TW202100585A - Coating agent and article treated with said coating agent - Google Patents

Abstract

Provided is a technique for imparting excellent water repellency and oil repellency and for imparting excellent slip properties. A coating agent according to the present invention includes a copolymer formed by polymerizing constituent monomers comprising a (meth)acrylate compound (A) having a fluoroalkyl group having 1-6 carbon atoms, a (meth)acrylate compound (B1) having an aromatic ring, and an alicyclic (meth)acrylate compound (B2), the sum of the (meth)acrylate compound (A), the (meth)acrylate compound (B1) having an aromatic ring, and the alicyclic (meth)acrylate compound (B2) accounting for 90 mass% or more of the total amount of the constituent monomers.

Description

Coating agent and articles treated with coating agent

The present invention relates to a coating agent and articles.

Conventionally, as a coating agent that imparts water repellency and oil repellency by coating on the surface of fiber products, leather products, etc., coatings containing fluoropolymers having a fluoroalkyl group with a carbon number of 8 or more are known. Agent. However, when a fluorine-based polymer having a fluoroalkyl group having a carbon number of 8 or more is decomposed, perfluorooctanoic acid, which may be accumulated in a living body, may be produced. Therefore, it is desired to develop alternatives to fluorine-based polymers having fluoroalkyl groups with 8 or more carbon atoms.

Patent Document 1 describes a technology regarding an alternative to a fluoropolymer having a fluoroalkyl group with 8 or more carbon atoms. Specifically, Patent Document 1 describes a coating agent comprising (i) a monomer having a perfluoroalkyl group having a carbon number of 6 or less, and (ii) cyclohexyl (meth)acrylate and ( A polymer obtained by polymerizing at least one of isobornyl meth)acrylate. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2011-99077

[The problem to be solved by the invention] Indeed, the coating agent described in Patent Document 1 can impart water repellency and oil repellency by coating it on the surface of a fiber product or leather product. However, the inventors of the present invention found that the coating agent described in Patent Document 1 cannot provide slippage properties, and therefore there is a problem that it is difficult to remove the droplets when they adhere to the portion coated with the coating agent. Therefore, it is desired to develop a technology related to a coating agent that imparts excellent water repellency and oil repellency while imparting excellent slippage properties. [Means to solve the problem]

The present invention was made to solve the above-mentioned problems, and it can be realized as follows.

(1) According to one aspect of the present invention, a coating agent is provided. The coating agent includes a copolymer formed by polymerizing constituent monomers, and the constituent monomers include: (Meth)acrylate compound (A) having a fluoroalkyl group having 1 to 6 carbon atoms; (Meth)acrylate compound (B1) having an aromatic ring; and Alicyclic (meth)acrylate compound (B2), in the coating agent, The total compounding amount of the (meth)acrylate compound (A), the (meth)acrylate compound having an aromatic ring (B1), and the alicyclic (meth)acrylate compound (B2) It is 90% by mass or more of the total compounding amount of the constituent monomers.

According to the coating agent of this aspect, excellent water repellency and oil repellency can be imparted, and at the same time, excellent slippage properties can be imparted.

(2) In the coating agent of the above aspect, the alicyclic (meth)acrylate compound (B2) contains isobornyl, isonorbornyl, dicyclopentyl, dicyclopentenyl, adamantane Any one of the functional groups.

According to the coating agent of this aspect, excellent water repellency and oil repellency can be imparted, and at the same time, more excellent slippage properties can be imparted.

(3) In the above-mentioned coating agent, the alicyclic (meth)acrylate compound (B2) may contain an isobornyl group.

According to the coating agent of this aspect, excellent water repellency and oil repellency can be imparted, and at the same time, more excellent slippage properties can be imparted.

(4) In the coating agent of the above aspect, the (meth)acrylate compound (B1) having an aromatic ring may contain a benzyl group.

According to the coating agent of this aspect, excellent water repellency and oil repellency can be imparted, and at the same time, more excellent slippage properties can be imparted.

Furthermore, the present invention can be implemented in various ways. For example, it can be implemented in the form of an article treated with a coating agent.

