thereof include silica fine particles, metal oxide fine particles, carbon black, fullerene, and carbon nanotubes. It is desirable that the polymerizable group be present on the surface of the fine particles.

The size of the fine particles is preferably 0.5 nm to 1000 nm, preferably 1 nm to 100 nm, more preferably 5 nm to 70 nm, as the average particle size at the time of primary dispersion defined by DIN 53206. When the particle diameter is within this range, it is easy to obtain the surface roughness necessary for imparting a super-repellent state. It is expected that the ratio of the roughness of the surface constructed from fine particles having an average particle diameter of 0.5 nm or more to the roughness of the smooth plane will be high. In addition, it is highly possible that the roughness of the surface constructed from an average particle diameter of 1000 nm or less does not become a large unevenness that should be called a surface shape as compared with the diameter of a droplet.

Measurement of the average particle size during primary dispersion of the fine particles can be performed using a transmission electron microscope or a scanning electron microscope. More specifically, the average particle diameter is obtained by photographing with a transmission electron microscope or a scanning electron microscope, measuring the diameter of 200 or more particles on the photograph, and calculating the arithmetic average value thereof. Can do. In addition to the average particle size at the time of primary dispersion of the particles to be used, higher-order aggregation states such as secondary aggregation defined by DIN 53206 may be imparted to the liquid repellency. If this higher-order aggregate is present at a certain ratio, it is easier to construct a pseudo-fractal state, so that the surface roughness becomes more rough, thereby improving the liquid repellency. In the dry powder state, the ratio of the higher-order aggregation state appears in the apparent density. Here, the apparent density is obtained by measuring the volume when 0.2 g of powder is put into a 10 ml measuring cylinder. The apparent density is preferably 0.01 ~ 0.5g / cm ^3, more preferably 0.015 ~ 0.3g / cm ^3, even more preferably at 0.02 ~ 0.05g / cm ³ .

The polymerizable group is not particularly limited, and examples thereof include a radical polymerizable group, a cationic polymerizable group, and an anion polymerizable group. In particular, a radical polymerizable group is preferable in terms of versatility and reactivity.

The radical polymerizable group is not particularly limited, and examples thereof include a vinyl group, a (meth) acryl group, a styryl group, and a maleimide group.

As the radical polymerizable group, a (meth) acryl group and a styryl group are preferable in view of versatility and reactivity.

The manner in which the polymerizable group is bonded to the surface of the fine particle is not particularly limited, and examples thereof include a covalent bond, a coordinate bond, an ionic bond, a hydrogen bond, and a bond by van der Waals force.

The method for producing the fine particles having a polymerizable group is not particularly limited, but it is generally obtained by reacting a compound having a polymerizable group and a site reactive with the particle surface with the fine particles. The site showing reactivity with the particle surface can be appropriately selected depending on the state of the particle surface. In general, the reaction is performed using silane coupling. In addition, when a compound is chemically bonded to the fine particles, it is difficult to select the number of compounds to be reacted. Generally, after the reaction, a plurality of compounds exist in a chemically bonded state on the surface of the fine particles.

The coating film of the present invention can be obtained by performing a polymerization reaction described later using at least one of the above fine particles.

At least one kind of the fine particles may have a fluoroalkyl group. In this case, the coating film of the present invention exhibits excellent liquid repellency by having a structural unit based on such fine particles. can do. In the above, as the fluoroalkyl group, a perfluoroalkyl group is preferable from the viewpoint of liquid repellency.

The fine particles can be used singly or in combination of two or more.
1.2 Compound having a polymerizable group The compound having a polymerizable group used in the present invention may be one kind or two or more kinds, but at least one kind has two or more polymerizable groups in the molecule. A compound.
1.2.1 Compound having two or more polymerizable groups in the molecule The compound having two or more polymerizable groups in the molecule (also referred to as a polyfunctional polymerizable compound) is not particularly limited, but wear resistance From the viewpoint of safety, those having 2 to 8 polymerizable groups in the molecule are preferable, those having 3 to 6 polymerizable groups are more preferable, and those having 3 polymerizable groups are more preferable. Further preferred.

Although it does not specifically limit as a polyfunctional radically polymerizable compound, What is represented by following General formula (2) is also mentioned.

(In the formula, X represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX ¹ X ² group (where 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 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a straight chain having 1 to 20 carbon atoms Or 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 (provided that , R ¹ is an alkyl group having 1 to 4 carbon atoms, and the right end of the formula is bonded to Z ¹ and the left end 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 Z ¹ and the left end is bonded to O.) or — (CH ₂ ) _n SO ₂ — group (n is 1 to 10, the right end of the formula is bonded to Z ¹ and the left end is bonded to O. Z ¹ is a residue obtained by removing m + 1 hydrogen atoms from a hydrocarbon optionally having an oxygen atom and / or a fluorine atom, or a carbon atom or an oxygen atom, and Z ² is A residue obtained by removing n hydrogen atoms from a hydrocarbon optionally having an oxygen atom and / or a fluorine atom, or a carbon atom or an oxygen atom, m is an integer of 1 to 3, and n is 1 to (It is an integer of 4 and the number obtained by multiplying m and n is 2 or more.)
In the general formula (2), the hydrocarbon may be cyclic or non-cyclic, and may be either linear or branched. Although not particularly limited, in the general formula (2), the hydrocarbon preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 2 carbon atoms.