A. Coating agent The coating agent as an embodiment of the present invention includes a copolymer formed by polymerizing constituent monomers including: (i) (meth)acrylate having a fluoroalkyl group having 1 to 6 carbon atoms Compounds (A) and (ii) (meth)acrylate compounds (B1) having an aromatic ring, (iii) alicyclic (meth)acrylate compounds (B2). In addition, the total compounding amount of the (meth)acrylate compound (A), the (meth)acrylate compound having an aromatic ring (B1), and the alicyclic (meth)acrylate compound (B2) is the constituent monomer More than 90% by mass of the total deployment amount. In addition, in this specification, "(meth)acrylate" means acrylate or methacrylate. In addition, in this specification, "constitutive monomer" means a monomer that constitutes a copolymer.

According to the coating agent of this embodiment, excellent water repellency and oil repellency can be imparted, and at the same time, excellent slippage properties can be imparted. Here, the sliding property indicates whether the droplets of water or the like adhering to the surface of the substrate are easily moved by gravity received by the tilt of the surface of the substrate. In this specification, it appears that the easier the droplet is to move by the gravity received by the inclination of the substrate surface, the better the sliding property. Hereinafter, the constituent monomers related to the coating agent of the present embodiment will be described.

＜(Meth)acrylate compound (A)＞ The (meth)acrylate compound (A) of the present embodiment has a fluoroalkyl group having 1 to 6 carbon atoms. As the (meth)acrylate compound (A), for example, fluoroalkyl (meth)acrylate, fluoroalkylalkyl (meth)acrylate, fluoroalkyl polyoxyfluoride (meth)acrylate can be cited. Alkyl esters and so on. Among these, in order to have excellent water repellency, oil repellency, and slippage properties, fluoroalkyl (meth)acrylate and fluoroalkylalkyl (meth)acrylate are preferred, and fluorine (meth)acrylate is more preferred. Alkyl alkyl ester. In order to achieve excellent water repellency, oil repellency, and slippage properties, the fluoroalkyl group is preferably a fluoroalkyl group having 2 to 6 carbon atoms, more preferably a fluoroalkyl group having 4 to 6 carbon atoms, and still more preferably a fluoroalkyl group having 6 carbon atoms. alkyl. Here, in this specification, "fluorine" includes perfluorinated. The fluoroalkyl group is preferably a perfluoroalkyl group.

Examples of the fluoroalkyl (meth)acrylate include fluoromethyl (meth)acrylate, fluoroethyl (meth)acrylate, fluoropropyl (meth)acrylate, fluorobutyl (meth)acrylate, Fluoropentyl (meth)acrylate, fluorohexyl (meth)acrylate, etc.

Here, the fluoroalkyl (meth)acrylate can be represented by the following general formula (1). Rf-O-X･･･(1) Among them, Rf is a fluoroalkyl group, and X is an acryloyl group or a methacryloyl group.

Examples of the fluoroalkyl alkyl (meth)acrylate include: fluoromethyl methyl (meth)acrylate, fluoromethyl ethyl (meth)acrylate, fluoroethyl methyl (meth)acrylate, Fluoroethyl ethyl (meth)acrylate, fluoropropyl methyl (meth)acrylate, fluoropropyl ethyl (meth)acrylate, fluorobutyl methyl (meth)acrylate, fluorobutyl (meth)acrylate Ethyl ester, fluoropentyl methyl (meth)acrylate, fluoropentyl ethyl (meth)acrylate, fluorohexyl methyl (meth)acrylate, fluorohexyl ethyl (meth)acrylate, etc. In addition, the fluoroalkyl alkyl (meth)acrylate can be represented by the following general formula (2). Rf-Y-O-X ･･･(2) Among them, Rf is a fluoroalkyl group, Y is an alkylene group, and X is an acryloyl group or a methacryloyl group.

Examples of fluoroalkyl polyoxyfluoroethylene (meth)acrylate include: fluoromethyl polyoxyfluoroethylene (meth)acrylate, fluoroethyl polyoxyfluoroethylene (meth)acrylate Base ester, fluoropropyl polyoxyfluoroethylene (meth)acrylate, fluorobutyl polyoxyfluoroethylene (meth)acrylate, fluoropentyl polyoxyfluoroethylene (meth)acrylate , Fluorohexyl polyoxyfluoroethylene (meth)acrylate, fluorohexyl polyoxyfluoroethylene (meth)acrylate, etc. In addition, the fluoroalkyl polyoxyfluoroalkylene (meth)acrylate can be represented by the following general formula (3). Rf-Z-O-X･･･(3) Wherein, Rf is a fluoroalkyl group, Z is a polyoxyfluoroalkylene group, and X is an acryloyl group or a methacryloyl group.

As the (meth)acrylate compound (A), in order to have excellent water repellency, oil repellency, and slippage properties, perfluorohexyl ethyl (meth)acrylate is preferred, and perfluorohexyl ethyl methacrylate is particularly preferred.

＜Aromatic ring (meth)acrylate compound (B1)＞ As a (meth)acrylate compound (B1) which has an aromatic ring in this embodiment, the (meth)acrylate compound which has a benzyl group, the (meth)acrylate compound which has a phenoxy group, etc. are mentioned, for example. As the (meth)acrylate compound (B1) having an aromatic ring, in order to have excellent water repellency, oil repellency, and slippage properties, a (meth)acrylate compound having a benzyl group is preferred.

As the (meth)acrylate compound (B1) having an aromatic ring in the present embodiment, more specifically, for example, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and the like can be cited. As the (meth)acrylate compound (B1) having an aromatic ring, in order to have excellent water repellency, oil repellency, and slippage properties, benzyl (meth)acrylate is preferred, and benzyl methacrylate is particularly preferred.

<Alicyclic (meth)acrylate compound (B2)> Examples of the alicyclic (meth)acrylate compound (B2) in the present embodiment include (meth)acrylate compounds having an isobornyl group, and (meth)acrylate compounds having an isonorbornyl group , (Meth)acrylate compound having dicyclopentyl group, (meth)acrylate compound having dicyclopentenyl group, (meth)acrylate compound having adamantyl group, etc. The alicyclic (meth)acrylate compound (B2) is preferably a (meth)acrylate compound having an isobornyl group in order to have excellent water repellency, oil repellency, and sliding properties.

As the alicyclic (meth)acrylate compound (B2), more specifically, for example, cyclohexyl (meth)acrylate, tertiary butylcyclohexyl (meth)acrylate, (meth) Isobornyl acrylate, 1-adamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, etc. The alicyclic (meth)acrylate compound (B2) is preferably isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, in order to have excellent water repellency, oil repellency, and sliding properties. Dicyclopentyl (meth)acrylate and dicyclopentenyl (meth)acrylate are particularly preferably isobornyl iso(meth)acrylate.

The constituent monomers constituting the copolymer of the present embodiment may include monomers other than the component (A), the component (B1), and the component (B2) as long as it does not violate the purpose of the invention. Likewise, the coating agent of the present embodiment may contain copolymers other than the above-mentioned copolymers within a range that does not violate the purpose of the invention.

In this embodiment, the total blending amount of the (meth)acrylate compound (A), the (meth)acrylate compound (B1) having an aromatic ring, and the alicyclic (meth)acrylate compound (B2) is 90% by mass or more of the total blended amount of constituent monomers. From the viewpoint of excellent sliding properties, the total formulation of the (meth)acrylate compound (A), the (meth)acrylate compound having an aromatic ring (B1), and the alicyclic (meth)acrylate compound (B2) The amount is preferably 92% by mass or more of the total compounding amount of the constituent monomers, more preferably 95% by mass or more. In addition, the total compounding amount of the (meth)acrylate compound (A), the (meth)acrylate compound (B1) having an aromatic ring, and the alicyclic (meth)acrylate compound (B2) is the constituent unit 100% by mass or less of the total blending amount of the body.

In addition, in order to have excellent sliding properties, the blending amount of the (meth)acrylate compound (A) relative to the total blending amount of the constituent monomers is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50 Mass% or more, particularly preferably 55% by mass or more. On the other hand, relative to the total compounding amount of the constituent monomers, the compounding amount of the (meth)acrylate compound (A) is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 87% by mass or less , Particularly preferably 85% by mass or less. Therefore, for example, the compounding amount of the (meth)acrylate compound (A) can be set to 80% by mass relative to the total compounding amount of the constituent monomers.

In addition, the compounding amount of the (meth)acrylate compound (B1) having an aromatic ring relative to the total compounding amount of the constituent monomers is preferably 5 mass% or more, more preferably 10 mass% or more, and still more preferably 13 mass% % Or more, particularly preferably 15% by mass or more. On the other hand, the compounding amount of the (meth)acrylate compound (B1) having an aromatic ring relative to the total compounding amount of the constituent monomers is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less, particularly preferably 25% by mass or less.