Specific examples of the acrylate ester represented by the general formula (2) are as follows.

The polyfunctional polymerizable compound may have a fluoroalkyl group. It is not particularly limited, specific examples, in the general formula (2), and the like that Z ¹ and / or Z ² is a fluoroalkyl group.

Without being bound by theory, the coating of the present invention has structural features that can be obtained by copolymerization using fine particles having the polymerizable group on the surface and the polyfunctional polymerizable compound, This seems to have led to the acquisition of excellent wear resistance.

The ratio of the polyfunctional polymerizable compound to the fine particles having a polymerizable group on the surface is not particularly limited, and can be appropriately adjusted within a range where the effects of the present invention are not impaired. Although not particularly limited, for example, it can be 5 to 1000 parts by weight, preferably 10 to 750 parts by weight, and more preferably 20 to 500 parts by weight with respect to 100 parts by weight of the fine particles.

The said polyfunctional polymerizable compound can be used individually by 1 type or in mixture of 2 or more types.
1.2.2 Compound having one polymerizable group in the molecule In order to obtain the coating film of the present invention, in addition to the fine particles having a polymerizable group on the surface and the polyfunctional polymerizable compound, one polymerizable group in the molecule. You may further copolymerize at least 1 type compound (it is also called a monofunctional polymerizable compound) which has these.

Although it does not specifically limit as a monofunctional radically polymerizable compound, For example, what is represented by following General formula (6) is mentioned.

(In the formula, X represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX ¹ X ² group (where 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 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a straight chain having 1 to 20 carbon atoms Or 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 (provided that , R ¹ is an alkyl group having 1 to 4 carbon atoms, and the right end of the formula is bonded to R 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, the right end of the formula is in the R . The left end is attached respectively to O), or _{_{_{- (CH 2) n SO 2}}} - group (n is 1 to 10, the right end of the formula is R, the left end is attached respectively to O). And R is a hydrocarbon group optionally having an oxygen atom and / or a fluorine atom.)
In the general formula (6), the hydrocarbon group may be cyclic or non-cyclic, and may be linear or branched. Although not particularly limited, in the general formula (4), the hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 2 carbon atoms.

The monofunctional radically polymerizable compound may have a fluoroalkyl group. For example, the monofunctional radically polymerizable compound is not particularly limited, but may have a fluoroalkyl group ester-bonded directly or via a divalent organic group to the carboxyl group and may have a substituent at the α-position. Fluorine-containing acrylic acid ester etc. are mentioned. More specifically, it is not particularly limited, but examples thereof include those represented by the following general formula (1).

(In the formula, X represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX ¹ X ² group (where 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 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a straight chain having 1 to 20 carbon atoms Or 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 (provided that , R ¹ is an alkyl group having 1 to 4 carbon atoms, and the right end of the formula is bonded to Rf 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, the right end of the formula is R In, attached respectively left end to O), or _{_{-. (CH 2) n SO}} 2 - group (n is 1 to 10, the right end of the formula is Rf, the left end is attached respectively to the O Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms or a fluoropolyether group having a molecular weight of 400 to 5,000.)
In the general formula (1), the hydrocarbon group may be cyclic or non-cyclic, and may be either linear or branched. Although not particularly limited, in the general formula (1), the hydrocarbon group preferably has 1 to 6 carbon atoms, and more preferably has 1 to 2 carbon atoms.

Specific examples of the acrylic acid ester represented by the above general formula (1) are as follows.

Further, when Rf is a fluoropolyether group, the molecular weight of the fluoropolyether group is 400 to 10,000, and a perfluoropolyether group is preferred. Particularly preferred are perfluoropolyether groups having 6 to 8 carbon atoms. Specific examples are given below.

The above-mentioned monofunctional polymerizable compounds can be used singly or in combination of two or more.

The ratio of the monofunctional polymerizable compound to the polyfunctional polymerizable compound is not particularly limited and can be appropriately adjusted within a range in which the effects of the present invention are not impaired. Although not particularly limited, for example, the amount can be 5 to 1,000 parts by weight, preferably 10 to 500 parts by weight, more preferably 20 to 300 parts by weight with respect to 100 parts by weight of the polyfunctional polymerizable compound.

A preferred embodiment of a combination of fine particles having a polymerizable group on the surface, a polyfunctional polymerizable compound, and a monofunctional polymerizable compound is not particularly limited, but fine particles having a polymerizable group on the surface and no fluoroalkyl group. A combination of a polyfunctional polymerizable compound and a monofunctional polymerizable compound having a fluoroalkyl group may be mentioned. By using this combination, it becomes easy to obtain a super-repellent coating film that achieves both super-liquid repellency and wear resistance.

The film of the present invention exhibits super liquid repellency. Although not particularly limited, in a preferred embodiment, the static contact angle of water during film formation is 150 ° or more, and the static contact angle of n-hexadecane (hereinafter sometimes referred to as n-HD) is 90 ° or more. It is. In the present invention, the static contact angle of water and the static contact angle of n-HD are measured as follows. The apparatus uses a contact angle meter Drop Master 701 to make water and n-HD both have a droplet volume of 2 μl and measure 5 points per sample. When the static contact angle becomes 150 ° or more, depending on the conditions, the liquid cannot stand on the surface of the base material. Therefore, in such a case, the static contact angle is measured using the needle of the syringe as a support, and the value obtained at that time is taken as the static contact angle.

The water falling angle of the coating of the present invention is preferably 0 ° to 10 °, more preferably 0 ° to 5 °, and still more preferably 0 ° to 3 °. The falling angle of water shall be measured as follows. The apparatus uses a contact angle meter Drop Master 701 to make a water droplet volume of 20 μl and measure three points for one sample. In addition, when the drop angle is 0 °, a 20 μl droplet from the needle cannot be allowed to stand on a horizontal substrate, or can be left still, but before measurement or between 0 ° and 1 ° during measurement. It means that the water falls.

The coating film of the present invention preferably satisfies the above-mentioned range of the falling angle of water, and the falling angle of n-HD is preferably 0 ° to 30 °, more preferably 0 ° to 15 °. More preferably, it is 0 ° to 5 °. The apparatus uses a contact angle meter Drop Master 701 to set the HD droplet volume to 20 μl and measure three points for one sample. Further, the fall angle of 0 ° here means that the HD falls before measurement or between 0 ° and 1 ° during measurement.

In addition, liquid repellency may be improved by performing a heat treatment after the coating is produced. The temperature of the heat treatment at that time is not particularly limited, but is preferably 30 ° C. to 200 ° C., more preferably 40 ° C. to 150 ° C., and further preferably 60 ° C. to 120 ° C. Also, the heat treatment time is not particularly limited, but is preferably 1 minute to 12 hours, more preferably 2 minutes to 6 hours, and further preferably 3 minutes to 2 hours.

2. Method for Producing Film The film (coat) of the present invention comprises the fine particles (1) and the compound (2):
It can be obtained by (i) simultaneously polymerizing on a workpiece or (ii) sequentially polymerizing in at least two stages.

Although not particularly limited, in the above (ii), it is preferable to polymerize in two stages.

The polymerization reaction can be performed in the presence or absence of a polymerization initiator. Although not particularly limited, for example, polymerization can be performed using electromagnetic waves in a wavelength region of 350 nm or less, that is, ultraviolet rays, electron beams, X-rays, γ rays, and the like.

Although not particularly limited, in the above (ii), it is preferable to polymerize at least one kind of the compound (2) having two or more polymerizable groups in the molecule on the object to be treated after the second stage. More preferably, at least one of the compounds (2) having two or more polymerizable groups in the molecule is preferably polymerized on the object to be treated in the final stage. Specifically, the fine particles (1) or a copolymer obtained by polymerizing the fine particles (1) and the compound (2) having one polymerizable group in the molecule in advance, have two or more molecules in the molecule. The compound (2) having a polymerizable group can be polymerized.

Regarding (i) above, it is preferable to use a solvent in which the fine particles (1) and the compound (2) and the polymerization initiator are uniformly dispersed or dissolved. More specifically, the fine particles (1), the compound (2) having two or more polymerizable groups in the molecule, and the compound (2) having one polymerizable group in the molecule are uniformly used in a solvent. Dispersing the fine particles (1) and a copolymer of the compound (2) having one polymerizable group in the molecule, and dissolving the copolymer and two or more polymerizable groups in the molecule An embodiment in which the compound (2) having a salt is uniformly dissolved in a solvent is exemplified. Such a solvent is not particularly limited, and examples thereof include isopropyl alcohol (hereinafter sometimes referred to as IPA). The surface to be treated can be coated by forming a film on the surface to be treated by this polymerization method.

The polymerization initiator used on the surface to be treated is not particularly limited. For example, radicals and cations are only obtained by irradiation with electromagnetic waves in a wavelength region of 350 nm or less, that is, ultraviolet rays, electron beams, X rays, γ rays, and the like. That act as a catalyst for initiating the curing (crosslinking reaction) of the carbon-carbon double bond of the fluoropolymer, and usually generating radicals and cations with ultraviolet light, especially generating radicals It is preferable to use one. For example, the following can be illustrated. In addition, it is possible to polymerize on an object to be treated without using an initiator, and the polymerization method at that time is not particularly limited. For example, a method of polymerizing using an electron beam, γ-ray, etc. Can be mentioned.