In addition, the compounding amount of the alicyclic (meth)acrylate compound (B2) relative to the total compounding amount of the constituent monomers is preferably 5 mass% or more, more preferably 10 mass% or more, and still more preferably 13 mass% Above, 15% by mass or more is particularly preferable. On the other hand, relative to the total compounding amount of the constituent monomers, the compounding amount of the alicyclic (meth)acrylate compound (B2) is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30 Mass% or less, particularly preferably 25 mass% or less.

In addition, in order to have excellent sliding properties, the ratio of the blending amount of the alicyclic (meth)acrylate compound (B2) to the blending amount of the (meth)acrylate compound (B1) having an aromatic ring ((B2)/( B1)) is preferably 10 or less, more preferably 8 or less, still more preferably 6 or less, particularly preferably 4 or less, and still more preferably 1.5 or less. The ratio ((B2)/(B1)) of the compounding amount of the alicyclic (meth)acrylate compound (B2) to the compounding amount of the (meth)acrylate compound (B1) having an aromatic ring is preferably 0.5 Above, more preferably 0.7 or more, and still more preferably 1 or more.

The solvent used in this embodiment is not particularly limited, and for example, it may be an organic solvent. Examples of organic solvents include aromatic solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane; alicyclic hydrocarbon solvents such as cyclohexane and isophorone; acetone and methyl ethyl Ketone solvents such as ketone and cyclohexanone; ester solvents such as ethyl acetate, butyl acetate, and propylene glycol diacetate; ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and dipropylene glycol methyl ether Glycol ether ester solvents such as acetate, diethylene glycol monoethyl acetate, diethylene glycol monoethyl ether acetate, 3-methoxy-3-methylbutyl acetate, etc. ; Ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol dibutyl ether, dimethyl triglycol (Dimethyltriglycol), methyl ethyl Glycol ether solvents such as diethylene glycol and dimethyl propylene diethylene glycol; dimethyl sulfide, dimethyl formamide, N-methyl-2-pyrrolidone, etc., among which, preferred are Acetone, methyl ethyl ketone, ethyl acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, methyl ethyl diethylene glycol, propylene glycol monomethyl ether acetate, 3-Methoxy-3-methylbutyl acetate, dimethyl propylene diethylene glycol.

Next, the manufacturing method of the coating agent of this embodiment is demonstrated. The manufacturing method of a coating agent is not specifically limited. For example, the following method can be cited: by combining a (meth)acrylate compound (A) having a fluoroalkyl group having 1 to 6 carbon atoms, a (meth)acrylate compound having an aromatic ring (B1), and an alicyclic ( The method of heating after mixing a meth)acrylate compound (B2) and a solvent, and obtaining a copolymer.

The polymerization method is not particularly limited, but solution polymerization is preferred. The polymerization temperature is not particularly limited, but it is usually preferably in the range of 40°C to 120°C. The polymerization time is not particularly limited, but it is usually preferably about 4 hours to 15 hours.

A polymerization initiator can be used when performing polymerization. The polymerization initiator is not particularly limited, and examples thereof include benzoyl peroxide, t-butyl peroxypivalate, t-butyl peroxy-2-ethylhexanoate, and tertiary hexyl peroxide. Propyl monocarbonate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate and other peroxides; azobisisobutyronitrile, 2,2'-azobis- Azo compounds such as 2-methylbutyronitrile, etc. The amount of the polymerization initiator used is not particularly limited, but it is generally preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the constituent monomers.

Within the scope of not violating the purpose of the invention, the coating agent of this embodiment may further include, for example, other hydrophilic agents, other oil repellents, water repellents, insect repellents, flame retardants, anti-wrinkle agents, and antistatic agents. , Softeners, preservatives, fragrances, antioxidants, emulsifiers, dispersants, resin additives, etc.

The coating agent of the present embodiment can be used as a coating agent for various articles including glass, plastic, metal, electronic substrates, fiber products, leather, stone, wood, paper, and the like. More specifically, the coating agent of this embodiment can be used for, for example, car bodies and car glass; building walls, building glass, and building roofs; umbrellas; smartphones, personal computers, portable radios, and digital Electronic equipment and electronic parts such as tape recorders and printed circuit boards; motor bearings; bicycle handlebars and bicycle frame and other metal parts; various metals; outdoor tents and tarpaulins; carpets, curtains, bags; leather, stone, wood , Paper, etc. A method of appropriately selecting coating methods such as spray coating, spin coating, and dipping according to the target article, and performing heat treatment to dry or crosslink as necessary can be used.