Acetophenone series: acetophenone, chloroacetophenone, diethoxyacetophenone, hydroxyacetophenone, α-aminoacetophenone, hydroxypropiophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinepropan-1-one, etc.

Benzoin series: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, and the like.

Benzophenone series: benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxy-propylbenzophenone, acrylated benzophenone, Michler's ketone, etc.

Thioxanthones: thioxanthone, chlorothioxanthone, methylxanthone, diethylthioxanthone, dimethylthioxanthone and the like.

Other: benzyl, α-acyl oxime ester, acyl phosphine oxide, glyoxy ester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, anthraquinone, etc.

In addition to the above-described initiator that generates radicals by light energy, an initiator that generates radicals by thermal energy may be used. The amount of the polymerization initiator that generates radicals by the above-mentioned light energy is not particularly limited, but it is usually preferably about 0.01 to 20 parts by weight with respect to 100 parts by weight of the monomer component. More preferably, it is about 1 to 10 parts by weight.

As the initiator for generating radicals by the thermal energy described above, any known polymerization initiator for thermal radical polymerization reaction can be used without particular limitation. For example, azo initiators such as azobisisobutyronitrile, methyl azoisobutyrate, azobisdimethylvaleronitrile; benzoyl peroxide, potassium persulfate, ammonium persulfate, benzophenone derivatives, phosphine oxide derivatives, benzoketone derivatives, phenylthioether derivatives, Azide derivatives, diazo derivatives, disulfide derivatives and the like can be used. These polymerization initiators can be used singly or in combination of two or more.

With regard to (ii), it can be appropriately set depending on the order of polymerization, but the case where the compound (2) having two or more polymerizable groups in the molecule is polymerized in the second and subsequent stages is exemplified below. explain. When the fine particles (1) and the compound (2) are polymerized in advance, it is preferable to perform solution polymerization using the above-described thermally initiated radical initiator in a fluorinated solvent. According to this method, since the formed fluoropolymer has good solubility in a fluorine-based solvent, a precipitate is hardly formed and the radical polymerization reaction can proceed smoothly.

The amount of the polymerization initiator used is not particularly limited, but usually it is preferably about 0.01 to 10 parts by weight and preferably about 3 to 7 parts by weight with respect to 100 parts by weight of the monomer component. More preferred.

The concentration of the fluorine-containing fine particles and / or fluorine-containing compound in the fluorine-based solvent is not particularly limited, but is usually preferably about 1 to 15% by weight, more preferably about 2 to 10% by weight. preferable.

The polymerization conditions such as the polymerization temperature and the polymerization time may be appropriately adjusted according to the type of monomer component, the amount used thereof, the type of polymerization initiator, the amount used, etc., but usually about 50 to 100 ° C. The polymerization reaction may be performed at a temperature for 4 to 10 hours.

Then, when performing the polymerization reaction using the compound (2) having two or more polymerizable groups in the molecule, the above-mentioned photoradical initiator can be used to uniformly dissolve the material in the system. A single solvent or a mixed solvent system may be used. For example, fluorinated solvent / IPA (50/50 (w / w)) mixed solution, fluorinated solvent / IPA (75/25 (w / w)) mixed solution, fluorinated solvent / IPA (95/5 (w / w)) w)) mixed solutions and the like.

The fluorine-based solvent may be any of hydrocarbon compounds, alcohols, ethers, etc., as long as it has a fluorine atom in the molecule and the formed fluorine-containing polymer has good solubility. Any of aliphatic and aromatic may be used. For example, chlorinated fluorinated hydrocarbons (particularly, having 2 to 5 carbon atoms), particularly HCFC225 (dichloropentafluoropropane) (AK-225 (manufactured by Asahi Glass Co.)), HCFC141b (dichlorofluoroethane), CFC316 (2, 2, 3,3-tetrachlorohexafluorobutane), Vertrel XF (chemical formula C ₅ H ₂ F ₁₀ ) (manufactured by DuPont), AC-6000 (chemical name tridecafluorooctane) (manufactured by Asahi Glass), hexafluoro-m- Xylene, pentafluoropropanol, fluorine ether, or the like can be used.

In the present invention, it is particularly preferable to use hydrofluoroether as the fluorinated solvent. Hydrofluoroether is a solvent having low chemical erosion with respect to various materials, and is a particularly suitable solvent as a solvent for forming a coating on an electronic component that is strongly required to eliminate the adverse effects of the solvent. Further, hydrofluoroether is an ideal solvent having excellent performance such as quick drying, low environmental pollution, nonflammability, and low toxicity.

In the present invention, as the hydrofluoroether, the following general formula (7),

(In the formula, n is a number from 1 to 6, and x is a number from 1 to 6.)
The compound shown by these is preferable. Examples of such a hydrofluoroether include Novec (trademark) 7100 (chemical formula C ₄ F ₉ OCH ₃ ) (boiling point 61 ° C.) manufactured by Sumitomo 3M Limited, and Novec (trademark) 7200 (chemical formula expressed by Sumitomo 3M Limited). C ₄ F ₉ OC ₂ H ₅ ) (boiling point 76 ° C.), Novec ™ 7300 (chemical formula C ₆ F ₁₃ OCH ₃ ) (boiling point 98 ° C.) manufactured by Sumitomo 3M Limited can be used.