In addition, the coating agent of the present embodiment can be used for, for example, a chemical-resistant coating agent that protects a substrate from the influence of salt water, electrolyte, corrosive gas, and the like, a stock solution of a waterproof spray, and the like. In addition, by adding the coating agent of this embodiment to the coating material, it can function as a coating agent.

In addition, the coating agent of the present embodiment and various resins may be dissolved and mixed with various solvents to function as a coating agent. The resin is not particularly limited, and examples thereof include acrylic resins, urethane resins, acrylic urethane resins, acrylic silicone resins, epoxy resins, vinyl resins, and silicone resins. Among them, acrylic resin is preferred.

The resin content in the coating agent of this embodiment is not particularly limited. The resin content in the coating agent of the present embodiment is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more. On the other hand, the resin content in the coating agent of the present embodiment is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.

The content of the copolymer in the coating agent of the present embodiment is not particularly limited. The content of the copolymer in the coating agent of this embodiment is preferably 0.01% by mass or more in terms of solid content, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more, and further More preferably, it is 1% by mass or more. On the other hand, the content of the copolymer in the coating agent of the present embodiment is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, particularly preferably 10% by mass or less, and further More preferably, it is 7 mass% or less.

B. Items treated with coating agent As another embodiment of the present invention, an article treated with the coating agent can be cited. The treatment method is not particularly limited, and examples thereof include a coating method, a spray method, and a dipping method. The treatment method can be selected according to each item. The article is not particularly limited, and examples include glass, plastic, metal, electronic substrates, fiber products, leather, stone, wood, paper, and the like. As the article, more specifically, for example: car body, car glass; building wall, building glass, building roof; umbrella; smart phone, personal computer, portable radio, digital Electronic equipment and electronic parts such as tape recorders and printed circuit boards; motor bearings; bicycle handlebars and bicycle frame and other metal parts; various metals; outdoor tents and tarpaulins; carpets, curtains, bags; leather, stone, wood , Paper, etc. Example

Hereinafter, the present invention will be explained more specifically with examples, but the present invention is not limited to the following examples.

(Use raw materials) ·(Meth)acrylate compound (A) having a fluoroalkyl group having 1 to 6 carbon atoms (A-1) Perfluorohexyl ethyl methacrylate (A-2) Perfluorobutyl ethyl methacrylate (A-3) Perfluorohexyl ethyl acrylate

·(Meth)acrylate compound with aromatic ring (B1) (B1) Benzyl methacrylate

·Alicyclic (meth)acrylate compound (B2) (B2-1) Isobornyl acrylate (B2-2) Isobornyl methacrylate (B2-3) Cyclohexyl acrylate

· Constituent monomers other than (A1), (B1), (B2) (C-1) Stearyl methacrylate

·Solvent (D-1) 3-Methoxy-3-methylbutyl acetate ((share) Solfit AC manufactured by Kuraray) (D-2) Ethylene glycol dimethyl ether (DMG) (D-3) Methyl ethyl ketone (MEK) (D-4) Propylene glycol methyl ether acetate (PGMEA) (D-5) Diethylene glycol diethyl ether (DEDG) (D-6) Ethyl acetate

(Example 1) In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux tube, add the compounds (A), (B1), (B2) and 3-methoxy as a solvent in the mass ratio described in Table 1 below. 300 parts of phenyl-3-methylbutyl acetate, and replaced with nitrogen. Then, 3 parts by mass relative to 100 parts by mass of the compound of (A), (B1), and (B2) were added tert-butyl peroxide pivalate (manufactured by NOF Corporation) , Trade name: Perbutyl (registered trademark) PV), after reacting at 65°C for 8 hours, the solvent is distilled off to obtain a copolymer solution (copolymer solid content: 25% by mass).

(Examples and comparative examples other than Example 1) For Examples and Comparative Examples other than Example 1, by the same method as Example 1, the materials and mass ratios described in Tables 1 to 2 described later were used to obtain copolymer solutions.

Using the prepared copolymer solution, the following test 1 and test 2 were performed. Specifically, the following performance evaluations were performed.

(Test 1) Ethyl acetate was added to the obtained copolymer solution and diluted so that the concentration of the copolymer was 1% by mass, thereby obtaining a treatment liquid A. On a glass slide plate (75 mm×25 mm, thickness 1 mm) manufactured by ASONE (stock), the treatment solution A was coated with a bar coating method with a thickness of 10 μm. Then, the treatment liquid was dried in an oven at 105° C. for 10 minutes to prepare a test piece for evaluating water repellency and oil repellency.