3. Coating composition The coating composition of the present invention is a composition used for forming the above-described coating film of the present invention on a surface to be treated. The surface to be treated can be coated by forming the film of the present invention on the surface to be treated using the coating composition of the present invention.

In the coating composition of the present invention, the solid component in the composition is preferably about 0.01 to 10% by weight, more preferably about 1 to 6% by weight, Of these, the concentration of the fluorine compound is preferably about 0.01 to 5% by weight, more preferably about 0.5 to 3% by weight as the solid content concentration. The concentration of the polyfunctional polymerizable group is preferably about 0.01 to 5% by weight, preferably about 0.5 to 3% by weight as the solid concentration, and the concentration of the fine particles is the solid concentration. Is preferably about 0.01 to 5% by weight, more preferably about 0.5 to 3% by weight.
In a preferred embodiment of the coating composition of the present invention, the surface of the coating obtained thereby has a static contact angle to water of 150 ° or more, and the n-HD static contact angle is 90 ° or more, more preferably, Is a coating composition having a static contact angle with water of 150 ° or more, an n-HD static contact angle of 90 ° or more, and a sliding angle with respect to water of 10 ° or less. A more preferable embodiment of the coating composition of the present invention is that the surface of the coating obtained thereby has a static contact angle with water of 150 ° or more, the static contact angle of n-HD is 90 ° or more, and water. The sliding angle with respect to n-HD is 10 ° or less, the sliding angle with respect to n-HD is 30 ° or less, more preferably the static contact angle with respect to water of the coating surface obtained is 150 ° or more, and the static contact angle of n-HD Is 120 ° or more, the falling angle with respect to water is 5 ° or less, the falling angle with respect to n-HD is 20 ° or less, and more preferably, the static contact angle with respect to water on the coating surface obtained thereby is 150 °. As described above, the coating composition has a static contact angle of n-HD of 150 ° or more, a sliding angle with respect to water of 3 ° or less, and a sliding angle with respect to n-HD of 5 ° or less.

The application target of the coating composition of the present invention is not particularly limited, and various durability such as solvent immersion, immersion in water, wiping, abrasion, high temperature and high humidity, etc., on various substrates such as plastic, metal, ceramics, etc. It is possible to form a film having good waterproof and moistureproof performance.

The treatment method using the coating composition of the present invention is not particularly limited, and the coating composition of the present invention may be brought into contact with the object to be treated, and then a polymerization reaction may be performed by an appropriate method. Although it does not specifically limit, The method etc. which make the composition for coating of this invention contact a process target object by methods, such as brush coating, a spray, a spin coat, a dispenser, etc. are applicable.

In order to form a film having higher durability, in order to remove contaminants on the surface of the substrate prior to the treatment with the coating composition of the present invention, the substrate is acetone, isopropyl alcohol (IPA), It is preferable to dry after washing with a solvent such as hydrofluoroether or a mixed solvent thereof. Furthermore, in addition to the above cleaning, if the substrate is made of silicon or metal, chemical cleaning such as acid (hydrochloric acid, nitric acid, hydrogen fluoride, etc.), UV ozone, sandblasting, glass beads, plasma, etc. Removing the oxide film formed on the surface by physical cleaning is also useful for improving durability. More preferably, the wear resistance is further improved by surface-modifying a compound having a site that is chemically adsorbed on the washed substrate and can chemically react with the coating composition in the structure.

The use of the coating of the present invention is not particularly limited. For example, water / oil repellent, protein / cell / microbe non-adhesive agent, frost-delay / anti-icing / snow-proofing agent, fingerprint anti-adhesive agent, fingerprint non-identification Agents, low friction agents and lubricants. Further, the treatment substrate is not particularly limited as long as it can be applied, and various primer treatments may be used as necessary to enable application.