In addition, ethyl acetate was added to the obtained copolymer solution and diluted so that the concentration of the copolymer was 25% by mass, thereby obtaining a treatment liquid B. Wipe the glass slide (standard large matte-edge t1.3 glass slide manufactured by Matsunami Glass Industry Co., Ltd.) with 1 ml tissue paper impregnated with 99.5 mass% ethanol (made by NACALAI TESQUE (stock)) (76 mm×52 mm, thickness 1 mm)) After degreasing, the slides were dried at 25°C for 10 minutes. The degreased slide glass was coated by a bar coating method so that the film thickness of the treatment solution B was 10 μm. Then, the treatment liquid B was dried in an oven at 150° C. for 10 minutes to prepare a test piece for evaluating sliding properties.

(Test 2) The obtained copolymer solution, converted to the solid content of the copolymer to 0.0125 parts by mass, and polymethyl methacrylate (manufactured by NACALAI TESQUE (stock), average degree of polymerization approximately 8000) 0.5 mass Part and 10 parts by mass of ethyl acetate were mixed, and then heated and dissolved at 70°C to prepare a coating agent. The coating agent was coated on a glass plate by a bar coating method so that the film thickness of the coating agent was 10 μm. Then, the coating agent was dried in an oven at 80°C for 10 minutes to prepare a test piece for evaluating water repellency, oil repellency, and sliding properties.

(Evaluation method of water repellency and oil repellency) The water repellency and oil repellency were evaluated using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., contact angle meter Drop Master 500). Specifically, the evaluation of water repellency is performed by measuring the contact angle of water on the coating surface, and the evaluation of oil repellency is performed by measuring the contact angle of hexadecane on the coating surface. The water repellency is the contact angle to water, and the oil repellency is the contact angle to hexadecane, and the evaluations were made based on each standard. Furthermore, the droplet volume of water is 2 μL, and the droplet volume of hexadecane is 4 μL. Each evaluation was performed by measuring the contact angle after 5 seconds of dropping.

The water repellency was evaluated in the following five levels. The larger the contact angle, the better the water repellency, so it is preferable. A: The contact angle is 110° or more B: The contact angle is more than 100° and less than 110° C: The contact angle is 90° or more and less than 100° D: The contact angle is 70° or more and less than 90° E: The contact angle is less than 70°

The oil repellency was evaluated according to the following 5 levels. The larger the contact angle, the better the oil repellency, so it is better. A: The contact angle is 60° or more B: The contact angle is 50° or more and less than 60° C: The contact angle is more than 40° and less than 50° D: The contact angle is more than 30° and less than 40° E: The contact angle is less than 30°

(Evaluation method of sliding property) The evaluation of the sliding property was performed using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., contact angle meter Drop Master 500). Specifically, 20 μL of water was dropped on the coating surface inclined at a predetermined angle, and the angle of sliding was regarded as the sliding angle. According to the sliding angle, the following 5 levels are used for evaluation. The smaller the sliding angle is, the better the sliding property is, so it is better. A: Sliding off at 25° B: Sliding down at 30° C: Sliding down at 40° D: Sliding down at 50° E: No slippage at 60°

[Table 1] Example 1 2 3 4 5 6 7 8 9 10 11 Composition (parts by mass) Copolymer (A-1) 60 60 60 40 60 60 60 60 (A-2) 60 (A-3) 60 60 (B1) 20 20 20 20 30 20 20 20 20 20 20 (B2-1) 10 20 10 20 (B2-2) 20 20 10 30 20 20 20 10 (B2-3) 20 (C-1) Solvent (D-1) 300 300 300 300 100 100 100 100 100 100 100 (D-2) (D-3) (D-4) (D-5) (D-6) (A+B1+B2)/All components 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% ((B2-l)+(B2-2))/A 33% 33% 33% 33% 75% 33% 33% 33% 33% 0% 33% B2/A 33% 33% 33% 33% 75% 33% 33% 33% 33% 33% 33% B1/A 33% 33% 33% 33% 75% 33% 33% 33% 33% 33% 33% B2/B1 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% Evaluation Experiment 1 Water repellency A A A A A A A A A A A Oil repellency A A A A A A A A A A A Slippage B B B B B A B A A B A Test 2 Water repellency A A A A A A A A A A A Oil repellency A A A A A A A A A A A Slippage B B B B B A B A A B A

[Table 2] Example Comparative example 12 13 14 15 16 17 1 2 3 4 5 6 Composition (parts by mass) Copolymer (A-1) 60 60 60 60 60 60 40 60 60 60 60 60 (A-2) (A-3) (B1) 5 20 20 20 20 20 10 (B2-1) 18 10 (B2-2) 35 20 20 20 20 20 (B2-3) 40 (C-1) 60 40 40 twenty one 20 Solvent (D-1) 100 300 300 100 100 300 300 (D-2) 100 (D-3) 100 (D-4) 100 (D-5) 100 (D-6) 100 (A+B1+B2)/All components 100% 100% 100% 100% 100% 100% 40% 60% 60% 78% 100% 80% ((B2-l)+(B2-2))/A 58% 33% 33% 33% 33% 33% 0% 0% 0% 30% 0% 17% B2/A 58% 33% 33% 33% 33% 33% 0% 0% 0% 30% 67% 17% B1/A 8% 33% 33% 33% 33% 33% 0% 0% 0% 0% 0% 17% B2/B1 700% 100% 100% 100% 100% 100% - - - - - 100% Evaluation Experiment 1 Water repellency A A A A A A A A A A A A Oil repellency A A A A A A C C C B B A Slippage B A A A A A E E E E C E Test 2 Water repellency A A A A A A A A A A A A Oil repellency A A A A A A C C C B B A Slippage A A A A A A E E E E C E

From Table 1 and Table 2, the following results can be seen. That is, it can be seen that Example 1 to Example 17 containing the (meth)acrylate compound (B1) having an aromatic ring and Comparative Examples 1 to Comparative Example not containing the (meth)acrylate compound (B1) having an aromatic ring Compared with 5, both oil repellency and slippage are excellent.

In addition, the total compounding amount of the (meth)acrylate compound (A), the (meth)acrylate compound having an aromatic ring (B1), and the alicyclic (meth)acrylate compound (B2) is the constituent monomer Examples 1 to 17 in which the total blending amount of was 90% by mass or more was superior to Comparative Example 6 in which the value was less than 90% by mass.

In addition, it can be seen from the results of Examples 13 to 17 that various solvents can be used to produce coating agents having excellent water repellency, oil repellency, and slippage properties.

In addition, by comparing Examples 6 to 8, it can be seen that in the (meth)acrylate compound (A), perfluorohexyl ethyl (meth)acrylate and perfluorobutyl ethyl methacrylate are used. Compared with the case, the sliding property is particularly excellent.

In addition, although not shown in the evaluation results, it can be seen from the experimental results that Example 6 is particularly excellent in sliding properties, and Example 11 is particularly excellent in oil repellency.

The present invention is not limited to the above-described embodiments, and can be implemented in various configurations without departing from the gist thereof. For example, in order to solve part or all of the above-mentioned problems or to achieve part or all of the above-mentioned effects, the technical features in the embodiments and examples corresponding to the technical features in each form described in the column of the summary of the invention may be appropriate. To replace or combine. In addition, if technical features are not described as necessary technical features in this specification, they can be deleted as appropriate.

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Claims (5)

A coating agent comprising a copolymer formed by polymerizing constituent monomers, the constituent monomers including: (Meth)acrylate compound (A) having a fluoroalkyl group having 1 to 6 carbon atoms; (Meth)acrylate compound (B1) having an aromatic ring; and Alicyclic (meth)acrylate compound (B2), in the coating agent, The total compounding amount of the (meth)acrylate compound (A), the (meth)acrylate compound having an aromatic ring (B1), and the alicyclic (meth)acrylate compound (B2) It is 90% by mass or more of the total compounding amount of the constituent monomers. The coating agent according to claim 1, wherein the alicyclic (meth)acrylate compound (B2) contains isobornyl, isonorbornyl, dicyclopentyl, dicyclopentenyl, diamond Any functional group in the alkyl group. The coating agent according to claim 1, wherein the alicyclic (meth)acrylate compound (B2) contains an isobornyl group. The coating agent according to any one of claims 1 to 3, wherein the (meth)acrylate compound (B1) having an aromatic ring contains a benzyl group. An article treated with a coating agent, which is treated with the coating agent according to any one of claims 1 to 4.