The substrate usable in the present invention is, for example, glass, resin (natural or synthetic resin, for example, a general plastic material, plate, film, or other forms), metal (aluminum, copper It may be a single metal such as iron or a composite such as an alloy), ceramics, semiconductor (silicon, germanium, etc.), fiber (woven fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, etc., building member, etc. Can be composed of any suitable material.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited by this Example.
Example 1 Preparation of [Rf (C2) methacrylate / fine particle] copolymer and TMPTA coating [ Preparation of [Rf (C2) methacrylate / fine particle] copolymer solution]
In a branched test tube, C ₂ F ₅ CH ₂ OCOC (CH ₃ ) = CH ₂ [hereinafter sometimes abbreviated as Rf (C2) methacrylate] 5.00 g, average having radical reactive groups on the surface First, 2.52 g of silica fine particles having a primary particle size of 12 nm and 140 g of perfluorobutyl ethyl ether were charged, nitrogen purged, and heated to 70 ° C. To this, 0.253 g of AIBN was added and reacted for 6 hours. After polymerization, the solid content concentration was calculated.
(Preparation of photosensitive solution)
In a vial, 0.204 g of trimethylolpropane triacrylate (hereinafter sometimes abbreviated as TMPTA), 0.0211 g of alkylphenone photopolymerization initiator, 0.999 g of IPA, and 8.81 g of perfluorobutyl ethyl ether. Then, after irradiating ultrasonic waves with an ultrasonic cleaner, 9.98 g of a 2.01% solid solution diluted with perfluorobutyl ethyl ether was added from the copolymer solution, and the ultrasonic cleaner Was irradiated with ultrasonic waves to obtain a photosensitive solution.
(Preparation of coating)
The photosensitive solution was treated on an acrylic substrate by a spray method. Then, the treated acrylic base material is put into a metal box that can flow gas, and the inside of the box is flown with nitrogen at a flow rate of 10 L / min for 3 minutes, and then the whole box is put into a belt conveyor type UV irradiation device. UV of 1,800 mJ / cm ² was irradiated.
Example 2 Preparation of [Rf (C4) Methacrylate / Fine Particles] Copolymer, TMPTA Coating Instead of Rf (C2) methacrylate, C ₄ F ₉ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ [hereinafter Rf (C4 ) May be abbreviated as methacrylate], and a thin film was prepared by the method described in Example 1.
Example 3 Preparation of [Rf (C6) Methacrylate / Fine Particles] Copolymer, TMPTA Coating Instead of Rf (C2) methacrylate, C ₆ F ₁₃ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ [hereinafter, Rf (C6 ) May be abbreviated as methacrylate], and a thin film was prepared by the method described in Example 1 except that silica having an average primary particle size of 7 nm was used instead of silica having an average primary particle size of 12 nm.
Example 4 Preparation of [Rf (C6) methacrylate / fine particle] copolymer and TMPTA coating A thin film was prepared by the method described in Example 1 except that Rf (C6) methacrylate was used instead of Rf (C2) methacrylate. .
Example 5 Preparation of [Rf (C6) Acrylate / Fine Particles] Copolymer, TMPTA Coating Instead of Rf (C2) methacrylate, C ₆ F ₁₃ CH ₂ CH ₂ OCOCH = CH ₂ [hereinafter abbreviated as Rf (C6) acrylate A thin film was prepared by the method described in Example 1 except that the above may be used.
Example 6 Preparation of [Rf (C8) Methacrylate / Fine Particles] Copolymer, TMPTA Coating
Instead of Rf (C2) methacrylate, C ₈ F ₁₇ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ [hereinafter sometimes abbreviated as Rf (C8) methacrylate] A thin film was prepared by the method described in Example 1 except that the substrate spray-treated in (Preparation of thin film) was heat-treated at 110 ° C.
Example 7 Preparation of [Rf (C6) methacrylate / fine particle] copolymer, TMPTA coating [ Preparation of [Rf (C6) methacrylate / fine particle] copolymer solution]
A branch test tube was charged with 9.9 g of Rf (C6) methacrylate, 4.81 g of silica fine particles having a radical reactive group on the surface and an average primary particle diameter of 12 nm, and 185 g of perfluorobutyl ethyl ether, Nitrogen purged and heated to 70 ° C. AIBN 0.477g was thrown into this and it reacted for 6 hours. After polymerization, the solid content concentration was calculated.
(Preparation of photosensitive solution)
0.805 g of TMPTA, 0.0821 g of alkylphenone photopolymerization initiator, 19.7 g of IPA, and 9.52 g of perfluorobutyl ethyl ether were put into a vial, and ultrasonic waves were irradiated with an ultrasonic cleaner. Thereafter, 9.90 g of the copolymer solution having a solid content of 8.34% was added, and an ultrasonic wave was irradiated with an ultrasonic cleaner to obtain a photosensitive solution.
(Preparation of coating)
In the same manner as in Example 1, the photosensitive solution was treated on an acrylic substrate by a spray method, and a film was formed by UV irradiation.
Example 8 Preparation of [Rf (C6) Methacrylate / Fine Particles] Copolymer and DPEHA Coating Example 7 except that TMPTA in Example 7 was changed to dipentaerythritol hexaacrylate (hereinafter sometimes abbreviated as DPEHA). Same prescription.
Example 9 Preparation of [Rf (C6) methacrylate / fine particle] copolymer, TMPTA coating [ Preparation of [Rf (C6) methacrylate / fine particle] copolymer solution]
It was produced by the same method as in Example 7.
(Preparation of photosensitive solution)
TMPTA 0.801 g, IPA 20.0 g, and perfluorobutyl ethyl ether 10.0 g were put into a vial, irradiated with ultrasonic waves by an ultrasonic cleaner, and then the above-mentioned co-polymer having a solid content of 8.34%. 9.90 g of the polymer solution was added and irradiated with ultrasonic waves with an ultrasonic cleaner to obtain a photosensitive solution.
(Preparation of coating)
The photosensitive solution was treated on an acrylic substrate by a spray method, and then a film was formed by irradiation with an electron beam of 50 kGy in a nitrogen atmosphere.
Comparative Example 1 Preparation of TMPTA coating ( Preparation of photosensitive solution)
A vial was charged with 0.823 g of TMPTA, 0.0408 g of an alkylphenone photopolymerization initiator and 9.51 g of IPA, and irradiated with ultrasonic waves with an ultrasonic cleaner to obtain a photosensitive solution.
(Preparation of coating)
After the acrylic base material is immersed in the above photosensitive solution and dried at 60 ° C., the treated acrylic base material is put into a metal box capable of flowing gas, and the inside of the box for 3 minutes at a flow rate of 10 L / min. Then, the box was put into a belt conveyor type UV irradiation apparatus and irradiated with 1,800 mJ / cm ² of UV.
Comparative Example 2 Preparation of fluorine-containing polyfunctional acrylate coating ( Preparation of photosensitive solution)
The vial was charged with 0.814 g of a fluorine-containing polyfunctional acrylate, 0.0443 g of an alkylphenone-based photopolymerization initiator, and 9.60 g of IPA, and irradiated with ultrasonic waves with an ultrasonic cleaner to obtain a photosensitive solution.
(Preparation of coating)
A film was prepared in the same manner as in Comparative Example 1.
Comparative Example 3 Preparation of microparticles and TMPTA coating TMPTA 0.405 g, alkylphenone photopolymerization initiator 0.0393 g, IPA 0.992 g, perfluorobutyl ethyl ether 19.3 g were put into a vial. After irradiating ultrasonic waves with a washing machine, 0.401 g of silica fine particles having a radical reactive group on the surface and an average primary particle diameter of 12 nm are introduced, and ultrasonic waves are emitted by an ultrasonic washing machine to make the photosensitivity. It was set as the solution.
(Preparation of coating)
A film was prepared in the same manner as in Example 1.
Comparative Example 4 Preparation of Rf (C6) methacrylate and TMPTA coating ( Preparation of photosensitive solution)
TMPTA 0.404 g, Rf (C6) methacrylate 0.413 g, alkylphenone photopolymerization initiator 0.0393 g, IPA 0.992 g, perfluorobutyl ethyl ether 18.8 g were added to the vial. Ultrasonic waves were irradiated with a sonic cleaner to obtain a photosensitive solution.
(Preparation of coating)
A film was prepared in the same manner as in Comparative Example 1.
Comparative Example 5 Preparation of Rf (C6) methacrylate homopolymer coating (polymer preparation)
A branch test tube was charged with 25.0 g of Rf (C6) methacrylate and 75.0 g of perfluorobutyl ethyl ether, and was purged with nitrogen for 10 minutes and heated to 70 ° C. This was charged with 0.136 g of AIBN and reacted for 6 hours. After polymerization, the solid content concentration was calculated.
(Preparation of coating)
The above-mentioned polymerization solution 0.50 g and perfluorobutyl ethyl ether 11.5 g were put into a vial. The acrylic base material was immersed in the solution, and the film was produced by air drying at room temperature for 30 minutes.
Comparative Example 6 Preparation of [Rf (C6) Methacrylate / Fine Particles] Copolymer Thin Film 7.47 g of [Rf (C6) Methacrylate / Fine Particles] copolymer solution and 9.92 g of IPA were put into a screw tube and subjected to ultrasonic waves. Was irradiated to disperse the [Rf (C6) methacrylate / fine particles] copolymer.

Thereafter, a thin film was produced in the same manner as in Example 7.
Test Examples 1 to 13
The test pieces obtained in Examples 1 to 6 and 8 and Comparative Examples 1 to 6 were measured for contact angles with water and n-HD. The contact angle measurement and apparatus were in accordance with the method described in the text. The results are shown in Table 1. A falling angle of 0 ° means that a liquid of 20 μl cannot be landed on the base material from the needle, or even if it can land, the liquid falls before the measurement or between 0 ° and 1 ° during measurement. This means that the instrument used this time cannot measure. In the present test example, the falling angles for water in Test Examples 1 to 7 and 13 and the falling angle for n-HD in Test Example 6 correspond thereto. In addition, when the static contact angle with respect to n-HD in Test Example 10 is 0 °, it means that the droplet spreads on the substrate and an accurate value is not obtained in this measurement.

In addition, the drop angle with respect to n-HD in Test Examples 1 and 2 is accurate because the liquid is falling without being able to maintain the advancing contact angle and the receding contact angle, or residual droplets remain on the substrate after the falling. The value of the pseudo falling angle is shown instead of the falling angle. Even when the water falling angle of Test Example 10 was 85 °, which is the maximum falling angle of the apparatus, the droplets did not fall. In the test examples 8 and 10, the drop angle of the n-HD in Test Example 8 was wet and spread while the droplets tumbled, and Test Example 10 could not be measured due to the chemical property that the static contact angle was approximately 0 °.

Test Examples 14-17
For each of the test pieces obtained in Examples 7 to 9 and Comparative Example 6, the water contact angle was measured to determine the initial contact angle, and then a rubbing tester (rubbing tester “Irimoto Seisakusho 151E 3 series made by Imoto Seisakusho) Spec. ”) (Paper contact area: 1 cm ² ) with a paper waste cloth, wipe the surface a predetermined number of times with a load of 100 g, measure the contact angle with water, and wear resistance against wiping Sex was evaluated. The wear resistance performance here is the number of wears that can maintain a super water-repellent state (the average value of the static contact angle of five times is 150 ° or more, or 150 ° or more when the average deviation is 140 ° or more and the standard deviation is combined). Defined. FIG. 1 shows the result of the rubbing test. The bar graph in the figure shows the average value of the number of wears that can maintain a super water-repellent state, and the samples evaluated multiple times show the lowest and highest values with the upper and lower bars.

As a result, it was confirmed that the wear resistance of Examples 7 to 9 was dramatically improved as compared with Comparative Example 6.

Claims

(1) at least one kind of fine particles having a polymerizable group; and (2) a film containing a polymer each having a polymerizable group and a structural unit based on at least one compound,
At least one of the fine particles (1) and / or at least one of the compounds (2) has a fluoroalkyl group, and at least one of the compounds (2) has two or more polymerizations in the molecule. A film, which is a compound having a functional group.
The polymer contains the fine particles (1) and the compound (2).
It is a polymer that can be obtained by polymerizing at the same time or sequentially polymerizing in at least two stages.
The coating according to claim 1.
The said polymer is a polymer which can be obtained by polymerizing at least 1 type of the said compound (2) which has a 2 or more polymeric group in a molecule | numerator after a 2nd step. Coating.
The film according to any one of claims 1 to 3, wherein the polymerizable groups are the same or different and are a vinyl group, a (meth) acryl group, a styryl group, or a maleimide group.
At least one of the compounds (2) is represented by the following general formula (1):

(In the formula, X represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX 1 X 2 group (where 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 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a straight chain having 1 to 20 carbon atoms Or 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 (provided that , R 1 is an alkyl group having 1 to 4 carbon atoms, and the right end of the formula is bonded to Rf 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, the right end of the formula is R In, attached respectively left end to O), or -. (CH 2) n SO 2 - group (n is 1 to 10, the right end of the formula is Rf, the left end is attached respectively to the O And Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, or a fluoropolyether group having a molecular weight of 400 to 5,000). The coating according to any one of 1 to 4.
The compound (2) having two or more polymerizable groups in the molecule is represented by the following general formula (2):

(In the formula, X represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX 1 X 2 group (where 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 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a straight chain having 1 to 20 carbon atoms Or 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 (provided that , R 1 is an alkyl group having 1 to 4 carbon atoms, and the right end of the formula is bonded to Z 1 and the left end 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 Z 1 and the left end is bonded to O.) or — (CH 2 ) n SO 2 — group (n is 1 to 10, the right end of the formula is bonded to Z 1 and the left end is bonded to O. Z 1 is a residue obtained by removing m + 1 hydrogen atoms from a hydrocarbon optionally having an oxygen atom and / or a fluorine atom, or a carbon atom or an oxygen atom, and Z 2 is A residue obtained by removing n hydrogen atoms from a hydrocarbon optionally having an oxygen atom and / or a fluorine atom, or a carbon atom or an oxygen atom, m is an integer of 1 to 3, and n is 1 to The film according to any one of claims 1 to 5, which is an integer of 4 and a number obtained by multiplying m and n is 2 or more.
The coating film according to any one of claims 1 to 6, wherein a static contact angle of water during film formation is 150 ° or more, and a static contact angle of n-hexadecane is 90 ° or more.
The coating film according to any one of claims 1 to 7, wherein a falling angle of water during film formation is 10 ° or less.
A coating method comprising a step of bringing a workpiece into contact with the coating film according to any one of claims 1 to 8.
A composition containing the fine particles (1) used for coating with the film according to any one of claims 1 to 8.
A composition containing the compound (2), which is used for coating with the film according to any one of claims 1 to 8.
A coating composition comprising (A) at least one fine particle having a polymerizable group on the surface; and (B) at least one compound having two or more polymerizable groups in the molecule.
A coating composition comprising (1) at least one fine particle having a polymerizable group on the surface; and (2) a polymer having a polymerizable group and a structural unit based on at least one compound.
The coating composition according to any one of claims 10 to 13, wherein when the composition is applied to a substrate, the static contact angle with respect to water of the coated surface is 150 ° or more, and n-hexadecane A coating composition having a static contact angle of 90 ° or more.
The coating composition according to any one of claims 10 to 14, wherein a falling angle with respect to water of an application surface when the composition is applied to a substrate is 10 ° or less. .